JP4494261B2 - Image forming apparatus, process cartridge, toner - Google Patents

Description

  BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming apparatus using an electrophotographic process such as a copying machine, a printer, and a facsimile, and more specifically, a lubricant on the surface of an image carrier such as a photoconductor for the purpose of reducing the friction coefficient. The present invention relates to an image forming apparatus provided with a lubricant application device for applying a toner. The present invention also relates to a process cartridge equipped with this lubricant application device, and a toner used in these.

  An image forming apparatus using an electrophotographic process includes a photoconductor as an image carrier, charges the surface of the photoconductor by discharging, charges the surface of the photoconductor to form an electrostatic latent image, The electrostatic latent image is supplied with toner to be visualized, and the formed visible image on the surface of the photoreceptor is transferred onto the transfer paper surface, and then fixed and discharged. Since the untransferred toner remains on the surface of the photoconductor after the transfer of the visible image, the photoconductor surface is cleaned by a cleaning device so that they do not adversely affect the next image formation. Be prepared for the process. As a cleaning device, a device that removes deposits such as untransferred toner by bringing a cleaning blade made of an elastic material such as rubber into contact with the surface of the photoreceptor is generally known.

  In recent years, there has been an increasing demand for higher image quality, and in particular, in order to realize high-definition color image formation, toner particles are being made smaller and spherical. The dot reproducibility is improved by reducing the particle size, and the developability and transferability can be improved by making the particles spherical. Since it is very difficult to produce such a small particle size and spherical toner by the conventional kneading and pulverization method, the polymerization produced by suspension polymerization method, emulsion polymerization method, dispersion polymerization method, etc. Toner is being adopted.

However, when a toner having a spherical shape and a reduced particle size is used, there are some problems in cleaning on the photoreceptor after image formation. One of them is that it is difficult to use a blade cleaning method in which cleaning of a toner having a spherical shape and a small particle size is generally used. The cleaning blade removes the toner while rubbing the surface of the photoreceptor, but the edge portion of the cleaning blade is deformed by the frictional resistance with the photoreceptor, so that a minute space is generated between the photoreceptor and the cleaning blade. The smaller the toner particle size, the easier it is to enter this space. Then, the closer to the spherical the shape of the toner that has entered, the smaller the rolling frictional force, so that the toner begins to roll in the space between the photosensitive member and the cleaning blade and passes through the cleaning blade. If a large amount of toner passes through the cleaning blade, the cleaning is poor, and an abnormal image such as a ground cover is generated.
Also, as a second problem, the toner that has passed through the cleaning blade continues to remain on the surface of the photoconductor, and then the release agent or fluidizing agent contained in the toner causes the photoconductor to become the causative substance. The so-called filming, which is considered to be formed in a film form on the surface, can be mentioned. When filming is possible, an abnormal image such as a white spot on the solid portion of the image is generated.

In order to improve the cleaning performance on the photoreceptor when using the above-described spherical or small-sized toner, a lubricant made of a fatty acid metal salt or the like is applied to the photoreceptor surface to form a thin film. Thus, a method of reducing the friction coefficient on the surface of the photoreceptor has been devised (for example, see Patent Document 1). It has been found that when the coefficient of friction on the surface of the photoconductor is lowered, the adhesion force acting between the photoconductor and the toner is reduced, so that blade cleaning is improved and filming is also suppressed.
On the other hand, there is also a problem that occurs when the coefficient of friction on the surface of the photoreceptor becomes too low. This is because the adhesion between the photoconductor and the toner is reduced, so that in the development process, toner transfer from the developing roller to the electrostatic latent image formed on the photoconductor is not sufficient, resulting in image loss or low For example, it becomes a density image (see, for example, Patent Document 1 and Patent Document 2).

JP 2002-287567 A JP 2002-207397 A

  In the prior art, the adjustment is performed by measuring the friction coefficient on the surface of the photosensitive member using the Euler belt type friction coefficient measuring method or the like. However, in order to find out and deal with filming that tends to occur on the surface of the photoreceptor when using a sphere-shaped or small-diameter toner before the occurrence of defects on the image such as white spots, More detailed analysis of the photoreceptor surface is required.

  In view of the above circumstances, the present invention analyzes the surface of an image carrier such as a photoconductor in more detail, further improves the cleaning properties of the surface of the image carrier and the effect of preventing filming, and achieves high image quality and high definition. It is an object of the present invention to provide an image forming apparatus that forms an image.

In order to solve the above problems, the present invention is characterized by the following.
1. The present invention relates to an image carrier that carries a latent image, a charging unit that charges the surface of the image carrier, and an exposure unit that exposes the charged surface of the image carrier based on image data and writes an electrostatic latent image. And a developing means for supplying toner to the latent image formed on the surface of the image carrier to make it visible, a transfer means for transferring the visible image on the surface of the image carrier to the transfer body, and an image carrier An image forming apparatus comprising: a cleaning unit that cleans the body surface with a cleaning blade; and a lubricant application unit that applies a lubricant to the surface of the image carrier, wherein the lubricant application unit is a lubricant molded body made of zinc stearate. And a brush-shaped roller, and the lubricant-shaped body is rubbed and scraped off while the brush-shaped roller rotates and applied to the surface of the image carrier. Over 200mN The peripheral speed ratio between the image carrier and the brush roller ((image carrier peripheral speed) / (brush roller peripheral speed)) is 0.8 to 1.m. The toner used in the developing unit has an average circularity of 0.93 or more, does not contain a component containing zinc element, and is cleaned by the cleaning unit and lubricated by the lubricant applying unit. In the image forming apparatus, the element amount of zinc existing on the surface of the image carrier after finishing the agent coating operation is 0.4 to 2.5 atm% .

