JP2007316256A - Cleaning device, electrifying device, image forming apparatus, process cartridge, image forming method and toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cleaning device of an electrifying device constituted to give preferable electrifying performance from the initial stage of use and to maintain the performance for a long period of time regardless to the use environment of the device. <P>SOLUTION: The cleaning device includes an electrifying roller 14a having at least an elastic layer or a conductive resin layer applied to the outer perimeter of a core metal and electrifying the surface of an image carrier by a voltage externally applied thereto, and an electrifying cleaning roller 14b to clean the electrifying roller surface, wherein the electrifying cleaning roller 14b has a layer made of a melamine resin foamed body and the roller is subjected to a cleaning step in the manufacturing stage of the roller. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a cleaning device, a charging device, an image forming device, a process cartridge, an image forming method, and a toner, and more particularly to cleaning for a charging device.

  2. Description of the Related Art As is well known, in an image forming apparatus using an electrophotographic system, a surface of a photoconductor as an image carrier is charged by discharging with a predetermined polarity, and the charged photoconductor surface is executed in an image writing process. An electrostatic latent image is formed by exposure, and toner charged to the same polarity as the charging polarity is supplied to the electrostatic latent image to form a toner image. The toner image formed on the photoreceptor is then transferred to a recording paper or the like, and fixed on the recording paper or the like by receiving heat and pressure.

  In addition, foreign matter such as toner remaining without being transferred or toner or paper dust scattered around the periphery may adhere to the surface of the photoconductor after the toner image is transferred. The surface of the photoreceptor is cleaned by a cleaning member such as a cleaning blade or a cleaning brush.

  In the image forming apparatus as described above, as a method for charging the surface of the photosensitive member, in recent years, a charging roller formed in a roller shape with a conductive member is brought close to or in contact with the surface of the photosensitive member, and the charging roller and the photosensitive member are exposed in this state. A charging device that charges the surface of the photosensitive member by applying a voltage between the photosensitive member and the body has been put to practical use because it has the advantage of reducing ozone and reducing power consumption.

  However, foreign matters such as transfer residual toner remaining on the surface of the photoconductor after the transfer of the toner image are not completely removed in the cleaning process. There is a problem of adhering to the charging roller.

For example, if the toner remaining in the transfer is charged to the same polarity as the charged polarity, and the normal polarity toner is used, the developer is not charged to the normal polarity but is charged to the opposite polarity when the developer is stirred. Toner is present.
Regularly charged toner repels electrostatically with the charging roller and is therefore difficult to adhere to the surface, but reversely charged toner attracts electrostatically and tends to adhere to the surface of the charging roller. In addition to the reversely charged toner, for example, dust such as paper dust may be attached if it is charged and electrostatically attracts the charging roller.

  On the other hand, in recent years, with increasing demand for high image quality and high definition of images, toners having a small particle size and a spherical shape have been used in the development process. By using such a toner, the toner is made to adhere precisely to the electrostatic latent image.

However, the above-mentioned toner having a reduced particle size and a spherical shape has a problem in that it tends to pass through the cleaning blade in the cleaning process and easily causes a cleaning failure.
Therefore, in order to prevent the toner remaining on the photosensitive member from being uncleaned from adhering to the charging roller in this way and uniformly charging the photosensitive member surface, it is necessary to clean the surface of the charging roller.

As a configuration used for cleaning the charging roller, a configuration using a sponge material such as polyurethane foam and foamed polyethylene (for example, Patent Document 1), a configuration using a brush roller (for example, see Patent Document 2), and the like have been proposed. ing.
These cleaning members are brought into contact with the surface of the charging roller and rubbed to remove deposits such as toner.
In the case of a sponge material, the adhering matter is accumulated in the internal pores, and in the case of a brush roller, it is accumulated between the fibers of the brush.
However, there is a limit to the amount of deposits accumulated in these cleaning members, and there remains a problem in maintaining the cleaning performance of the cleaning member over a long period of time. For example, in a process cartridge including a charging roller, it is necessary to maintain the performance of the charging roller, and thus the cleaning function of the surface of the charging roller, in accordance with the lifetime of other components. A member is insufficient.

Therefore, in place of the cleaning member, it has been proposed to use a cleaning member made of a melamine resin foam having a three-dimensional network structure so that the performance of the charging roller can be maintained for a long time (for example, a patent Reference 3).
Since this cleaning member does not clog dirt in one pore as in the conventional sponge material, the cleaning function of the surface of the charging roller can be maintained for a long time.

JP-A-5-297690 JP 2002-211883 A JP 2003-66807 A

  However, for example, a configuration in which the cleaning member disclosed in each patent document is brought into contact with the charging roller by its own weight, or a configuration in which the cleaning member is pressed against the charging roller with a spring or the like. If the charging device is stopped and the contact between the charging roller and the cleaning member continues for a long time, contact marks are formed on the surface of the charging roller, and the subsequent charging is not uniformly performed, leading to the generation of an abnormal image. There is a problem. In particular, when the contact time is long under a high temperature environment, there is a possibility that a new problem that such a phenomenon is likely to occur occurs.

