JP2005141109A - Cleaning device, image forming apparatus and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent degradation of image quality over a prolonged period of time in an image forming apparatus using toner made spherical and reduced in particle diameter by providing a cleaning device effectively removing residual toner after transfer and foreign matter on a photoreceptor, retaining its cleaning function over a prolonged period of time, and having a good cleaning function. <P>SOLUTION: The cleaning device has a cleaning blade 8a for cleaning a surface of an electrophotographic photoreceptor 1 having at least a photosensitive layer located on a conductive substrate and containing one or more friction reducing agents for reducing the friction coefficient (μ) of the surface of the electrophotographic photoreceptor 1 in an outermost layer, and has one or more secondary polishing members 8b for polishing a surface layer of the electrophotographic photoreceptor 1 besides the cleaning blade 8a. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a cleaning device for an electrophotographic photosensitive member mounted on an image forming apparatus using an electrophotographic system such as a copying machine, a printer, and a facsimile. The present invention also relates to a process cartridge including the cleaning device and an image forming apparatus.

In recent years, color image forming apparatuses using an electrophotographic method have become widespread, and further high definition of printed images has been demanded due to the fact that digitized images can be easily obtained. ing. As higher resolution and gradation of images are being studied, as a toner-side improvement that visualizes latent images, further spheroidization and smaller particle size have been studied in order to form high-definition images. ing.
For example, a pulverized pulverized toner having a specific particle size distribution (see, for example, Patent Documents 1 to 4) and a method for obtaining a sphere-shaped and small-sized toner by suspension polymerization (for example, patents). Reference 5), a method in which a binder resin and a colorant are mixed in a solvent immiscible with water and dispersed in an aqueous solvent in the presence of a dispersion stabilizer to obtain a spheroidized and small particle size toner. (For example, refer to Patent Document 6.) A binder resin containing a partially modified resin and a colorant are mixed in an organic solvent and dispersed in an aqueous solvent, and a polyaddition reaction of the modified resin is performed. And a method for obtaining a spherical and small particle size toner (see, for example, Patent Document 7) has been proposed. With such toner, image quality and fluidity are improved.

However, when a toner having a spherical shape and a reduced particle size is used, there are some problems in cleaning on the electrophotographic photosensitive member performed after image formation.
One of them is the cleaning of untransferred toner on the electrophotographic photosensitive member. In the cleaning method using a cleaning blade, spherical toner rotates between the blade and the electrophotographic photosensitive member and enters the gap. It is difficult to clean. In this regard, for example, the polymer after suspension polymerization is heated above the glass transition point in a dispersion medium to obtain aggregated particles, which are then introduced into a heated jet stream to break up the aggregated particles. At the same time, a method of obtaining an irregularly shaped small particle size toner by drying is proposed (for example, see Patent Document 8). Also, the binder resin and the colorant are mixed in a solvent immiscible with water, dispersed in an aqueous medium in the presence of a dispersion stabilizer, and the solvent is removed from the resulting suspension by heating and / or decompression. Thus, a method for obtaining toner particles having irregularities on the surface (for example, see Patent Document 9) has been proposed.

The other is that wax added to the toner to improve the releasability added internally or externally, or inorganic fine particles to improve the fluidity are separated from the toner on the electrophotographic photosensitive member. It means that it adheres. As the toner becomes smaller in particle size, the content ratio of these additives in the toner becomes higher than that in the conventional toner, and therefore, the amount of adhered substances on the electrophotographic photosensitive member tends to increase.
As means for removing the adhered substance on the electrophotographic photosensitive member, Patent Document 10 proposes a cleaning device in which a cleaning blade and a cleaning roller having an abrasive attached to the surface thereof are arranged. However, the abrasive adhered to the surface of the cleaning roller is easily peeled off, and it is difficult to maintain the cleaning function for a long time. Further, Patent Document 11 has a configuration in which an adhering agent is removed by adhering an abrasive to the tip of a cleaning blade provided in a cleaning device. However, it is difficult to simultaneously perform the cleaning of the transfer residual toner and the removal of the adhering substances, and in the configuration in which the abrasive is adhered to the tip of the cleaning blade, the abrasive is easily peeled off.