2. The present invention also provides an image carrier that carries a latent image, a developing unit that supplies toner to the latent image formed on the surface of the image carrier and visualizes the image, and a lubricant on the surface of the image carrier. A process cartridge which is integrally supported and includes at least a lubricant application unit to be applied and is detachable from the main body of the image forming apparatus, wherein the lubricant application unit includes a lubricant molded body made of zinc stearate; The brush-shaped roller is configured to slide and scrape and scrape off the lubricant molded body while the brush-shaped roller rotates, and apply the lubricant molded body to the surface of the image carrier. The pressure is 200 mN or more and 3000 mN or less, and the peripheral speed ratio between the image carrier and the brush roller ((image carrier peripheral speed) / (brush roller peripheral speed)) is 0.8 to 1.2 range, previous The toner used in the developing unit has an average circularity of 0.93 or more, does not include a component containing zinc element, and has finished the cleaning operation by the cleaning unit and the lubricant applying operation by the lubricant applying unit. The process cartridge in which the elemental amount of zinc existing on the surface of the image carrier is 0.4 to 2.5 atm%.

3. The present invention also provides an image carrier for carrying a latent image, a charging means for charging the surface of the image carrier, and exposing the charged surface of the image carrier based on image data to write an electrostatic latent image. An exposure unit; a developing unit that supplies toner to the latent image formed on the surface of the image carrier to make it visible; and a transfer unit that transfers the visible image on the surface of the image carrier to a transfer target; An image forming apparatus comprising: a cleaning unit that cleans the surface of an image carrier with a cleaning blade; and a lubricant application unit that applies a lubricant to the surface of the image carrier. The lubricant application unit is made of zinc stearate. It consists of a lubricant molded body and a brush-like roller, and the brush-like roller rotates and rubs and scrapes the lubricant molded body and applies it to the surface of the image carrier. 200m of molded lubricant The pressure is 3000 mN or less, and the peripheral speed ratio between the image carrier and the brush roller ((image carrier peripheral speed) / (brush roller peripheral speed)) is 0.8 to 1. .2 in which the element amount of zinc present on the surface of the image carrier after finishing the cleaning operation by the cleaning means and the lubricant applying operation by the lubricant applying means is 0.4-2. A toner used for developing means of an image forming apparatus of 5 atm%, wherein the toner comprises at least a binder resin and a colorant, does not contain a component containing zinc element, and has an average circularity of 0.93 or more Is a toner.

4). The toner is a negatively chargeable toner containing a fluorine-containing compound.
5. The toner is obtained by treating the surface of toner base particles in a liquid containing the fluorine-containing compound.
6). The fluorine-containing compound used for the treatment of the toner base particle surface is a surfactant having a polarity different from that of the toner base particle surface before the treatment.
7). The fluorine-containing compound is a compound represented by the general formula (1) shown above.

8). In the toner, 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 dissolved or dispersed in an organic solvent is contained in an aqueous medium containing resin fine particles. It is obtained by crosslinking and / or elongation reaction.

9. The toner has a volume average particle diameter of 3 to 8 μm and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is in the range of 1.00 to 1.40. It is characterized by.
10. The toner has 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.
11. The toner has a substantially spherical shape, and the shape is defined by a major axis r1, a minor axis r2, and a thickness r3 (where r1 ≧ r2 ≧ r3), and a ratio between the major axis r1 and the minor axis r2. (R2 / r1) is in the range of 0.5 to 1.0, and the ratio (r3 / r2) of the thickness r3 to the minor axis r2 is in the range of 0.7 to 1.0. .

  According to the present invention, by performing detailed analysis of the surface of the image carrier, blade cleaning can be performed well even when an appropriate amount of zinc stearate is applied to the surface of the image carrier and a toner having a reduced particle size and a spherical shape is used. Therefore, it is possible to provide an image forming apparatus capable of preventing filming.

Embodiments of 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 photoreceptor unit.
This image forming apparatus includes four image forming units 1Y, 1M, 1C, and 1K for forming images of respective colors of yellow (Y), magenta (M), cyan (C), and black (K). Note that the color order of Y, M, C, and K is not limited to that shown in FIG.
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 / conveying 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 and a lubricant application means 17.
The charging device 14 includes, as a charging member, a charging roller 14a configured by covering a conductive cored bar with an intermediate resistance elastic layer. The charging roller 14a is connected to a power source (not shown) and is applied with a predetermined voltage. A pressure spring is provided as a biasing member that biases both end portions toward the photosensitive drum 11. The charging roller 14 a may be provided in contact with the photosensitive drum 11, but may be provided 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.
In addition, a charging cleaning roller 14b 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 is formed by, for example, winding a resin foam around a metal core in a cylindrical shape.

  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.