  An object of the present invention is to provide a satisfactory charging performance from the initial use regardless of the use environment of the apparatus in view of the problems in the cleaning for the conventional charging apparatus, and to maintain the performance for a long period of time. It is an object of the present invention to provide a cleaning device, a charging device, an image forming apparatus, an image forming method, and a toner having a configuration that can be used.

In order to achieve the above object, the present invention has the following configuration.
(1) Cleaning provided with at least an elastic layer or a conductive resin layer on the outer periphery of the cored bar, and a charging roller that charges the surface of the image carrier by applying a voltage from the outside and a charging cleaning roller that cleans the surface of the charging roller In the device
The charging cleaning roller includes a layer made of a melamine resin foam, and a cleaning process is performed in a manufacturing stage.
(2) Cleaning provided with at least an elastic layer or a conductive resin layer on the outer periphery of the cored bar, and a charging roller that charges the surface of the image carrier by applying a voltage from the outside, and a charging cleaning roller that cleans the surface of the charging roller In the device
The charging cleaning roller includes a layer made of a melamine resin foam and is subjected to compression processing, and a cleaning process is performed in a manufacturing stage.
(3) A charging device using the cleaning device according to claim 1 or 2,
A charging device, wherein the charging cleaning roller abuts against the charging roller by its own weight and rotates together.
(4) A charging device using the cleaning device according to claim 1 or 2,
The charging device according to claim 1, wherein the charging cleaning roller is allowed to rotate by contacting the charging roller in a pressurized state.
(5) A process cartridge comprising the charging device according to any one of claims 3 and 4, and the charging device according to any one of claims 3 or 4.
A process cartridge, wherein the charging device is housed integrally with an image carrier on which at least a charging process by the charging device is executed.
(6) An image forming apparatus comprising the process cartridge according to claim 5,
The process cartridge is provided with developing means for processing a visible image using toner with an electrostatic latent image formed by image writing after the charging process by the image carrier and the charging device. An image forming apparatus, wherein a visible toner image is fixed by a fixing unit.
(7) In the image forming apparatus according to (6),
The toner used for the developing means has a weight average particle diameter of 3 to 8 μm and a ratio (D4 / D1) of the weight average particle diameter (D4) to the number average particle diameter (D1) of 1.00 to 1.40. An image forming apparatus characterized by being in a range.
(8) Toner used in the developing means in the image forming apparatus according to claim 6,
The toner has a weight average particle diameter of 3 to 8 μm and a ratio (D4 / D1) of the weight average particle diameter (D4) to the number average particle diameter (D1) is in the range of 1.00 to 1.40. Toner.
(9) In the image forming apparatus of (6),
The image forming apparatus according to claim 1, wherein the toner used in the developing unit is one having a shape factor SF-1 in the range of 100 to 180 and a shape factor SF-2 in the range of 100 to 180.
(10) A toner used in developing means in an electrophotographic process executed in the image forming apparatus according to claim 6,
The toner is characterized in that a toner having a shape factor SF-1 in the range of 100 to 180 and a shape factor SF-2 in the range of 100 to 180 is used.
(11) In the image forming method executed in the image forming apparatus according to claim 6,
As the toner used in the developing means, a toner obtained by externally adding fine particles having an average primary particle diameter of 50 to 500 nm and a bulk density of 0.3 g / cm ³ or more on the surface of the toner base particles is selected. An image forming method.
(12) In the image forming method executed in the image forming apparatus according to (6),
The toner used in the developing unit is composed of at least a binder resin, a colorant, and a release agent, and a toner having a glass transition temperature of 45 to 65 ° C. and an outflow start temperature of 90 to 115 ° C. is selected. Image forming method.
(13) A toner used for developing means in an electrophotographic process executed in the image forming apparatus according to claim 6,
The toner comprises at least a binder resin, a colorant, and a release agent, and has a glass transition temperature of 45 to 65 ° C. and an outflow start temperature of 90 to 115 ° C.
(14) In the image forming apparatus according to (6),
The toner used in the developing means is a toner material liquid in which at least a polyester prepolymer having a functional group containing a nitrogen atom, polyester, a colorant, and a release agent is dispersed in an organic solvent. An image forming apparatus comprising: a toner obtained by an extension reaction.
(15) A toner used in a developing step in an electrophotographic process executed in the image forming apparatus according to claim 6,
In the toner, a toner material liquid in which at least a polyester prepolymer having a functional group containing a nitrogen atom, polyester, a colorant, and a release agent is dispersed in an organic solvent is crosslinked and / or extended in an aqueous medium. A toner obtained by allowing the toner to be obtained.

