JP5915207B2 - Image forming apparatus and image forming method - Google Patents

Description

  The present invention relates to an image forming apparatus and an image forming method, such as a copying machine, a printer, a facsimile, or a complex machine thereof.

  2. Description of the Related Art Conventionally, in an image forming apparatus such as a copying machine, a toner replenishing device in which a plurality of toner bottles (toner containers) are installed is known for the purpose of containing a large amount of toner and increasing the operation rate. (For example, see Patent Document 1)

  Specifically, each of the plurality of toner bottles includes an opening serving as a toner discharge port, and a cap is installed in the opening. Then, in a state where a plurality of toner bottles are set in each bottle installation portion of the toner bank, the cap of one toner bottle for discharging the toner is removed by the cap opening / closing mechanism. The toner bottle whose cap is removed and the opening is opened is appropriately rotated by the bottle driving unit, and the toner is discharged from the toner bottle.

  Next, the discharged toner is stored in the toner storage unit and is transported to the developing unit via a toner transport path from the bottom to the developing unit. A toner transport screw is installed in the toner transport path. When one toner bottle is empty (toner end), the discharge of toner from the other toner bottle is started. Thus, it is possible to form an image with a high operation rate using a large amount of toner. However, since it is possible to form an image with a high operating rate, the power consumption is greatly increased.

  On the other hand, in recent years, in image forming apparatuses such as copying machines, demand for apparatuses that reduce power consumption and the like in consideration of the environment is high, and slimming of apparatuses has become mainstream. As the slimming of the toner replenishing portion, as represented by Patent Document 2, a technology for replenishing the toner contained in the toner container to the developing portion by sucking the toner contained in the toner container with a Mono pump is disclosed. As described above, when the MONO pump is used, the toner transport path using the flexible tube is used instead of the toner transport path using the toner transport screw. For this reason, the toner replenishing unit using the Mono pump has a high degree of freedom in layout and is relatively inexpensive, and is suitable for slimming down the apparatus and reducing the cost.

  On the other hand, as represented by Patent Document 3, as an approach from toner to reduce power consumption, low temperature fixability is expressed by coexisting crystalline polyester in addition to conventional amorphous polyester, and fixing. Attempts have been made to reduce the amount of power sometimes consumed.

  However, when using toner containing crystalline polyester as a resin component, the toner has poor toner transportability and toner replenishment in the path from the toner bottle to the developing unit due to the properties of crystalline polyester, especially when using a MONO pump. There was a problem that conveyance and replenishment were extremely difficult.

This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives.
That is, an object of the present invention is to provide an image forming apparatus and an image forming method that are excellent in low-temperature fixability, toner transportability, and toner replenishability, reduce power consumption, and obtain a high-quality image.

In order to solve the above problems, an image forming apparatus according to the present invention includes an image carrier, latent image forming means for forming an electrostatic latent image on the image carrier, and the electrostatic latent image using toner. A developing unit for developing and forming a toner image, a transfer unit for transferring the toner image to a recording medium, a fixing unit for fixing the toner image transferred to the recording medium to the recording medium, and a container Conveying means for conveying toner to the developing means, wherein the toner includes a toner base and an external additive attached to the surface of the toner base, the toner base including a crystalline resin, An amorphous resin, a release agent, and a colorant are contained, and the external additive contains a fatty acid metal salt and one or more kinds of inorganic fine particles, and the following measurement method for the fatty acid metal salt in Ri der free of 90% or less than 30% to be measured, before The transport unit includes a toner storage unit that stores the toner, and a transport unit that transports the toner stored in the toner storage unit to the developing unit, and the transport unit includes a rotor and a stator, The toner stored in the toner storage unit is sucked and conveyed while rubbing the rotor and the stator against each other .
[Method of measuring release rate]
[1] A dispersion is prepared by sufficiently mixing toner, ion-exchanged water, and a surfactant.
[2] Using an ultrasonic homogenizer (trade name homogenizer, model VCX750, CV33, manufactured by SONICS & MATERIALS Co., Ltd.), a dial is set at an output of 50%, and ultrasonic energy is applied for 1 minute. The ultrasonic conditions are a vibration time of 60 seconds and a continuous amplitude of 20 W (30%).
[3] Next, the dispersion is washed with ion-exchanged water and dried.
[4] The amount of fatty acid metal salt in the toner after dispersion and removal of the fatty acid metal salt and the amount of fatty acid metal salt in the toner before removal of the dispersion and fatty acid metal salt are quantified and substituted into Calculate the liberation rate.
Free rate [%] = (Amount of fatty acid metal salt before dispersion and removal−Amount of residual fatty acid metal salt after dispersion and removal) / Amount of fatty acid metal salt before dispersion and removal × 100

In addition, an image forming method according to the present invention for solving the above problems includes a latent image forming step of forming an electrostatic latent image on an image carrier, and developing the electrostatic latent image with toner to form a toner. A development step for forming an image; a transfer step for transferring the toner image to a recording medium; and a fixing step for fixing the toner image transferred to the recording medium to the recording medium. And an external additive attached to the surface of the toner base, wherein the toner base contains a crystalline resin, an amorphous resin, a release agent, and a colorant, The additive contains a fatty acid metal salt and one or more kinds of inorganic fine particles, and the release rate of the fatty acid metal salt measured by the following measuring method is 30% or more and 90% or less.
[Method of measuring release rate]
[1] A dispersion is prepared by sufficiently mixing toner, ion-exchanged water, and a surfactant.
[2] Using an ultrasonic homogenizer (trade name homogenizer, model VCX750, CV33, manufactured by SONICS & MATERIALS Co., Ltd.), a dial is set at an output of 50%, and ultrasonic energy is applied for 1 minute. The ultrasonic conditions are a vibration time of 60 seconds and a continuous amplitude of 20 W (30%).
[3] Next, the dispersion is washed with ion-exchanged water and dried.
[4] The amount of fatty acid metal salt in the toner after dispersion and removal of the fatty acid metal salt and the amount of fatty acid metal salt in the toner before removal of the dispersion and fatty acid metal salt are quantified and substituted into Calculate the liberation rate.
Free rate [%] = (Amount of fatty acid metal salt before dispersion and removal−Amount of residual fatty acid metal salt after dispersion and removal) / Amount of fatty acid metal salt before dispersion and removal × 100

  According to the present invention, it is possible to provide an image forming apparatus and an image forming method that are excellent in low-temperature fixability, toner transportability, and toner replenishment capability, reduce power consumption, and obtain a high-quality image.

1 is a schematic diagram illustrating a configuration in an embodiment of an image forming apparatus according to the present invention. FIG. 2 is a schematic diagram illustrating a configuration of a toner supply device and a developing unit. FIG. 3 is a schematic enlarged view showing a partial configuration of the toner supply device. FIG. 3 is a schematic cross-sectional view illustrating a configuration of a part of a toner supply device and a developing unit. FIG. 6 is a schematic enlarged view illustrating a partial configuration of a toner supply device according to a second embodiment.

  The image forming apparatus according to the present invention includes an image carrier 54, latent image forming means (53, 55) for forming an electrostatic latent image on the image carrier, and developing the electrostatic latent image using toner. Developing means 56 for forming a toner image, transfer means 58 for transferring the toner image to the recording medium P, fixing means for fixing the toner image transferred to the recording medium P to the recording medium P, and a container Transporting means for transporting the toner stored in the developing means 56 to the developing means 56, wherein the toner includes a toner base and an external additive attached to the surface of the toner base. A crystalline resin, an amorphous resin, a release agent, and a colorant; and the external additive contains a fatty acid metal salt and one or more inorganic fine particles, and the fatty acid metal. 30% or more and 90% or less of the liberation rate measured by the following measurement method of salt An image forming apparatus characterized in that.

[Method of measuring release rate]
[1] A dispersion is prepared by sufficiently mixing toner, ion-exchanged water, and a surfactant.
[2] Using an ultrasonic homogenizer (trade name homogenizer, model VCX750, CV33, manufactured by SONICS & MATERIALS Co., Ltd.), a dial is set at an output of 50%, and ultrasonic energy is applied for 1 minute. The ultrasonic conditions are a vibration time of 60 seconds and a continuous amplitude of 20 W (30%).
[3] Next, the dispersion is washed with ion-exchanged water and dried.
[4] The amount of fatty acid metal salt in the toner after dispersion and removal of the fatty acid metal salt and the amount of fatty acid metal salt in the toner before removal of the dispersion and fatty acid metal salt are quantified and substituted into Calculate the liberation rate.
Free rate [%] = (Amount of fatty acid metal salt before dispersion and removal−Amount of residual fatty acid metal salt after dispersion and removal) / Amount of fatty acid metal salt before dispersion and removal × 100

Next, the image forming apparatus and the image forming method according to the present invention will be described in more detail.
Although the embodiments described below are preferred embodiments of the present invention, various technically preferable limitations are attached thereto, but the scope of the present invention is intended to limit the present invention in the following description. Unless otherwise described, the present invention is not limited to these embodiments.
Moreover, in each figure, the same code | symbol is attached | subjected to the part which is the same or it corresponds, The duplication description is simplified or abbreviate | omitted suitably.

(Embodiment 1)
The image forming apparatus according to the first embodiment of the present invention will be described in detail with reference to FIGS. 1, 2, 3 and 4. FIG.
FIG. 1 is a schematic diagram showing a configuration of an image forming apparatus according to Embodiment 1 of the present invention.
First, the configuration and operation of the entire image forming apparatus according to the first embodiment will be described with reference to FIG.