The lubricant application unit 17 scrapes the lubricant in contact with the lubricant molded body 17b, the lubricant molded body 17b, and is attached to the surface of the photosensitive drum 11 and the brush-shaped roller 17a. A brush-shaped roller scraper 17c that removes toner and a pressure spring 17d that presses the lubricant molded body 17b against the brush-shaped roller 17a with a predetermined pressure are mainly configured.
The lubricant molded body 17b is formed by molding zinc stearate into a block shape. The brush-like roller 17 a has a shape extending in the axial direction of the photosensitive drum 11. The pressure spring 17d is urged against the brush roller 17a so that almost all of the lubricant molding 17b is used up. Since the lubricant molded body 17b is a consumable product, its thickness decreases with time, but since it is pressurized by the pressure spring 17d, the lubricant molded body 17b is always brought into contact with the brush roller 17a. After scraping, the photosensitive drum 11 is supplied and applied. 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 lubricant molded body 17b is applied by directly contacting the surface of the photosensitive drum 11 or a powdery lubricant is supplied to the surface of the photosensitive drum 11. However, as a means for more efficiently adjusting the amount of lubricant applied to the surface of the photosensitive drum 11, it is configured by the lubricant molded body 17b and the brush roller 17a described above. There should be.

The image forming operation of the image forming apparatus having the above configuration is as follows.
First, a predetermined voltage is applied to the charging roller 14a from a power source (not shown) to charge the surface of the opposing photosensitive drum 11. The surface of the photosensitive drum 11 charged to a predetermined potential is subsequently scanned with laser light based on the image data by the optical writing unit 3 to write an electrostatic latent image. When the surface of the photosensitive drum 11 carrying the electrostatic latent image reaches the developing device 10, toner is supplied to the electrostatic latent image on the surface of the photosensitive drum 11 by a developing roller disposed opposite to the photosensitive drum 11, A toner image is formed.
The above operation is performed at a predetermined timing in the same manner for all the photosensitive units 2Y, 2M, 2C, and 2K, and toner images of predetermined colors are formed on the surfaces of the photosensitive drums 11Y, 11M, 11C, and 11K, respectively. .

The transfer paper 100 is conveyed from any of the paper feed cassettes 4a and 4b or the manual feed tray MF, and stops once when it reaches the registration roller 5. Then, the transfer paper 100 is sent out by the registration rollers in synchronization with the above-described image forming operations of the photoconductor units 2Y, 2M, 2C, and 2K, and is conveyed by the transfer conveyance belt 60 while being transferred onto each photoconductor drum 11. The toner images are sequentially transferred. The transfer of the toner image onto the transfer paper is performed by a power supply (not shown) from primary transfer rollers 67Y, 67M, 67C, and 67K arranged to face the photosensitive drums 11Y, 11M, 11C, and 11K with the transfer conveyance belt 60 interposed therebetween. This is done by applying a voltage having a polarity opposite to the polarity of the toner on the photosensitive drum 11.
Then, the transfer paper 100 that has passed through the position facing the photosensitive drum 11K and on which the four color toner images are superimposed is subsequently conveyed to the fixing unit 7, where the image is fixed by receiving heat and pressure.

On the other hand, when the surface of the photosensitive drum 11 after the transfer of the toner image reaches the surface facing the lubricant applying means 17 and the cleaning device 15, zinc stearate as a lubricant is applied by the brush roller 17a. The toner remaining on the surface of the photosensitive drum 11 is cleaned by the cleaning blade 15a to prepare for the next image forming operation.
At this time, the zinc stearate applied by the brush-like roller 17a is uniformly stretched so that the surface of the photosensitive drum 11 is rubbed by the cleaning blade 15a, forming a thin film and the surface of the photosensitive drum 11 Cover. By forming a thin film of zinc stearate on the surface of the photoconductive drum 11 in this way, the friction coefficient of the surface of the photoconductive drum 11 can be reduced, and the transferability of the developed toner can be improved or transferred. This contributes to improving the cleaning properties of the remaining toner.

In the image forming apparatus of the present invention, the toner used in the developing device 10 is a toner having an average circularity of 0.93 or more in order to form a high-quality and high-definition image.
The average circularity of the toner is a value obtained by optically detecting particles and dividing by the perimeter of an equivalent circle having the same projected area. Specifically, the measurement is performed using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 mL of water from which impure solids are removed in advance is added, 0.1 to 0.5 mL of a surfactant is added as a dispersant, and about 0.1 to 9.5 g of a measurement sample is further added. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the concentration and dispersion of the dispersion are set to 3,000 to 10,000 / μL, and the shape and distribution of the toner are measured.
Since the toner having a high average circularity value is used as described above, the image forming apparatus is under a condition that the margin for cleaning is small. Therefore, it is important how to form a thin film of zinc stearate on the surface of the photosensitive drum 11.