  According to the present invention, as a charging cleaning roller used in a cleaning device intended for a charging device, dirt is clogged in a single mechanism as in the case of using a conventional sponge material, resulting in a reduction in cleaning performance. When using a melamine resin foam to prevent the occurrence of contact marks due to long-term contact between the melamine resin foam and the charging member, it is prevented by setting a cleaning process at the manufacturing stage of the charging cleaning roller can do. That is, the substance in the melamine resin foam is washed away by the long-term contact of the melamine resin foam, thereby making it possible to eliminate the occurrence of contact marks due to the substance of the melamine resin foam. It is possible to prevent deterioration of the uniform charging performance.

The best mode for carrying out the present invention will be described below with reference to the drawings.
FIG. 1 is a diagram showing a schematic configuration of an image forming apparatus according to the present invention, and FIG. 2 is a diagram showing a schematic configuration of a photoconductor unit corresponding to a process cartridge.
The image forming apparatus shown in FIG. 1 includes four image forming units 1Y, 1M, 1C, and 1K for forming images of each color of yellow (Y), magenta (M), cyan (C), and black (K). Prepare. The color order of Y, M, C, and K is not limited to that in FIG. Hereinafter, the configuration of each member will be described.
Each of the image forming units 1Y, 1M, 1C, and 1K includes photosensitive drums 11Y, 11M, 11C, and 11K as image carriers, and a charging unit, a developing unit, and a cleaning unit. The arrangement of the image forming units 1Y, 1M, 1C, and 1K is set so that the rotation axes of the photosensitive drums are parallel to each other and arranged at a predetermined pitch in the transfer sheet moving direction.

Above the image forming units 1Y, 1M, 1C, and 1K, a light source, a polygon mirror, an f-θ lens, a reflection mirror, and the like are provided, and on the surface of each photosensitive drum 11Y, 11M, 11C, and 11K based on image data. The optical writing unit 3 that irradiates while scanning with laser light carries a transfer sheet as a belt driving device having a transfer conveyance belt 60 that carries a transfer paper below and conveys it so as to pass through a transfer portion of each image forming unit. Unit 6 is arranged.
A cleaning device 85 including a brush roller and a cleaning blade is disposed on the outer peripheral surface of the transfer conveyance belt 60 so as to come into contact therewith. The cleaning device 85 removes foreign matters such as toner adhering to the transfer conveyance belt 60.
On the side of the transfer unit 6, a belt fixing type fixing unit 7, a paper discharge tray 8, and the like are provided.

Under the image forming apparatus, paper feed cassettes 4a and 4b on which transfer paper 100 is placed are provided. A manual tray MF that manually feeds paper from the side of the image forming apparatus is also provided.
In addition, a toner replenishing container TC is provided, and a waste toner bottle, a duplex / reversing unit, a power supply unit, and the like (not shown) are also provided in a space S indicated by a two-dot chain line.

  The developing devices 10Y, 10M, 10C, and 10K as the developing means have the same configuration, and are two-component developing type developing devices 10Y, 10M, 10C, and 10K that differ only in the color of the toner used. A developer composed of toner and a magnetic carrier is contained. The developing devices 10Y, 10M, 10C, and 10K include a developing roller that faces the photosensitive drum 11, a screw that conveys and stirs the developer, a toner density sensor, and the like. The developing roller is composed of an outer rotatable sleeve and an inner magnet. In accordance with the output of the toner density sensor, toner is supplied from the toner supply device.

  The photoconductor unit 2 has the same configuration in 2Y, 2M, 2C, and 2K. As shown in FIG. 2, the photoconductor drum 11 on which an electrostatic latent image is formed, a charging device 14, and a cleaning device. 15.

The cleaning device 15 includes a cleaning blade 15 a and a cleaning brush 15 b for cleaning the transfer residual toner remaining on the surface of the photosensitive drum 11. A scraper 15c for removing toner adhering to the brush fibers is in contact with the cleaning brush 15b.
The toner scraped off by the cleaning blade 15a is moved to the toner transport auger 15d side by the cleaning brush 15b, and the waste toner collected by rotating the toner transport auger 15d is transported to a waste toner storage unit (not shown). ing.

Next, the charging device 14 will be described in detail. FIG. 3 is a perspective view for explaining the outline of the charging device according to the present invention.
The charging device 14 includes a charging roller 14a configured by covering a conductive cored bar with a medium-resistance elastic layer as a charging member.

The charging roller 14a is connected to a power source (not shown) and is applied with a predetermined voltage. Then, pressure springs 19 and 19 which are urging members for urging both end portions toward the photosensitive drum 11 are provided.
The charging roller 14 a may be provided in contact with the photosensitive drum 11, but in the present embodiment, the charging roller 14 a is disposed with a minute gap with respect to the photosensitive drum 11.

  Although not shown in the drawings, the minute gaps are such that a spacer member having a certain thickness is wound around the non-image forming regions at both ends of the charging roller 14a, so that the surface of the spacer member is brought into contact with the surface of the photosensitive drum 11. You can set it.

  A charging cleaning roller 14b used in a cleaning device for the charging roller 14a is provided so that the charging roller 14a contacts the surface opposite to the surface facing the photosensitive drum 11.