Japanese Patent Laid-Open No. 1-112253 JP-A-2-284158 Japanese Patent Laid-Open No. 3-181952 JP-A-4-162048 Japanese Patent Laid-Open No. 5-72808 Japanese Patent Laid-Open No. 9-15902 Japanese Patent Laid-Open No. 11-133668 Japanese Patent Laid-Open No. 5-188642 JP 9-15903 A JP-A-10-111629 JP 2001-296781 A

  In a conventional cleaning device equipped with a cleaning blade, it is very difficult to remove spherical toner and small-diameter toner, and further, it is difficult to sufficiently remove adhering substances on the electrophotographic photosensitive member. . The adhered substance that is not removed causes thin filming if it is mainly composed of wax, and if it is composed mainly of inorganic fine particles, it becomes the core, and calcium carbonate contained in the recording paper. It grows with additives such as the like, and will adversely affect the image over time. Therefore, it has been proposed to reduce the friction coefficient (μ) on the surface of the electrophotographic photosensitive member in order to reduce the amount of adhesion between the electrophotographic photosensitive member and the toner. As a means for reducing the μ on the surface of the electrophotographic photosensitive member, a lubricant for reducing μ, such as zinc stearate or calcium stearate, is applied to the surface of the electrophotographic photosensitive member. However, since a mechanism for applying the lubricant is necessary, problems such as an increase in the size of the apparatus and an increase in cost have occurred, and it has been extremely difficult to uniformly apply a certain amount of lubricant. Therefore, as a means for reducing the μ of the electrophotographic photoreceptor itself, studies have been made to obtain the necessary μ by dispersing and dispersing a lubricant such as fluorine fine particles and silicon fine particles in the surface of the electrophotographic photoreceptor. However, since the lubricant is present in the surface layer of the electrophotographic photosensitive member, it is always necessary to expose the lubricant on the surface of the outermost layer.

  In view of the above problems, the present invention can effectively remove transfer residual toner and adhering substances on an electrophotographic photosensitive member in an image forming apparatus using spherical and small-diameter toner. Another object of the present invention is to provide an image forming apparatus capable of maintaining the cleaning function for a long period of time. It is another object of the present invention to provide a process cartridge and an image forming apparatus that include the above-described cleaning device or charging device having a good cleaning function and that do not cause deterioration of image quality over a long period.

In order to solve the above problems, the present invention described in claim 1 is an electrophotographic photosensitive member in which at least a photosensitive layer is provided on a conductive support, and a friction coefficient ( A cleaning device for cleaning the surface of an electrophotographic photosensitive member containing at least one friction-reducing agent for reducing μ), comprising a cleaning blade for cleaning the surface of the electrophotographic photosensitive member, other than the cleaning blade A cleaning apparatus comprising at least one polishing member for polishing the surface layer of the electrophotographic photosensitive member.
According to a second aspect of the present invention, in the cleaning device according to the first aspect, the polishing member is a rubber blade containing an abrasive.
A third aspect of the present invention is the cleaning apparatus according to the second aspect, wherein the abrasive contained in the rubber blade is cerium oxide or silica.

According to a fourth aspect of the present invention, there is provided a process cartridge which includes at least an electrophotographic photosensitive member and a cleaning means for cleaning the electrophotographic photosensitive member, and is integrally supported and detachable from the image forming apparatus. The cleaning unit is a process cartridge according to any one of claims 1 to 3.
The present invention according to claim 5 is an electrophotographic photosensitive member for forming a latent image, a charging means for uniformly charging the surface of the electrophotographic photosensitive member, and exposing the surface of the charged electrophotographic photosensitive member based on image data. Exposure means for writing the latent image, developing means for supplying toner to the latent image formed on the surface of the electrophotographic photosensitive member to visualize it, cleaning means for cleaning the surface of the electrophotographic photosensitive member, and image bearing Static elimination means for eliminating the charge on the surface of the body, contact transfer means for transferring the visible image on the surface of the electrophotographic photosensitive member directly or to the intermediate transfer body, and then transferring it to the recording medium, and heating for fixing the toner image on the recording medium In an image forming apparatus comprising a fixing unit, the electrophotographic photosensitive member is an electrophotographic photosensitive member having at least a photosensitive layer provided on a conductive support, and the outermost layer has a friction coefficient (μ) on the surface of the electrophotographic photosensitive member. Reduce A cleaning blade for cleaning the surface of the electrophotographic photosensitive member containing at least one kind of friction reducing agent for the purpose, and at least one polishing member for polishing the surface layer of the electrophotographic photosensitive member in addition to the cleaning blade. The image forming apparatus is characterized.