In the image forming apparatus of the present invention, the elemental amount of zinc present on the surface of the photosensitive drum 11 after finishing the cleaning operation by the cleaning device 15 and the application operation of zinc stearate by the lubricant applying unit 17 is 0.4 to 0.4. It is adjusted to the range of 2.5 atm%. The elemental amount of zinc can be obtained by analyzing the surface of the photosensitive drum 11 after the image forming operation by XPS (X-ray Photoelectron Spectroscopy). Since the depth detectable by XPS is several nm from the outermost surface, the amount of elements present on the outermost surface of the photosensitive drum 11 can be measured.
In the image forming apparatus of the present invention, since the toner used in the developing device 10 does not contain a component containing zinc element, the amount of zinc element present on the surface of the photosensitive drum 11 is determined as a lubricant. This is the amount of zinc element contained in zinc stearate applied to the surface of the body drum. If the elemental amount of zinc is less than 0.4 atm%, the amount of zinc stearate is small, so the zinc stearate thin film formed on the surface of the photosensitive drum 11 is not uniform, and a sufficient friction reducing effect is obtained. I can't get it. For this reason, when toner with a high degree of circularity is used, the toner passes through the cleaning blade, resulting in poor cleaning or filming on the surface of the photosensitive drum 11.
On the other hand, as the elemental amount of zinc increases, the zinc stearate thin film on the surface of the photosensitive drum 11 becomes more uniform, improving the cleaning property of the surface of the photosensitive drum 11 and preventing filming. If the elemental amount of zinc exceeds 2.5 atm%, the effect on cleaning and filming will not be improved even if the elemental amount of zinc further increases. This is not preferable because it causes problems such as insufficient transfer of toner to the electrostatic latent image surface of the drum 11.

In order to make the element amount of zinc existing on the surface of the photosensitive drum 11 fall within the above range, the lubricant application operation of the lubricant application means 17 is preferably as follows.
It is preferable to press the lubricant molding 17b against the brush roller 17a, and the pressing force is preferably a pressure of 200 mN or more with a pressure spring including its own weight. As the pressure increases, the amount of lubricant that the brush roller 17a scrapes off from the molded lubricant 17b increases, and the amount of application to the surface of the photosensitive drum 11 also increases. On the other hand, if the pressing force is too large, more than necessary lubricant is supplied to the surface of the photosensitive drum 11 and the friction coefficient is reduced more than necessary, and the surface of the charging roller 14a is contaminated and causes of the collapse of the lubricant molding 17b. It also becomes. Therefore, the pressing force is preferably 3000 mN or less.

  Further, the rotation direction of the brush-like roller 17 a is the same direction at the portion in contact with the photosensitive drum 11. By rotating in this direction, the lubricant adhering to the brush roller 17a can be supplied without giving an impact to the surface of the photosensitive drum 11. The peripheral speed ratio (photoconductor peripheral speed) / (peripheral speed of the brush roller) between the photosensitive drum 11 and the brush-like roller 17a is preferably in the range of 0.8 to 1.2. This is because if the peripheral speed ratio is less than 0.8, the supply amount of the lubricant decreases, and if it exceeds 1.2, the surface of the photosensitive drum 11 is damaged by an impact and the life of the photosensitive drum 11 is shortened. This peripheral speed ratio is more preferably in the range of 1.0 to 1.1.

Next, the toner used in the image forming apparatus of the present invention will be described in detail.
As described above, the toner according to the present invention is a toner having a high circularity with an average circularity of 0.93 or more. Such a toner with a high degree of circularity can be produced by emulsifying, suspending or agglomerating the oil phase using a polymerizable monomer or an organic solvent in an aqueous medium.
Further, the toner contains a fluorine-containing compound and exhibits a negative chargeability, and does not contain a component containing zinc element. Therefore, the amount of zinc stearate applied to the surface of the photosensitive drum 11 is reduced. It does not affect the quantitative determination of the elemental amount of zinc, which is an index.
Hereinafter, the constituent material of the toner and the manufacturing method will be specifically described.

(Suspension polymerization method)
A colorant, a release agent and the like are dispersed in an oil-soluble polymerization initiator and a polymerizable monomer, and then emulsified and dispersed by an emulsification method described later in an aqueous medium containing a surfactant and other solid dispersants. Thereafter, after the polymerization reaction to form particles, the toner particles may be subjected to a surface treatment described later.

(Emulsion polymerization aggregation method)
A water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by an ordinary emulsion polymerization technique. Separately, a dispersion in which a colorant, a release agent and the like are dispersed in an aqueous medium is prepared, mixed, aggregated to a toner size, and heat-fused to obtain a toner. Thereafter, a surface treatment of toner particles described later may be performed.

(Polymer suspension method)
As an aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.
In the oil phase of the toner composition, a colorant such as resin, prepolymer and pigment, a release agent, a charge control agent and the like are dissolved or dispersed in a volatile solvent.
An oil phase composed of a toner composition is dispersed in an aqueous medium in the presence of a surfactant, a solid dispersant and the like, and a prepolymer is reacted to form particles. Thereafter, a surface treatment of toner particles described later may be performed.

(Surface treatment method)
In common with any of these toner manufacturing methods, surface treatment with charge control can be applied in the liquid. It is preferable to perform this step after toner particles are formed in an aqueous medium and the used surfactant and the like are removed by washing. Excess surfactant present in the aqueous medium is removed by solid-liquid separation operations such as filtration and centrifugation, and the resulting cake and slurry are redispersed in the aqueous medium.
Thereafter, a surfactant aqueous solution having a polarity opposite to the polarity of the toner particle surface is gradually added with stirring. The reverse polarity surfactant can be used in an amount of 0.01 to 1% by weight based on the solid content of the toner particles.

As the polarity of the toner particle surface, one surfactant is involved. That is, the surfactant present in the aqueous medium during the toner particle formation process as described above has a high affinity with the polymerizable monomer and the organic solvent, and therefore tends to remain on the toner particle surface. The polarity of the active agent is the polarity of the toner particle surface.
In the case of the polymer suspension method, the resin used is of low molecular weight, the viscosity of the dispersed phase is lowered, emulsification is facilitated, and further, crosslinking and / or elongation reaction is carried out in the particles after emulsification. Particles containing a resin can be produced. At this time, the polarity of the polymer obtained by the crosslinking and / or elongation reaction is the polarity of the toner particle surface.
Such a polar substance present on the surface of the toner particles may not provide a stable chargeability of the toner. However, as described above, the surface treatment is performed with a surfactant having a polarity opposite to the polarity of the toner particle surface. Thus, the influence on the toner charging property can be shielded.