  In FIG. 1, 50 is a digital copying machine as an image forming apparatus, 51 is a document conveying unit that conveys a set document D to a document reading unit 52, and 52 is a document reading unit that optically reads image information of the document D. Show. 53 is an exposure unit (a part of the latent image forming unit) that irradiates the photosensitive drum 54 with exposure light L based on image information read by the document reading unit 52, 54 is a photosensitive drum as an image carrier, 55 Indicates a charging portion (a part of the latent image forming means) for charging the photosensitive drum 54. Reference numeral 56 denotes a developing unit as a developing unit that develops an electrostatic latent image formed on the photosensitive drum 54 with toner to form a toner image. Reference numeral 57 denotes a toner hopper (toner containing toner) installed above the developing unit 56. Part). Reference numeral 58 denotes a transfer unit as a transfer unit that transfers a toner image formed on the photosensitive drum 54 to a transfer material P as a recording medium, and 59 denotes a cleaning unit that collects untransferred toner on the photosensitive drum 54. Reference numerals... To 63 denote paper feeding units in which a transfer material P such as transfer paper is stored. 64 is a fixing unit as a fixing unit that fixes an unfixed toner image on the transfer material P to the transfer material P; 90 is a waste toner bottle that stores waste toner collected by the cleaning unit 59 and the transfer unit 58; Indicates a toner bank of a toner replenishing section in which a plurality of toner bottles 1 are installed.

  The image forming apparatus according to the present invention includes the toner reservoir 7 to the toner hopper 57 (details thereof will be described later) in the first embodiment shown in FIG. That is, in the first embodiment, the toner stored in the toner bottle 1 as a container is stored in the toner storage unit 7 and the toner stored in the toner storage unit 7 is transported to the developing unit 56 (tube) 20, the MONO pump 30, etc.) to reach the developing section. However, the present invention is not limited to the first embodiment, and the conveying means in the present invention may be any means as long as it conveys from the toner bottle 1 to the developing unit 56.

With reference to FIG. 1, an operation during normal image formation in the copying machine 50 will be described. First, the document D is conveyed from the document table in the direction of the arrow in FIG. 1 by the conveyance roller of the document conveyance unit 51 and passes over the document reading unit 52. At this time, the document reading unit 52 optically reads the image information of the document D passing above.
Then, the optical image information read by the document reading unit 52 is converted into an electric signal and then transmitted to the exposure unit 53 (writing unit). Then, the exposure unit 53 emits exposure light L such as laser light based on the image information of the electrical signal toward the photosensitive drum 54.

  On the other hand, the photosensitive drum 54 rotates in the clockwise direction in FIG. 1, and first, the surface thereof is uniformly charged at a position facing the charging unit 55. Then, the surface of the photosensitive drum 54 charged by the charging unit 55 reaches the irradiation position of the exposure light L. At this position, an electrostatic latent image corresponding to the image information of the document D is formed.

  Thereafter, the surface of the photosensitive drum 54 on which the electrostatic latent image is formed reaches a portion facing the developing unit 56. Then, the electrostatic latent image on the photosensitive drum 54 is developed by the developing unit 56. Specifically, the toner in the developing unit 56 is mixed with the carrier by the stirring roller provided in the developing unit 56 together with the toner supplied from the toner hopper 57. The frictionally charged toner is supplied together with a carrier onto a developing roller provided in the developing unit 56. Thereafter, the toner carried on the developing roller passes through the position of a doctor blade provided in the developing unit 56 and then reaches a position facing the photosensitive drum 54. At the opposite position, the toner adheres to the electrostatic latent image formed on the surface of the photosensitive drum 54.

  The toner supplied from the toner hopper 57 is appropriately supplied into the developing unit 56 as the toner in the developing unit 56 is consumed. Consumption of the toner in the developing unit 56 is indirectly detected by an optical sensor (toner density sensor) (not shown) facing the photosensitive drum 54. Further, the toner in the toner hopper 57 is appropriately replenished from a toner replenishing device including the toner bank 100 and a Mono pump. The toner replenishing device will be described in detail later.

  Thereafter, the surface of the photosensitive drum 54 developed by the developing unit 56 reaches a portion facing the transfer unit 58. At this position, the toner image on the photosensitive drum 54 is transferred onto the transfer material P. At this time, a small amount of untransferred toner that is not transferred onto the transfer material P remains on the photosensitive drum 54.

  Thereafter, the surface of the photosensitive drum 54 having untransferred toner that has passed through the transfer portion 58 reaches a portion facing the cleaning portion 59. Then, the untransferred toner is collected in the cleaning unit 59 by the cleaning blade in contact with the photosensitive drum 54. The toner collected by the cleaning unit 59 is transported as waste toner toward the waste toner bottle 90 via a waste toner transport path (not shown). Thereafter, the surface of the photosensitive drum 54 that has passed through the cleaning unit 59 reaches a static elimination unit (not shown). Then, the potential on the surface of the photosensitive drum 54 is eliminated, and a series of image forming processes is completed.

  On the other hand, the transfer material P conveyed to the transfer unit 58 operates as follows. First, one of the plurality of sheet feeding units 61, 62, and 63 of the copying machine 50 is automatically or manually selected (for example, the upper sheet feeding unit 61 is selected). Then, one of the materials to be transferred P stored in the paper feeding unit 61 is conveyed toward the position of the conveyance path K.

  Thereafter, the transfer material P that has passed through the transport path K reaches the position of the registration roller. Then, the material P to be transferred that has reached the position of the registration roller is conveyed toward the transfer unit 58 at the same timing in order to align with the toner image formed on the photosensitive drum 54. After the transfer process, the transfer material P passes through the position of the transfer unit 58 and then reaches the fixing unit 64 through the conveyance path. At this position, the unfixed toner image on the transfer material P is fixed by heat and pressure. Thereafter, the transfer material P after the fixing process is discharged from the copying machine 50 as an output image. Thus, a series of image forming processes is completed.

Next, the toner replenishing device will be described with reference to FIG. As shown in FIG. 2, the toner replenishing device includes a toner bank 100, a tube 20, a Mono pump 30 and the like. The toner replenishing device is connected to the developing unit 56. Specifically, the Mono pump 30 of the toner replenishing device is connected to the toner hopper 57 of the developing unit 56.
The conveying means in the first embodiment is a combination of the toner storage unit 7 and the conveying units (20, 30).

The toner stored in the toner storage section 7 of the toner bank 100 is transported to the Mono pump 30 through the tube 20 by the suction force of the Mono pump 30. (The movement in the direction of the arrow in FIG. 2)
The toner that has reached the MONO pump 30 is supplied to the toner hopper 57 of the developing unit 56. The configuration and operation of the MONO pump 30 will be described in detail later.

  Next, the configuration and operation of the toner bank 100 will be described in detail with reference to FIG. As shown in FIG. 3, the toner bank 100 includes two toner bottles 1, two bottle setting units 12, a cap opening / closing mechanism 3, a bottle driving unit 11 as a toner discharging unit, a casing 2, a toner storage unit 7, and a detection unit. Sensor 4, cleaning member 5 (scraping member), stirring member 6, and the like. Although not shown, the cap opening / closing mechanism 3 and the bottle driving unit 11 are respectively installed for the two toner bottles 1.

  Each of the two toner bottles 1 includes an opening 1a serving as a toner discharge port, and a cap 1b is detachably installed in the opening 1a. The cap 1b of one toner bottle 1 (the lower toner bottle 1 in FIG. 3) that discharges toner in a state where the two toner bottles 1 are set in the respective bottle setting sections 12 is a cap opening / closing mechanism. Departed by 3. Specifically, the chuck that is integrated with the rack and holds the cap 1b moves in the direction of the arrow in FIG. 3 by the rotation of the pinion connected to the stepping motor. Thereby, the opening 1a of the toner bottle 1 is opened.

  The toner bottle 1 with the opening 1a opened is rotated in the direction of the arrow in FIG. Here, a spiral protrusion is provided on the inner peripheral surface of the toner bottle 1, and the toner in the bottle 1 is conveyed toward the opening 1a when the toner bottle 1 is rotationally driven. In addition, a driven gear is formed on the outer peripheral portion of the toner bottle 1 and meshes with the drive gear of the bottle drive unit 11, whereby drive transmission from the bottle drive unit 11 to the toner bottle 1 is transmitted.

  The toner discharged from the opening 1 a of the toner bottle 1 falls below the casing 2 and is stored in the toner storage portion 7. Here, a sensor 4 (toner end sensor) for detecting the upper surface position of the stored toner is provided on the side of the toner storage unit 7. When the sensor 4 detects toner during normal operation (the toner bottle 1 has a sufficient amount of toner), the bottle driving unit 11 is stopped and toner discharge from the toner bottle 1 is suspended. . On the other hand, when the sensor 4 does not detect toner, the bottle driving unit 11 is operated to discharge the toner from the toner bottle 1. Thus, the toner amount in the toner storage unit 7 can always be kept constant.

  A stirring member 6 is rotatably installed in the toner storage unit 7. The stirring member 6 includes a rotating shaft 6a and a stirring unit 6b held on the rotating shaft. Then, rotation of the agitating member 6 prevents the toner accumulated in the toner reservoir 7 from being blocked or cross-linked, or the toner accumulated in the toner reservoir 7 due to suction of the Monopump 30 from being prevented from being defective. Is done.

  Next, the configuration and operation of the MONO pump 30 and the developing device 56 will be described in detail with reference to FIG. The tube 20 is made of a flexible rubber material with low toner affinity, and one end is connected to the toner storage portion and the other end is connected to the suction port 31 of the MONO pump 30. The Mono pump 30 includes a rotor 32, a stator 33, a suction port 31, a rotor drive shaft 34, a drive gear 35, a clutch 36, and the like. The rotor 32 is formed such that a shaft made of a metal material is spirally twisted. One end of the rotor 32 is rotatably connected to a clutch 36 via a rotor drive shaft 34 and a drive gear 35. The stator 33 is made of a rubber material, and the hole is formed such that an oval cross section is twisted in a spiral shape. A rotor 32 is inserted into the hole of the stator 33.