The present invention described in claim 6 is the image forming apparatus according to claim 5, wherein the polishing member for polishing the surface layer of the electrophotographic photosensitive member is a charging roller.
According to a seventh aspect of the present invention, in the image forming apparatus according to the sixth aspect, the charging roller is driven with a linear velocity difference from the electrophotographic photosensitive member.
The invention according to claim 8 is the image forming apparatus according to claim 6 or 7, wherein the charging roller has a surface roughness (Rz) of 10 μm or more.
According to a ninth aspect of the present invention, in the image forming apparatus according to any one of the sixth to eighth aspects, the cleaning unit is the cleaning apparatus according to any one of the first to third aspects. The image forming apparatus.
According to a tenth aspect of the present invention, there is provided an electrophotographic photosensitive member for forming a latent image, a charging means for uniformly charging the surface of the electrophotographic photosensitive member, and exposing the charged electrophotographic photosensitive member surface based on image data. Exposure means for writing the latent image, developing means for supplying toner to the latent image formed on the surface of the electrophotographic photosensitive member to visualize it, cleaning means for cleaning the surface of the electrophotographic photosensitive member, and image bearing Static elimination means for eliminating the charge on the surface of the body, contact transfer means for transferring the visible image on the surface of the electrophotographic photosensitive member directly or to the intermediate transfer body, and then transferring it to the recording medium, and heating for fixing the toner image on the recording medium An image forming apparatus comprising a fixing unit, wherein the cleaning unit is the cleaning device according to any one of claims 1 to 3.

The present invention described in claim 11 is the image forming apparatus according to claim 9 or 10, wherein the process cartridge according to claim 4 is used.
According to a twelfth aspect of the present invention, in the image forming apparatus according to any one of the fifth to eleventh aspects, the shape factor (SF1) of the toner to be used is 150 or less.
The invention according to claim 13 is a toner material liquid in which a toner to be used has a polyester prepolymer having at least a functional group containing a nitrogen atom, a polyester, a colorant, and a release agent dispersed in an organic solvent. 13. The image forming apparatus according to claim 5, wherein the image forming apparatus is a toner obtained by crosslinking and / or elongation reaction in an aqueous medium.

According to the present invention, the charging roller is driven with a linear velocity difference from that of the electrophotographic photosensitive member, and the surface roughness (Rz) is set to 10 μm or more, so that the surface of the electrophotographic photosensitive member can be polished. It is possible to expose the lubricant on the surface of the photoreceptor, and to provide an image forming apparatus that does not cause deterioration in image quality over a long period of time.
Further, according to the present invention, the polishing blade can be brought into contact with the electrophotographic photosensitive member in addition to the cleaning blade to polish the surface of the electrophotographic photosensitive member, so that the lubricant can be exposed on the surface of the electrophotographic photosensitive member. Thus, the surface friction coefficient of the electrophotographic photosensitive member can be lowered over a long period of time, and an image forming apparatus that does not cause deterioration in image quality can be provided.
In addition, the process cartridge is advantageous in terms of maintenance. If a failure occurs due to the electrophotographic photosensitive member, the cleaning device, the charging device or the developing device, etc., it is possible to replace the cartridge at an early stage. Therefore, the service time can be shortened. Further, by making the electrophotographic photosensitive member easy to clean, it greatly contributes to extending the life of the process cartridge.

  The best mode for carrying out the present invention will be described below with reference to the drawings. The following description is an example of the best mode of the present invention, and it is easy for those skilled in the art to make other embodiments within the scope of the claims by making changes and modifications within the scope of the claims. However, this does not limit the scope of the claims.

FIG. 1 is a schematic diagram showing a configuration of an image forming apparatus according to the present invention. FIG. 2 is a schematic view showing a configuration around the electrophotographic photosensitive member of the image forming apparatus according to the present invention.
A charging device 2, an exposure device 3, a developing device 4, a transfer device 6, a fixing device 7, and a cleaning device 8 are arranged around an electrophotographic photosensitive member 1 (hereinafter also referred to as a photosensitive member) that is a latent image carrier. Yes.
An image forming apparatus using a charging roller as a polishing member according to one embodiment of the present invention will be described.
The photoconductor 1 is a photoconductor made of an organic compound, and is formed by dispersing fluorine-based fine particles or silicon-based fine particles on the outermost layer, and the charging device 2 is a contact roller type charging device 2. The charging device 2 includes a charging roller 2a, a cleaning pad 2b in contact with the charging roller 2a for cleaning, and a power supply (not shown) connected to the charging roller 2a. A high voltage is applied to the charging roller 2a, a predetermined voltage is applied between the charging roller 2a having a curvature and the photoconductor 1, and a gap discharge is generated between the photoconductor 1 and the surface of the photoconductor 1 Are uniformly charged. The charging roller usually carries the photoconductor by its own weight or the like. However, in the present invention, a gear (not shown) for driving the charging roller is provided, and a constant linear velocity is provided between the photoconductor and the charging roller. Make a difference. Further, the surface roughness (Rz) of the surface layer of the charging roller was set to 10 μm or more so that the surface layer of the photoreceptor could be effectively polished.