The charging cleaning roller 14b can be formed by, for example, winding a resin foam around a core metal in a cylindrical shape. As the resin foam, a resin foam having an open cell structure showing a physical property value of a density of 5 to 15 kg / m ³ and a tensile strength of 1.7 ± 0.5 kg / cm ² is used.

4a and 4b are diagrams showing the relationship between the density and tensile strength values of the resin foam constituting the charging cleaning roller 14b and the cleaning and scratching properties of the surface of the charging roller 14a.
The cleaning property and scratching property of the surface of the charging roller 14a can be evaluated by the image rank of the image to be formed. That is, if the cleaning performance of the charging cleaning roller 14b is insufficient and dirt is attached to the surface of the charging roller 14a, the photosensitive drum 11 is not charged well and soiling occurs. 4A and 4B, the plot of “□” indicates the relationship with the background stain, and the higher the image rank, the less the background stain, and the lower the image rank, the greater the background stain.

  Further, if the surface of the charging roller 14a is scratched by the rubbing of the charging cleaning roller 14b, a streak-like defect occurs on the image. In FIGS. 4a and 4b, “o” plots indicate the occurrence of streak-like defects, with higher image ranks indicating fewer streak-like defects and lower values indicating more defects. The highest image rank is 5.0, and the image rank required for practical use is 3.0 or more.

As shown in FIG. 4a, when the density of the resin foam is 5 kg / m ³ or more, sufficient cleaning performance of the charging cleaning roller 14b can be obtained. If the density is less than 5 kg / m ³ , sufficient cleaning performance cannot be obtained, charging failure occurs at an early stage, and problems such as background smearing occur in the image. On the other hand, if the density is greater than 15 kg / m ³ , the surface of the charging roller 14a is greatly scraped even if the cleaning performance is good, and the surface of the charging roller 14a is scratched at an early stage, causing a streak-like defect in the image. Let
Further, as shown in FIG. 4b, when the tensile strength of the resin foam is 1.2 kg / cm ² or more, sufficient cleaning performance of the charging cleaning roller 14b can be obtained. If the tensile strength is less than 1.2 kg / cm ² , the strength is not sufficient, the resin foam becomes tattered at an early stage, and the cleaning performance is not exhibited. On the other hand, if the tensile strength is greater than 2.2 kg / cm ² , even if the cleaning performance is good, the surface of the charging roller 14a is scratched at an early stage, causing streak-like defects in the image.
Therefore, the physical properties of the resin foam constituting the charging cleaning roller 14b are required to have a density of 5 to 15 kg / m ³ and a tensile strength of 1.7 ± 0.5 kg / cm ² .

The resin foam having an open-cell structure having a density in the above range exhibits a network-like form having fine pores, and can remove scraps such as toner on the surface of the charging roller 14a at the skeleton portion of the foam. In addition, the resin foam having a tensile strength in the above range exhibits a brittle property and peels off due to the frictional force received on the contact surface with the charging roller 14a. Since the deposits such as toner held in the pores of the resin foam are also peeled off at this time, the deposits are not collected in the pores of the foam unlike the resin foams used conventionally. , Cleaning on a fresh surface is always possible. In addition, good cleaning performance can be obtained over a long period of time without scratching the surface of the charging roller.
Furthermore, when the elongation percentage of the resin foam is in the range of 20 to 40%, the characteristics of the resin foam can be better exhibited.

  Among the resin foams showing the above physical property values, melamine resin foam is particularly preferable. Since the foam formed of the melamine resin has a hard mesh-like fiber, the deposits on the charging roller 14a can be easily scraped or removed. As described above, since the cleaning performance is excellent and the above-described brittle properties are exhibited, the fresh surface of the charging cleaning roller 14b is always in contact with the surface of the charging roller 14a, and good cleaning performance can be maintained.

  The charging cleaning roller 14b is rotatably supported, abuts against the surface of the charging roller 14a by its own weight, and rotates with the rotation of the charging roller 14a shown in FIG. Thus, by driving the charging cleaning roller 14b according to the rotation of the charging roller 14a, the charging cleaning roller 14b does not require a driving device, and the configuration can be simplified. Further, since the charging cleaning roller 14b is made of the above resin foam, a sufficient cleaning performance can be obtained even if no pressing force is particularly required for contact with the surface of the charging roller 14a.