A surfactant having the opposite polarity to the polarity of the toner particle surface, and the following compounds can be preferably used as the fluorine-containing compound. By containing a fluorine-containing compound on the surface of the toner particles, a toner having stable negative charging performance and good charge rising property can be obtained.
(Fluorosurfactant)
Preferred anionic surfactants having a fluoroalkyl group include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (C6-C11) oxy. ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid and metal Salt, perfluoroalkylcarboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy ethyl) -Fluorooctanesulfonamide, 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 Taikin Kogyo Co., Ltd.), Mega-Fac F-l10, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

Examples of cationic surfactants include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, and benzaza. Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.
In particular, by using a fluorine-containing quaternary ammonium salt compound represented by the following general formula (1), a stable developer can be obtained with little change in charge amount when the environment changes.

（式中、Ｘ、Ｙ、Ｒ１〜Ｒ４、ｒ及びｓは、それぞれ以下のものを表す。Ｘ：−ＳＯ_２−又は−ＣＯ−、Ｒ１，Ｒ２，Ｒ３，Ｒ４：水素原子、炭素数１〜１０の低級アルキル基又はアリール基、Ｙ：Ｉ又はＢｒ、ｒ，ｓ：１〜２０の整数。）

(In the formula, X, Y, R 1 to R 4, r and s each represent the following: X: —SO ₂ — or —CO—, R 1, R 2, R 3, R 4: hydrogen atom, carbon number 1 to 10 lower alkyl group or aryl group, Y: I or Br, r, s: integer of 1-20.)

Furthermore, the resin fine particle dispersion may be present in the slurry redispersed for the purpose of reinforcing the chargeability. By adding a surfactant having a reverse polarity, the charge in the resin fine particle dispersion in water is neutralized, and can be agglomerated and adhered to the toner particle surface. The resin fine particles can be used in an amount of 0.01 to 5% by weight based on the solid content of the toner particles.
(Charge control resin fine particles)
As the charge controllable resin fine particles, known ones can be used, but polymer fine particles, for example, resin fine particle dispersions obtained by soap-free emulsion polymerization, suspension polymerization or dispersion polymerization are preferable. Particularly preferable are polystyrene copolymerized with a monomer having a carboxyl group such as methacrylic acid, a copolymer obtained by emulsion polymerization and dispersion polymerization of a fluorine-based methacrylate ester or a fluorine-based acrylic ester, silicone, benzoguanamine. , Polymer condensation particles such as nylon and polymer fine particles by thermosetting resin.

  These charge control agent fine particles and resin fine particles adhered to the toner surface can be fixed to the toner surface by heating the slurry thereafter to prevent detachment. At that time, it is desirable to heat at a temperature higher than the Tg of the resin constituting the toner. You may heat-process after drying.

  In the toner according to the present invention, the base particles are produced by the following raw materials and production methods, for example.

(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). The polyester prepolymer (A) having an isocyanate group is a polycondensate of a polyhydric alcohol (PO) and a polyvalent carboxylic acid (PC) and a polyester having an active hydrogen group, and a polyisocyanate compound (PIC). ) And the like. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

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

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

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

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

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

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

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

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

The modified polyester (i) used in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. The peak molecular weight at this time is preferably 1000 to 10,000, and if it is less than 1,000, the elongation reaction hardly occurs and the elasticity of the toner is small, and as a result, the resistance to hot offset deteriorates. On the other hand, if it exceeds 10,000, the problem in production becomes high in the case of a decrease in fixability, particle formation or pulverization. The number average molecular weight of the modified polyester (i) is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. (I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.
In the crosslinking and / or extension reaction between the polyester prepolymer (A) and the amines (B) for obtaining 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) can be 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. When (ii) is contained, the weight ratio of (i) to (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. When the weight ratio of (i) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

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

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

  The colorant can also be used as a master batch combined with a resin. As a binder resin to be kneaded 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 resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

(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 those shown below. 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 release agent can be melt-kneaded together with the master batch and the binder resin, and of course, it 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 rising characteristics. It can be considered large. However, when the added amount of the hydrophobic silica fine particles and the hydrophobic titanium oxide fine particles is in the range of 0.3 to 1.5 wt%, the charge rising characteristics are not greatly impaired, and the desired charge rising characteristics can be obtained, that is, repeated copying. Stable image quality can be obtained even if

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

2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor, and 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) perf Luooctanesulfonamide, 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).

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

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 Of acid ester, 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 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 imidazole , Nitrogen-containing compounds such as ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, Cypropylene, 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-based toner base particles can be produced by removing the solvent. . In addition, when an acid such as calcium phosphate salt or an alkali-soluble one is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by, for example, washing with water after dissolving the calcium phosphate salt with an acid such as hydrochloric acid. 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 as necessary, 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.