The exposure device 3 converts data read by a scanner in the reading device 20 and an image signal sent from the outside such as a PC (not shown), scans the laser beam 3a with a polygon motor, and reads the image signal read through the mirror. Based on this, an electrostatic latent image is formed on the photoreceptor 1.
The developing device 4 includes a developer carrier 4a that carries a developer and supplies the developer 1 to the photoreceptor 1, a toner supply chamber, and the like. It has a cylindrical developer carrier 4a arranged at a minute distance from the photosensitive member 1, and a developer regulating member for regulating the amount of developer on the developer carrier 4a. The developer carrier 4a includes a hollow cylindrical developer carrier 4a that is rotatably supported, and a magnet roll fixed coaxially with the developer carrier 4a. The developer is magnetically attracted to the outer peripheral surface of the carrier 4a and conveyed. The developer carrier 4a is electrically conductive and is made of a nonmagnetic member, and is connected to a power source for applying a developing bias. A voltage is applied from the power source between the developer carrying member 4a and the photoreceptor 1, and an electric field is formed in the developing region.

The transfer device 6 includes a transfer belt 6a, a transfer bias roller 6b, and a tension roller 6c. The transfer bias roller 6b is configured by providing an elastic layer on the surface of a core metal such as iron, aluminum, and stainless steel. The transfer bias roller 6 b is applied with a necessary pressure on the photosensitive member 1 side in order to bring the recording paper into close contact with the photosensitive member 1. The transfer belt 6a can obtain an effect by selecting various heat-resistant materials as a base material, and can be composed of, for example, a seamless polyimide film. A configuration in which a fluororesin layer is provided on the outside can be employed. Further, if necessary, a silicone rubber layer may be provided on the polyimide film, and a fluororesin layer may be provided thereon. Inside the transfer belt 6a, a tension roller 6c is provided to drive and stretch the transfer belt 6a.
The fixing device 7 includes a fixing roller having a heater that is a heating unit such as a halogen lamp, and a pressure roller that is in pressure contact. In the fixing roller, an elastic layer such as silicone rubber is provided on the surface of the core metal to a thickness of 100 to 500 μm, preferably 400 μm, and for the purpose of preventing adhesion due to toner viscosity, a resin surface layer having good releasability such as fluororesin Is formed. The resin surface layer is composed of a PFA tube or the like, and its thickness is preferably about 10 to 50 μm in consideration of mechanical deterioration. A temperature detecting means is provided on the outer peripheral surface of the fixing roller, and the heater is controlled so as to keep the surface temperature of the fixing roller substantially constant within a range of about 160 to 200 ° C. In the pressure roller, the core metal surface is coated with an anti-offset layer such as tetrafluoroethylene-perfluoroalkyl vinyl ether (PFA) or polytetrafluoroethylene (PTFE). Similar to the fixing roller, an elastic layer such as silicone rubber may be provided on the surface of the core metal.

As a second embodiment of the present invention, an image forming apparatus using a cleaning blade as an abrasive member will be described.
FIG. 3 is a schematic view showing the configuration around the photosensitive member of the image forming apparatus equipped with the cleaning device of the present invention. The photosensitive member 1 is a photosensitive member made of an organic compound, and is formed by dispersing fluorine-based fine particles or silicon-based fine particles on the outermost layer. The cleaning device 8 serves as a cleaning unit upstream of the rotation direction of the photosensitive member 1. The first cleaning blade 8a and the second cleaning blade 8b are provided in order. Further, a toner collection blade 8d for collecting the cleaned toner and a collection coil 8c for conveying the toner are provided. Further, a toner collection box (not shown) is provided.
The first cleaning blade 8a is made of a material such as metal, resin, rubber, etc., and rubbers such as fluorine rubber, silicone rubber, butyl rubber, butadiene rubber, isoprene rubber, urethane rubber are preferably used, and among these, urethane rubber is particularly preferable. . The first cleaning blade 8a mainly removes toner remaining on the photoreceptor 1 after the transfer process.

