JP2005195755A5 - - Google Patents

Description

Image forming method, developer for replenishment used in the method, and cartridge for developer replenishment

The present invention is an electrophotographic method, a method such as an electrostatic recording method, an image forming method for forming an image by developing the electrostatic latent image, beauty Oyo replenishing developer used in the method, as well as for the developer supply It relates to the cartridge.

In electrophotography, an electrostatic latent image formed on the surface of a latent image carrier (photoreceptor) is developed with toner containing a colorant, and the resulting toner image is transferred to a transfer medium such as paper. An image can be obtained by fixing with a heat roll or the like. On the other hand, the surface of the latent image carrier after the toner image transfer is generally cleaned to form an electrostatic latent image again.
The dry developer used in such an electrophotographic method includes a one-component developer that uses a toner in which a colorant or the like is blended in a binder resin, and a two-component developer in which the toner is mixed with a carrier. Broadly divided. In the one-component developer, magnetic powder is used, and the magnetic one-component developer is transported and developed by a developer carrier by magnetic force, and the non-magnetic one is transported and developed by the developer carrier by charging without using magnetic powder. It can be classified into component developers.

From the latter half of the 1980s, the demand for downsizing and high functionality in the market for digital photography became stronger with the key to digitization. Especially for full color image quality, high-quality printing and high-quality image similar to silver halide photography are desired. . Digitization processing is indispensable as a means for achieving high image quality, and the effect of digitization related to such image quality is that complex image processing can be performed at high speed. This makes it possible to control characters and photographic images separately, and the reproducibility of both qualities is greatly improved compared to analog technology. In particular, for photographic images, gradation correction and color correction are possible, and this is advantageous in comparison with the analog system in terms of gradation characteristics, definition, sharpness, color reproduction, and graininess.
For image output, it is necessary to faithfully form a latent image created by an optical system, and as a toner, the particle size is increasingly reduced, and the activity aimed at faithful reproduction is accelerated. However, it is difficult to stably obtain a high-quality image simply by reducing the particle size of the toner, and improvement of basic characteristics in development, transfer, and fixing characteristics is more important.
When obtaining a color image, generally, an image is formed by superposing three or four color toners. Therefore, if any one of these color toners shows different characteristics from the initial stage in terms of development, transfer, and fixing, or performance different from that of other colors, image quality deterioration such as deterioration in color reproduction, deterioration in graininess, and color unevenness. Will be caused. In order to maintain a stable high-quality image over time as in the initial stage, it is important how to stably control the characteristics of each color toner.

In recent years, from the viewpoint of speeding up when obtaining a color image (sometimes referred to as simply “color speeding up”), a developing unit including a developer carrying member and a latent image carrier is provided. A plurality of so-called tandem development systems are employed, and the diameter of each latent image carrier is reduced from the viewpoint of reducing the size of the apparatus in order to save space. There have also been many patent applications related to tandem development systems (see, for example, Patent Documents 1 and 2).
By adopting such a tandem development system, it is easy to increase the color speed as compared with the rotary development system. However, when obtaining a monochrome image such as black, the developer carrier of other colors is also a latent image carrier. It is common to be forced to rotate in the process direction at the same time. In such a case, the stress applied to the developer is large, which induces a decrease in the charging performance of the developer, tends to cause a decrease in the development performance and the transfer performance, and ultimately leads to a decrease in image quality. In the tandem development system, the space around the latent image carrier or the size of the apparatus is limited due to the limitation of the size of the apparatus, and the developer amount sufficient in each developer due to the space. Cannot be secured. Therefore, the stress applied to the developer tends to be large also in the apparatus structure. For this reason, as the developer deteriorates, the developer is exchanged, which leads to a significant increase in service cost.

  As a means for suppressing developer deterioration, a technique using several types of replenishment developers containing carriers having different physical properties is disclosed (for example, see Patent Document 3). This is because the toner fluidity, toner color characteristics, etc. are affected by changing the physical properties of the carrier, which complicates the control system and leads to an increase in the size or cost of the apparatus. In addition, a technique for supplying a replenishment developer containing a carrier having a charge amount higher than the charge amount of the carrier used for the start developer is disclosed (for example, see Patent Document 4). Although these technologies are very effective in extending the life of the developer, it is important that the physical properties of the developer do not change with the environment and time when considering the image quality stability, but it is difficult to control. is there.

Carriers are generally classified into a coated carrier having a coating layer on the surface and an uncoated carrier having no coating layer on the surface, but the coated carrier is superior when considering the developer life and the like. Therefore, various types of coated carriers have been developed and put into practical use. Although there are various properties required for the coated carrier, it is necessary to impart an appropriate chargeability (charge amount and charge distribution) to the toner, to maintain the appropriate chargeability for a long period of time, agitation and transportability as a developer. For this purpose, it is important not to change the chargeability of the toner even with respect to the impact resistance, abrasion resistance, contamination resistance, and environmental changes such as humidity and temperature of the carrier. Coated carriers have been proposed. Conventionally, various methods have been proposed for carrier charging and resistance design. Methods that use the charging characteristics of materials such as glass beads and steel shots, or methods such as surface treatment such as silane coupling treatment on carrier core materials have been generally used for a long time. However, the carrier thus obtained is difficult to adjust because the chargeability and resistance characteristics of the carrier are determined by the material type, and the toner component migrates to the carrier surface and contaminates the carrier surface. There is a problem that the resistance characteristic is likely to change. Furthermore, these carriers have a problem that the influence of the use environment is great. For this reason, at present, a resin-coated carrier obtained by coating a resin on a carrier core is often used. The resin-coated carrier has characteristics that it can easily control the charging and resistance characteristics independently of the characteristics of the carrier core material by controlling the material of the coating film, the structure of the coating film, and the coating state of the core material. Have. As a charging characteristic control for a resin-coated carrier, a proposal of “having at least a quaternary ammonium compound on the surface” has been proposed (for example, see Patent Document 5). Specifically, a quaternary ammonium compound is adhered to the surface of the carrier, or the carrier is treated by mixing a quaternary ammonium compound in a resin solution. Although this method has a certain effect in controlling the chargeability of the developer, when used for a long time, there is a decrease in the chargeability of the developer and a deterioration in the charge distribution, and it is possible to output a high-quality image for a long time. It was difficult. Furthermore, a technique has also been proposed in which the chargeability is controlled by mechanically attaching a charge control agent to the surface of the resin-coated carrier (see, for example, Patent Documents 6 and 7). Carriers obtained by these methods also have a certain effect on the initial chargeability, but are insufficient in terms of maintaining chargeability. Further, in recent years, there is a high demand for high image quality, and the diameter of toner has been reduced in order to faithfully develop an electrostatic latent image and improve fine line reproducibility. If a small-diameter toner is used in a resin-coated carrier to which a charge control agent has been added, there will be more in-machine contamination and output image quality contamination due to toner blow-off and drop-off from the developing device, making it difficult to stably obtain high-quality images. there were. In addition, a method of fixing polymer particles containing a charge control agent to a carrier core material has also been proposed (see, for example, Patent Document 8). However, when the charge control agent is contained in the polymer particles, there is a problem that the function of the charge control agent is hardly exhibited. There has also been proposed a method in which magnetic powder, a charge control agent, and a binder resin are melt-mixed and then pulverized and classified to create a magnetic material-dispersed carrier (see, for example, Patent Document 9). However, these magnetic material-dispersed carriers are difficult to control independently of the magnetic characteristics and resistance characteristics of the carriers, and have a problem that the resistance characteristics become too low when trying to obtain carriers with high magnetic force / high saturation magnetization. Furthermore, although it is known that the carrier particle size reduction is highly effective for high image quality, the small-diameter carrier prepared using this method is easily transferred to the latent image carrier during the development process. There is a problem that image quality defects such as white spots are likely to occur. In addition, since these methods focus on chargeability control, it is difficult to maintain resistance characteristics over a long period of time using carriers, and it is difficult to maintain high image quality.

On the other hand, the toner developability varies due to variations in shape and particle size, and is selectively consumed from toner with good developability, and toner with low developability remains in the developer. There is a problem of selective development that causes a decrease in developability as a whole. As the developer deteriorates due to the selective development, it becomes necessary to replace the developer, which leads to a significant increase in service cost. In particular, in the tandem development system, a sufficient amount of developer cannot be secured in each developing device due to space, so that the developer deterioration easily occurs due to variations in the developability of the toner. Improvement was desired.
Further, it has been reported that the toner is agitated in the developing device, and the change in the fine structure of the toner surface easily occurs, thereby greatly changing the transferability (see, for example, Patent Document 10). Due to the change in the fine structure of the toner surface, the variation in the developability of the toner tends to increase, resulting in the above-described selective development being promoted, and the problem of a decrease in developer maintainability becomes more prominent.

  In addition, it is necessary to faithfully form an electrostatic latent image created by an optical system, and the particle size is increasingly reduced, and activities aimed at faithful reproduction are accelerated. However, it is difficult to obtain a stable high image quality simply by reducing the toner particle size, and improvement of basic characteristics in development, transfer, fixing, and cleaning is more important. In particular, in the transfer process, it is necessary to faithfully transfer the developed toner image in order to improve the image quality. However, the transfer performance is deteriorated by reducing the diameter of the toner. For this reason, various techniques for using small-diameter toner have been reported. For example, it has been reported that the transfer performance is improved by bringing the toner closer to a spherical shape (see, for example, Patent Document 11). In this case, the transfer efficiency is improved by making the toner spherical, but on the other hand, the rise in chargeability is fast and good, but a so-called charge-up phenomenon occurs in which the chargeability gradually increases. Easily, resulting in a decrease in developability and image quality deterioration.

Therefore, for the purpose of improving the problems so far and maintaining high image quality over a long period of time, a copolymer of acrylic acid ester containing carboxyl group and fluorine is used for the carrier coating agent, and a conductive material is contained in the carrier coating layer. However, the use of a trickle development method using a spherical toner has been proposed (see, for example, Patent Document 12). However, the fine line reproducibility is slightly deteriorated in the carrier in the present proposal, and the fine line reproducibility tends to become a constant level as the number of prints increases, and although it is an acceptable level, there is a slight deterioration in image quality. This is presumably due to the uneven distribution of the conductive material in the coat layer and the change in carrier resistance due to peeling of the carrier coat layer.
JP-A-6-35287 JP-A-6-100195 JP-A-8-234550 JP-A-11-202630 JP-A-61-120164 Japanese Unexamined Patent Publication No. 64-29859 Japanese Unexamined Patent Publication No. 64-29858 Japanese Unexamined Patent Publication No. 64-29864 JP 63-301965 A Japanese Patent Laid-Open No. 10-312089 JP-A-62-184469 Japanese Patent Laid-Open No. 2003-140402

Accordingly, an object of the present invention is to solve the conventional problems and achieve the following objects. That is, the present invention provides an image forming method capable of significantly extending the developer life and realizing maintenance-free while using a tandem-type image forming apparatus corresponding to downsizing and high-speed color, and for replenishment used in the method. developer, and an object of the invention to provide a developer supply cartridge.

  As a result of intensive research, the inventors of the present invention appropriately replenished the developer with a replenishment developer composed of toner and carrier in the tandem type image forming apparatus, and collects the developer from the inside. A so-called trickle development system having a mechanism is adopted, and it has been found that it is effective to use a specific carrier or toner as the replenishment developer, and the present invention has been conceived.

A latent image carrier, charging means for charging the surface of the latent image carrier, latent image forming means for forming a latent image on the surface of the charged latent image carrier, and a developer composed of toner and a carrier are contained therein. A developer that accommodates and develops the latent image by the developer layer formed on the surface of the developer carrying member and forms a toner image on the surface of the latent image carrying member, and transfers the toner image to the transfer member An image forming method for forming an image by an image forming apparatus including a plurality of developing units including a transfer unit, wherein a developing device of at least one developing unit in the image forming apparatus includes the toner and the carrier therein. with the replenishment developer appropriately replenishing containing, a mechanism for collecting the developer from the inside, the content of the carrier in the replenishment developer, the toner 100 parts by weight of 15 to 40 weight By weight, the carrier is a conductive material and a resin containing a charge control agent is coated on the core material, and the charge control agent to the carrier core material 100 parts by weight content in the carrier, 0.001 The volume specific resistance value of all the carriers mixed with the toner is 10 ⁶ to 10 ¹⁴ Ω · cm, the volume average particle diameter of the toner is 3 to 10 μm, and the formula An image forming method, wherein the toner shape factor SF1 represented by (1) is in a range of 110 to 140.
SF1 = (R ² × π) / (A × 4) × 100 ... Formula (1)
(In the above formula, R represents the maximum toner length, and A represents the projected area of the toner.)