By the way, in the charging device 14 including the charging roller 14a and the charging cleaning roller 14b as described above, if the contact between the two continues for a long time with the device stopped, the charging roller 14a that has been in contact with the charging cleaning roller 14b. Striped contact marks are generated on the surface. As a result of analyzing what this contact mark is caused by, it became clear that the substance derived from the resin foam constituting the charging cleaning roller 14b was adhered. Furthermore, it is also known that when a melamine resin is used as a cleaning member and a compression process is performed, a noticeable contact mark appears when a substance generated in the compression process adheres to the charging roller. In such a situation, for example, after the charging device is manufactured and before it is mounted on the image forming apparatus, or after the process cartridge incorporating the charging device is manufactured, the process cartridge is connected to the image forming apparatus. It can be considered that the image forming apparatus is not used for a long time until it is mounted on the printer. When the contact mark as described above is formed on the surface of the charging roller 14a, the surface of the photosensitive drum 11 facing the contact mark portion is not sufficiently charged immediately after the start of the image forming operation. An abnormal image in which omissions and disturbances occur at intervals.
Therefore, in the present invention, in order to avoid the occurrence of such an abnormal image, the charging cleaning roller 14b is washed with water in the manufacturing process. That is, a substance that exists on the charging cleaning roller 14b and can cause an abnormal image when it adheres to the charging roller is washed away in advance.
Thus, even when the charging device is manufactured and then mounted on the image forming apparatus for a long time, contact marks of the charging cleaning roller 14b are not generated on the surface of the charging roller 14a.
In the case of a cleaning roller subjected to compression processing, a similar effect can be obtained by providing a cleaning step after the compression step.

  Regarding the drying after washing, since the cleaning ability of the charging roller is lowered if the drying is not sufficiently performed, as shown in FIG. The relationship with drying time has also been obtained as a result of experiments.

  The charging device 14 having the charging cleaning roller 14b described above can be used as a process cartridge that is integrally supported with the photosensitive member and is detachably formed on the main body of the image forming apparatus. In addition to this, the process cartridge may include any means selected from developing means and cleaning means.

The image forming apparatus of the present invention may include a lubricant application unit that applies a lubricant to the surface of the photosensitive drum 11.
FIG. 6 is a diagram illustrating a configuration of a photoreceptor unit including a lubricant application unit. The configuration other than the lubricant application unit 17 is the same as that of the photoconductor unit shown in FIG.

  The lubricant application unit 17 scrapes off the lubricant in contact with the solid lubricant 17b, the solid lubricant 17b, and supplies the toner attached to the brush roller 17a to the surface of the photosensitive drum 11. The brush-shaped roller scraper 17c to be removed and the pressure spring 17d that presses the solid lubricant 17b against the brush-shaped roller 17a with a predetermined pressure are mainly configured.

  Examples of the solid lubricant 17b include lead oleate, zinc oleate, copper oleate, zinc stearate, cobalt stearate, iron stearate, copper stearate, zinc palmitate, copper palmitate and zinc linolenate. Fatty acid metal salts, polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polytrifluorochloroethylene, dichlorodifluoroethylene, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-oxafluoropropylene copolymer, etc. The one obtained by molding and processing a fluororesin in a block shape is used.

  The brush-like roller 17 a has a shape extending in the axial direction of the photosensitive drum 11. The pressure spring 17d is biased against the brush roller 17a so that almost all of the solid lubricant 17b is used up.

Since the solid lubricant 17b is a consumable item, its thickness decreases with time, but since it is pressurized by the pressure spring 17d, the solid lubricant 17b is scraped off by always contacting the brush-like roller 17a. Thereafter, the photosensitive drum 11 is supplied and coated. Here, the brush-like roller 17a also serves as a cleaning brush, and also has a role of moving the toner scraped off by the cleaning blade 15a to the toner conveying auger 15d side.
The lubricant application means 17 is not limited to the above-described configuration, and a configuration in which the solid lubricant 17b is applied in direct contact with the surface of the photosensitive drum 11, or a powdery lubricant is applied to the surface of the photosensitive drum 11. The structure etc. which are supplied to may be sufficient.

  Thus, by providing the means for applying the lubricant to the surface of the photosensitive drum 11, the friction coefficient of the surface of the photosensitive drum 11 can be reduced, the adhesion between the surface of the photosensitive drum 11 and the toner is weakened, In addition to improving the transferability of the developed toner, it is possible to improve the cleaning performance of the toner remaining on the surface of the photosensitive drum 11 after the transfer by the cleaning blade 15a.

  In particular, this is an effective means in the case of using a toner having a reduced particle size and a spherical shape as shown below. By satisfactorily cleaning the toner remaining on the surface of the photosensitive drum 11, contamination on the surface of the charging roller 14a can be reduced, and as a result, the life of the charging cleaning roller 14b can be extended.

  In the image forming apparatus according to the present invention, the toner used in the developing device 10 has a volume average particle diameter of 3 to 8 μm, and a ratio (Dv / Dn) between the volume average particle diameter (Dv) and the number average particle diameter (Dn). ) Is preferably a toner having a small particle size and a narrow particle size distribution in the range of 1.00 to 1.40. By using a toner having a small particle diameter, the toner can be densely attached to the latent image. Further, by narrowing the particle size distribution, the toner charge amount distribution becomes uniform, a high-quality image with little background fogging can be obtained, and the transfer rate can be increased. Further, since the amount of the reversely charged toner can be reduced, contamination on the surface of the charging roller 14a can be reduced, and the life of the charging cleaning roller 14b can be extended.