  The MONO pump 30 configured as described above sucks the toner in the toner reservoir 7 to the suction port 31 via the tube 20 by rotating the rotor 32 in the stator 33 in a predetermined direction by the clutch 36. The toner sucked up to the suction port 31 is sent into the gap between the stator 33 and the rotor 32 and sent to the other end side along the rotation of the rotor 32. The delivered toner is discharged from the outlet of the MONO pump 30 and is supplied into the toner hopper 57 of the developing unit 56. A conveying screw 58 is installed in the toner hopper 57, and the toner replenished in the toner hopper 57 is conveyed to a replenishing port of the developing unit 56 (a port immediately below the conveying screw 58 in FIG. 4). The toner replenished from the replenishing port is mixed and stirred with the two-component developer in the developing unit 56.

As described above, the toner sucked up to the suction port 31 is fed into the gap between the stator 33 and the rotor 32, and is sent to the other end along the rotation of the rotor 32. At this time, the toner is moved between the stator and the rotor. Damage is caused by rubbing force between members.
In particular, a toner containing a crystalline resin in order to develop low-temperature fixability suitable for low power consumption increases the adhesion between toner particles and the adhesion between members due to the characteristics of the crystalline resin, and the rotor and stator. In a rubbing environment, adhesion to the rotor and the stator is more likely to occur. As a result, when a toner containing a crystalline resin is used, there is a problem that the toner adheres to the rotor portion due to long-term use and the toner cannot be supplied to the developing portion.

Therefore, it is necessary to reduce the adhesion between the stator and the toner and between the toner and the rotor. In the present invention, a fatty acid metal salt is adhered to the toner surface separately from the inorganic fine particles, and the fatty acid metal salt is measured by the following measuring method. The liberation rate is preferably 30% or more and 90% or less. The liberation rate of the fatty acid metal salt is more preferably 45% or more and 70% or less.
In order for the fatty acid metal salt to exert an effect as a lubricant between the stator and the rotor and the toner, the fatty acid metal salt needs to be present on the toner surface within a certain range, and even if it exceeds that, Even if it exists, the effect is not demonstrated.

(Rate of fatty acid metal salt)
A method for measuring the liberation rate of the fatty acid metal salt will be described.
[1] To a 200 ml ointment bottle, add 100 ml of ion-exchanged water and 4.4 ml of 33% dry well aqueous solution (trade name dry well, manufactured by Fuji Photo Film Co., Ltd.) containing a surfactant. Add 5 g of toner, mix well by hand shaking 30 times, and let stand for 1 hour or more.
[2] After stirring by hand shaking 20 times, using an ultrasonic homogenizer (trade name homogenizer, model VCX750, CV33, manufactured by SONICS & MATERIALS Co., Ltd.), a dial is set at an output of 50% and ultrasonic energy is applied for 1 minute. The ultrasonic conditions are a vibration time of 60 seconds, a continuous amplitude of 20 W (30%), and a vibration start temperature of 23 ± 1.5 ° C.
[3] The dispersion is suction filtered with filter paper (trade name qualitative filter paper (No. 2, 110 mm), manufactured by Advantech Toyo Co., Ltd.), washed twice with ion-exchanged water and filtered again to remove free fatty acid metal salts. Thereafter, the toner particles are dried.
[4] The amount of fatty acid metal salt in the toner before dispersion and removal of the fatty acid metal salt and the amount of fatty acid metal salt in the toner after removal of the dispersion and the fatty acid metal salt obtained in [1] to [3] The value obtained by quantifying by the method and substituting into the following formula is evaluated as the liberation rate of the fatty acid metal salt.

  In addition, about a fluorescent X ray, what is necessary is just to calculate a liberation rate by measuring the metal contained in an aliphatic metal salt. As the toner before dispersion and removal of the fatty acid metal salt, a toner produced under the same production conditions as the toner used for dispersion and removal of the fatty acid metal salt can be used as it is.

  Free rate [%] = (Amount of fatty acid metal salt before dispersion and removal−Amount of residual fatty acid metal salt after dispersion and removal) / Amount of fatty acid metal salt before dispersion and removal × 100

(Surface wax amount)
Further, the surface wax amount of the toner used in the image forming apparatus of the present invention is preferably 0.05 to 0.25. If it is less than 0.05, there is an effect of reducing adhesion between the stator and the rotor and the toner, but the fixability in a high temperature region is deteriorated. On the other hand, if the value exceeds 0.25, the adhesion between the toner and between the stator and the rotor and the toner is increased due to the property of wax like the crystalline resin. As a result, the toner adheres to the rotor portion after a long period of use. As a result, the toner cannot be supplied to the developing unit.

Hereinafter, a method for measuring the surface wax amount will be described.
The amount of the release agent (surface wax amount) contained in the toner surface layer was the strength ratio of the binder resin to the release agent by FTIR-ATR (total reflection absorption infrared spectroscopy) method. The analysis depth of the FTIR-ATR method is about 0.3 μm from the measurement principle, and this analysis determines the relative weight of the release agent (wax) in the 0.3 μm depth region from the surface of the toner particles. Can be sought.
The measuring method is as follows.

First, as a sample, 3 g of toner was accurately weighed with an electronic balance, pressed with an automatic pellet molding machine (Type M No. 50 BRP-E; manufactured by MAEKAWA TESTING MACHINE CO.) For 1 minute at a load of 6 t and 40 mmΦ (thickness) (About 2 mm) pellets were produced. The toner pellet surface was measured by the FTIR-ATR method. The micro FTIR apparatus used was a MultiScope FTIR unit installed in SpectrumOne manufactured by PERKINELMER, and was measured by a micro ATR of a germanium (Ge) crystal having a diameter of 100 μm. Measurement was performed with an infrared incident angle of 41.5 °, a resolution of 4 cm ⁻¹ and a total of 20 times.

At this time, each material such as a binder resin (binder resin) serving as a base and a release agent for measurement purposes can be specified, and wavelengths that do not overlap are selected. Each material will be described later. Here, as an example, a peak Pwax derived from the obtained release agent (for example, 2850 cm ⁻¹ for carnauba wax) and a peak Presin derived from a binder resin (for example, 828 cm ⁻¹ for polyester resin). The intensity ratio (Pwax / Presin) was defined as the amount of release agent contained in the toner surface layer. In addition, the value used the average value after measuring 3 times, changing a measurement place.

  On the other hand, the developing device 56 mainly includes a developing roller 56a facing the photosensitive drum 54, a first transporting screw 56b facing the developing roller 56a, and a second transporting facing the first transporting screw 56b via a partition member. The screw 56c and the doctor blade 56d facing the developing roller 56a. In the developing device 56, a two-component developer composed of a carrier and toner is accommodated.

  The above-described image forming process will be described in more detail with a focus on the developing process. The developing roller 56a rotates in the direction of the arrow in FIG. The developer in the developing device 56 circulates in the longitudinal direction while being agitated and mixed with the toner replenished from the toner hopper 57 through the replenishing port by the rotation of the first transport screw 56b and the second transport screw 56c in the direction of the arrow ( This is the circulation in the direction perpendicular to the paper surface of FIG.

The toner that is frictionally charged and adsorbed on the carrier is carried on the developing roller 56a together with the carrier.
The developer carried on the developing roller 56a then reaches the position of the doctor blade 56d. The developer on the developing roller 56a is adjusted to an appropriate amount at the position of the doctor blade 56d, and then reaches a position facing the photosensitive drum 54 (development area).
Thereafter, in the developing area, the toner in the developer adheres to the electrostatic latent image formed on the surface of the photosensitive drum 54. Specifically, the toner is generated by an electric field (developing electric field) formed by a potential difference (developing potential) between the latent image potential (exposure potential) of the image portion irradiated with the laser light and the developing bias applied to the developing roller 56a. Adheres to the electrostatic latent image.

(Embodiment 2)
Further, an embodiment of a system different from that of the first embodiment will be described with reference to FIG. 5 as a toner conveying means for conveying toner from the toner container to the developing unit. FIG. 5 shows the lower part of the toner bank 100 shown in FIG. 3, and the toner in the storage container 7a is removed by the stirring member 7b formed into a spiral shape from the toner supplied into the toner storage section 7. FIG. It is conveyed to the developing unit while being fluidly stirred.

[toner]
The toner used in the image forming apparatus of the present invention has at least one kind of inorganic fine particles on the surface of a toner base containing at least a crystalline resin, an amorphous resin, a release agent, and a colorant. It contains a fatty acid metal salt.
In other words, the toner includes a toner base and an external additive attached to the surface of the toner base. The toner base includes a crystalline resin, an amorphous resin, a release agent, and a colorant. The external additive contains a fatty acid metal salt and one or more kinds of inorganic fine particles.
Hereinafter, each constituent material and manufacturing method of the toner will be described in detail.

(Crystalline resin)
The crystalline resin that is a toner-containing component used in the image forming apparatus of the present invention is not particularly defined, but a crystalline polyester resin that is suitable for full color toners from the viewpoint of color developability and image strength is used.

Specific examples of the crystalline polyester resin that can be suitably used in the present invention include saturated aliphatic diol compounds having 2 to 12 carbon atoms such as 1,4-butanediol, 1,6-hexanediol, 1, 8-octanediol, 1,10-decanediol, 1,12-dodecanediol and derivatives thereof, and a dicarboxylic acid having 2 to 12 carbon atoms having at least a double bond (C═C bond) as an acidic component, or C2-C12 saturated dicarboxylic acid, especially fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1,12- It is synthesized using dodecanedioic acid and derivatives thereof.
Among these, from the viewpoint of high crystallinity of the crystalline polyester and a rapid viscosity change near the melting point, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decane are particularly preferable. A saturated diol component having 4 to 12 carbon atoms such as diol and 1,12-dodecanediol, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10 -It is preferable to comprise only a saturated dicarboxylic acid component having 4 to 12 carbon atoms of either decanedioic acid or 1,12-dodecanedioic acid.