  In these image forming methods of the present invention, it is preferable that the developing unit having the developer recovery mechanism further includes a cleaning unit for cleaning the surface of the latent image carrier after the toner image is transferred by the transfer unit.

  As described above, the present invention has a plurality of latent image carriers and developer carriers, and changes in physical properties such as charge deterioration and resistance change over a long period of time in a tandem type image forming apparatus that requires high reliability. By using a development system with a small amount of developer and a developer, it is possible to provide an image with excellent image quality stability.

  In order to achieve high image quality at a high level, a trickle development system is adopted, and in the present invention, a resin containing a conductive material and a charge control agent is used for the coating layer of toner and carrier close to a spherical shape.

  According to the present invention, a carrier using a resin containing a conductive material and a charge control agent in the coating layer has excellent chargeability under high humidity, suppresses an increase in charge under low humidity, has excellent charging environment stability, and development. It is possible to provide a carrier for electrostatic latent image development and a development system that are excellent in development maintainability without changing the fluidity and transportability of the agent. In addition, by disposing a conductive material and a charge control agent in the resin coating layer, there is no resistance change or charge change over a long period even when subjected to carrier-carrier stress or carrier-toner stress, and high-quality image formation is possible. It becomes possible.

  Since the toner uses a toner having a high degree of spheroidization (close to a sphere), fluidity, chargeability, and transferability are improved. In particular, since the shape of the toner is nearly spherical and uniform as a whole, variations in toner developability are suppressed, problems due to selective development are reduced, and developer maintainability is improved. Further, since the shape of the toner is close to a spherical shape, a change in the fine structure of the toner surface hardly occurs due to various stresses, and the selective development is not promoted.

  Further, the image forming method of the present invention can be suitably applied to an image forming apparatus capable of switching process speeds automatically or manually according to predetermined conditions. Furthermore, in the developing unit having the developer recovery mechanism, the charging unit is preferably a roll charging type charger.

On the other hand, the replenishment developer according to the present invention is used in the image forming method according to the present invention, and an excessive development recovered by the developer recovery mechanism in the image forming method according to the present invention. It is preferable that the toner is produced by selecting the carrier from the agent and mixing it into the toner as all or part of the carrier .

  The developer replenishing cartridge of the present invention is a cartridge for replenishing the developer for replenishment to the developing device of the image forming apparatus, and contains the replenishing developer of the present invention.

As described above, according to the present invention, while using a tandem-type image forming apparatus corresponding to downsizing and high-speed colorization, an image forming method capable of significantly extending the developer life and realizing maintenance-free, replenishing developer used in the method, as well as to provide a developer supply cartridge.

The present invention will be described in detail below.
The developer used in the present invention includes a developer (hereinafter sometimes referred to as “start developer”) accommodated in a developing device and a replenishment developer. The configuration is basically the same except that the ratio is different.

In the present invention, the carrier to be used is formed by coating a core material with a resin containing a conductive material and a charge control agent, and the charge control agent has a content in the carrier of 0.001 to 100 parts by mass of the carrier core material. It is 5 parts by mass.
By using the carrier having such a configuration, even if the resin coating layer is peeled off, it is possible to achieve high image quality over a long period of time without greatly changing the charge imparting ability and the volume resistivity.

  Coating resins and matrix resins used for the resin coating layer include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, polyvinyl ketone, vinyl chloride-acetic acid. Vinyl copolymer, styrene-acrylic acid copolymer, straight silicone resin composed of organosiloxane bond or modified product thereof, fluorine resin, polyester, polyurethane, polycarbonate, phenol resin, amino resin, melamine resin, benzoguanamine resin, urea resin, Examples include amide resins and epoxy resins, but are not limited thereto. Particularly preferred are polystyrene resin, acrylic resin, and styrene acrylic copolymer. When these resins are used, the coating film strength is high and the conductive material and the charge control agent can be dispersed.

  Examples of the charge control agent include nigrosine dye, benzimidazole compound, quaternary ammonium salt compound, alkoxylated amine, alkylamide, molybdate chelate pigment, triphenylmethane compound, salicylic acid metal salt complex, azo chromium complex, copper phthalocyanine Any known ones may be used. Particularly preferred are quaternary ammonium salt compounds, alkoxylated amines and alkylamides. These charge control agents are easy to control the dispersion state and have good adhesion to the coating resin interface, so that desorption of the charge control agent from the carrier coating film can be suppressed. Further, the charge control agent acts as a dispersion aid for the conductive material, the dispersion state of the conductive material in the coat layer is made uniform, and the carrier resistance change can be suppressed even if the coat layer is slightly peeled off. The reason is that the conductive material described later is easily oxidized on the surface or is affected by moisture, and thus has a high hydrophilicity and has a structure that easily aggregates due to water on the particle surface. When this is dispersed in the coating resin, since the polarity of the resin is generally low, the agglomeration described above remains as it is, so that uneven distribution tends to occur inside the coating resin. On the other hand, the charge control agent described above has good adhesion to the coating resin interface and has a certain degree of polarity, so that the adhesion with the conductive material is also improved, so it is estimated that the dispersibility can be improved. Is done.

The addition amount of the charge control agent used in the present invention when the carrier core material and 100 parts by weight, and 0.001 to 5 parts by weight. More preferably, it is 0.01-0.5 mass part. If the amount is excessive, the strength of the carrier coating film is lowered, and the carrier is easily deteriorated by stress during use. If the amount is too small, not only the function of the charge control agent cannot be fully exhibited, but also the dispersibility of the conductive material cannot be improved.

  Examples of the conductive material include metals such as gold, silver, and copper, and titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate, tin oxide, and carbon black. Black is preferable in terms of uniform dispersion in the resin and resistance control. However, it is not limited to these. The content of the conductive material is preferably 1 to 50 parts by mass and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the resin in order to make the carrier volume resistivity a desired characteristic.

  Examples of the core material include those in which magnetic powder is used alone for the core material, or those in which magnetic powder is finely divided and dispersed in a resin. Examples of the material of the magnetic powder include magnetic metals such as iron, nickel, and cobalt, and magnetic oxides such as ferrite and magnetite.

The magnetic powder is made into fine particles and dispersed in the resin. The resin and magnetic powder are kneaded and pulverized, the resin and magnetic powder are melted and spray dried, and the polymerization method is used to contain the magnetic powder in the solution. Examples include a method of polymerizing a resin. The carrier preferably contains fine magnetic powder in an amount of 80 parts by mass or more with respect to the total weight of the carrier from the viewpoint of preventing carrier scattering.
The volume average particle diameter of the core material is generally 10 to 500 μm, preferably 25 to 80 μm.

  As a method of forming the resin coating layer on the surface of the core material, a carrier core material is prepared by a dipping method in which a solution for forming a coating layer containing the resin, a conductive material and a solvent is immersed in the solution, and coating layer formation Spray method of spraying the solution for carrier onto the surface of the carrier core material, fluidized bed method of spraying the solution for forming the coating layer in a state where the carrier core material is suspended by the flowing air, and the carrier core material and the coating layer forming solution in the kneader coater And kneader coater method in which the solvent is removed.

  The solvent used for preparing the coating layer forming solution is not particularly limited as long as it dissolves the resin. For example, aromatic hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, and the like. And ethers such as tetrahydrofuran and dioxane can be used.

  The average film thickness of the resin coating layer is usually 0.1 to 10 μm, but in the present invention, it is preferably 0.5 to 3 μm in order to develop a stable volume resistivity of the carrier over time.

Volume resistivity of the carrier used in the present invention, in order to achieve high image quality, in 1000V time corresponding to the upper and lower limits of normal development contrast potential required to have a 10 ⁶ ~10 ¹⁴ Ω · cm 10 ⁸ to 10 ¹³ Ω · cm is more preferable. When the volume specific resistance value of the carrier is less than 10 ⁶ Ω · cm, the reproducibility of fine lines is poor, and the amount of carrier transferred to the photoconductor (latent image carrier) increases and the photoconductor is easily damaged. On the other hand, if the volume resistivity of the carrier is larger than 10 ¹⁴ Ω · cm, the reproduction of solid black and halftone becomes worse.

The toner used in the present invention has a volume average particle diameter of 3 to 10 μm and a toner shape factor SF1 represented by the formula (1) of 110 to 140.
SF1 = (R ² × π) / (A × 4) × 100 ... Formula (1)
(In the above formula, R represents the maximum toner length, and A represents the projected area of the toner.)
The “toner” defined in the present invention refers to a mother particle of a toner excluding the external additive even when an external additive is added, and is generally referred to as “toner particle” or “colored particle”. It is called. In the following description, this may be referred to as “toner particles” in order to clarify the difference from the toner composition to which an external additive is added.

  In the present invention, the volume average particle size of the toner particles is in the range of 3 to 10 μm. By setting the volume average particle diameter of the toner particles in the above range, a high-definition image can be obtained and the powder fluidity, charging stability, transferability, etc. are excellent. The volume average particle diameter of the toner particles is preferably in the range of 3 to 6 μm, particularly from the viewpoint of high image quality.

  In the present invention, it is essential that the toner shape factor SF1 represented by the formula (1) is 110 to 140. By setting the toner shape factor SF1 within the above range, an image with high developability, transferability and high image quality can be obtained. In addition, since the shape is nearly spherical and uniform as a whole, variations in toner chargeability are suppressed, problems due to selective development are reduced, and developer maintainability is improved. Further, since the shape of the toner is close to a spherical shape, a change in the fine structure of the toner surface hardly occurs due to various stresses, and the selective development is not promoted.

  In the present invention, the toner shape factor SF1 can be obtained by sampling the toner particles to be measured and analyzing the projected image of the toner particles photographed with an optical microscope with an image analyzer. A value obtained by averaging the values was defined as a toner shape factor SF1. In the case of a true sphere, the toner shape factor SF1 is 100, and the larger the value, the more indefinite the shape is from the true sphere.

  In the present invention, the method for producing the toner (toner particles) is not particularly limited, but in order to obtain toner particles having a good sphericity SF described above, it is desirable that the toner (toner particles) be produced by a wet production method. As a wet manufacturing method, a polymerizable monomer of a binder resin is emulsion-polymerized, and the formed dispersion is mixed with a dispersion of a colorant, a release agent, and a charge control agent as necessary, and agglomerated. An emulsion polymerization aggregation method to obtain toner particles by heat fusion; a solution of a polymerizable monomer, a colorant, a release agent, and a charge control agent, if necessary, to obtain a binder resin in an aqueous solvent. Suspension polymerization method for turbid polymerization; dissolution suspension method in which a binder resin, a colorant, a release agent, and a charge control agent, if necessary, are suspended in an aqueous solvent and granulated; It is done. Further, a manufacturing method may be performed in which the toner particles obtained by the above method are used as a core, and further, aggregated particles are attached and heat-fused to have a core-shell structure. In addition, the toner shape factor SF1 may be set within a predetermined range by subjecting the toner particles obtained by a general pulverization classification method to a spheronization process by heating and melting and solidifying again.

  The toner (toner particles) used in the present invention contains at least a binder resin and a colorant, and if necessary, a release agent and other components. In addition to the so-called toner particles having the above structure, it is desirable that an external additive is added to the toner used in the present invention for various purposes.

  Examples of the binder resin include styrenes such as styrene and chlorostyrene; monoolefins such as ethylene, propylene, butylene, and isoprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, and vinyl butyrate; acrylics Α-methylene aliphatic monocarboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone; and homopolymers and copolymers of In particular, typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, and styrene-anhydrous. A maleic acid copolymer, polyethylene, polypropylene, etc. are mentioned. Furthermore, polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax and the like can be mentioned.