The toner used in the developing device 10 is preferably a spherical toner that can be defined by the values of the following shape factors SF-1 and SF-2.
FIG. 7 is a diagram schematically illustrating the shape of the toner in order to explain the shape factor SF-1 and the shape factor SF-2.
The shape factor SF-1 indicates the ratio of the roundness of the toner shape. The square of the maximum length MXLNG of the shape formed by projecting the toner onto the two-dimensional plane represented by the following formula (1) Divide by AREA and multiply by 100π / 4.
SF-1 = {(MXLNG) ² / AREA} × (100π / 4) (1) When the value of SF-1 is 100, the shape of the toner becomes a true sphere, and the value of SF-1 increases. It becomes indefinite.

The shape factor SF-2 indicates the ratio of unevenness in the shape of the toner, and is expressed by the square of the perimeter PERI of the figure formed by projecting the toner on the two-dimensional plane represented by the following formula (2). It is a value obtained by dividing the figure area AREA and multiplying by 100 / 4π.
SF-2 = {(PERI) ² / AREA} × (100 / 4π) (2) When the value of SF-2 is 100, the toner surface has no irregularities and the value of SF-2 is large. As the result, the unevenness of the toner surface becomes remarkable.
Specifically, the shape factor is measured by taking a photograph of the toner with a scanning electron microscope (S-800: manufactured by Hitachi, Ltd.), introducing it into an image analyzer (LUSEX 3: manufactured by Nireco) and analyzing it. Calculated.

  The toner according to the present invention is a toner having SF-1 in the range of 100 to 180 and SF-2 in the range of 100 to 180. When the shape of the toner is close to a spherical shape, the contact between the toner and the toner or the toner and the photosensitive drum 11 is close to a point contact, so that the adsorbing force between the toners is weakened and the fluidity is increased. The adhesion force to the surface of the photosensitive drum 11 is also reduced, and the transfer rate is increased. On the other hand, since the spherical toner easily enters the gap between the cleaning blade 15a and the photosensitive drum 11, the shape factors SF-1 and SF-2 of the toner are preferably 100 or more. Further, when SF-1 and SF-2 are increased, toner is scattered on the image and the image quality is lowered. For this reason, it is preferable that SF-1 and SF-2 do not exceed 180.

The toner suitably used in the image forming apparatus of the present invention is, for example, a toner material liquid in which at least a polyester prepolymer having a functional group containing a nitrogen atom, a polyester, a colorant, and a release agent are dispersed in an organic solvent. Is a toner obtained by crosslinking and / or elongation reaction in an aqueous solvent. Hereinafter, the constituent materials and the manufacturing method of the toner will be described.
(Modified polyester)
The toner according to the present invention contains a modified polyester (i) as a binder resin.
The modified polyester (i) refers to a state in which a bonding group other than an ester bond is present in the polyester resin, or resin components having different configurations are bonded to the polyester resin by a covalent bond, an ionic bond, or the like. Specifically, the polyester terminal is modified by introducing a functional group such as a carboxylic acid group or an isocyanate group that reacts with a hydroxyl group into the polyester terminal and further reacting with an active hydrogen-containing compound.

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

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

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

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

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

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

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

Next, as amines (B) to be reacted with the polyester prepolymer (A), a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4) ), Amino acid (B5), and amino acid block of B1 to B5 (B6).
Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like. Examples of the trivalent or higher polyvalent amine compound (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.

  Examples of the compound (B6) obtained by blocking the amino group of B1 to B5 include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

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

  The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The modified polyester (i) used in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably 1000 to 10,000, and if it is less than 1,000, the elongation reaction is difficult and the elasticity of the toner is small, and as a result, the hot offset resistance is deteriorated. On the other hand, if it exceeds 10,000, the problem in production becomes high in the case of a decrease in fixability, particle formation or pulverization. The number average molecular weight of the modified polyester (i) is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight.
(I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

  In the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B) to obtain the modified polyester (i), a reaction terminator is used as necessary to adjust the molecular weight of the resulting urea-modified polyester. be able to. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

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

The peak molecular weight of (ii) is 1000-10000 normally, Preferably it is 2000-8000, More preferably, it is 2000-5000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
As for the acid value of (ii), 1-5 are preferable, More preferably, it is 2-4. Since a high acid value wax is used for the wax, the binder is easily matched with the toner used for the two-component developer because the low acid value binder leads to charging and high volume resistance.

The glass transition point (Tg) of the binder resin is usually 35 to 70 ° C, preferably 55 to 65 ° C. If the temperature is lower than 35 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low as compared with known polyester-based toners. Show.
(Coloring agent)
As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher , Yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sared, Parachlor Ortoni Roaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine 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, pyrazolone , Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Fu Talocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

The colorant can also be used as a master batch combined with a resin. As a binder resin to be kneaded together with the production of a master batch or a master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax
Can be used alone or in combination.
(Charge control agent)
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.