  In addition, as a method for controlling the crystallinity and softening point of the crystalline polyester resin, a trivalent or higher polyhydric alcohol such as glycerin as an alcohol component and a trivalent or higher polyvalent such as trimellitic anhydride as an acid component can be used during polyester synthesis. Examples thereof include a method of designing and using a non-linear polyester that has been subjected to condensation polymerization by adding a polyvalent carboxylic acid.

The molecular structure of the crystalline polyester resin used in the present invention can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement using a solution or solid. In the absorption spectrum, those having absorption based on δCH (out-of-plane variable vibration) of olefin at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ can be exemplified.

With regard to the molecular weight of the crystalline polyester used in the present invention, the molecular weight distribution is sharp and the low molecular weight is excellent in low-temperature fixability, while the heat resistant storage stability deteriorates when there are many components having a low molecular weight. As a result, it is preferable to satisfy the relationship shown below.
That is, the weight average molecular weight Mw is 5,000 or more and 20,000 or less and the ratio of the number average molecular weight Mn of 500 or less is 0% or more and 2.5 in the molecular weight distribution by GPC of the soluble part of o-dichlorobenzene. It has been found that when the ratio of not more than% and the number average molecular weight Mn of not more than 1000 is 0% or more and 5.0% or less, both low-temperature fixability and heat-resistant storage stability can be achieved. More preferably, the ratio of the number average molecular weight Mn of 500 or less is 0% or more and 2.0% or less, and the ratio of the number average molecular weight Mn of 1000 or less is 0% or more and 4.0% or less.

(Non-crystalline resin)
In the present invention, a well-known and commonly used non-crystalline binder resin can be used as the non-crystalline resin, but an amorphous polyester resin is preferably used.
The non-crystalline non-modified polyester resin (non-crystalline polyester resin) is at least partly a modified polyester resin obtained by crosslinking and / or elongation reaction of a binder resin precursor made of a modified polyester resin described later. Are preferably compatible with each other. Thereby, low temperature fixability and hot offset resistance can be improved. For this reason, it is preferable that the polyol and polycarboxylic acid of the modified polyester resin and the unmodified polyester resin have similar compositions.

  When the acid value of the crystalline polyester is A and the acid value of the unmodified polyester resin is C, it is preferable that the following relational expression is satisfied.

  −10 mgKOH / g <A−C <10 mgKOH / g

  When the difference in acid value between the crystalline polyester and the amorphous polyester is 10 or more, the compatibility and affinity between the crystalline polyester and the amorphous polyester are poor, and the low-temperature fixability may be poor. Further, the crystalline polyester is likely to be exposed on the toner surface, and contamination and filming of the developing part are likely to occur.

  In addition, the urea-modified polyester resin described later can be used in combination with a polyester resin modified with a chemical bond other than a urea bond, for example, a polyester resin modified with a urethane bond, in addition to an unmodified polyester resin.

  When the toner composition contains a modified polyester resin such as a urea-modified polyester resin, the modified polyester resin can be produced by a one-shot method or the like.

As an example, a method for producing a urea-modified polyester resin will be described.
First, a polyol and a polycarboxylic acid are heated to 150 to 280 ° C. in the presence of a catalyst such as tetrabutoxy titanate or dibutyltin oxide, and if necessary, water generated while removing pressure is removed to have a hydroxyl group. A polyester resin is obtained. Next, a polyester resin having a hydroxyl group is reacted with polyisocyanate at 40 to 140 ° C. to obtain a polyester prepolymer having an isocyanate group. Furthermore, the polyester prepolymer having an isocyanate group is reacted with amines at 0 to 140 ° C. to obtain a urea-modified polyester resin.

  The number average molecular weight of the urea-modified polyester resin is usually 1000 to 10000, preferably 1500 to 6000.

  In addition, when reacting the polyester resin which has a hydroxyl group, and polyisocyanate, and reacting the polyester prepolymer which has an isocyanate group, and amines, a solvent can also be used as needed.

  Solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.); ethers (tetrahydrofuran) And the like which are inert with respect to the isocyanate group.

  In addition, when using unmodified polyester resin together, you may mix to the solution after reaction of the urea modified polyester resin what was manufactured similarly to the polyester resin which has a hydroxyl group.

In the present invention, the binder resin component contained in the oil phase includes a crystalline polyester resin,
An amorphous polyester resin, a binder resin precursor, and an unmodified resin may be used in combination, but may further contain a binder resin component other than these resins. The binder resin component preferably contains a polyester resin, and more preferably contains 50% by weight or more of the polyester resin. If the content of the polyester resin is less than 50% by weight, the low-temperature fixability may be lowered. It is particularly preferable that all of the binder resin components are polyester resins.

  Non-binding resins other than polyester resins include polystyrene, poly (p-chlorostyrene), styrene-substituted polymers such as polyvinyltoluene, styrene-substituted polymers, styrene-p-chlorostyrene copolymers, styrene-propylene. Copolymer, Styrene-vinyltoluene copolymer, Styrene-vinylnaphthalene copolymer, Styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, Styrene-butyl acrylate copolymer, Styrene-acrylic Octyl acid copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer Copolymerization, styrene-vinyl methyl ketone copolymer Styrene copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; Methyl acid, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like.

The non-binding resin preferably contains a binder resin precursor.
The toner used in the present invention includes, in an organic solvent, at least a colorant, a release agent, a crystalline polyester resin, a non-crystalline polyester resin, a binder resin precursor composed of a modified polyester resin, and the others. In the oil phase obtained by dissolving and dispersing the binder resin component, the binder resin precursor and a compound that extends or crosslinks are dissolved, and then the oil phase is dispersed in an aqueous medium containing a fine particle dispersant. The toner is preferably obtained by obtaining an emulsified dispersion, causing the binder resin precursor to undergo a crosslinking reaction and / or elongation reaction in the emulsified dispersion, and removing the organic solvent.

(Binder resin precursor)
As the binder resin precursor, a binder resin precursor made of a modified polyester resin is preferable, and examples thereof include a polyester prepolymer modified with isocyanate or epoxy. This undergoes an extension reaction with a compound having an active hydrogen group (such as amines), and has an effect of improving the release width (difference between the minimum fixing temperature and the hot offset generation temperature).
As a method for synthesizing the polyester prepolymer, the polyester prepolymer can be easily synthesized by reacting a base polyester resin with a conventionally known isocyanate agent or epoxidizing agent.

Isocyanating agents 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.); isocyanurates; And combinations of two or more of these.
Moreover, epichlorohydrin etc. can be mentioned as the representative example as an epoxidizing agent.

  The ratio of the isocyanate agent is usually 5/1 to 1/1, preferably 4/1 to 1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the base polyester. 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, the urea content of this polyester prepolymer becomes low, and the hot offset resistance deteriorates.

  The content of the isocyanate agent in the polyester prepolymer is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, and more preferably 2 to 20% by weight. If it is less than 0.5% by weight, 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% by weight, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the polyester prepolymer is usually 1 or more, preferably 1.5 to 3 on average, and more preferably 1.8 to 2.5 on average. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester resin after the elongation reaction is lowered, and the hot offset resistance is deteriorated.

The binder resin precursor preferably has a weight average molecular weight of 1 × 10 ⁴ or more and 3 × 10 ⁵ or less.

(Compound that stretches or crosslinks with binder resin precursor)
Examples of the compound that extends or crosslinks with the binder resin precursor include compounds having an active hydrogen group, and typical examples thereof include amines. Examples of amines include diamine compounds, trivalent or higher polyamine compounds, amino alcohol compounds, amino mercaptan compounds, amino acid compounds, and compounds in which these amino groups are blocked.

Examples of diamine compounds include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine). Etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like.
Examples of the trivalent or higher polyamine compound include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol compounds include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan compound include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of amino acid compounds include aminopropionic acid and aminocaproic acid.
Examples of the compounds in which these amino groups are blocked include ketimine compounds and oxazoline compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).
Among these amines, preferred are a diamine compound, a mixture of a diamine compound and a small amount of a polyamine compound, and a ketimine compound obtained from the diamine compound.

(Coloring agent)
As the colorant used in the present invention, 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, Phisera Red , Parachlor Rutonitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, 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, thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazo Red, polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, indance Ren 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, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green , Phthalocyanine 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 used in the present invention can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

  This master batch can obtain a master batch by mixing and kneading the above-mentioned binder resin for a master batch and a colorant under high shearing force. In this case, an organic solvent can be used to enhance the interaction between the colorant and the binder resin. In addition, the so-called flushing method, which is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water of a colorant together with a binder resin and an organic solvent, transferring the colorant to the binder resin side, is also possible. Since the cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
The release agent is preferably a wax having a melting point of 50 to 120 ° C.
Such a wax can effectively act as a release agent between the fixing roller and the toner interface, thus improving high-temperature offset resistance without applying a release agent such as oil to the fixing roller. Can be made.
In addition, melting | fusing point of wax is calculated | required by measuring the maximum endothermic peak using TG-DSC system TAS-100 (made by Rigaku Corporation) which is a differential scanning calorimeter.
As the mold release agent, the following materials can be used.

As waxes and waxes, plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin, microcrystalline, petrolatum, etc. And petroleum wax.
In addition, examples of mold release agents other than these natural waxes include synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; and synthetic waxes such as esters, ketones, and ethers.
Furthermore, fatty acid amides such as 1,2-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; low molecular weight crystalline polymer, poly (n-stearyl methacrylate), poly (methacrylic acid n) -A crystalline polymer having a long-chain alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl (for example, n-stearyl acrylate-ethyl methacrylate copolymer, etc.) should also be used as a release agent. Can do.

(Charge control agent)
The toner used in the present invention may contain a charge control agent as necessary. All 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). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives.

  Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, 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), copper phthalocyanine, perylene, quinaclide And azo pigments, and other high molecular compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  The amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. However, it is preferably 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 attractive force with the developing roller is increased, the developer fluidity is lowered, and the image density is lowered. Invite. On the other hand, if the amount is less than 0.1 part by weight, the effect of the charge control agent is not sufficient.

  These charge control agents can be melted and kneaded together with the masterbatch and binder resin and then dissolved and dispersed. Of course, they can be added directly when dissolved and dispersed in organic solvents, and fixed on the toner surface after toner particles are prepared. You may make it.

(Toner production method in aqueous medium)
The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  Binder resin precursor, colorant, release agent, crystalline polyester dispersion, charge control agent, unmodified polyester resin (non-crystalline resin), etc. that form toner particles form a dispersion in an aqueous medium. However, it is more preferable to mix these toner raw materials in advance and then add and disperse the mixture in an aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  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. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. 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 60 minutes. The temperature during dispersion is usually 0 to 80 ° C. (under pressure), preferably 10 to 40 ° C.

  The amount of the aqueous medium used is usually 100 to 1000 parts by weight with respect to 100 parts by weight of the toner composition. If the amount is less than 100 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 1000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  As a method of reacting the polyester prepolymer and the compound having active hydrogen groups, the compound having active hydrogen groups may be added and reacted before dispersing the toner composition in the aqueous medium, or dispersed in the aqueous medium. Then, a compound having an active hydrogen group may be added to cause a reaction from the particle interface. In this case, a polyester modified with a polyester prepolymer is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided inside the particles.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamines, etc. as dispersants for emulsifying and dispersing the oil phase in which the toner composition is dispersed in a liquid containing water Amine salts such as salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl- Amphoteric surfactants such as N- dimethyl ammonium betaine.

  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- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts thereof, 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 ) Perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate Etc.

  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 (Daikin Kogyo Co., Ltd.), Mega-Fac F-l0, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  Examples of cationic surfactants include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, and benzaza. Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.

  Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.

  Further, the dispersed droplets may be stabilized by a polymer protective colloid or organic fine particles insoluble in water. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, acrylic acid-3- Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, 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 esters of compounds containing vinyl alcohol and carboxyl groups For example, 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 imidazole, ethylene Homopolymers or copolymers such as those having a nitrogen atom such as imine or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, polyethylene Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner to wash away after the reaction.

  Further, in order to lower the viscosity of the toner composition, a solvent in which the polyester prepolymer reacts and is modified with a modified polyester can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal.

Examples of the solvent include 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 the solvent with respect to 100 parts of polyester prepolymers is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after elongation and / or crosslinking reaction.

  The elongation and / or crosslinking reaction time is selected depending on the reactivity depending on the combination of the polyester prepolymer and the compound having an active hydrogen group, and is usually 10 minutes to 40 hours, preferably 30 minutes to 24 hours. The reaction temperature is usually 0 to 100 ° C., preferably 10 to 50 ° C. Moreover, a well-known catalyst can also be used as needed. Specific examples include tertiary amines such as triethylamine and imidazoles.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short processing time such as spray dryer, belt dryer, rotary kiln.

When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

  The obtained toner powder after drying is mixed with different kinds of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles (external additive), and colorant fine particles, or mechanically mixed with the mixed powder. By applying an impact force, the particles can be immobilized and fused on the surface, and detachment of the foreign particles from the surface of the resulting composite particles can be prevented.

  Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) is modified to reduce the grinding air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron system (Made by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

(External additive)
The toner used in the present invention may contain an external additive to assist fluidity, developability, chargeability, and cleaning properties.
As the external additive, a fatty acid metal salt and one or more kinds of inorganic fine particles can be preferably used.

  The addition amount of the fatty acid metal salt and the one or more kinds of inorganic fine particles is preferably 0.05 to 2.5 parts by weight with respect to 100 parts by weight of the toner base. Moreover, it is preferable that the addition amount of a fatty acid metal salt is smaller than the addition amount of any one of one or more types of inorganic fine particles.

Examples of the cleaning property improver for removing the developer after transfer remaining on the photosensitive member and the primary transfer medium (such as an intermediate transfer belt used in an electrophotographic image forming apparatus) include zinc stearate and calcium stearate. Fatty acid metal salts such as stearic acid are preferred, and zinc stearate is particularly preferred.
The fatty acid metal salt preferably has a volume average particle diameter of 2 μm to 7 μm attached to the surface of the toner base (mixed with the toner base).

  Furthermore, other cleaning property improving agents can be used in combination, and examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.

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.
Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resins Examples include polymer particles.

  Such a fluidizing agent 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. .

(Layered inorganic mineral)
In addition, the toner used in the present invention may contain a layered inorganic mineral that is at least partially modified with organic ions.
A layered inorganic mineral refers to an inorganic mineral formed by overlapping layers having a thickness of several nanometers, and modifying with organic ions means introducing organic ions into ions existing between the layers. Specifically, it is described in JP-T-2003-515795, JP-T-2006-500605, and JP-T-2006-503313. This is called intercalation in a broad sense. As the layered inorganic mineral, smectite group (montmorillonite, saponite, etc.), kaolin group (kaolinite, etc.), magadiite, and kanemite are known.

  The modified layered inorganic mineral is highly hydrophilic due to its modified layered structure. Therefore, when used in toners that are dispersed in an aqueous medium and granulated without modifying the layered inorganic mineral, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed. By doing so, the hydrophilicity becomes high, and such a modified layered inorganic mineral becomes finer and deformed during the production of the toner, and is particularly present in the surface portion of the toner particle, and it functions as a charge control and also at low temperature fixing. To contribute. At this time, the content of the modified layered inorganic mineral in the toner material is preferably 0.05 to 5% by weight.

  The modified layered inorganic mineral used in the present invention is preferably one having a smectite basic crystal structure modified with an organic cation. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.

  Examples of the organic ion modifier of the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts and imidazolium salts. A quaternary alkyl ammonium salt is desirable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.

  Examples of the organic ion modifier include branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, and the like. Sulfates, sulfonates, carboxylates, or phosphates having A carboxylic acid having an ethylene oxide skeleton is desirable.

By modifying at least part of the layered inorganic mineral with organic ions, it has moderate hydrophobicity, the oil phase containing the toner composition and / or toner composition precursor has non-Nutnian viscosity, and the toner is deformed Can be At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner material with organic ions is preferably 0.05 to 5% by weight.
The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

  Commercially available layered inorganic minerals partially modified with organic cations include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Examples include quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. Moreover, as a layered inorganic mineral partially modified with an organic anion, a material obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable. The following general formula (1) includes, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).

^{_{R 1 (OR 2) n OSO}} 3 M ··· formula (1)

[Wherein, R ¹ represents an alkyl group having 13 carbon atoms, and R ² represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element]

  By using the modified layered inorganic mineral, it has moderate hydrophobicity, and the oil phase containing the toner composition has a non-Newtonian viscosity in the production process of the toner having this, and the toner can be deformed.

(1 component developer, 2 component developer)
When the toner used in the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 100 parts by weight of the carrier. 10 parts by weight is preferred.

  As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used.

Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, and polyamide resin.
Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro such as terpolymers of non-fluoride monomers including, and silicone resins, epoxy resins, and the like and.

  Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The toner used in the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

  The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner for developing an electrostatic charge image of the present invention are measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm. Then, analysis was performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) was added to a glass 100 ml beaker, 0.5 g of each toner was added, and the mixture was stirred with a micropartel. Subsequently, 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). Subsequently, the dispersion liquid subjected to the dispersion treatment was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. At this time, it is important that the concentration is 8 ± 2% from the viewpoint of measurement reproducibility of the particle diameter. Within this concentration range, no error occurs in the particle size.

(Method for producing toner when reactive modified polyester is contained)
In the present invention, a urea-modified polyester (UMPE) or the like can be obtained by reacting a reactive modified polyester such as a polyester prepolymer (A) having an isocyanate group with an amine (B) in an aqueous medium. As a method for stably forming a dispersion comprising a modified polyester such as urea-modified polyester or a reactive modified polyester such as prepolymer (A) in an aqueous medium, a modified polyester such as urea-modified polyester or a pre-polymer can be used in an aqueous medium. Examples thereof include a method in which a composition of a toner raw material composed of reactive modified polyester such as polymer (A) is added and dispersed by shearing force. Reactive modified polyester such as prepolymer (A) and other toner composition (hereinafter referred to as toner raw material) colorant, colorant masterbatch, release agent, charge control agent (charge control agent), unmodified polyester The resin or the like may be mixed when the dispersion is formed in the aqueous medium, but it is more preferable to mix the toner raw material in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  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. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. 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. Higher temperatures are preferred in that the dispersion of the urea-modified polyester or prepolymer (A) has a low viscosity and is easy to disperse.

  The amount of the aqueous medium used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts of the toner composition containing a polyester such as urea-modified polyester and prepolymer (A). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  In order to disperse the oily phase in which the toner composition is dispersed in a liquid containing water, various dispersing agents for emulsifying and dispersing are used. Such a dispersant includes a surfactant, an inorganic fine particle dispersant, a polymer fine particle dispersant and the like. The above-mentioned dispersants are preferably used for these dispersants.

  Further, the same effect as that of the inorganic dispersant was confirmed for the fine particle polymer. For example, MMA polymer fine particles 1 μm and 3 μm, styrene fine particles 0.5 μm and 2 μm, styrene-acrylonitrile fine particle polymer 1 μm, (PB-200H (Kao) SGP (Soken), Technopolymer SB (Sekisui Plastics), SGP-3G (Soken) Micropearl (Sekisui Fine Chemical)).

  In addition, as a dispersant that can be used in combination with the above inorganic dispersant and fine particle polymer, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloroacrylate 2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, 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, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In order to produce coalesced particles by stirring and converging the obtained emulsified dispersion (reactant) in a certain temperature range lower than the resin glass transition temperature and the organic solvent concentration range, The shaped toner particles can be produced by gradually raising the temperature in a laminar stirring state and removing the solvent. In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant can remain on the toner particle surface.