  Examples of the colorant include magnetic powders such as magnetite and ferrite, carbon black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, Lamp Black, Rose Bengal, C.I. Pigment Red 48: 1, C.I. Pigment Red 122, C.I. Pigment Red 57: 1, C.I. Pigment Yellow 97, C.I. Pigment Yellow 17, C.I. Pigment Blue 15: 1, C.I. Pigment Blue 15: 3, and the like can be exemplified.

The amount of the colorant added is preferably 3 to 20 parts by mass and more preferably 4 to 10 parts by mass with respect to 100 parts by mass of the binder resin when a pigment or a dye is used. If the addition amount is less than 3 parts by mass, the coloring power of the toner may be insufficient, and it is preferable that the addition amount be as large as possible without impairing the smoothness of the image surface after fixing. When the content of the colorant is increased, the thickness of the image can be reduced when an image having the same density is obtained, which is advantageous in terms of high image quality and prevention of offset.
When magnetite or ferrite is used as the colorant, the amount added is 3 to 60 parts by mass, preferably 10 to 30 parts by mass with respect to 100 parts by mass of the binder resin.

Typical examples of the release agent include low molecular polyethylene, low molecular polypropylene, Fischer-Tropsch wax, montan wax, carnauba wax, rice wax, and candelilla wax.
The addition amount of the release agent is preferably 1 to 15 parts by mass and more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the binder resin. If the addition amount is less than 1 part by mass, the effect may not be exhibited. On the other hand, if the addition amount is more than 15 parts by mass, the fluidity may be extremely deteriorated and the charge distribution may be very wide. .
As other components, a charge control agent may be added to the toner as necessary. Known charge control agents can be used, but azo metal complex compounds, metal complex compounds of salicylic acid, ammonium salts, and resin type charge control agents containing polar groups can be preferably used. In particular, when a toner is manufactured by a wet manufacturing method, it is preferable to use a material that is difficult to dissolve in water in terms of controlling ionic strength and reducing wastewater contamination. In the present invention, the toner may be either a magnetic toner containing a magnetic material or a non-magnetic toner containing no magnetic material.

  There is no restriction | limiting in particular as an external additive, The various external additives conventionally used as an external additive can be used without a problem. For example, fine particles such as metals, metal oxides, metal salts, ceramics, resins, and carbon black may be externally added for the purpose of improving chargeability, conductivity, powder fluidity, lubricity, and the like.

  By the way, the development / transfer is influenced by the uniform transportability of the developer, the current at the time of transfer, etc., but basically the toner from the binding force of the carrier (carrier or latent image carrier) carrying the toner particles. Since this is a process of separating the particles and adhering them to the object (latent image carrier or transferred object), the electrostatic force and the toner particles and carrier (charge imparting member) or the toner particles and the latent image carrier are attached. It depends on the balance of “wear strength”. Control of this balance is very difficult, but this process directly affects the image quality, and if the efficiency is improved, it is expected to improve reliability and save labor by cleaning less. Therefore, higher development / transfer properties are required.

  Such development / transfer occurs when “electrostatic attraction”> “adhesion”. Therefore, in order to improve the development / transfer efficiency, the electrostatic attraction force may be increased (increase the development / transfer force) or the adhesion force may be controlled to decrease, but when the development / transfer force is increased, for example, If the transfer electric field is increased, secondary problems such as reverse polarity toner are likely to occur. Therefore, it is more effective to reduce the adhesion.

Examples of the adhesion force include van der Waals force (non-electrostatic adhesion force) and mirror image force due to charge of toner particles. There is a level difference of almost one order between the two, and it can be interpreted that it is almost discussed by van der Waals force. The van der Waals force F between spherical particles is represented by the following formula (2).
_{F = H · r 1 · r} 2/6 (r 1 + r 2) · A 2 ... (2)
(H: constant, r ₁ , r ₂ : radius of two particles in contact, A: distance between particles)
In order to reduce the adhesion force, a fine powder having a very small r compared to the toner particles is interposed between the toner particles and the surface of the latent image carrier or the surface of the charging member so that each has a distance A and further contact. A technique for reducing the area (number of contact points) is effective, and the effect can be stably maintained by using monodispersed spherical silica.

In the case of using a toner having a shape close to a sphere shape, generally, the cleaning of the image bearing member is difficult. Usually, the cleaning pressure is optimized by optimizing the blade pressure of the cleaning blade. At the same time, as the external additive of the toner, the true specific gravity is 1.3 to 1.9, and the volume average particle diameter is 80 to It is effective to use monodispersed spherical silica that is 300 nm. By using such monodispersed spherical silica, the adhesion between the toner and the latent image carrier is reduced, and the blade passes (cleaning) due to the rolling of the toner near the contact portion between the cleaning blade and the latent image carrier. This is because (defect) can be suppressed.

  On the other hand, the discharge product formed on the latent image carrier by the charging roll increases the friction coefficient between the cleaning blade and the latent image carrier, causing the cleaning blade to be distorted and squealed as the process speed changes. It may cause cleaning failure. Since the discharge product is proportional to the current value and the number of discharges, in a device capable of switching the process speed, for example, when switching from the high speed mode to the normal mode or the low speed mode, the cleaning blade and the latent image are carried. Since the process speed is slowed in the state where the body is in contact with the body, problems such as distortion of the cleaning blade, squealing, and poor cleaning become prominent.

In order to prevent such problems, it is effective to use an abrasive as an external additive in combination with the toner. By adding an abrasive, the discharge product can be polished and refreshed.
Therefore, in the present invention, it is desirable to use monodispersed spherical silica and / or an abrasive in combination as an external additive for the toner. Of course, the external additives are not limited to these, and other external additives may be included in the present invention.

(A) Monodispersed spherical silica Monodispersed spherical silica particularly preferably used in the present invention has a true specific gravity of 1.3 to 1.9 and a volume average particle size of 80 to 300 nm.
By controlling the true specific gravity to 1.9 or less, peeling from the toner particles can be suppressed. Further, by controlling the true specific gravity to be 1.3 or more, aggregation and dispersion can be suppressed. Preferably, the true specific gravity of the monodispersed spherical silica in the present invention is 1.4 to 1.8. Since the monodispersed spherical silica is monodispersed and spherical, the monodispersed spherical silica is uniformly dispersed on the surface of the toner particles, and a stable spacer effect can be obtained.

  On the other hand, when the volume average particle size of the monodispersed spherical silica is less than 80 nm, it tends not to work effectively for reducing non-electrostatic adhesion. In particular, due to stress in the developing device, the toner particles are easily embedded in the toner particles, and the development and transfer improvement effects are remarkably reduced. On the other hand, if it exceeds 300 nm, it will be easy to detach from the toner particles, and it will not work effectively for reducing non-electrostatic adhesion, and at the same time, it will easily move to the contact member, secondary obstructions such as charging inhibition and image quality defects. It is easy to cause. Preferably, the volume average particle diameter of the monodispersed spherical silica in the present invention is 100 to 200 nm.

In addition, as the definition of monodispersion in the present invention, it is possible to discuss the standard deviation with respect to the average particle diameter including aggregates, and the standard deviation is preferably volume average particle diameter D50 × 0.22 or less. As the definition of the sphere in the present invention, it can be discussed in terms of the W a dell sphericity expressed by the following formula (3), and the sphericity is preferably 0.6 or more, and more preferably 0.8 or more. More preferred.
Sphericality = S ₁ / S ₂ (3)
(In the above formula, S ₁ represents the surface area of a sphere having the same volume as the actual particle, and S ₂ represents the surface area of the actual particle itself.)
As the silica is preferred reasons as the material, the refractive index is 1.5 before and after a decrease in transparency even by light scattering by increasing the particle size, in particular an image taken when the PE value onto OHP (Projection Efficienc y) or the like It does not affect

  General fumed silica has a true specific gravity of 2.2, and a maximum particle size of 50 nm is the limit in terms of production. Moreover, although the particle size can be increased as an aggregate, uniform dispersion and a stable spacer effect are difficult to obtain. On the other hand, other typical inorganic fine particles used as external additives include titanium oxide (true specific gravity 4.2, refractive index 2.6), alumina (true specific gravity 4.0, refractive index 1.8), zinc oxide (true specific gravity 5.6, refractive index). However, if the particle size is larger than 80 nm, which effectively exhibits the spacer effect, the toner particles are likely to be peeled off, and the peeled particles are carried on the charge imparting member or latent image carrier. It may easily shift to the body and the like, which may cause a decrease in charge or an image quality defect. In addition, since the refractive index is high, it is not suitable for color image formation to use these inorganic materials having a large particle diameter.

  Monodispersed spherical silica can be obtained by a sol-gel method that is a wet method. Since it is produced by a wet method and without firing, the true specific gravity can be controlled to be lower than that of the vapor phase oxidation method. In addition, the true specific gravity value can be further adjusted by controlling the type of hydrophobic treatment agent or the amount of treatment in the hydrophobization treatment step. The particle size can be freely controlled by the hydrolysis of the sol-gel method, the weight ratio of alkoxysilane, ammonia, alcohol, water in the condensation polymerization step, the reaction temperature, the stirring rate, and the supply rate. The monodispersity and spherical shape desired for the monodispersed spherical silica can also be sufficiently achieved by producing this method.

Specific examples of the method for producing monodispersed spherical silica by the sol-gel method include the following methods.
Tetramethoxysilane or tetraethoxysilane is dropped and stirred while applying temperature using ammonia water as a catalyst in the presence of water and alcohol. Next, the silica sol suspension obtained by the reaction is centrifuged to separate it into wet silica gel, alcohol and aqueous ammonia. A solvent is added to wet silica gel to form a silica sol again, and a hydrophobizing agent is added to hydrophobize the silica surface. Next, the target monodispersed spherical silica can be obtained by removing the solvent from the hydrophobized silica sol, drying, and sieve. Further, the silica thus obtained may be treated again.
In the present invention, the method for producing monodispersed spherical silica is not limited to the above production method.

The said silane compound can use a water-soluble thing.
As such a silane compound, chemical structural formula R _A Si X _4-A (wherein A is an integer of 0 to 3, R represents an organic group such as a hydrogen atom, an alkyl group and an alkenyl group, X represents a hydrolyzable group such as a chlorine atom, a methoxy group, and an ethoxy group.) Can be used, and any type of chlorosilane, alkoxysilane, silazane, and a special silylating agent is used. It is also possible to do.

  Specific examples of the silane compound include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, and diphenyldimethoxy. Silane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) acetamide N, N-bis (trimethylsilyl) urea, tert-butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxy Silane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxy Typical examples include silane, γ-mercaptopropyltrimethoxysilane, and γ-chloropropyltrimethoxysilane.

  Particularly preferred examples of the hydrophobizing agent include dimethyldimethoxysilane, hexamethyldisilazane, methyltrimethoxysilane, isobutyltrimethoxysilane, and decyltrimethoxysilane.

  The addition amount of the monodispersed spherical silica is preferably 0.5 to 5 parts by mass and more preferably 1 to 3 parts by mass with respect to 100 parts by mass of the toner particles. When the addition amount is less than 0.5 parts by mass, the effect of reducing non-electrostatic adhesion is small, and development and transfer improvement effects may not be sufficiently obtained.On the other hand, when the addition amount is more than 5 parts by mass, Exceeding the amount that can be coated on the surface of the toner particles by one layer, the coating becomes excessive, and the silica moves to the contact member and tends to cause secondary obstacles.

(B) Abrasives As abrasives preferably used in the present invention, cerium oxide, silicon carbide, strontium titanate, alumina, titania, composite materials, etc. can be generally exemplified, but are not limited thereto. It is not something. Of these, cerium oxide is most preferred.
The average particle size of the abrasive is preferably in the range of 0.1 to 2 μm. The amount of the abrasive added to the toner particles is preferably 0.3 to 2 parts by mass, and more preferably 0.5 to 1.5 parts by mass with respect to 100 parts by mass of the toner particles. If the addition amount is less than 0.3 parts by mass, the polishing effect may not be sufficiently obtained. If the addition amount is more than 2 parts by mass, the abrasive promotes toner soft blocking, and induces clouding during development, transfer omission, etc. May cause problems.