The second cleaning blade 8b is a polishing blade having an abrasive particle-containing layer formed by containing abrasive particles in an elastic material. In addition to the untransferred toner, inorganic fine particles detached from the toner, additives such as exuded wax, or additives such as calcium carbonate contained in paper dust of the recording paper adhere to the photoreceptor 1. These substances cause filming and eventually grow from nuclei to lumps. The second cleaning blade 8b is a polishing blade that scrapes and removes the adhering substances on the photosensitive member 1.
The polishing blade 8b is formed by mixing abrasive particles with an elastic material such as fluorine rubber, silicone rubber, butyl rubber, butadiene rubber, isoprene rubber, urethane rubber, etc., and forming it into a sheet by centrifugal molding. Made. As the elastic material, the above rubber material having a rubber hardness of 65 degrees or more and 85 degrees or less is preferable. This is because if the hardness is less than 65 degrees, the wear of the blade progresses quickly, and if the hardness is greater than 85 degrees, the blade edge tends to be chipped. More preferably, urethane rubber having the rubber hardness is used from the viewpoint of wear resistance.
As abrasive particles, nitrides such as silicon nitride, silicates such as aluminum silicate, magnesium silicate, mica and calcium silicate, calcareous substances such as calcium carbonate and gypsum, silicon carbide, boron carbide, tantalum carbide, titanium carbide, carbonized Examples thereof include carbides such as aluminum and zirconium carbide, and oxides such as cerium oxide, silica, chromium oxide, titanium oxide, and aluminum oxide. Among these, cerium oxide and silica having excellent polishing power are preferable.

FIG. 4 is a view showing a state in which the polishing blade 8b is in contact with the surface of the photoreceptor 1. The polishing blade 8b is installed so that the abrasive particle-containing layer 8b-1 is in contact with the surface of the photosensitive member 1. At this time, it is important that the contact surface of the polishing blade 8b is filled with the abrasive particles. It is that you are. Therefore, the polishing blade 8b of the present invention is characterized in that the volume occupancy of the abrasive particles on the contact surface is 50% or more and 90% or less. If the volume occupancy of the abrasive particles on the contact surface is less than 50%, the amount of abrasive particles in contact with the surface of the photoreceptor 1 is small, and filming on the photoreceptor 1 cannot be efficiently removed. Further, if the volume occupancy exceeds 90%, it is not preferable because abrasive particles appearing on the surface are easily peeled off.
The polishing blade 8b may have a one-layer structure of an abrasive particle-containing layer, or may have a two-layer structure of an abrasive particle-containing layer and a blade base layer.
In the case of a one-layer structure, as shown above, the abrasive blade 8b is obtained by mixing abrasive particles with an elastic material, forming the sheet by centrifugal molding, and cutting it, so that the manufacturing process There is an advantage that can be simplified.

On the other hand, in the case of the two-layer structure, the amount of the elastic material and abrasive particles is reduced as compared with the case of the above-mentioned one-layer structure, and a thin sheet is formed, and the abrasive particle-containing layer obtained by cutting it is used. The thin blade is made by adhering to a blade base layer made of a material such as rubber, resin, or metal. On the one hand, the dimensional accuracy of each of the abrasive particle layer and the blade base layer is required. On the other hand, a blade base layer that supports the abrasive particle-containing layer and determines physical properties such as the elasticity of the blade, and the photoreceptor 1. It is also possible to design the function separately for the abrasive particle-containing layer for removing the adhering substance on the top.
Here, rubber is preferably used for the blade base layer, and urethane rubber is particularly preferable from the viewpoint of wear resistance. Further, the amount of the elastic material and abrasive particles for forming the abrasive particle-containing layer can be reduced as compared with the case of the single layer structure.
The content of abrasive particles contained in the abrasive particle-containing layer of the polishing blade 8b is preferably 0.5 wt% or more and 50 wt% or less. If the content of the abrasive particles is less than 0.5 wt%, the amount of abrasive particles that come into contact with the surface of the photoconductor 1 to exhibit the polishing effect is too small, and the adhered substances on the photoconductor 1 can be sufficiently removed. Can not. On the other hand, when the content of the abrasive particles exceeds 50 wt%, the concentration of the abrasive particles becomes too high, and molding becomes difficult. In addition, the cost increases.