The toner obtained as described above has a volume average particle diameter of 3 to 8 μm and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of 1.00 to 1.40. A toner having a small particle size and a narrow particle size distribution in the range is preferable. 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, when a toner having a small particle diameter is used, the blade cleaning property has been a problem. However, the image forming apparatus of the present invention allows the surface of the photosensitive drum 11 to be coated with an appropriate amount of zinc stearate. It is possible to improve blade cleaning properties and suppress toner filming.

The toner is preferably a spherical toner that can be defined by the values of the following shape factors SF-1 and SF-2. FIG. 3 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 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 (2) Divide by AREA and multiply by 100π / 4.
SF-1 = {(MXLNG) ² / AREA} × (100π / 4) (2)
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 the square of the perimeter PERI of the figure formed by projecting the toner onto the two-dimensional plane represented by the following formula (3) is a figure. It is a value obtained by dividing by the area AREA and multiplying by 100 / 4π.
SF-2 = {(PERI) ² / AREA} × (100 / 4π) (3)
When the value of SF-2 is 100, unevenness does not exist 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 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 has a substantially spherical shape and can be represented by the following shape rule.
FIG. 4 is a diagram schematically showing the shape of the toner according to the present invention. In FIG. 4, 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. 4B) is 0.5 to 1.0, and the ratio of thickness to short axis (r3 / r2) (see FIG. 4C) 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.

  Hereinafter, the present invention will be described in detail based on examples. In addition, all the description of a part is a weight part.

A toner was prepared as follows.
(Synthesis of polyester resin)
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of terephthalic acid and 2 parts of dibutyltin oxide are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and polycondensed at 230 ° C. for 8 hours at normal pressure. The reaction was further performed at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain an unmodified polyester having a peak molecular weight of 4800. Thereafter, 10 parts of trimellitic anhydride was added and reacted at 200 ° C. for 2 hours under reduced pressure of 10 to 15 mmHg to convert the hydroxyl group at the end of the resin into a carboxyl group. 100 parts of the obtained resin was dissolved and mixed in 100 parts of ethyl acetate to obtain an ethyl acetate solution of a toner binder. A portion of the mixture was dried under reduced pressure to isolate the polyester resin. The Tg was 62 ° C. and the acid value was 32.

(Synthesis of polyester prepolymer)
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube and reacted at 230 ° C. for 8 hours at normal pressure. The reaction was further carried out at a reduced pressure of 10 to 15 mmHg for 5 hours, followed by cooling to 160 ° C., and 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Next, the mixture was cooled to 80 ° C. and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain an isocyanate-containing polyester prepolymer.

(Synthesis of ketimine compounds)
A reaction vessel equipped with a stir bar and a thermometer was charged with 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone, and reacted at 50 ° C. for 5 hours to obtain a ketimine compound. The amine value of this ketimine compound was 418.

(Synthesis of resin fine particles)
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 138 parts of styrene, 138 parts of methacrylic acid, When 1 part of ammonium persulfate was charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to give an aqueous dispersion of vinyl resin (styrene salt copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate). Obtained. The volume average particle size of the obtained fine particle dispersion measured by LA-920 (manufactured by Horiba Ltd.) was 0.15 μm.

  In a sealed pot, 200 parts of an ethyl acetate solution of the polyester resin, 5 parts of carnauba wax, and 4 parts of copper phthalocyanine blue pigment were charged, and ball mill dispersion was performed for 24 hours using 5 mmφ zirconia beads. Thereafter, 20 parts of an isocyanate-containing polyester prepolymer in terms of solid content was added and mixed by stirring to obtain a toner composition.

In a beaker, 600 parts of ion-exchanged water, 20 parts of the obtained resin fine particle dispersion and 3 parts of sodium dodecylbenzenesulfonate were uniformly dissolved and dispersed. Next, while maintaining the internal temperature of the beaker at 20 ° C. and stirring at 15000 rpm with Robomix (made by Tokushu Kika Kogyo Co., Ltd.), an oil phase in which 1 part of a ketimine compound was mixed just before emulsification was prepared and charged for 3 minutes. Stirred and emulsified.
Subsequently, this mixed liquid was transferred to a flask equipped with a stirring bar and a thermometer, and the solvent was removed at 30 ° C. under reduced pressure of 50 mmHg for 8 hours. It was confirmed by gas chromatography that ethyl acetate in the dispersion was 100 ppm or less. Then, the operation of separating by filtration and redispersing the obtained cake in distilled water and filtering was repeated 3 times for washing. According to SEM, about 0.15 μm resin fine particles adhered to the surface of the obtained toner particles so as to cover the surface. The obtained cake was further redispersed in distilled water to a solid content of 10% by weight.

  There, 1 of N, N, N, -trimethyl- [3- (4-perfluorononenyloxybenzamido) propyl] ammonium, iodide (product name: Footage 310 (manufactured by Neos)), which is a compound of formula (1) A weight% aqueous solution was gradually added with stirring so as to be 0.2% by weight based on the solid content of the toner. Thereafter, the mixture was stirred at room temperature for 1 hour, and then separated by filtration. The obtained cake was dried under reduced pressure at 40 ° C. for 24 hours to obtain toner particles subjected to surface treatment. Subsequently, 100 parts of toner particles were mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain the toner of the present invention. The toner has a volume average particle diameter of 4.9 μm and an average circularity of 0.96.