(C) Other external additives In the present invention, in order to control the fluidity and chargeability of the toner, it is desirable to sufficiently coat the surface of the toner particles. because there may not Ki out that only get sufficient coating, it is preferable to use an inorganic compound having a small particle size. As the inorganic compound having a small particle diameter, an inorganic compound having a volume average particle diameter of 80 nm or less is preferable, and an inorganic compound having a volume average particle diameter of 50 nm or less is more preferable.
As the inorganic compound having a small particle diameter, known compounds can be used, and examples thereof include silica, alumina, titanium compounds (titanium oxide, metatitanic acid, etc.), calcium carbonate, magnesium carbonate, calcium phosphate and the like. Further, a known surface treatment may be applied to the surface of these inorganic fine particles depending on the purpose.

  In particular, a titanium compound having a thickness of 15 to 50 nm does not affect transparency, and development with excellent chargeability, environmental stability, fluidity, caking resistance, stable negative chargeability, and stable image quality maintenance. An agent can be provided.

  Further, by using silica having a volume average particle diameter of 20 to 50 nm in combination, the toner can be uniformly covered, and the toner blocking property can be suppressed and the initial transfer property can be improved.

In the present invention, the external additive is mixed is added to the toner particles, the mixing can be performed, for example, I by the V-type blender, a Henschel mixer, a known mixer such as a Loedige mixer.

  At this time, various additives may be added as necessary. Examples of the additive include other fluidizing agents, cleaning aids such as polystyrene fine particles, polymethyl methacrylate fine particles, and polyvinylidene fluoride fine particles, or transfer aids.

  The added amount of the 15-50 nm titanium compound and the 20-50 nm silica is preferably 0.3-3 parts by mass, more preferably 0.5-2.5 parts by mass with respect to 100 parts by mass of the toner particles. When the addition amount is less than 0.3 parts by mass, the fluidity of the toner may not be sufficiently obtained, and blocking suppression due to thermal storage tends to be insufficient. On the other hand, when the added amount is more than 3 parts by mass, an excessively coated state occurs, and the excess inorganic oxide may migrate to the contact member and cause a secondary failure.

In the present invention, the adhesion state of the external additive to the toner particle surface may be merely mechanical adhesion or may be loosely fixed to the surface. Further, the entire surface of the toner particles may be coated or a part thereof may be coated.
Moreover, it does not matter even if it goes through a sieving process after external addition mixing.

Next, a method for adding an external additive to the toner particles will be described.
If necessary, a method in which the monodispersed spherical silica, an inorganic compound having a small particle diameter, and an abrasive are simultaneously added to and mixed with toner particles, and a method of mixing in stages can be taken up.
When various addition methods were examined, the toner particles were first mixed with monodispersed spherical silica having a true specific gravity of 1.3 to 1.9 and a volume average particle size of 80 to 300 nm, and a smaller particle size than the monodispersed spherical silica with a smaller share. By adding and mixing various inorganic compounds and abrasives, it was possible to obtain a high effect by externally adding them.
In the present invention, the monodispersed spherical silica is added to and mixed with toner particles. The mixing can be performed by a known mixer such as a V-type blender, a Henschel mixer, or a Redige mixer.

(Preparation of developer)
The developer used in the present invention is prepared by mixing the carrier and toner described above together with an appropriate blending ratio together with the start developer and the replenishment developer.
The carrier content in the start developer ((carrier) / (carrier + toner) × 100) is preferably in the range of 85 to 99 parts by mass, more preferably in the range of 87 to 98 parts by mass, and even more preferably 89 to 99 parts by mass. The range is 97 parts by mass.

On the other hand, the carrier content in the replenishment developer is necessarily in the range of 15 to 40 parts by mass and preferably in the range of 6 to 30 parts by mass with respect to 100 parts by mass of the toner . If the carrier content is less than 15 parts by mass , sufficient effects cannot be exerted for suppressing charging deterioration, preventing resistance change, and consequently suppressing image quality change. Further, the developer that becomes excessive in the developing device is recovered from the inside of the developing device. However, if the carrier content in the replenishing developer is more than 40 parts by mass, the recovered amount is large, and the developer after recovery is recovered. Therefore, it is necessary to increase the capacity of the container for storing the container, which is not suitable for downsizing of the apparatus that requires space restriction.

<Image forming apparatus>
In the image forming method of the present invention, as an image forming apparatus for forming an image, a latent image carrier, a charging means for charging the surface of the latent image carrier, and a latent image on the surface of the charged latent image carrier. A latent image forming means to be formed and a developer composed of toner and carrier are housed therein, and the latent image is developed by the developer layer formed on the surface of the developer carrier, and the surface of the latent image carrier is developed. A tandem type image forming apparatus including a plurality of developing units including a developing unit that forms a toner image and a transfer unit that transfers the toner image to a transfer medium is used.

  In particular, in the case of creating a full-color image in the image forming method of the present invention, the color toner image of each color is applied to the surface of an intermediate transfer belt or intermediate transfer drum as a transfer target from the viewpoint of versatility of paper and high image quality. Once transferred and laminated, the laminated color toner images are preferably transferred onto the surface of a recording medium such as paper at once. Of course, it is also possible to use a recording medium such as paper as a transfer medium and directly laminate color toner images of respective colors.

  In the present invention, the developing device of at least one developing unit in the image forming apparatus appropriately replenishes the developer for replenishment composed of the toner and the carrier, and removes the excess developer from the inside. A trickle developing system having a developer collecting mechanism for collecting, that is, a trickle developing system is employed. If at least one developing unit adopts the trickle developing system, the effect of the present invention can be obtained in the unit, and the maintenance of the developer can be saved and maintenance-free can be realized. It is desirable to employ a trickle development system for the unit, and most desirably for all the development units.

  Since carrier (replenishment developer) replenishment in the trickle development system is usually mixed in toner, a certain amount of carrier is replenished with toner consumption. Further, as a general control method, there is a method in which toner supply control is sequentially performed so that the toner density is within a certain range by a toner density sensor in the developing device. Further, the developer in the developing device that has become excessive due to replenishment is usually recovered by overflow and stored in a recovery container.

  The image forming apparatus used in the present invention is a tandem system having a plurality of developing units, and if the developing device of at least one developing unit adopts a trickle developing system, there is no limitation on each component. Absent. Hereinafter, an example of the image forming apparatus used in the present invention will be described.

  FIG. 1 is a schematic sectional view showing an example of an image forming apparatus used in the present invention. In this image forming apparatus, as shown in FIG. 1, four developing units 40Y, 40M, 40C, and 40K that respectively form yellow, magenta, cyan, and black images are arranged in parallel at predetermined intervals. (In tandem). Here, the developing units 40Y, 40M, 40C, and 40K are basically configured in the same manner except for the color of the toner in the contained developer. Therefore, the yellow developing unit 40Y will be representatively described below. explain.

  The yellow developing unit 40Y includes a photosensitive drum (latent image carrier) 1Y as an image carrier, and the photosensitive drum 1Y has an axis in a direction perpendicular to the paper on which FIG. 1 is drawn. And it is rotationally driven at a predetermined process speed by a driving means (not shown) along the direction of the arrow A shown. As the photoreceptor drum 1Y, for example, an organic photoreceptor having sensitivity in the infrared region is used.

  It should be noted that the process speed may be switched automatically or manually according to a predetermined condition. The image forming method of the present invention can realize high-quality image formation and developer maintainability even in such an apparatus in which the process speed is switched in the middle. Here, “automatically according to a predetermined condition” means that, for example, when image information including a high-definition image portion such as a photographic image is input, the normal mode is automatically switched to the low-speed mode in order to obtain a high-quality image. The case where it switches is mentioned.

  A roll charging type charging device (charging means) 20Y is provided above the photosensitive drum 1Y in FIG. 1, and a predetermined voltage is applied to the charging device 20Y by a power source (not shown). The surface of 1Y is charged to a predetermined potential (the same applies to chargers 20M, 20C, 20K and photosensitive drums 1M, 1C, 1K).

  Around the photosensitive drum 1Y, a latent image forming unit that forms an electrostatic latent image by performing image exposure on the surface of the photosensitive drum 1Y on the downstream side in the rotation direction of the photosensitive drum 1Y with respect to the charger 20Y. 3Y is arranged. Here, as the latent image forming means 3Y, an LED array that can be miniaturized is used because of space, but it is not limited to this, and other latent image forming means using a laser beam or the like is used. Of course there is no problem.

  Further, around the photosensitive drum 1Y, a yellow developing device 4Y is disposed downstream of the latent image forming unit 3Y in the rotation direction of the photosensitive drum 1Y, and is formed on the surface of the photosensitive drum 1Y. The electrostatic latent image is visualized with yellow toner, and a toner image is formed on the surface of the photoreceptor drum 1Y.

  An intermediate transfer belt 15 for primary transfer of a toner image formed on the surface of the photosensitive drum 1Y extends below the four photosensitive drums 1Y, 1M, 1C, and 1K below the photosensitive drum 1Y in FIG. The intermediate transfer belt 15 is pressed against the surface of the photosensitive drum 1Y by the primary transfer roll 5Y. In addition, the intermediate transfer belt 15 is stretched by driving means including three rolls of a drive roll 11, a support roll 12, and a backup roll 13, and rotates in the direction of arrow B at a moving speed equal to the process speed of the photosensitive drum 1Y. It comes to be moved. In addition to the yellow toner image primarily transferred as described above, magenta, cyan, and black toner images are sequentially primary-transferred on the surface of the intermediate transfer belt 15 and stacked.

  Also, around the photosensitive drum 1Y, the toner remaining on the surface of the photosensitive drum 1Y and the retransferred toner are cleaned downstream of the primary transfer roll 5Y in the rotation direction (arrow A direction) of the photosensitive drum 1Y. A cleaning means 6Y composed of a cleaning blade is arranged, and the cleaning blade in the cleaning means 6Y is attached so as to come into contact with the surface of the photosensitive drum 1Y in the counter direction.

  A secondary transfer roll 14 is pressed against the backup roll 13 that stretches the intermediate transfer belt 15 via the intermediate transfer belt 15, and the toner image that is primarily transferred and laminated on the surface of the intermediate transfer belt 15 is transferred to the backup roll. It is configured to electrostatically transfer to the surface of the transfer medium 16 fed from a paper cassette (not shown) to the nip portion between 13 and the secondary transfer roll 14.

  Further, a cleaning member 17 for the intermediate transfer belt is arranged on the outer periphery of the intermediate transfer belt 15 at a position substantially corresponding to the surface of the drive roll 11 so as to contact the surface of the intermediate transfer belt 15.

  In addition, below the driving roll 11 of the intermediate transfer belt 15 in FIG. 1, the toner image that has been multiplex-transferred onto the transfer target 16 is transferred to the surface of the transfer target 16 by heat and pressure to form a permanent image. A fixing device 18 is provided.

  Next, the operation of each of the developing units 40Y, 40M, 40C, and 40K that forms an image of each color of yellow, magenta, cyan, and black configured as described above will be described. Since the operations of the developing units 40Y, 40M, 40C, and 40K are the same, the operation of the yellow developing unit 40Y will be described as a representative here.

  In the yellow developing unit 40Y, the photosensitive drum 1Y rotates at a predetermined process speed in the direction of arrow A, and a surface of the photosensitive drum 1Y applies a predetermined voltage to the charger 20Y by a power source (not shown). As a result, the charge is negatively charged to a predetermined potential by discharge generated in a minute gap between the charger 20Y and the photosensitive drum 1Y or by injection of electric charge. Thereafter, image exposure is performed on the surface of the photosensitive drum 1Y by the latent image forming unit 3Y, and an electrostatic latent image corresponding to the image information is formed. Subsequently, the electrostatic latent image formed on the surface of the photosensitive drum 1Y is reversely developed with negatively charged toner by the developing device 4Y, and is visualized on the surface of the photosensitive drum 1Y to form a toner image. The Thereafter, the toner image on the surface of the photosensitive drum 1Y is primarily transferred onto the surface of the intermediate transfer belt 15 by the primary transfer roll 5Y. After the primary transfer, the photoreceptor drum 1Y has toner or the like remaining on the surface thereof scraped off and cleaned by the cleaning blade of the cleaning means 6Y to prepare for the next image forming process.