Further, as shown in FIG. 3, the abrasive particle-containing layer 8b-1 of the polishing blade 8b can be inclined to the volume occupancy ratio of the abrasive particles in the process of centrifugal molding. In particular, the abrasive particle rich layer r1 having a volume occupation ratio of 50% or more preferably has a thickness of 5 μm or more and 100 μm or less in the thickness direction of the blade. When the thickness of the abrasive particle rich layer r1 is less than 5 μm, the amount of abrasive particles that come into contact with the surface of the photoconductor 1 to exhibit the polishing effect is too small, and the adhered substances on the photoconductor 1 are sufficiently removed. I can't. On the other hand, when the thickness of the abrasive particle rich layer r1 exceeds 100 μm, the elasticity of the polishing blade 8b is affected, and the edge of the blade is likely to be chipped.
The thickness of the abrasive particle-rich layer r1 is the amount of abrasive particles contained in the abrasive particle-containing layer 8b-1, or the abrasive particles used to form the abrasive particle-containing layer 8b-1. By adjusting the absolute amount of the toner, it is possible to obtain a sufficient photoconductor polishing effect immediately after the start of use of the cleaning device 8 by exposing the abrasive particles.

Further, the cleaning device 8 according to the present invention includes a photosensitive member and an arbitrary device selected from the charging device 2 or the developing device 4 and is integrally supported, and a process cartridge formed detachably on the image forming apparatus main body. can do. A process cartridge that maintains the cleaning function on the photosensitive member for a long period of time and does not cause deterioration in image quality even in an image forming process in which development using a small particle size toner is performed by the process cartridge. can do. In addition, the process cartridge is advantageous in terms of maintenance. If a failure occurs due to the photoconductor, cleaning device, charging device or developing device, etc., it can be restored to its original state by simply replacing the cartridge. Since it can be recovered, the service time can be shortened. Further, by making the electrophotographic photosensitive member easy to clean, it greatly contributes to extending the life of the process cartridge.
The image forming apparatus equipped with the cleaning device 8 of the present invention is not limited to the configuration shown in FIG. 1, but includes a configuration including an intermediate transfer body that once transfers and carries the toner image on the photoreceptor 1, and a multicolor image. In order to form it, the structure provided with two or more photoconductors may be sufficient.

  In particular, in the image forming apparatus that can obtain the effect of mounting the leaning device 8 of the present invention, the toner used in the developing device 4 has a volume average particle size of 3 to 8 μm, and the volume average particle size (Dv) This is a case where the ratio (Dv / Dn) to the number average particle diameter (Dn) is a small particle diameter in the range of 1.00 to 1.40 and the particle diameter distribution is narrow. 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.

  On the other hand, the toner as described above has a small proportion of wax in the toner that is added internally or externally to improve the releasability and inorganic fine particles that are improved in fluidity. The particle size is higher than that of conventional toner. These additives are the cause of the adhered substances generated on the photoreceptor 1. Therefore, the cleaning device 8 of the present invention removes the transfer residual toner and paper dust on the photoreceptor 1 with the first cleaning blade 8a, and the photosensitive material mainly composed of wax and inorganic fine particles with the downstream polishing blade 8b. The adhered substance on the body 1 can be removed by scraping. Further, toner, paper dust, etc. leaking from the first cleaning blade 8a can be removed by the polishing blade 8b. The polishing blade 8b has a configuration in which the abrasive particle layer 8b-1 has a thickness and contains abrasive particles, so that the abrasive particles do not peel off and maintain a good cleaning function for a long period of time. can do.

  The toner suitably used in the image forming apparatus of the present invention includes 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. A toner obtained by crosslinking and / or elongation reaction in an aqueous solvent. Hereinafter, the constituent material 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 a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

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

Examples of the polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) with a small amount of (TC) Mixtures are preferred. Divalent carboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polyvalent carboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).
The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.
Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; Those blocked with caprolactam or the like; and combinations of two or more of these.

The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.
The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40 wt%, preferably 1 to 30 wt%, more preferably 2 to 20 wt%. . If it is less than 0.5 wt%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40 wt%, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

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

The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). Is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.
The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.
The modified polyester (i) used in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably 1000 to 10000. When the molecular weight is less than 1000, the elongation reaction hardly occurs, the elasticity of the toner is small, and as a result, the resistance to hot offset deteriorates. On the other hand, when it exceeds 10,000, the problem in production becomes high in the deterioration of fixability, particle formation and pulverization. The number average molecular weight of the modified polyester (i) is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. (I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.
In the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B) to obtain the modified polyester (i), a reaction terminator is used as necessary to adjust the molecular weight of the resulting urea-modified polyester. be able to. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