The amount of the charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is lowered, and the image density is lowered. Invite.
(Release agent)
As a release agent, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface. The effect on high temperature offset is exhibited without applying a release agent such as oil. Examples of such a wax component include the following.

Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, and paraffin, microcrystalline, And petroleum waxes such as petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones, and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n- A crystalline polymer having a long alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used. .
The charge control agent and the release agent can be melt-kneaded together with the master batch and the binder resin, and of course, they may be added when dissolved and dispersed in the organic solvent.
(External additive)
Inorganic fine particles are preferably used as an external additive for assisting the fluidity, developability and chargeability of the toner particles. The primary particle diameter of the inorganic fine particles is preferably 5 × ¹⁰ -3 ~2μm, it is particularly preferably 5 × ¹⁰ -3 ~0.5μm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5 wt% of the toner, and particularly preferably 0.01 to 2.0 wt%.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, as the fluidity imparting agent, it is preferable to use hydrophobic silica fine particles and hydrophobic titanium oxide fine particles in combination. In particular, when stirring and mixing are performed using particles having an average particle diameter of 5 × 10 ⁻² μm or less, the electrostatic force and van der Waals force with the toner are remarkably improved. Even when stirring and mixing inside the developing device is performed to obtain a good image quality that does not cause the release of the fluidity imparting agent from the toner and does not generate firefly, etc., and further reduces the residual toner. It is done.

  Titanium oxide fine particles are excellent in environmental stability and image density stability, but have a tendency to deteriorate the charge rise characteristics. Therefore, if the amount of titanium oxide fine particles added is larger than the amount of silica fine particles added, this side effect is affected. It can be considered large. However, when the addition amount of the hydrophobic silica fine particles and the hydrophobic titanium oxide fine particles is in the range of 0.3 to 1.5 wt%, the charge rising characteristics are not greatly impaired, and the desired charge rising characteristics can be obtained, that is, repeated copying. Stable image quality can be obtained even if

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

The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.
Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.

  As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

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

  Cationic surfactants include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids that are right on the fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Benzalkonium 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) ), Megafuck F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos).

As the resin fine particles, any resin can be used as long as it can form an aqueous dispersion, and it may be a thermoplastic resin or a thermosetting resin. Examples thereof include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin, two or more of the above resins may be used in combination.
Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained. For example, vinyl resins are polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester copolymers, styrene-butadiene copolymers, (meth) acrylic acid-acrylic acid esters. Examples thereof include resins such as a polymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer. The average particle size of the resin fine particles is 5 to 200 nm, preferably 20 to 300 nm.
In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

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

The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.
3) At the same time as the preparation of the emulsion, the amines (B) are added to cause a reaction with the polyester prepolymer (A) having an isocyanate group.
This reaction involves molecular chain crosslinking and / or elongation. The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.
4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.
5) A charge control agent is injected into the toner base particles obtained by the above method as required, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain a toner.
The injection of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the spherical shape and the rugby ball shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. be able to.

  Further, the toner according to the present invention has a substantially spherical shape and can be represented by the following shape rule.

FIG. 8 is a diagram schematically showing the shape of the toner according to the present invention.
In FIG. 8, when a substantially spherical toner is defined by a major axis r1, a minor axis r2, and a thickness r3 (where r1 ≧ r2 ≧ r3), the toner of the present invention has a major axis and a minor axis. Ratio (r2 / r1) (see FIG. 8B) is 0.5 to 1.0, and the ratio of thickness to minor axis (r3 / r2) (see FIG. 8C) is 0.7 to 1.0. It is preferable to be in the range of 1.0.
If the ratio of the major axis to the minor axis (r2 / r1) is less than 0.5, the dot reproducibility and transfer efficiency are inferior because of the separation from the true spherical shape, and high-quality image quality cannot be obtained. On the other hand, if the ratio of thickness to minor axis (r3 / r2) is less than 0.7, the shape is close to a flat shape, and a high transfer rate like a spherical toner cannot be obtained. In particular, when the ratio of the thickness to the minor axis (r3 / r2) is 1.0, the rotating body has a major axis as a rotation axis, and the fluidity of the toner can be improved. Note that r1, r2, and r3 were measured with a scanning electron microscope (SEM) while changing the angle of field of view and taking pictures.
The toner produced as described above can also be used as a one-component magnetic toner that does not use a magnetic carrier or a non-magnetic toner.