  The above operation is performed in each of the developing units 40Y, 40M, 40C, and 40K, and the toner images visualized on the surfaces of the photosensitive drums 1Y, 1M, 1C, and 1K are successively multiplexed on the surface of the intermediate transfer belt 15. It will be transcribed. In full color mode, toner images of each color are transferred in multiple order in the order of yellow, magenta, cyan, and black, but only the toner images of the required colors are also in the same order in the single color, two color, and three color modes. Single or multiple transcription is performed. Thereafter, the toner image which is individually or multiply transferred onto the surface of the intermediate transfer belt 15 is secondarily transferred onto the surface of the transfer material 16 conveyed from a paper cassette (not shown) by the secondary transfer roll 14, and then the fixing device. 18 is fixed by heating and pressing. The toner remaining on the surface of the intermediate transfer belt 15 after the secondary transfer is cleaned by a cleaning member 17 that is a cleaning blade for the intermediate transfer belt 15.

As described above, in the present invention, the developing device (at least one of 4Y, 4M, 4C, and 4K) of at least one of the developing units 40Y, 40M, 40C, and 40K is a trickle. A developing system is employed, and the developer of the present invention described above is accommodated in the developing device .

  In the tandem image forming apparatus as described above, it is easy to increase the color speed as compared with the rotary development system. However, for example, when a black image is obtained using only the development unit 40K, other colors can be obtained. Since the developing units 40Y, 40M, and 40C are also operated together, the developer carrier incorporated in the developing units 4Y, 4M, and 4C rotates in conjunction with the photosensitive drums 1Y, 1M, and 1C. The stress received by the developer contained in 4Y, 4M, and 4C is extremely large. In addition, the space around the photosensitive drums 1Y, 1M, 1C, and 1K, or the size of the device, the size of each developer 4Y, 4M, 4C, and 4K is limited, and each space development is limited. Since a sufficient amount of developer cannot be secured in the container, the stress applied to the developer tends to be large in terms of the apparatus structure.

  However, in the image forming method of the present invention, a trickle development system is employed in at least one of the developing devices 4Y, 4M, 4C, and 4K, and the replenishment developer with high maintainability is replenished. The service life of the developer can be greatly extended and maintenance-free can be realized.

  In the image forming apparatus used in the image forming method of the present invention, each component is not particularly limited, other than those defined in the present invention. For example, any known components such as a latent image carrier, an intermediate transfer belt (or an intermediate transfer drum), and a charger can be used.

  However, the charging means is preferably a roll charging type charger in that environmental conservation due to the reduction of ozone generation can be realized at a high level.

  Further, as the cleaning means 6Y, a blade cleaning type is generally preferably used because of its excellent performance stability, and is also employed in the above example. In order to enable cleaning of toner close to a spherical shape, it is desirable to optimize the physical property control and contact conditions of the blade, and at the same time, the developer defined in the present invention, particularly the monodispersed spherical silica described above. By using a developer containing a toner added with an external additive combined with an abrasive, it becomes possible to stably clean the residual toner on the surface of the latent image carrier, and the wear resistance of the latent image carrier Can greatly extend the service life. Further, an electrostatic brush may be arranged either upstream or downstream of the cleaning means in the rotation direction of the latent image carrier.

  As the electrostatic brush, a fibrous substance made of a resin containing a conductive filler such as carbon black or a metal oxide, or a fibrous substance coated on the surface with the conductive filler can be used. However, it is not limited to these.

  The image forming method of the present invention has been described above with reference to the drawings of an example of the image forming apparatus used in the image forming method of the present invention. However, the present invention is not limited to this as long as the configuration of the present invention is provided. The element can be changed or modified in any manner based on known knowledge, and is not limited.

The replenishment developer of the present invention is used in the image forming method of the present invention described above. In the replenishment developer of the present invention, a carrier is formed by coating a core material with a resin containing a conductive material and a charge control agent, and the charge control agent has a carrier content of 100 parts by mass in the carrier core material. in contrast, Ru 0.001 to 5 parts by weight of der.

The volume average particle size of the toner is 3 to 10 [mu] m, and toner shape factor SF1 of the formula (1) is, Ru der 110-140.
SF1 = (R ² × π) / (A × 4) × 100 ... Formula (1)
(In the above formula, R represents the maximum toner length, and A represents the projected area of the toner.)
Details of the replenishment developer of the present invention and other preferred embodiments are as described above .

  The replenishment developer of the present invention is produced by mixing a predetermined toner and carrier as described above. At this time, in the image forming method of the present invention, the carrier may be selected from the excess developer collected by the developer collecting mechanism and mixed into the toner as all or part of the carrier. Absent.

In the image forming method of the present invention, since a trickle development system is employed, the developer is collected from the inside of the developing device together with the replenishment of the developer for replenishment. The carrier is selected from the collected developer. If this is further used as at least part of the raw material of the developer for replenishment, it is preferable in that it can contribute to resource saving.

At this time, if the volume resistivity value of the selected carrier is in the range of 10 ⁶ to 10 ¹⁴ Ω · cm, it is possible to cover all of the carrier for the replenishment developer to be manufactured with the regenerated carrier. However, when it is out of the range, it is preferable to adjust the volume resistivity by mixing with a new carrier, for example, so that it falls within the above range. By keeping the volume specific resistance value of the carrier within the above range, good developability for the toner is ensured, and the whole has the same characteristics as a new product. The volume specific resistance value of all carriers mixed in the toner is more preferably in the range of 10 ⁸ to 10 ¹³ Ω · cm.

  In a trickle developing type image forming apparatus, a developer replenishment cartridge containing a replenishment developer is mounted, and the replenishment developer can be replenished continuously or intermittently into the developing device of the image forming apparatus. Done. The replenishment developer according to the present invention is preferably accommodated as the replenishment developer accommodated in the developer replenishment cartridge.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to these Examples at all. In the following description, all “parts” mean “parts by mass”.

[Each measurement method]
In the following examples and comparative examples, each measurement of toner, carrier and developer was performed by the following method.
<Measurement of true specific gravity>
The true specific gravity was measured in accordance with JIS K-0061 5-2-1 using a Le Chatelier specific gravity bottle. The operation was performed as follows.
(1) Put about 250ml of ethyl alcohol in a Lechatelier specific gravity bottle and adjust so that the meniscus is at the position of the scale.
(2) Immerse the specific gravity bottle in a constant temperature water bath, and when the liquid temperature reaches 20.0 ± 0.2 ° C, read the position of the meniscus accurately with the scale of the specific gravity bottle (accuracy 0.025 ml).
(3) Weigh about 100 g of the sample, weigh its weight precisely, and let this be W (g).
(4) Place the weighed sample in a specific gravity bottle and remove bubbles in the liquid.
(5) Immerse the specific gravity bottle in a constant temperature water bath, and when the liquid temperature reaches 20.0 ± 0.2 ° C, read the position of the meniscus accurately with the scale of the specific gravity bottle (accuracy 0.025 ml).
(6) Calculate the true specific gravity using the following formula.
D = W / (L ₂ −L ₁ )
S = D / 0.9982
In the formula, D is the density of the sample (20 ° C) (g / cm ³ ), S is the true specific gravity of the sample (20 ° C), W is the weight of the sample (g), L ₁ is before the sample is put into the density bottle Meniscus reading (20 ° C) (ml), L ₂ is the meniscus reading (20 ° C) (ml) after placing the sample in the density bottle, 0.9982 is the water density at 20 ° C (g / cm ³ ) .

<Measurement of primary particle size of external additive and its standard deviation>
Measurement was performed using a laser diffraction / scattering particle size distribution analyzer (HORIBA LA-910).

<Sphericality of external additive>
For the sphericity Ψ of the external additive, the W a dell sphericity expressed by the following formula (3) was adopted.
Sphericality Ψ = S ₁ / S ₂ (3)
(In the above formula, S ₁ represents the surface area of a sphere having the same volume as the actual particle, and S ₂ represents the surface area of the actual particle itself.)
At this time, S ₁ was calculated from the average particle size. Also, S ₂ uses a Shimadzu powder specific surface area measuring apparatus SS-100 Model, was substituted by a BET specific surface area.

<Toner shape factor SF1 of toner particles>
The toner shape factor SF1 of the toner particles is as described above. As a specific method, an enlarged image of the toner particles is taken from an optical microscope into an image analyzer (LUZEX III, manufactured by Nireco Corporation). Was obtained by image analysis.

<Carrier shape factor>
The shape factor of the carrier was determined in the same manner as the toner shape factor SF1 of the toner particles.

<Measurement of saturation magnetization>
Using a vibrating sample magnetometer BHV-525 (manufactured by Riken Denshi Co., Ltd.), a certain amount of sample was taken for room temperature sample case powder for VSM (H-2902-151) and weighed accurately, then 398 kA / m (5 kOe ) In a magnetic field.

<Measurement of volume resistivity>
The volume resistivity value was measured using the apparatus shown in FIG. As shown in FIG. 2, the measurement sample 53 is sandwiched between the lower electrode 54 and the upper electrode 52, the thickness H of the measurement sample 53 is measured with a dial gauge while pressing from above, and the volume resistivity of the measurement sample 53 is measured. Was measured with a high voltage resistance meter 55.
Specifically, when titanium oxide as an external additive is used as the measurement sample 53, a pressure of 500 kg / cm ² is applied with a molding machine to produce a measurement disk of 100 mmφ and a thickness of about 2 mm, The surface of the disk was cleaned with a brush, sandwiched between the upper electrode 52 and the lower electrode 54 (both electrodes 100 mmφ) in the cell, and the thickness H was measured with a dial gauge. Thereafter, a voltage was applied by the high voltage resistance meter 55 and the current value was read to obtain the volume specific resistance value.
On the other hand, when the carrier is the measurement sample 53, the lower electrode 54 of 100 mmφ is filled, the upper electrode 52 of the same diameter is set, a load of 3.43 kg is applied from above, and the thickness H is measured with a dial gauge. . Next, a voltage was applied by the high voltage resistance meter 55 and the current value was read to obtain the volume specific resistance value.

[External additive]
In the following Examples and Comparative Examples, any of the following external additives (A) to (D) was used as an external additive for the toner.
(A) Monodispersed spherical silica A
The silica sol obtained by the sol-gel method is hydrophobized with hexamethyldisilazane (hereinafter simply referred to as “HMDS treatment”), dried, and pulverized to obtain a true specific gravity of 1.50, a sphericity of Ψ = 0.85, A spherical monodispersed silica A having a volume average particle diameter D50 = 140 nm (standard deviation = 29 nm) was obtained.
(B) Fumed silica B
Commercially available fumed silica RY50 (manufactured by Nippon Aerosil Co., Ltd.), true specific gravity 2.2, sphericity Ψ = 0.58, volume average particle diameter D50 = 40 nm (standard deviation = 20 nm) were prepared, and this was designated as fumed silica B.
(C) Titanium oxide Commercially available rutile type titanium oxide MT-3103 (manufactured by Teika Co., Ltd.), true specific gravity 4.2, minor axis 15 nm, major axis 35 nm were prepared, and this was used as titanium oxide.
(D) Cerium oxide Commercially available cerium oxide E10 (Mitsui Metals Co., Ltd.)) [volume average particle size 0.7 μm] was used as it was.

[Production of toner particles]
(Production of toner particles A (black))
・ Styrene-n-butyl acrylate copolymer (Tg = 58 ℃, Mn = 4000, Mw = 24000) ・ ・ ・ 100 parts ・ Carbon black (Mogal L: Cabot) ・ ・ ・ 3 parts The mixture was kneaded with an extruder, pulverized with a jet mill, and then dispersed with a wind classifier to prepare toner particles A (black) having a volume average particle diameter D50 = 5.0 μm and a toner shape factor SF1 = 142.3. .