(Unmodified polyester)
In the present invention, not only the modified polyester (i) is used alone, but also the unmodified polyester (ii) can be contained as a binder resin component together with the (i). By using (ii) in combination, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to 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. If the weight ratio of (i) is less than 5%, the hot offset resistance deteriorates, 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 as the wax, the low acid value binder leads to electrification and high volume resistance, so that it is easy to match the toner used for the two-component developer.
The glass transition point (Tg) of the binder resin is usually 35 to 70 ° C, preferably 55 to 65 ° C. If it is less than 35 ° C., the heat resistant storage stability of the toner is deteriorated, and if it exceeds 70 ° C., the low-temperature fixability is insufficient. Since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the toner of the present invention tends to have good heat storage stability even when the glass transition point is low, as compared with known polyester-based toners. Show.

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

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

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

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

(External additive)
Inorganic fine particles are preferably used as an external additive for assisting the fluidity, developability and chargeability of the toner 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 added amount of the hydrophobic silica fine particles and the hydrophobic titanium oxide fine particles is in the range of 0.3 to 1.5 wt%, the charge rising characteristics are not greatly impaired, and the desired charge rising characteristics can be obtained, that is, repeated copying. Stable image quality can be obtained even if
Next, a toner manufacturing method will be described. Here, although a preferable manufacturing method is shown, it is not limited to this.

(Toner production method)
1) A toner material solution is prepared by dispersing a colorant, unmodified polyester, a polyester prepolymer having an isocyanate group, and a release agent in an organic solvent.
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of an organic solvent is 0-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part.

2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor, and 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, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.

Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).
Moreover, as the cationic surfactant, aliphatic quaternary ammonium such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt which has a right fluoroalkyl group is used. Salt, benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries) Smoke), Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footage F-300 (Neos), and the like.

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

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

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

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

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

5) A charge control agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain a toner.
The injection of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the true spherical shape and the rugby ball shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. be able to.
The toner according to the present invention is a spherical toner that can be defined by the values of the following shape factors SF-1 and SF-2.

FIG. 5 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 and is represented by the following formula (1). This is a value obtained by dividing the square of the maximum length MXLNG of the shape formed by projecting the toner on a two-dimensional plane by the figure area AREA and multiplying 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 becomes larger as the value of SF-1 increases.
The shape factor SF-2 indicates the ratio of the unevenness of the toner shape, and is represented by the following formula (2). A value obtained by dividing the square of the perimeter PERI of the figure formed by projecting the toner on the two-dimensional plane by the figure area AREA and multiplying by 100π / 4.
SF-2 = {(PERI) ² / AREA} × (100π / 4) Expression (2)
When the value of SF-2 is 100, there is no unevenness on the toner surface, and as the value of SF-2 increases, the unevenness of the toner surface becomes more prominent.
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 150 and SF-2 in the range of 100 to 150. When the shape of the toner is close to a sphere, the contact point between the toner and the toner or the toner and the photoconductor 1 is brought into contact, so that the adsorbing force between the toners becomes weak and the fluidity becomes high. The attraction force becomes weaker and the transfer rate becomes higher. On the other hand, since the spherical toner easily enters the gap between the first cleaning blade 8a and the photoreceptor 1, the toner shape factors SF-1 and SF-2 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 150.
Further, the toner according to the present invention has a substantially spherical shape and can be represented by the following shape rule.

FIG. 6 is a diagram schematically showing the shape of the toner according to the present invention. In FIG. 6, 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. 6B) is 0.5 to 1.0, and the ratio of thickness to minor axis (r3 / r2) (see FIG. 6C) is 0.7 to 1.0. It is preferable to be in the range of 1.0. When the ratio of the major axis to the minor axis (r2 / r1) is less than 0.5, the dot reproducibility and transfer efficiency are inferior because of being away from the true spherical shape, and high-quality image quality cannot be obtained. On the other hand, if the ratio of thickness to minor axis (r3 / r2) is less than 0.7, the shape is close to a flat shape, and a high transfer rate like a spherical toner cannot be obtained. In particular, when the ratio of the thickness to the minor axis (r3 / r2) is 1.0, the rotating body has a major axis as a rotation axis, and the fluidity of the toner can be improved.
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 schematic diagram illustrating a configuration of an image forming apparatus according to the present invention. 1 is a schematic diagram illustrating a configuration around a photoconductor of an image forming apparatus according to the present invention. FIG. 2 is a schematic diagram showing a configuration around a photoconductor of an image forming apparatus equipped with the cleaning device of the present invention. It is a figure which shows the state which made the grinding | polishing blade contact | abutted on the photoreceptor surface. 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 Photoconductor 2 Charging device 2a Charging roller 2b Cleaning pad 3 Exposure device 3a Laser beam 4 Developing device 4a Developer carrier 6 Transfer device 6a Transfer belt 6b Transfer bias roller 6c Tension roller 7 Fixing device 8 Cleaning device 8a First cleaning blade 8b Second cleaning blade (polishing blade)
8b-1 abrasive particle containing layer 8c recovery coil 8d toner recovery blade r1 abrasive particle rich layer