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

1 is a diagram illustrating a schematic configuration of an image forming apparatus according to the present invention. FIG. 2 is a diagram illustrating a schematic configuration of a process cartridge used in the image forming apparatus illustrated in FIG. 1. It is a perspective view explaining the outline of the charging device concerning the present invention. It is a diagram for explaining the relationship between the density of the resin foam constituting the charging cleaning roller and the cleaning and scratching properties of the charging roller surface. It is a diagram for explaining the relationship between the tensile strength of the resin foam constituting the charging cleaning roller and the cleaning and scratching properties of the charging roller surface. It is a diagram which shows the experimental result regarding the influence on the charging characteristic by the temperature and time at the time of drying after washing | cleaning for melamine resin foam which is one of the resin foams used for a charging cleaning roller. It is a figure which shows the structure of the photoreceptor unit provided with the lubrication agent application means. FIG. 6 is a diagram schematically illustrating the shape of a toner in order to explain the shape factor SF-1 and the shape factor SF-2. FIG. 3 is a diagram schematically illustrating the shape of a toner according to the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Image forming unit 2 Photoreceptor unit equivalent to a process cartridge 3 Optical writing unit 10 Developing device 11 Photoreceptor drum (image carrier)
14 charging device 14a charging roller 14b charging cleaning roller 15 cleaning device 15a cleaning blade 15b cleaning brush 17 lubricant applying means 17a brush-like roller 17b solid lubricant 17d pressure spring 60 transfer conveying belt

Claims (15)

In a cleaning device provided with at least an elastic layer or a conductive resin layer on the outer periphery of a mandrel, and a charging roller for charging the surface of the image carrier by applying a voltage from the outside, and a charging cleaning roller for cleaning the surface of the charging roller,
The charging cleaning roller includes a layer made of a melamine resin foam, and a cleaning process is performed in a manufacturing stage. In a cleaning device provided with at least an elastic layer or a conductive resin layer on the outer periphery of a mandrel, and a charging roller for charging the surface of the image carrier by applying a voltage from the outside, and a charging cleaning roller for cleaning the surface of the charging roller,
The charging cleaning roller includes a layer made of a melamine resin foam and is subjected to compression processing, and a cleaning process is performed in a manufacturing stage. A charging device using the cleaning device according to claim 1,
A charging device, wherein the charging cleaning roller abuts against the charging roller by its own weight and rotates together. A charging device using the cleaning device according to claim 1,
The charging device according to claim 1, wherein the charging cleaning roller is allowed to rotate by contacting the charging roller in a pressurized state. A process cartridge comprising the charging device according to claim 3,
A process cartridge, wherein the charging device is housed integrally with an image carrier on which at least a charging process by the charging device is executed. An image forming apparatus comprising the process cartridge according to claim 5,
The process cartridge is provided with developing means for processing a visible image with toner using an electrostatic latent image formed by image writing after the charging process by the image carrier and the charging device. An image forming apparatus, wherein a visible toner image is fixed by a fixing unit. The image forming apparatus according to claim 6.
The toner used for development has a weight average particle diameter of 3 to 8 μm and a ratio (D4 / D1) of the weight average particle diameter (D4) to the number average particle diameter (D1) is in the range of 1.00 to 1.40. An image forming apparatus, comprising: A toner used in the developing device in the image forming apparatus according to claim 6,
The toner has a weight average particle diameter of 3 to 8 μm and a ratio (D4 / D1) of the weight average particle diameter (D4) to the number average particle diameter (D1) is in the range of 1.00 to 1.40. Toner. The image forming apparatus according to claim 6.
The image forming apparatus according to claim 1, wherein the toner used in the developing unit is one having a shape factor SF-1 in the range of 100 to 180 and a shape factor SF-2 in the range of 100 to 180. A toner used in developing means in an electrophotographic process executed in the image forming apparatus according to claim 6,
The toner is characterized in that a toner having a shape factor SF-1 in the range of 100 to 180 and a shape factor SF-2 in the range of 100 to 180 is used. The image forming method executed in the image forming apparatus according to claim 6.
As the toner used in the developing means, a toner obtained by externally adding fine particles having an average primary particle diameter of 50 to 500 nm and a bulk density of 0.3 g / cm ³ or more on the surface of the toner base particles is selected. An image forming method. The image forming method executed in the image forming apparatus according to claim 6.
The toner used in the developing unit is composed of at least a binder resin, a colorant, and a release agent, and a toner having a glass transition temperature of 45 to 65 ° C. and an outflow start temperature of 90 to 115 ° C. is selected. Image forming method. A toner used for developing means in an electrophotographic process executed in the image forming apparatus according to claim 6,
The toner comprises at least a binder resin, a colorant, and a release agent, and has a glass transition temperature of 45 to 65 ° C. and an outflow start temperature of 90 to 115 ° C. The image forming apparatus according to claim 6.
The toner used in the developing means is a toner material liquid in which at least a polyester prepolymer having a functional group containing a nitrogen atom, polyester, a colorant, and a release agent is dispersed in an organic solvent. An image forming apparatus comprising: a toner obtained by an extension reaction. A toner used in a developing step in an electrophotographic process executed in the image forming apparatus according to claim 6,
In the toner, a toner material liquid in which at least a polyester prepolymer having a functional group containing a nitrogen atom, polyester, a colorant, and a release agent is dispersed in an organic solvent is crosslinked and / or extended in an aqueous medium. A toner obtained by allowing the toner to be obtained.

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