(Production of toner particles B (black))
-Preparation of resin dispersion (1)-
・ Styrene ・ ・ ・ 370 parts ・ n-Butyl acrylate ・ ・ ・ 30 parts ・ Acrylic acid ・ ・ ・ 8 parts ・ Dodecanethiol ・ ・ ・ 24 parts ・ Carbon tetrabromide ・ ・ ・ ・・ 4 parts The above ingredients are mixed and dissolved, and this is mixed with 6 parts of a nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) and an anionic surfactant (Neogen SC: Daiichi Kogyo Seiyaku Co., Ltd.) ) Produced) 10 parts dissolved in 550 parts ion-exchanged water was emulsified and dispersed in a flask, and while slowly mixing for 10 minutes, 4 parts ammonium persulfate dissolved in 50 parts ion-exchanged water was added thereto. After carrying out nitrogen substitution, while stirring the inside of the flask, it was heated in an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin dispersion (1) in which resin particles having an average particle diameter of 155 nm, Tg = 59 ° C., and weight average molecular weight Mw = 12000 was dispersed was obtained.

-Preparation of resin dispersion (2)-
・ Styrene ・ ・ ・ 280 parts ・ n-Butyl acrylate ・ ・ ・ 120 parts ・ Acrylic acid ・ ・ ・ ・ ・ 8 parts The above ingredients are mixed and dissolved. Nonipol 400 (manufactured by Sanyo Chemical Co., Ltd.) and 12 parts of an anionic surfactant (Neogen SC: Daiichi Kogyo Seiyaku Co., Ltd.) are dissolved in 550 parts of ion-exchanged water and emulsified and dispersed in a flask. While slowly mixing for 10 minutes, a solution obtained by dissolving 3 parts of ammonium persulfate in 50 parts of ion-exchanged water was added thereto. After carrying out nitrogen substitution, while stirring the inside of the flask, it was heated in an oil bath until the contents reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin dispersion liquid (2) in which resin particles having an average particle diameter of 105 nm, Tg = 53 ° C., and weight average molecular weight Mw = 550000 were dispersed was obtained.

-Preparation of colorant dispersion (1)-
・ Carbon black (Mogal L: Cabot) 50 parts ・ Nonionic surfactant (Nonipol 400: Sanyo Chemical Co., Ltd.) ・ 5 parts ・ Ion exchange water -200 parts The above components are mixed and dissolved, and dispersed for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA). Colorant (carbon black) particles having an average particle size of 250 nm are dispersed. Dispersion liquid (1) was prepared.

-Release agent dispersion-
・ Paraffin wax (HNP0190: Nippon Seiwa Co., Ltd., melting point 85 ° C.) 50 parts ・ Cationic surfactant (Sanisol B50: Kao Co., Ltd.) ・ 5 parts ・ Ion Exchanged water: 200 parts The above ingredients were mixed, heated to 95 ° C., and dispersed in a round stainless steel flask using a homogenizer (Ultra Turrax T50: manufactured by IKA) for 10 minutes. A release agent dispersion liquid in which release agent particles having an average particle diameter of 550 nm were dispersed was prepared by dispersion treatment with a pressure discharge type homogenizer.

-Preparation of toner particles B (black)-
・ Resin dispersion (1) ・ ・ ・ 120 parts ・ Resin dispersion (2) ・ ・ ・ 80 parts ・ Colorant dispersion (1) ・ ・ ・ 200 parts ・ Releasing agent dispersion ・··· 40 parts · Cationic surfactant (Sanisol B50: manufactured by Kao Corporation) ··· 1.5 parts The above ingredients in a round stainless steel flask, homogenizer (Ultra Turrax T50: IKA) And the mixture was dispersed and then heated to 50 ° C. with stirring in the flask in an oil bath for heating. After maintaining at 45 ° C. for 20 minutes, when confirmed with an optical microscope, it was confirmed that aggregated particles having a volume average particle diameter of about 4.0 μm were formed. Further, 60 parts of the resin dispersion (1) was slowly added to the above mixture. Then, the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. Observation with an optical microscope confirmed that aggregated particles having a volume average particle diameter of about 4.8 μm were formed.
After adding 3 parts of an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) to the above mixture, the stainless steel flask was sealed and heated to 105 ° C. with stirring using a magnetic seal. Hold for 4 hours. Then, after cooling, the reaction product was filtered, thoroughly washed with ion-exchanged water, and dried to prepare toner particles B (black). The obtained toner particles B (black) had a toner shape factor SF1 = 118.5 and a volume average particle diameter D50 = 5.2 μm.

(Production of toner particles B (cyan))
Same as (Preparation of Toner Particle B (Black)) except that the following Colorant Dispersion (2) was used instead of Colorant Dispersion (1) in (Preparation of Toner Particle B (Black)) Thus, toner particles B (cyan) having a toner shape factor SF1 = 119 and a volume average particle diameter D50 = 5.4 μm were prepared.

-Preparation of colorant dispersion (2)-
・ Cyan pigment B15: 3 ・ ・ ・ 70 parts ・ Nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) ...... 5 parts ・ Ion-exchanged water ・ ・ ・ 200 parts A colorant dispersion (2) in which colorant (cyan pigment) particles having an average particle size of 250 nm are dispersed by mixing for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA) Was prepared.

(Production of toner particles B (magenta))
Same as (Preparation of toner particles B (black)) except that the following colorant dispersion (3) was used instead of the colorant dispersion (1) in (Preparation of toner particles B (black)). Thus, toner particles B (magenta) having a toner shape factor SF1 = 120.5 and a volume average particle diameter D50 = 5.5 μm were prepared.

-Preparation of colorant dispersion (3)-
・ Magenta pigment R122 ・ ・ ・ ・ ・ 70 parts ・ Nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) ...... 5 parts ・ Ion-exchanged water ・ ・ ・ 200 parts Then, a colorant dispersion (3) in which colorant (magenta pigment) particles having an average particle size of 250 nm are dispersed by dissolving and dispersing for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA) Prepared.

(Production of toner particles B (yellow))
Same as (Preparation of toner particles B (black)) except that the following colorant dispersion (4) was used instead of the colorant dispersion (1) in (Preparation of toner particles B (black)). Thus, toner particles B (yellow) having a toner shape factor SF1 = 120 and a volume average particle diameter D50 = 5.3 μm were prepared.

-Preparation of colorant dispersion (4)-
・ Yellow pigment Y180 ・ ・ ・ ・ ・ 100 parts ・ Nonionic surfactant (Nonipol 400: manufactured by Sanyo Chemical Co., Ltd.) ・ ・ ・ ・ ・ 5 parts ・ Ion-exchanged water ・ ・ ・ 200 parts Dissolve and disperse for 10 minutes using a homogenizer (Ultra Turrax T50: manufactured by IKA) to prepare a colorant dispersion (4) in which colorant (yellow pigment) particles having an average particle size of 250 nm are dispersed. did.

(Production of toner particles C (black))
・ Resin dispersion (1) ・ ・ ・ 120 parts ・ Resin dispersion (2) ・ ・ ・ 80 parts ・ Colorant dispersion (1) ・ ・ ・ 200 parts ・ Release dispersion ・ ・・ ・ ・ 40 parts ・ Cationic surfactant (Sanisol B50: manufactured by Kao Corporation) ・ ・ ・ 1.5 parts Homogenizer (Ultra Turrax T50: made by IKA) in a round stainless steel flask ), And the mixture was dispersed and heated in an oil bath for heating to 50 ° C. while adjusting the pH.
After holding at 40 ° C. for 20 minutes, it was confirmed with an optical microscope that it was confirmed that aggregated particles having a volume average particle diameter of about 5.0 μm were formed. Further, 60 parts of the resin dispersion (1) was slowly added to the above mixture. The temperature of the heating oil bath was raised to 45 ° C. and held for 20 minutes. Observation with an optical microscope confirmed that aggregated particles having a volume average particle size of about 5.6 μm were formed.
After adding 3 parts of an anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) to the above mixture, the stainless steel flask is sealed and heated to 88 ° C. with stirring using a magnetic seal. Hold for 4 hours. Then, after cooling, the reaction product was filtered, thoroughly washed with ion-exchanged water, and dried to prepare toner particles C (black). The obtained toner particles C (black) had a toner shape factor SF1 = 139.0 and a volume average particle diameter D50 = 5.6 μm.

(Production of toner particles C (cyan))
Same as (Preparation of Toner Particles C (Black)) except that (Colorant Dispersion (2) was used instead of Colorant Dispersion (1) in (Preparation of Toner Particles C (Black)) Thus, toner particles C (cyan) having a toner shape factor SF1 = 137.5 and a volume average particle diameter D50 = 5.7 μm were prepared.

(Production of toner particles C (magenta))
Same as (Preparation of Toner Particle C (Black)) except that (Colorant Dispersion Liquid (3) is used instead of Colorant Dispersion Liquid (1) in (Preparation of Toner Particle C (Black)) Thus, toner particles C (magenta) having a toner shape factor SF1 = 138.9 and a volume average particle diameter D50 = 5.5 μm were prepared.

(Production of toner particles C (yellow))
Same as (Preparation of Toner Particles C (Black)) except that (Colorant Dispersion (1)) was used instead of Colorant Dispersion (1) in (Preparation of Toner Particles C (Black)) Thus, toner particles B (yellow) having a toner shape factor SF1 = 135.0 and a volume average particle diameter D50 = 5.7 μm were prepared.

(Production of toner particles D (black))
The toner particles B (black) were treated with hot air in an atmosphere at 70 ° C. for 1 hour and further brought close to a spherical shape, and this was designated as toner particles D (black). Toner particles D (black) had a toner shape factor SF1 = 112.0 and a volume average particle diameter D50 = 5.6 μm.

(Production of toner particles E (black))
The toner particles B (black) were treated with hot air in an atmosphere at 70 ° C. for 2 hours and further brought close to a spherical shape, and this was designated as toner particles E ( black). Toner particles E (black) had a toner shape factor SF1 = 108.5 and a volume average particle diameter D50 = 5.6 μm.

(Production of toner particles F (black))
In (Production of toner particle B (black)), the toner shape factor is the same as (Production of toner particle B (black)), except that the temperature of the heating oil bath at the time of toner particle production is 30 ° C. Toner particles F (black) having SF1 = 131.8 and volume average particle diameter D50 = 3.2 μm were prepared.

(Production of toner particles G (black))
In (preparation of toner particles A (black)), after pulverizing with a jet mill, classification with an air classifier to obtain a volume average particle diameter D50 = 9.5 μm, toner shape factor SF1 = 142.3, and 70 ° C. The hot air treatment was performed for 1 hour in an atmosphere to approximate the spherical shape, and this was designated as toner particles G (black). Toner particles G (black) is the toner shape factor SF1 = 133.8, was a volume average particle size D50 = 9.5 .mu.m.

(Production of toner particles H (black))
For (Production of Toner Particle B (Black)), the toner shape factor is the same as (Production of Toner Particle B (Black)), except that the temperature of the heating oil bath at the time of toner particle preparation was 28 ° C. Toner particles H (black) having SF1 = 133.8 and volume average particle diameter D50 = 2.8 μm were prepared.

(Production of toner particles I (black))
In (Production of toner particles A (black)), after pulverizing with a jet mill, classification with an air classifier, a volume average particle diameter D50 = 11.0 μm, a toner shape factor SF1 = 142.3, and further 70 ° C. The hot air treatment was performed for 1 hour in an atmosphere to approximate the spherical shape, and this was designated as toner particles I (black). Toner particles I (Black), the toner shape factor SF1 = 133.8, was a volume average particle diameter D50 = 11.0 .mu.m.