5 parts by weight of the prepared toner and 95 parts by weight of the carrier described below were mixed for 10 minutes with a blender to prepare a developer.
(Manufacture of carrier particles)
Core material: Spherical ferrite particles with an average particle size of 50 μm Coating material constituent material: Silicone resin in which aminosilane coupling agent is dispersed Aminosilane coupling agent and silicone resin are dispersed in toluene, the dispersion is adjusted, and then heated The core material was spray-coated, and after firing and cooling, carrier particles having an average coated resin film thickness of 0.2 μm were prepared.

Example 1
Using the image forming apparatus shown in FIG. 1, the produced developer is set in the developing apparatus, the pressing force of the zinc stearate molded body against the brush-like roller of the lubricant application means is 500 mN, the brush-like roller, the photosensitive drum, An image was formed with a peripheral speed ratio of 1.0.

(Comparative Example 1)
Image formation was performed in the same manner as in Example 1 except that the pressing force of the zinc stearate molded body against the brush roller of the lubricant applying means was 0 mN.

In Example 1 and Comparative Example 1, the surface of the photosensitive drum after the output of a predetermined number of sheets as described below was evaluated.
1) Quantification of the amount of zinc element present on the surface of the photoconductive drum The surface of the photoconductive drum after outputting 100 band charts containing 0% and 100% image area ratio is analyzed by XPS (AXIS ULLA: manufactured by Shimadzu Corporation). The amount of zinc element present on the surface was quantified.
2) Evaluation of cleaning performance After outputting 1,000 sheets of a 5% image area ratio chart, the transfer residual toner on the photosensitive drum that has passed the cleaning process is transferred to white paper with Scotch tape (manufactured by Sumitomo 3M), and it is reflected in Macbeth reflection density. When measured by a total RD514 type, the difference from the blank is less than 0.005, “◎”, 0.005-0.010 “◯”, 0.011-0.02 “Δ” The value exceeding “0.02” was evaluated as “x”.
3) Occurrence of filming After the 1,000% image area ratio 5% chart has been output, a chart with an image area ratio of 100% was output, and the occurrence of filming on the photosensitive drum was examined depending on whether or not image blanking occurred. .

The results are shown in Table 1.

  As shown in Table 1, in Example 1 in which the amount of zinc element on the surface of the photosensitive drum after outputting 100 belt charts including image area ratios of 0% and 100% is 0.4 atm% or more, photosensitive The body drum surface was excellent in cleanability and no filming occurred. On the other hand, in Comparative Example 1 where the amount of zinc element on the surface of the photosensitive drum was less than 0.4 atm% when the image area ratio was 100%, the photosensitive drum surface was poorly cleaned and filming was also observed. .

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 photosensitive unit of the image forming apparatus in FIG. 1. FIG. 5 is a diagram schematically illustrating the shape of a toner for explaining 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 Photosensitive unit 3 Optical writing unit 10 Developing apparatus 11 Photosensitive drum (image carrier)
DESCRIPTION OF SYMBOLS 14 Charging device 14a Charging roller 14b Charging cleaning roller 15 Cleaning device 15a Cleaning blade 17 Lubricant application means 17a Brush-like roller 17b Lubricant molding 17d Pressure spring 60 Transfer conveyance belt

Claims (19)

An image carrier that carries a latent image; a charging unit that charges the surface of the image carrier; an exposure unit that exposes the charged surface of the image carrier based on image data and writes an electrostatic latent image; and Developing means for supplying toner to the latent image formed on the surface of the carrier to make it visible, transfer means for transferring the visible image on the surface of the image carrier to the transfer body, and cleaning the surface of the image carrier In an image forming apparatus comprising: a cleaning unit that cleans with a blade; and a lubricant application unit that applies a lubricant to the surface of the image carrier.
The lubricant application means comprises a lubricant molded body made of zinc stearate and a brush-like roller, and the lubricant molded body is rubbed and scraped off while the brush-like roller rotates and applied to the surface of the image carrier. The lubricant molded body is pressed with a pressure of 200 mN or more and 3000 mN or less against the brush roller.
The peripheral speed ratio between the image carrier and the brush roller ((image carrier peripheral speed) / (brush roller peripheral speed)) is in the range of 0.8 to 1.2.
The toner used in the developing unit has an average circularity of 0.93 or more and does not contain a component containing zinc element.
The elemental amount of zinc present on the surface of the image carrier after the cleaning operation by the cleaning unit and the lubricant application operation by the lubricant application unit is 0.4 to 2.5 atm%.
An image forming apparatus. The image forming apparatus according to claim 1.
The toner used in the developing unit is a negatively chargeable toner containing a fluorine-containing compound.
An image forming apparatus. The image forming apparatus according to claim 1, wherein
The toner used in the developing means is obtained by treating the surface of toner base particles in a liquid containing the fluorine-containing compound.
An image forming apparatus. The image forming apparatus according to any one of claims 1 to 3,
The fluorine-containing compound used for the treatment of the toner base particle surface is a surfactant having a polarity different from the polarity of the toner base particle surface before the treatment.
An image forming apparatus. The image forming apparatus according to claim 1,
The fluorine-containing compound is represented by the following general formula (1).
An image forming apparatus.