  Furthermore, in order to reduce the viscosity of the dispersion medium containing the toner composition, a solvent in which a polyester such as urea-modified polyester or prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp.

  The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include 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 the solvent with respect to 100 parts of prepolymers (A) is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts. When a solvent is used, the solvent (solvent) is removed from the resultant reaction product under normal pressure or reduced pressure after the extension and / or crosslinking reaction of the modified polyester (prepolymer) with an amine.

  The elongation and / or crosslinking reaction time is selected, for example, depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. It's time. 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. In addition, as an extender and / or a crosslinking agent, the above-described amines (B) are used.

  In the present invention, prior to desolvation from the dispersion (reaction liquid) after the elongation and / or cross-linking reaction, the dispersion is stirred and converged in a certain temperature range lower than the resin glass transition temperature and in the organic solvent concentration range. It is preferable to remove the solvent at 10 to 50 ° C. after preparing the coalesced particles and confirming the shape. The toner is deformed by liquid agitation before the removal of the solvent. Since this condition is not an absolute condition, it is necessary to appropriately select the condition.

  When the concentration of the organic solvent contained in the granulation is high, the viscosity of the emulsion is lowered, and when the droplets are united, the particle shape tends to be spherical. Further, when the concentration of the organic solvent contained in the granulation is low, when the droplets coalesce, the viscosity of the droplets is high and the particles do not become complete particles but come off. For this reason, it is necessary to set an optimum condition, and the toner shape can be appropriately adjusted by selecting a condition.

Further, the shape can be adjusted by the content of the organically modified layered inorganic mineral. The organically modified layered inorganic mineral is preferably contained in an amount of 0.05 to 10% in the solid content in the solution or dispersion.
If it is less than 0.05%, the target oil phase viscosity cannot be obtained, and the target shape cannot be obtained. Since the droplet viscosity is low, even if the droplets coalesce during the stirring and converging, the target coalesced particles cannot be obtained, resulting in a spherical shape.
If it exceeds 10%, the manufacturability deteriorates, the droplet viscosity becomes too high, the particles do not become coalesced particles, and the fixing performance deteriorates.

  On the other hand, the ratio Dv / Dn of the volume average particle diameter Dv and the number average diameter (Dn) of the toner is controlled mainly by adjusting, for example, the water layer viscosity, the oil layer viscosity, the characteristics of the resin fine particles, the addition amount, and the like. can do. Further, Dv and Dn can be controlled by adjusting, for example, characteristics of resin fine particles, addition amount, and the like.

(Toner production method using emulsion aggregation and fusion method)
In the emulsion aggregation fusion method, a resin particle dispersion prepared by emulsifying dispersion, a separately prepared colorant dispersion, and a release agent dispersion are mixed and aggregated to form aggregated particles. And a step of preparing a liquid (hereinafter sometimes referred to as “aggregation step”) and a step of heating and coalescing the aggregated particles to form toner particles (hereinafter sometimes referred to as “fusion step”).

  In the aggregating step, the agglomerated particles are formed by heteroaggregation or the like. At that time, for the purpose of stabilizing the agglomerated particles and controlling the particle size / particle size distribution, an ionic surfactant or metal salt having a different polarity from the agglomerated particles A compound having a monovalent or higher charge can be added. In the fusion step, the resin is melted by heating to a temperature equal to or higher than the glass transition point of the resin in the aggregated particles.

  In the previous stage of the fusing step, there can be provided an attaching step in which other fine particle dispersion is added to and mixed with the aggregated particle dispersion to uniformly attach the fine particles to the surface of the aggregated particles to form adhered particles.

  The fused particles fused in the fusion step exist as a colored fused particle dispersion in the aqueous medium, and at the same time the fused particles are taken out of the aqueous medium in the washing step, the impurities mixed in the respective steps are removed. The toner is removed and dried to obtain a toner for developing an electrostatic image as powder.

  In the washing step, acidic and possibly basic water is added in several times the amount to the fused particles and stirred, followed by filtration to obtain a solid content. The pure water is added several times to the solid content and stirred, followed by filtration. This is repeated several times until the pH of the filtrate after filtration reaches about 7, and colored toner particles are obtained. In the drying step, the toner particles obtained in the washing step are dried at a temperature below the glass transition point. At this time, it is possible to circulate dry air or heat under vacuum as necessary.

  In the present invention, it is preferable to melt by heating to a temperature equal to or higher than the glass transition temperature. However, when a crystalline polyester and an amorphous polyester are used at that time, they are in a compatible state. Therefore, it is necessary to perform annealing in the toner manufacturing process. Annealing can be performed before and during the cleaning process, and further in any process after the drying process and after the drying process.

  Examples of such surfactants include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type And nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an ionic surfactant is preferable, and an anionic surfactant and a cationic surfactant are more preferable. In the toner for developing an electrostatic charge image of the present invention, an anionic surfactant generally has a strong dispersibility and excellent dispersibility of resin particles and a colorant. As the agent, a cationic surfactant is advantageous. The nonionic surfactant is preferably used in combination with an anionic surfactant or a cationic surfactant. Surfactant may be used individually by 1 type and may use 2 or more types together.

  Specific examples of anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate, and castor oil sodium; sulfate esters such as octyl sulfate, lauryl sulfate, lauryl ether sulfate, and nonyl phenyl ether sulfate; lauryl sulfonate Sulfone such as sodium alkylnaphthalene sulfonate such as dodecylbenzene sulfonate, triisopropyl naphthalene sulfonate, dibutyl naphthalene sulfonate, naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric acid amide sulfonate, oleic acid amide sulfonate Acid salts; lauryl phosphate, isopropyl phosphate, nonylphenyl ether Phosphoric acid esters such as Sufeto; dialkyl sulfosuccinate salts such as sodium dioctyl sulfosuccinate, sulfosuccinic acid salts, such as sodium lauryl sulfosuccinate 2; and the like.

  Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride, oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate, and other amine salts; lauryltrimethylammonium chloride, dilauryldimethylammonium Chloride, distearyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dihydroxyethyl methyl ammonium chloride, oleyl bispolyoxyethylene methyl ammonium chloride, lauroylaminopropyldimethylethylammonium ethosulphate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzene dimethyl Ammonium chloride, alkyltri And quaternary ammonium salts such as chill ammonium chloride.

  Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octyl phenyl ether, polyoxy Alkyl phenyl ethers such as ethylene nonyl phenyl ether; alkyl esters such as polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene oleate; polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene Alkylamines such as oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; Alkyl amides such as ethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid Alkanolamides such as diethanolamide and oleic acid diethanolamide; sorbitan ester ethers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan monooleate Etc.

  The content of the surfactant in each dispersion may be a level that does not impair the characteristics of the present invention, and is generally a small amount. Specifically, in the case of a resin particle dispersion, 0.01 to 1 wt. %, Preferably 0.02 to 0.5% by weight, more preferably 0.1 to 0.2% by weight. When the content is less than 0.01% by weight, aggregation may occur particularly when the pH of the resin particle dispersion is not sufficiently basic. The content in the case of the colorant dispersion and the release agent dispersion is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, more preferably 0.5 to 0.2% by weight. If the content is less than 0.01% by weight, the stability between the particles is different at the time of agglomeration, which causes problems such as the release of specific particles. If the content exceeds 10% by weight, the particle size distribution of the particles becomes wider. In addition, there are problems such as difficulty in controlling the particle diameter, which is not preferable.

In addition to those described above, fine particles of other components such as an internal additive, a lubricant, and an abrasive can be added to the toner base used in the present invention.
As an internal additive, it is used to such an extent that it does not hinder the chargeability as a toner characteristic. For example, a metal such as ferrite, magnetite, reduced iron, cobalt, manganese, nickel, an alloy, or a magnetic compound such as a compound containing these metals. The body is used.
Examples of the lubricant include fatty acid amides such as ethylene bis stearic acid amide and oleic acid amide, and fatty acid metal salts such as zinc stearate and calcium stearate.
As an abrasive | polishing agent, the above-mentioned silica, alumina, cerium oxide etc. are mentioned, for example.

  As described above, when the resin particle dispersion, the layered inorganic mineral dispersion modified at least partially with organic ions, the colorant dispersion, and the release agent dispersion are mixed, the content of the colorant is 50% by weight. The following is sufficient, and the range of 2 to 40% by weight is preferable. The content of the layered inorganic mineral at least partially modified with organic ions is preferably in the range of 0.05 to 10% by weight. Further, the content of the other components only needs to be a level that does not hinder the object of the present invention, and is generally extremely small, specifically in the range of 0.01 to 5% by weight, 0.5 A range of ˜2% by weight is preferred.

  In the present invention, as a dispersion medium for the resin particle dispersion, a layered inorganic mineral dispersion at least partially modified with organic ions, a colorant dispersion, a release agent dispersion, and a dispersion of other components, for example, an aqueous medium Is used. Specific examples of the aqueous medium include water such as distilled water and ion exchange water, alcohol, and the like. These may be used individually by 1 type and may use 2 or more types together.

In the step of preparing the aggregated particle dispersion of the present invention, the aggregated particles can be adjusted by adjusting the emulsifying power of the emulsifier with pH to generate aggregation.
At the same time, an aggregating agent may be added in order to stably and rapidly aggregate the particles to obtain aggregated particles having a narrower particle size distribution.
As the flocculant, a compound having a monovalent or higher charge is preferable. Specifically, water-soluble surfactants such as the above-mentioned ionic surfactants and nonionic surfactants, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, Acids such as oxalic acid, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, ammonium sulfate, aluminum nitrate, silver nitrate, copper sulfate, sodium carbonate and other inorganic acid metal salts, sodium acetate, potassium formate, sodium oxalate, phthalic acid Aliphatic acids such as sodium and potassium salicylates, metal salts of aromatic acids, metal salts of phenols such as sodium phenolate, metal salts of amino acids, triethanolamine hydrochloride, aniline hydrochloride and other aliphatic and aromatic amines Inorganic acid salts and the like. When considering the stability of the aggregated particles, the stability of the aggregating agent with respect to heat and time, and the removal during washing, a metal salt of an inorganic acid is preferable in terms of performance and use.