[Creation of carrier]
(Production of carrier A)
・ Ferrite particles (average particle size: 40μm) ・ ・ ・ 100 parts ・ Toluene ・ ・ ・ 14 parts ・ Styrene-methyl methacrylate copolymer ・ ・ ・ 2 parts ・ Carbon black (R330: Cabot Corporation) 0.2 parts ・ Quaternary ammonium salt charge control agent (Borotron P51: Orient Co., Ltd.) ・ 0.05 parts First, all the ingredients except the ferrite particles are stirred with a stirrer for 10 minutes. Then, a dispersed coating layer forming solution was prepared. Next, this coating layer forming solution and ferrite particles are put into a vacuum degassing type kneader, stirred at 60 ° C. for 30 minutes, further depressurized while heating, degassed, and dried to dry carrier A. Produced. The obtained carrier A had a shape factor = 118, true specific gravity = 4.5, saturation magnetization = 63 emu / g, and a volume resistivity value of 10 ¹¹ Ω · cm at an applied electric field of 1000 V / cm.

(Preparation of carrier B)
(Preparation of Carrier A) In the same manner as (Preparation of Carrier A) except that 0.001 part of a quaternary ammonium salt charge control agent (Borotron P51: manufactured by Orient) was used, shape factor = 119, true specific gravity = 4.5 A carrier B having a volume resistivity of 10 ¹¹ Ω · cm at an applied electric field of saturation magnetization = 63 emu / g and 1000 V / cm was produced.

(Preparation of carrier C)
(Preparation of Carrier A) Same as (Preparation of Carrier A) except that 4 parts of styrene-methyl methacrylate copolymer and 5 parts of quaternary ammonium salt charge control agent (Borotron P51: manufactured by Orient) were used. A carrier C having a volume resistivity of 10 ¹⁴ Ω · cm at an applied electric field of shape factor = 115, true specific gravity = 4.5, saturation magnetization = 63 emu / g, and 1000 V / cm was produced.

(Production of carrier D)
(Preparation of Carrier A) In the same manner as (Preparation of Carrier A), except that the quaternary ammonium salt charge control agent (Borotron P51: manufactured by Orient) was 0.0008 parts, the shape factor = 119, true specific gravity = 4.5 A carrier D having a volume resistivity of 10 ¹¹ Ω · cm at an applied electric field of saturation magnetization = 63 emu / g and 1000 V / cm was produced.

(Production of Carrier E)
(Preparation of Carrier A) Same as (Preparation of Carrier A) except that 7 parts of styrene-methyl methacrylate copolymer and 7 parts of quaternary ammonium salt charge control agent (Borotron P51: manufactured by Orient) were used. A carrier E having a shape factor = 118, true specific gravity = 4.5, saturation magnetization = 63 emu / g, and a volume resistivity of 10 ¹⁶ Ω · cm at an applied electric field of 1000 V / cm was produced.

(Preparation of Carrier F)
(Preparation of Carrier A) In the same manner as (Preparation of Carrier A), except that 0.3 part of carbon black (R330: manufactured by Cabot) was used, shape factor = 117, true specific gravity = 4.5, saturation magnetization = 63 emu / g, Carrier F having a volume resistivity of 10 ⁶ Ω · cm at an applied electric field of 1000 V / cm was prepared.

(Creation of carrier G)
(Fabrication of carrier A) In the same manner as (Fabrication of carrier A) except that the carbon black (R330: manufactured by Cabot) was 0.35 part, the shape factor = 118, true specific gravity = 4.5, saturation magnetization = 63 emu / g, Carrier G having a volume resistivity of 10 ⁵ Ω · cm at an applied electric field of 1000 V / cm was prepared.

[Example 1]
To each 100 parts of the toner particles B (black), toner particles B (cyan), toner particles B (magenta), and toner particles B (yellow), 2 parts of the monodispersed spherical silica A as an external additive, 1 part of titanium oxide, 0.8 part of fumed silica B and 0.5 part of cerium oxide are mixed, blended for 15 minutes at a peripheral speed of 32 m / s with a Henschel mixer, and then coarse particles are removed using a sieve of 45 μm mesh, Four color toners were obtained. Each toner obtained is primarily stored in a hopper, and after filling the cartridge from the hopper through the auger, the carrier A is filled at a ratio of 20 parts of the carrier to 100 parts of the toner, and packaging is performed. Developer replenishment cartridges were obtained (the carrier content in the replenishment developer was about 16.7%).
On the other hand, 8 parts of each toner and 100 parts of carrier A were each stirred at 40 rpm for 20 minutes using a V-blender, and sieved with a sieve having a 177 μm mesh to obtain a four-color start developer.

[Example 2]
To each 100 parts of the toner particles C (black), toner particles C (cyan), toner particles C (magenta), and toner particles C (yellow), 2 parts of the monodispersed spherical silica A as an external additive, 1 part of titanium oxide, 0.8 part of fumed silica B and 0.5 part of cerium oxide are mixed, blended for 15 minutes at a peripheral speed of 32 m / s with a Henschel mixer, and then coarse particles are removed using a sieve of 45 μm mesh, Four color toners were obtained. Each toner obtained is primarily stored in the hopper, and after filling the cartridge from the hopper through the auger, the carrier A is filled at a ratio of 15 parts of the carrier to 100 parts of the toner, and the four colors are prepared. A developer replenishing cartridge was obtained (the carrier content in the replenishing toner was about 13.0%).
On the other hand, 8 parts of each toner and 100 parts of carrier A were each stirred at 40 rpm for 20 minutes using a V-blender, and sieved with a sieve having a 177 μm mesh to obtain a four-color start developer.

[Example 3]
100 parts of the above toner particles B (black) are mixed with 2 parts of the above monodispersed spherical silica A, 1 part of titanium oxide, 0.8 part of fumed silica B, and 0.5 part of cerium oxide. After blending for 15 minutes at a peripheral speed of 32 m / s, coarse particles were removed using a sieve of 45 μm mesh to obtain a black toner. The resulting collected by toner stored primary to the host wrapper, after the filling through an auger from the hopper to the cartridge, the toner 100 parts, filling the carrier B at a ratio of carrier 20 parts, by performing the packaging, black A developer supply cartridge was obtained (the carrier content in the supply developer was about 16.7%).
On the other hand, each of the 8 parts on Quito toner and the carrier B100 parts, stirred for 20 minutes at 40rpm using a V- blender, by sieving with sieves having a mesh of 177 .mu.m, was obtained black starting developer.

[Example 4]
For the black toner obtained in Example 3, a black toner developer supply cartridge and a start developer were obtained in the same manner as in Example 3 except that carrier C was used instead of carrier B.

[Example 5]
For the black toner obtained in Example 3, a black toner-supply cartridge and a start developer were obtained in the same manner as in Example 3 except that Carrier F was used instead of Carrier B.

[Example 6]
To 100 parts of the above toner particles D (black), 2 parts of the above monodispersed spherical silica A, 1 part of titanium oxide, 0.8 part of fumed silica B and 0.5 part of cerium oxide are mixed as an external additive. After blending for 15 minutes at a peripheral speed of 32 m / s, coarse particles were removed using a sieve of 45 μm mesh to obtain a black toner. The resulting collected by toner stored primary to the host wrapper, after the filling through an auger from the hopper to the cartridge, the toner 100 parts of the carrier A was charged at a rate of carrier 20 parts, by performing the packaging, black A developer supply cartridge was obtained (the carrier content in the supply developer was about 16.7%).
On the other hand, each of the 8 parts on Quito toner and the carrier A100 parts, stirred for 20 minutes at 40rpm using a V- blender, by sieving with sieves having a mesh of 177 .mu.m, was obtained black starting developer.

[Example 7]
100 parts of the above toner particles F (black) are mixed with 2 parts of the above monodispersed spherical silica A, 1 part of titanium oxide, 0.8 part of fumed silica B, and 0.5 part of cerium oxide. After blending for 15 minutes at a peripheral speed of 32 m / s, coarse particles were removed using a sieve of 45 μm mesh to obtain a black toner. The resulting collected by toner stored primary to the host wrapper, after the filling through an auger from the hopper to the cartridge, the toner 100 parts of the carrier A was charged at a rate of carrier 20 parts, by performing the packaging, black A developer supply cartridge was obtained (the carrier content in the supply developer was about 16.7%).
On the other hand, each of the 8 parts on Quito toner and the carrier A100 parts, stirred for 20 minutes at 40rpm using a V- blender, by sieving with sieves having a mesh of 177 .mu.m, was obtained black starting developer.

[Example 8]
100 parts of the above toner particles G (black) are mixed with 2 parts of the above monodispersed spherical silica A, 1 part of titanium oxide, 0.8 part of fumed silica B, and 0.5 part of cerium oxide. After blending for 15 minutes at a peripheral speed of 32 m / s, coarse particles were removed using a sieve of 45 μm mesh to obtain a black toner. The resulting collected by toner stored primary to the host wrapper, after the filling through an auger from the hopper to the cartridge, the toner 100 parts of the carrier A was charged at a rate of carrier 20 parts, by performing the packaging, black A developer supply cartridge was obtained (the carrier content in the supply developer was about 16.7%).
On the other hand, each of the 8 parts on Quito toner and the carrier A100 parts, stirred for 20 minutes at 40rpm using a V- blender, by sieving with sieves having a mesh of 177 .mu.m, was obtained black starting developer.

[ Reference Example 1 ]
100 parts of the above toner particles B (black) are mixed with 2 parts of the above monodispersed spherical silica A, 1 part of titanium oxide, 0.8 part of fumed silica B, and 0.5 part of cerium oxide. After blending for 15 minutes at a peripheral speed of 32 m / s, coarse particles were removed using a sieve of 45 μm mesh to obtain a black toner. Obtained was stored primary bets toner to ho wrapper, after the filling through an auger from the hopper to the cartridge, the toner 100 parts of the carrier A was charged at a ratio of 5 parts of the carrier, performing packaging black developing An agent supply cartridge was obtained (the carrier content in the supply developer was about 4.76%).
On the other hand, each of the 8 parts on Quito toner and the carrier A100 parts, stirred for 20 minutes at 40rpm using a V- blender, by sieving with sieves having a mesh of 177 .mu.m, was obtained black starting developer.

[Example 9 ]
In Reference Example 1 , with respect to 100 parts of toner, carrier A was charged at a rate of 40 parts of carrier A and packaged to obtain a black developer supply cartridge (the carrier content in the supply developer is about 28.57%) than outside, in the same manner as in reference example 1 to obtain a developer replenishing cartridge and a start developer.

[ Reference Example 2 ]
Evaluation was performed using an evaluation machine in which the developer replenishing cartridge and the start developer in Reference Example 1 were used and the photoreceptor cleaning device was removed.

[Comparative Example 1]
100 parts of the above toner particles A (black) are mixed with 2 parts of the above monodispersed spherical silica A, 1 part of titanium oxide, 0.8 part of fumed silica B, and 0.5 part of cerium oxide as an external additive. After blending for 15 minutes at a peripheral speed of 32 m / s, coarse particles were removed using a sieve of 45 μm mesh to obtain a black toner. The resulting collected by toner stored primary to the host wrapper, after the filling through an auger from the hopper to the cartridge, the toner 100 parts of the carrier A was charged at a rate of carrier 20 parts, by performing the packaging, black A developer supply cartridge was obtained (the carrier content in the supply developer was about 16.7%).
On the other hand, each of the 8 parts on Quito toner and the carrier A100 parts, stirred for 20 minutes at 40rpm using a V- blender, by sieving with sieves having a mesh of 177 .mu.m, was obtained black starting developer.

[Comparative Example 2]
100 parts of the above toner particles E (black) are mixed with 2 parts of the above monodispersed spherical silica A, 1 part of titanium oxide, 0.8 part of fumed silica B, and 0.5 part of cerium oxide. After blending for 15 minutes at a peripheral speed of 32 m / s, coarse particles were removed using a sieve of 45 μm mesh to obtain a black toner. The resulting collected by toner stored primary to the host wrapper, after the filling through an auger from the hopper to the cartridge, the toner 100 parts of the carrier A was charged at a rate of carrier 20 parts, by performing the packaging, black A developer supply cartridge was obtained (the carrier content in the supply developer was about 16.7%).
On the other hand, each of the 8 parts on Quito toner and the carrier A100 parts, stirred for 20 minutes at 40rpm using a V- blender, by sieving with sieves having a mesh of 177 .mu.m, was obtained black starting developer.