Claims (13)

An electrophotographic photosensitive member in which at least a photosensitive layer is provided on a conductive support, and an electron containing at least one friction reducing agent for reducing the friction coefficient (μ) of the surface of the electrophotographic photosensitive member on the outermost layer. A cleaning device for cleaning the surface of a photographic photoreceptor, comprising a cleaning blade for cleaning the surface of the electrophotographic photoreceptor, and one or more polishing members for polishing the surface layer of the electrophotographic photoreceptor in addition to the cleaning blade A cleaning device comprising: The cleaning device according to claim 1, wherein the polishing member is a rubber blade containing an abrasive. The cleaning apparatus according to claim 2, wherein the abrasive contained in the rubber blade is cerium oxide or silica. In a process cartridge that at least includes an electrophotographic photosensitive member and a cleaning unit that cleans the electrophotographic photosensitive member and is integrally supported and detachable from the image forming apparatus.
The process cartridge according to claim 1, wherein the cleaning unit is the cleaning device according to claim 1. An electrophotographic photosensitive member that forms a latent image; a charging unit that uniformly charges the surface of the electrophotographic photosensitive member; an exposure unit that exposes the charged electrophotographic photosensitive member surface based on image data and writes the latent image; A developing unit that supplies toner to the latent image formed on the surface of the electrophotographic photosensitive member to make it visible; a cleaning unit that cleans the surface of the electrophotographic photosensitive member; and a neutralizing unit that neutralizes the charge on the surface of the image bearing member. An image forming apparatus comprising: a contact transfer unit that transfers a visible image on the surface of an electrophotographic photosensitive member directly or to an intermediate transfer member and then a transfer to a recording medium; and a heat fixing unit that fixes a toner image on the recording medium.
The electrophotographic photosensitive member is an electrophotographic photosensitive member in which at least a photosensitive layer is provided on a conductive support, and a friction reducing agent for reducing the friction coefficient (μ) of the surface of the electrophotographic photosensitive member is provided as an outermost layer. An image forming apparatus comprising: a cleaning blade for cleaning the surface of an electrophotographic photosensitive member containing at least seeds; and one or more polishing members for polishing the surface layer of the electrophotographic photosensitive member in addition to the cleaning blade. 6. The image forming apparatus according to claim 5, wherein the polishing member for polishing the surface layer of the electrophotographic photosensitive member is a charging roller. The image forming apparatus according to claim 6, wherein the charging roller is driven with a linear velocity difference from the electrophotographic photosensitive member. The image forming apparatus according to claim 6, wherein the charging roller has a surface roughness (Rz) of 10 μm or more. The image forming apparatus according to any one of claims 6 to 8,
The image forming apparatus according to claim 1, wherein the cleaning unit is the cleaning apparatus according to claim 1. An electrophotographic photosensitive member that forms a latent image; a charging unit that uniformly charges the surface of the electrophotographic photosensitive member; an exposure unit that exposes the charged electrophotographic photosensitive member surface based on image data and writes the latent image; A developing unit that supplies toner to the latent image formed on the surface of the electrophotographic photosensitive member to make it visible; a cleaning unit that cleans the surface of the electrophotographic photosensitive member; and a neutralizing unit that neutralizes the charge on the surface of the image bearing member. An image forming apparatus comprising: a contact transfer unit that transfers a visible image on the surface of an electrophotographic photosensitive member directly or to an intermediate transfer member and then a transfer to a recording medium; and a heat fixing unit that fixes a toner image on the recording medium.
The image forming apparatus according to claim 1, wherein the cleaning unit is the cleaning apparatus according to claim 1. 11. The image forming apparatus according to claim 9, wherein the process cartridge according to claim 4 is used. 12. The image forming apparatus according to claim 5, wherein the toner has a shape factor (SF1) of 150 or less. The toner used is a toner material solution 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, and a crosslinking and / or elongation reaction in an aqueous medium. The image forming apparatus according to claim 5, wherein the image forming apparatus is a toner obtained by processing the toner.

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