  The amount of these flocculants to be added varies depending on the valence of the charge, but all of them are small amounts. The monovalent is 3% by weight or less, the divalent is 1% by weight or less, and the trivalent is 0. It is about 5% by weight or less. A smaller amount of the flocculant is preferable, and a compound having a higher valence is preferable because the amount added can be reduced.

(Toner production method by pulverization method)
The kneading and pulverization method includes, for example, melting and kneading the toner material (toner material other than the external additive) described above, pulverizing and classifying the obtained kneaded material, thereby obtaining the toner base particles (toner base). It is a manufacturing method.

  In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay Co., Ltd., a PCM type twin screw extruder manufactured by Ikegai Co., Ltd. Used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. In this case, a method of pulverizing by colliding with a collision plate in a jet stream, a method of pulverizing particles by colliding with each other in a jet stream, or a method of pulverizing in a narrow gap between a mechanically rotating rotor and a stator are preferably used. It is done.

  In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.

  After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.

  Next, the above-described external additive is externally added to the toner base particles. By mixing and stirring the toner base particles and the external additive using a mixer, the surface of the toner base particles is coated while being crushed. At this time, it is important from the viewpoint of durability that the external additives such as inorganic fine particles and resin fine particles are uniformly and firmly attached to the toner base particles.

  The present invention will be described below, but the present invention is not limited to the following examples.

(Developer Embodiment 1)
The developing unit shown in the first embodiment is a developing device 1.

(Embodiment 2 of developing device)
A developing unit in which the toner bank shown in the second embodiment is replaced with the toner bank shown in the first embodiment is referred to as a developing device 2.

[toner]
(Production Example 1)
-Synthesis of crystalline polyester resin 1-
In a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, 2,120 g of 1,10-decanedioic acid, 1000 g of 1,8-octanediol, 1520 g of 1,4-butanediol, hydroquinone 3.9 g was added, reacted at 180 ° C. for 10 hours, heated to 200 ° C., reacted for 3 hours, and further reacted at 8.3 kPa for 2 hours to obtain crystalline polyester resin 1. The melting point measured by the above method was 67 ° C.

(Production Example 2)
~ Synthesis of amorphous polyester resin 1 ~
A 5-liter four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was added to 229 parts of bisphenol A ethylene oxide side 2 mol adduct, 529 parts of bisphenol A propylene oxide 3 mol adduct, isophthalic acid. 100 parts, 108 parts of terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 10 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10-15 mmHg. 30 parts of merit acid was added and reacted at 180 ° C. and normal pressure for 3 hours to obtain [Amorphous Polyester 1]. [Amorphous polyester 1] had a number average molecular weight of 1,800, a weight average molecular weight of 5,500, a Tg of 42 ° C., and an acid value of 20.

(Production Example 3)
~ Synthesis of polyester prepolymer ~
In a reaction vessel equipped with a cooling pipe, 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, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, 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 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

(Production Example 4)
~ Synthesis of ketimine ~
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 1]. The amine value of [ketimine compound 1] was 418.

(Production Example 5)
~ Synthesis of master batch (MB) ~
Add 1200 parts of water, carbon black (Printex35; manufactured by Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5], 540 parts, and 1200 parts of polyester resin, and mix with a Henschel mixer (Mitsui Mining Co., Ltd.). Was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

(Production Example 6)
~ Creation of oil phase ~
In a container in which a stir bar and a thermometer are set, 378 parts of [Non-crystalline polyester 1], 110 parts of wax (Hi-mic-1090; manufactured by Nippon Seiki), CCA (salicylic acid metal complex E-84: Orient Chemical Industries) The mixture was charged with 22 parts and 947 parts of ethyl acetate, heated to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are 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 are 80 vol% Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1042.3 parts of a 65% ethyl acetate solution of [Amorphous Polyester 1] was 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] was 50%.

(Production Example 7)
~ Crystalline polyester dispersion 1 production ~
1600 g of [Crystalline Polyester Resin 1] and 11200 g of ethyl acetate were placed in a metal 20 L container, dissolved by heating at 75 ° C., and then rapidly cooled in an ice-water bath at a rate of 27 ° C./min. Thereafter, 3200 g of [Non-crystalline polyester resin 1] was added and stirred for 5 hours to dissolve [Non-crystalline polyester resin 1]. Using a bead mill (LMZ2; manufactured by Ashizawa Finetech Co., Ltd.), 0.3 mm zirconia beads were dispersed at a volume of 85% by volume, 20 passes, and the bead mill shaft seal liquid temperature was 15 ° C. 1] was obtained.

(Production Example 8)
~ Crystalline polyester dispersion 2 production ~
Further, [Crystalline Polyester Dispersion 2] was obtained in the same manner as “Crystalline Polyester Dispersion 1” except that the dispersion was performed at a bead mill shaft seal liquid temperature of 25 ° C.

(Production Example 9)
~ Synthesis of organic fine particle emulsion ~
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 138 parts of styrene, 138 parts of methacrylic acid, When 1 part of ammonium persulfate was added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature 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 1] was obtained. The volume average particle diameter of the [fine particle dispersion 1] measured by LA-920 was 0.14 μm.

(Production Example 10)
-Adjustment of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred to give a milky white liquid. Got. This is designated as [Aqueous Phase 1].

(Production Example 11)
-Emulsification / solvent removal-
[Pigment / WAX Dispersion 1] 664 parts, [Prepolymer 1] 109.4 parts, [Crystalline Polyester Dispersion 1] 73.9 parts, [Ketimine Compound 1] 4.6 parts, After mixing for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika), add 1200 parts of [Aqueous Phase 1] to the container and mix with a TK homomixer at 13,000 rpm for 20 minutes [emulsified slurry 1] was obtained.
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

~ Washing and drying ~
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3) and heat the dispersion slurry at a rate of 2 ° C./min until reaching 45 ° C. while being immersed in a water bath. Hold for a minute. During a series of operations of heating and holding, the mixture was constantly held with a TK homomixer. (Rotation speed: 12,000 rpm) Thereafter, filtration was performed to obtain [Filter cake 1].
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier to obtain [Base toner 1] having a mesh size of 75 μm and a sieving toner surface wax amount of 0.15.

(Production Example 12)
A toner surface wax was prepared in the same manner as in the preparation of the base toner 1 except that [Crystalline Polyester Dispersion 1] in (Production Example 11) was changed to [Crystalline Polyester Dispersion 2] shown in (Production Example 8). The amount of [Base toner 2] was 0.14.

(Production Example 13)
[Mother toner 3] having a toner surface wax amount of 0.23 is obtained by performing the same operation as in the production of the mother toner 1 except that the wax dispersion condition by the bead mill in (Production Example 6) is changed from 3 passes to 10 passes. It was.

(Production Example 14)
[Mother toner 4] having a toner surface wax amount of 0.27 is obtained by performing the same operation as in the production of the mother toner 1 except that the wax dispersion condition by the bead mill in (Production Example 6) is changed from 3 passes to 15 passes. It was.

(Production Example 15)
(Raw material composition)
Binder resin: Crystalline polyester 1 8 parts Binder resin: Amorphous polyester 1 86 parts Colorant: Carbon black C-44 7 parts (Mitsubishi Chemical Corporation average particle size: 24 nm, BET specific surface area: 125 m ² / g)
CCA: Bontron E-84 (manufactured by Orient Chemical Co., Ltd.) 1 part Wax: Hi-mic-1090 (manufactured by Nippon Seiki) 6 parts

The toner powder raw material was thoroughly mixed with a super mixer (SMV-200, manufactured by Kawata) to obtain a toner powder raw material mixture. This toner powder raw material mixture was supplied to a raw material supply hopper of a Busco kneader (TCS-100, manufactured by Buss Co.), and kneaded at a supply amount of 120 kg / h.
The obtained kneaded product is rolled and cooled with a double belt cooler, coarsely pulverized with a hammer mill, finely pulverized with a jet airflow pulverizer (I-20 jet mill, manufactured by Nippon Pneumatic Co., Ltd.), and a wind classifier. Fine powder classification was performed with a DS-20 / DS-10 classifier (manufactured by Nippon Pneumatic Co., Ltd.) to obtain [Base toner 5] having a toner surface wax amount of 0.12.

(Production Example 16)
Except not using [Crystalline Polyester Dispersion 1] in (Production Example 11), the same operation as in the preparation of base toner 1 was performed to obtain [Base toner 6] having a toner surface wax amount of 0.15.

~ External additive mixing ~
[Base toner 1] 1.2 parts by weight of small particle size silica (HDK-2000, manufactured by Clariant), 1.2 parts by weight of large particle size silica (RY-50, manufactured by Nippon Aerosil Co., Ltd.) Part by weight and 0.6 part of titanium oxide (MT-150AI, manufactured by Teica) were mixed for 10 min at a peripheral speed of 40 m / s while maintaining the inner temperature at 25-30 ° C. using a Henschel mixer 20B. After mixing, 0.15 part of fatty acid metal salt A was added, and further mixed for 2 minutes at a peripheral speed of 40 m / s. After mixing, sieving was performed with a 36 μm ultrasonic vibration device to obtain [Toner 1] having a liberation rate of fatty acid metal salt of 55%.

Production Examples of [Toner 2] to [Toner 17] [Toner 2] to [Toner 17] are obtained by changing the formulation and mixing conditions of toner 1 to the formulations shown in Table 1 and the mixing conditions shown in Table 2 below. It was. As the fatty acid metal salts A to C, the following were used.