[Comparative Example 3]
100 parts of the above toner particles H (black) are mixed with 2 parts of the above monodispersed spherical silica A, 1 part of titanium oxide, 0.8 part of fumed silica B, and 0.5 part of cerium oxide. After blending for 15 minutes at a peripheral speed of 32 m / s, coarse particles were removed using a sieve of 45 μm mesh to obtain a black toner. The resulting collected by toner stored primary to the host wrapper, after the filling through an auger from the hopper to the cartridge, the toner 100 parts of the carrier A was charged at a rate of carrier 20 parts, by performing the packaging, black A developer supply cartridge was obtained (the carrier content in the supply developer was about 16.7%).
On the other hand, each of the 8 parts on Quito toner and the carrier A100 parts, stirred for 20 minutes at 40rpm using a V- blender, by sieving with sieves having a mesh of 177 .mu.m, was obtained black starting developer.

[Comparative Example 4]
To 100 parts of the above toner particles I (black), 2 parts of the above monodispersed spherical silica A, 1 part of titanium oxide, 0.8 part of fumed silica B and 0.5 part of cerium oxide are mixed as a Henschel mixer. After blending for 15 minutes at a peripheral speed of 32 m / s, coarse particles were removed using a sieve of 45 μm mesh to obtain a black toner. The resulting collected by toner stored primary to the host wrapper, after the filling through an auger from the hopper to the cartridge, the toner 100 parts of the carrier A was charged at a rate of carrier 20 parts, by performing the packaging, black A developer supply cartridge was obtained (the carrier content in the supply developer was about 16.7%).
On the other hand, each of the 8 parts on Quito toner and the carrier A100 parts, stirred for 20 minutes at 40rpm using a V- blender, by sieving with sieves having a mesh of 177 .mu.m, was obtained black starting developer.

[Comparative Example 5]
For the black toner obtained in Example 3, a black toner developer supply cartridge and a start developer were obtained in the same manner as in Example 3 except that carrier D was used instead of carrier B.

[Comparative Example 6]
For the black toner obtained in Example 3, a black toner developer supply cartridge and a start developer were obtained in the same manner as in Example 3 except that carrier E was used instead of carrier B.

[Comparative Example 7]
For the black toner obtained in Example 3, a black toner developer supply cartridge and a start developer were obtained in the same manner as in Example 3 except that carrier G was used instead of carrier B.

[Comparative Example 8]
A developer replenishing cartridge and a start developer were obtained in the same manner as in Reference Example 1 except that a black developer replenishing cartridge that was not filled with a carrier was used in Reference Example 1 .

[Comparative Example 9]
In Reference Example 1 , the carrier A is filled at a rate of 50 parts of carrier with respect to 100 parts of toner, and the cartridge is packed. The black developer supply cartridge (the carrier content in the supply developer is about 33.33%. However, it was not possible to fill 200 g of the carrier for the specified toner mass of 400 g due to the limitation of the cartridge capacity.

[Evaluation test]
Fuji Xerox adopting tandem trickle development system and photoreceptor cleaning device using developer replenishment cartridge and start developer obtained in Examples 1-9 , Reference Examples 1-2 and Comparative Examples 1-9 A modified C2220 machine (start developer and developer replenishment cartridge can be replaced for each test, process speed can be adjusted from the outside, and forced stop can be performed. Development property and transferability were evaluated by a method modified so that the toner can be sampled from the surface of the transfer member as described later.

<Development evaluation>
(Solid development amount)
a ) Initial stage Leave the start developer overnight under the specified temperature and humidity (29 ° C 90% RH and 10 ° C 20% RH), copy an image with two solid patches of 2cm x 5cm, The apparatus was forcibly stopped before transfer to, and the amount of development (amount of toner before transfer to paper) was measured. Specifically, two precisely-measured tapes are prepared, and two development parts on the surface of the photosensitive member (latent image carrier) are transferred to the tape using adhesiveness, and the tape after toner collection is prepared. Weighed again, subtracted the tape weight before collecting the toner, and averaged the results to determine the development amount, which was used as the initial evaluation of developability. A preferred value is 4.0 to 5.0 g / m ² .

b) After 100,000 sheets Using the start developer, 100,000 sheets (A4 vertical) copies were collected under the specified temperature and humidity (29 ° C 90% RH and 10 ° C 20% RH). Furthermore, after leaving overnight without changing the temperature and humidity conditions, an image having two solid patches of 2 cm × 5 cm was copied, the apparatus was stopped, and the development amount was measured. Specifically, prepare two precisely weighed tapes, transfer the two developed parts on the surface of the photoreceptor to the tape using adhesiveness, reweigh the tape weight after collecting the toner, The amount of development was obtained by subtracting the tape weight before collection and averaging, and this was evaluated as the developability after 100,000 sheets.

(Cover)
In the above (solid development amount), at the time of collecting toner with the tape from the surface of the photoreceptor at the initial stage and after 100,000 sheets, the background portion at a position approximately 10 mm away from the solid patch is the same as in the case of <Evaluation of developability> transferred to tape, count the toner number per 1 cm ² of the tape, the less than 100 ○, from 100 up to 200 △, was evaluated if more than a ×.

<Measurement of charge amount at the initial stage and after 100,000 sheets>
The developer on the surface of the mag sleeve (developer carrier) in the developing unit was collected at the initial stage and after 100,000 sheets in the above <development evaluation>, and the Toshiba TB200 was manufactured under the condition of 25 ° C. and 55% RH. Was used to measure the charge amount.

<Evaluation of transferability at the initial stage and after 100,000 sheets>
In the above <Evaluation of developability>, at the initial stage and after 100,000 sheets, an image having two 2 cm x 5 cm solid patches was copied, and the apparatus was forcibly stopped after the transfer process and before the fixing process. The transfer efficiency was measured. Specifically, four precisely weighed tapes are prepared, and the toner on the surface of the intermediate transfer member where the two solid patches are formed is transferred to the tape using adhesiveness. Weighed again and subtracted the tape weight before collecting the toner, and averaged it to obtain the transfer toner amount a. Using the remaining tape, the two patches on the surface of the photoreceptor were formed in the same manner. The toner amount b remaining in the remaining portion was determined, and the transfer efficiency η (%) was determined by the following equation (4) .
Transfer efficiency η (%) = a x 100 / (a + b)
The preferred transfer efficiency η (%) is η ≧ 95%, which is evaluated as ◯, 85% ≦ η <95% as Δ, 80% ≦ η <85% as ▲, and η <80% as ×. did.

<Evaluation of cleaning properties: Stress test>
(Full solid evaluation)
In the above <Evaluation of developability>, at the initial stage and after 100,000 sheets, the latent image carrier was rotated 100 times while being charged in an undeveloped state and at a process speed of 104 mm / s. Thereafter, a solid image was formed on the entire surface of the latent image carrier at a process speed of 104 mm / s, and the surface of the latent image carrier was cleaned with a cleaning device in the apparatus in an untransferred state. This was repeated several times to evaluate how far cleaning was possible, and this was regarded as the evaluation of the cleanability of the entire surface. The evaluation index is as follows. If it is G1 to G3, there is no practical problem.
G1: Cleaning is possible without problems over 3 consecutive times.
G2: Can be cleaned once without any problems.
G3: The entire surface cannot be cleaned from the first time, and several streaks of poor cleaning occur.
G4: The entire surface cannot be cleaned from the first time, and band-like poor cleaning occurs.
(Thin wire reproducibility evaluation)
A fine line image was formed on the photoconductor so as to have a line width of 50 μm, and this was transferred and fixed on a transfer material. The fine line on the transfer material was observed at a magnification of 175 times using a VH-6200 micro high scope (manufactured by Keyence Corporation). Specific evaluation criteria are as follows. Note that G1 and G2 were within the allowable range.
G1: Fine lines are uniformly filled with toner, and there is no disturbance at the edges.
G2: Fine lines are evenly filled with toner, but slight jaggedness is observed at the edges.
G3: The fine line is uniformly filled with toner, but the edge portion is noticeable.
G4: Fine lines are not uniformly filled with toner, and jagged edges are noticeable.
G5: Fine lines are not uniformly filled with toner, and the jagged edges are very noticeable.

[Example 10 ]
Using the start developer and developer replenishment cartridge in Example 2, after printing 100,000 sheets in the above evaluation test, all the excess four colors collected by the trickle development system (developer recovery mechanism) were removed. The toner and the carrier were separated using a turbo shifter equipped with a 20 μm mesh. The separated carrier had a volume resistivity of 10 ¹⁵ Ω · cm. A new carrier I was obtained by adding 50 parts of the new carrier A to 100 parts of the obtained carrier. The volume resistivity of carrier I was 10 ¹³ Ω · cm.
For the cyan toner obtained in Example 2, a cyan-only developer supply cartridge and a start developer were obtained in the same manner as in Example 2 except that Carrier I was used instead of Carrier A.
Various evaluation tests were performed in the same manner as in the other Examples and Comparative Examples using the obtained developer replenishing cartridge and the start developer.
The evaluation results obtained by the above Examples , Reference Examples and Comparative Examples are summarized in Tables 1 to 4 below. Tables 1 and 2 show the initial results, and Tables 3 and 4 show the results after 100,000 sheets, respectively.

It is a schematic sectional drawing which shows an example of the image forming apparatus used in this invention. It is a schematic explanatory drawing for demonstrating the method to measure the volume specific resistance value of a carrier.

Explanation of symbols

1Y, 1M, 1C, 1K Photosensitive drum (latent image carrier)
3Y, 3M, 3C, 3K latent image forming means
4Y, 4M, 4C, 4K developer
5Y, 5M, 5C, 5K primary transfer roll
6Y, 6M, 6C, 6K cleaning means
11 Drive roll
12 Support roll
13 Backup roll
14 Secondary transfer roll
15 Intermediate transfer belt
16 Transferee
17 Cleaning material
18 Fixing unit
20Y, 20M, 20C, 20K charger (charging means)
40Y, 40M, 40C, 40K development unit
52 Upper electrode
53 Measurement sample
54 Bottom electrode
55 High voltage resistance meter

Claims (5)

A latent image carrier, charging means for charging the surface of the latent image carrier, latent image forming means for forming a latent image on the surface of the charged latent image carrier, and a developer composed of toner and a carrier are contained therein. A developer that accommodates and develops the latent image by the developer layer formed on the surface of the developer carrying member and forms a toner image on the surface of the latent image carrying member, and transfers the toner image to the transfer member An image forming method for forming an image with an image forming apparatus including a plurality of developing units including a transfer unit,
The developing device of at least one developing unit in the image forming apparatus has a mechanism for appropriately replenishing a replenishment developer containing the toner and a carrier therein and collecting the developer from the inside, The carrier content in the replenishment developer is in the range of 15 to 40 parts by mass with respect to 100 parts by mass of the toner ,
The carrier comprises a core material coated with a resin containing a conductive material and a charge control agent, and the content of the charge control agent in the carrier is 0.001 to 5 parts by mass with respect to 100 parts by mass of the carrier core material. The volume specific resistance value of all carriers mixed with the toner is 10 ⁶ to 10 ¹⁴ Ω · cm, the volume average particle diameter of the toner is 3 to 10 μm, and expressed by the formula (1) An image forming method, wherein the toner shape factor SF1 is in a range of 110 to 140.
SF1 = (R ² × π) / (A × 4) × 100 ... Formula (1)
(In the above formula, R represents the maximum toner length, and A represents the projected area of the toner.)   2. The image forming method according to claim 1, further comprising a cleaning unit for cleaning the surface of the latent image carrier after the toner image is transferred by the transfer unit in the developing unit having the developer recovery mechanism.   A replenishment developer comprising the toner and a carrier used in the image forming method according to claim 1.   4. The replenishment developer according to claim 3, wherein a carrier is selected from excess developer collected by the developer collecting mechanism, and the carrier is mixed with the toner as all or part of the carrier. 4. A cartridge for replenishing developer according to claim 3, which is a cartridge for replenishing a developer for replenishment to a developing device of an image forming apparatus.