(In the formula, X, Y , R 1 to R 4 , r and s each represent the following: X: —SO ₂ — or —CO—, R 1, R 2, R 3, R 4: hydrogen atom, carbon number 1 to 10 lower alkyl group or aryl group, Y: I or Br, r, s: integer of 1-20.) The image forming apparatus according to claim 1,
The toner used in the developing unit is a resin fine particle obtained by dissolving or dispersing at least a polyester prepolymer having a functional group containing a nitrogen atom, a polyester, a colorant, and a release agent in an organic solvent. Obtained by crosslinking and / or elongation reaction in an aqueous medium containing
An image forming apparatus. The image forming apparatus according to claim 1,
The toner used in the developing unit has a volume average particle diameter of 3 to 8 μm and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of 1.00 to 1.n. In the range of 40
An image forming apparatus. The image forming apparatus according to claim 1,
The toner used in the developing unit has 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.
An image forming apparatus. The image forming apparatus according to claim 1,
The toner used in the developing unit has a substantially spherical shape, and the shape is defined by a major axis r1, a minor axis r2, and a thickness r3 (provided that r1 ≧ r2 ≧ r3), and the major axis r1. The ratio (r2 / r1) to the minor axis r2 is in the range of 0.5 to 1.0, and the ratio (r3 / r2) of the thickness r3 to the minor axis r2 is in the range of 0.7 to 1.0. is there
An image forming apparatus. An image carrier that carries a latent image, a developing unit that supplies toner to the latent image formed on the surface of the image carrier and visualizes the image, and a lubricant application unit that applies a lubricant to the surface of the image carrier In a process cartridge that is integrally supported and includes a removable image cartridge body.
The lubricant application means comprises a lubricant molded body made of zinc stearate and a brush-like roller, and the lubricant molded body is rubbed and scraped off while the brush-like roller rotates and applied to the surface of the image carrier. The lubricant molded body is pressed with a pressure of 200 mN or more and 3000 mN or less against the brush roller.
The peripheral speed ratio between the image carrier and the brush roller ((image carrier peripheral speed) / (brush roller peripheral speed)) is in the range of 0.8 to 1.2.
The toner used in the developing unit has an average circularity of 0.93 or more and does not contain a component containing zinc element.
The elemental amount of zinc present on the surface of the image carrier after the cleaning operation by the cleaning unit and the lubricant application operation by the lubricant application unit is 0.4 to 2.5 atm%.
A process cartridge characterized by that. An image carrier that carries a latent image; a charging unit that charges the surface of the image carrier; an exposure unit that exposes the charged surface of the image carrier based on image data and writes an electrostatic latent image; and Developing means for supplying toner to the latent image formed on the surface of the carrier to make it visible, transfer means for transferring the visible image on the surface of the image carrier to the transfer body, and cleaning the surface of the image carrier An image forming apparatus comprising: cleaning means for cleaning with a blade; and lubricant application means for applying a lubricant to the surface of the image carrier.
The lubricant application means comprises a lubricant molded body made of zinc stearate and a brush-like roller, and the lubricant molded body is rubbed and scraped off while the brush-like roller rotates and applied to the surface of the image carrier. The lubricant molded body is pressed with a pressure of 200 mN or more and 3000 mN or less against the brush roller.
The peripheral speed ratio between the image carrier and the brush roller ((image carrier peripheral speed) / (brush roller peripheral speed)) is in the range of 0.8 to 1.2.
  An image forming apparatus having an element amount of zinc of 0.4 to 2.5 atm% present on the surface of the image carrier after finishing the cleaning operation by the cleaning unit and the lubricant application operation by the lubricant application unit. Toner used in the developing means of
The toner comprises at least a binder resin and a colorant, does not contain a component containing zinc element, and has an average circularity of 0.93 or more.
Toner characterized by the above. The toner according to claim 11.
The toner is a negatively chargeable toner containing a fluorine-containing compound.
Toner characterized by the above. The toner according to claim 11 or 12,
The toner is obtained by treating the surface of toner base particles in a liquid containing the fluorine-containing compound.
Toner characterized by the above. The toner according to any one of claims 11 to 13,
The fluorine-containing compound used for the treatment of the toner base particle surface is a surfactant having a polarity different from the polarity of the toner base particle surface before the treatment.
Toner characterized by the above. The toner according to any one of claims 11 to 14,
The fluorine-containing compound is represented by the following general formula (1).
Toner characterized by the above.

(In the formula, X, Y , R 1 to R 4 , r and s each represent the following: X: —SO ₂ — or —CO—, R 1, R 2, R 3, R 4: hydrogen atom, carbon number 1 to 10 lower alkyl group or aryl group, Y: I or Br, r, s: integer of 1-20.) The toner according to any one of claims 11 to 15,
In the toner, 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 dissolved or dispersed in an organic solvent is contained in an aqueous medium containing resin fine particles. Obtained by crosslinking and / or elongation reaction
Toner characterized by the above. The toner according to any one of claims 11 to 16,
The toner has a volume average particle diameter of 3 to 8 μm and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is in the range of 1.00 to 1.40.
Toner characterized by the above. The toner according to any one of claims 11 to 17,
The toner has 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.
Toner characterized by the above. The toner according to any one of claims 11 to 18,
The toner has a substantially spherical shape, and the shape is defined by a major axis r1, a minor axis r2, and a thickness r3 (where r1 ≧ r2 ≧ r3), and a ratio between the major axis r1 and the minor axis r2. (R2 / r1) is in the range of 0.5 to 1.0, and the ratio (r3 / r2) of the thickness r3 to the minor axis r2 is in the range of 0.7 to 1.0.
Toner characterized by the above.

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