  Fatty acid metal salt A: 0.5% by mass of sodium stearate aqueous solution was adjusted to 75 ° C., and 0.5% by mass of zinc sulfate aqueous solution was added little by little, followed by mixing for 1 hour after completion of the addition. After mixing and cooling to 20 ° C., the fatty acid metal salt slurry was filtered and washed. The obtained washed fatty acid metal salt cake is dried using a heating vacuum dryer, dried and pulverized with a jet mill, and then classified with an elbow jet classifier to obtain zinc stearate particles (fatty acid metal salt A). It was. Dv of the zinc stearate particles was 5.3 μm.

  Fatty acid metal salt B: dried in the same manner as fatty acid metal salt A, pulverized with a nanogrinding mill (NJ-300: manufactured by Sanrex), and then collected only fine powder by cyclone classification. Zinc stearate particles (Fatty acid metal salt B) DV = 0.98 μm.

  Fatty acid metal salt C: Calcium stearate particles (fatty acid metal salt C) were obtained in the same manner except that the zinc sulfate of fatty acid metal salt A was changed to a 0.8% calcium chloride solution. Dv of calcium stearate particles was 6.5 μm.

Example 1
A Ricoh Ricoh Pro C751ex machine was remodeled and the following evaluation was performed. Remodeling was carried out in such a way that the contact charging device, process linear velocity, development device development gap, etc. could be changed.

Actual image creation is 23 ° C / 50% RH up to 0-10,000 sheets, 28 ° C / 85% RH up to 10,000-20,000 sheets, 15 ° C / 30 up to 20,000-30,000 sheets. Under% RH, an image area ratio of 5% image and 20% image were alternately output every 1000 sheets.
The actual machine image formation was carried out up to 90,000 sheets in three sets, and the effect was confirmed.
(Unless otherwise specified, the process linear velocity is 500 mm / S, contact charging, and the development gap is 0.3 mm.)
In this embodiment, [Developing device 1] is used as the developing device, and [Toner 1] is used as the toner.

(Fixability)
The cold offset temperature (fixing lower limit temperature) and the hot offset temperature (fixing upper limit temperature) were determined visually by changing the fixing temperature.
The evaluation conditions for the minimum fixing temperature were a paper feed linear velocity of 120 to 150 mm / second, a surface pressure of 1.2 kgf / cm ² , and a nip width of 3 mm.
The evaluation conditions for the upper limit fixing temperature were a paper feed linear velocity of 50 mm / second, a surface pressure of 2.0 kgf / cm ² , and a nip width of 4.5 mm.

(Toner scattering)
After the actual machine image formation, the cover was opened and the degree of toner contamination inside the machine was confirmed.
A symbol “◯” indicates that there was no significant occurrence visually, “Δ” indicates that it was not observed on the outside of the cover, and “x” indicates that the toner was clearly scattered in the machine.

(Toner fixing)
After the actual machine image formation, the toner fixing state of the toner conveying portion and the developing portion where the rubbing is mainly large (the rubbing portion of the stator and the rotor in the developing device 1 and the screw stirring portion in the developing device 2), and the image Confirmation was carried out.
When sticking occurs in this portion and the toner is conveyed, a toner aggregated image or the like is generated on the image. Further, when the fixing state deteriorates, the toner cannot be conveyed to the developing device, and printing becomes impossible.
A case where no sticking was observed, a case where a slight sticking was observed in the rubbing portion but no problem on the image was indicated by Δ, a case where sticking occurred and detected in the image was indicated by ×, and a toner conveyance failure due to sticking was indicated by ×.

  Table 3 shows the results of the above evaluation and the toners and developing devices used in each of the examples / comparative examples.

  As described above, according to Examples 1 to 12, it is possible to provide an image forming apparatus and an image forming method that are excellent in low-temperature fixability, toner transportability, and toner replenishability, reduce power consumption, and obtain high-quality images. I found out that On the other hand, Comparative Examples 1 to 5 do not satisfy any of the low-temperature fixability, the toner transportability and the toner replenishability, and cannot realize low power consumption and high quality images.

D Document P Transfer material 1 Toner bottle 1a Opening portion 1b Cap 2 Casing 3 Cap opening / closing mechanism 4 Sensor 5 Cleaning member 6 Stirring member 6a Rotating shaft 6b Stirring portion 7a Storage container 7b Stirring member 7 Toner storage portion 12 Bottle setting portion 11 Bottle Drive unit 20 Tube 30 Mono pump 31 Suction port 32 Rotor 33 Stator 34 Rotor drive shaft 35 Drive gear 36 Clutch 50 Copying machine 51 Document transport unit 52 Document reading unit 53 Exposure unit 54 Photosensitive drum 55 Charging unit 56 Development unit 56a Development roller 56b First conveying screw 56c Second conveying screw 56d Doctor blade 57 Toner hopper 58 Transfer unit 59 Cleaning units 61, 62, 63 Paper feeding unit 100 Toner bank

Japanese Patent No. 4658261 Japanese Patent No. 3939110 Japanese Patent No. 4213067

Claims (7)

An image carrier, a latent image forming unit for forming an electrostatic latent image on the image carrier, a developing unit for developing the electrostatic latent image with toner to form a toner image, and the toner image Transfer means for transferring to a recording medium, fixing means for fixing the toner image transferred to the recording medium to the recording medium, and conveying means for conveying the toner stored in a container to the developing means,
The toner includes a toner base and an external additive attached to the surface of the toner base,
The toner base contains a crystalline resin, an amorphous resin, a release agent, and a colorant,
The external additive contains a fatty acid metal salt and one or more inorganic fine particles,
Ri following measuring method of 90% der less free rate is 30% or more as measured by the fatty acid metal salt,
The transport unit includes a toner storing unit that stores the toner, and a transport unit that transports the toner stored in the toner storing unit to the developing unit,
The conveyance unit includes a rotor and a stator, and conveys the toner stored in the toner storage unit by sucking and conveying the rotor and the stator while rubbing each other. apparatus.
[Method of measuring release rate]
[1] A dispersion is prepared by sufficiently mixing toner, ion-exchanged water, and a surfactant.
[2] Using an ultrasonic homogenizer (trade name homogenizer, model VCX750, CV33, manufactured by SONICS & MATERIALS Co., Ltd.), a dial is set at an output of 50%, and ultrasonic energy is applied for 1 minute. The ultrasonic conditions are a vibration time of 60 seconds and a continuous amplitude of 20 W (30%).
[3] Next, the dispersion is washed with ion-exchanged water and dried.
[4] The amount of fatty acid metal salt in the toner after dispersion and removal of the fatty acid metal salt and the amount of fatty acid metal salt in the toner before removal of the dispersion and fatty acid metal salt are quantified and substituted into Calculate the liberation rate.
Free rate [%] = (Amount of fatty acid metal salt before dispersion and removal−Amount of residual fatty acid metal salt after dispersion and removal) / Amount of fatty acid metal salt before dispersion and removal × 100   The image forming apparatus according to claim 1, wherein the liberation rate is 45% or more and 70% or less. Wherein the fatty acid metal salt, an image forming apparatus according to claim 1 or 2, wherein the zinc stearate. The toner image forming apparatus according to any one of claims 1 to 3 wherein the volume average particle size toner base surface, characterized in that it is obtained by adhering the metal salts of fatty 2Myuemu～7myuemu. The addition amount of the fatty acid metal salt and the one or more kinds of inorganic fine particles is 0.05 to 2.5 parts by weight with respect to 100 parts by weight of the toner base, and the addition amount of the fatty acid metal salt is 1 the image forming apparatus according to any one of claims 1 to 4, characterized in that less than one amount either or more inorganic fine particles. The toner image forming apparatus according to any one of claims 1 to 5 the surface wax amount is characterized in that 0.05 to 0.25. A latent image forming step for forming an electrostatic latent image on an image carrier, a developing step for developing the electrostatic latent image with toner to form a toner image, and a transfer for transferring the toner image to a recording medium A fixing step for fixing the toner image transferred to the recording medium to the recording medium, and a conveying step for conveying the toner stored in a container to the developing step.
The toner includes a toner base and an external additive attached to the surface of the toner base,
The toner base contains a crystalline resin, an amorphous resin, a release agent, and a colorant,
The external additive contains a fatty acid metal salt and one or more inorganic fine particles,
Ri following measuring method of 90% der less free rate is 30% or more as measured by the fatty acid metal salt,
The conveying step is performed by a conveying unit that conveys the toner to the developing step.
The transport unit includes a toner storing unit that stores the toner, and a transport unit that transports the toner stored in the toner storing unit to the developing unit,
The conveyance unit includes a rotor and a stator, and conveys the toner stored in the toner storage unit by sucking and conveying the rotor and the stator while rubbing each other. Method.
[Method of measuring release rate]
[1] A dispersion is prepared by sufficiently mixing toner, ion-exchanged water, and a surfactant.
[2] Using an ultrasonic homogenizer (trade name homogenizer, model VCX750, CV33, manufactured by SONICS & MATERIALS Co., Ltd.), a dial is set at an output of 50%, and ultrasonic energy is applied for 1 minute. The ultrasonic conditions are a vibration time of 60 seconds and a continuous amplitude of 20 W (30%).
[3] Next, the dispersion is washed with ion-exchanged water and dried.
[4] The amount of fatty acid metal salt in the toner after dispersion and removal of the fatty acid metal salt and the amount of fatty acid metal salt in the toner before removal of the dispersion and fatty acid metal salt are quantified and substituted into Calculate the liberation rate.
Free rate [%] = (Amount of fatty acid metal salt before dispersion and removal−Amount of residual fatty acid metal salt after dispersion and removal) / Amount of fatty acid metal salt before dispersion and removal × 100

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