JP4958582B2 - Toner and method for producing the same - Google Patents

Description

  The present invention relates to a toner and a manufacturing method thereof, a developer, an image forming method, a process cartridge, and an image forming apparatus.

  In an electrophotographic apparatus, an electrostatic recording apparatus, and the like, toner is attached to the electrostatic latent image formed on the photosensitive member and developed, and the visible image is transferred to the transfer material and then fixed to the transfer material by heating. Thus, an image is formed. Further, when forming a full-color image, generally, a black, yellow, magenta, and cyan toner is used to develop each color, and a visible image in which each color toner layer is superimposed on a transfer material. Is heated and fixed at the same time.

  However, for users who are familiar with printing, the image in a full-color copying machine is not yet satisfactory, and there is a demand for higher image quality that satisfies photography and high definition and high resolution. Therefore, it is known that a toner having a small particle size and a narrow particle size distribution is effective for improving the image quality of an electrophotographic image.

  Conventionally, an electrical or magnetic latent image has been developed with toner. The toner used when developing the electrostatic latent image is generally colored particles containing a colorant, a charge control agent and other additives in a binder resin. Such toner production methods are roughly classified into a pulverization method and a polymerization method.

  In the pulverization method, a toner composition is produced by pulverizing and classifying a toner composition obtained by melt-mixing a colorant, a charge control agent, an offset preventing agent, and the like in a thermoplastic resin and uniformly dispersing the mixture. According to the pulverization method, a toner having some excellent characteristics can be produced, but the selection of the toner material is limited. For example, a toner composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable apparatus. From this requirement, the melt-mixed composition must be made sufficiently brittle. For this reason, when the toner composition is pulverized to form toner base particles, a high-range particle size distribution is likely to be formed. There is a problem that it is necessary to remove fine powder having a diameter of 5 μm or less and coarse powder having a diameter of 20 μm or more by classification, resulting in a very low yield. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent and the like in the thermoplastic resin. If such a compounding agent is dispersed unevenly, it adversely affects toner fluidity, developability, durability, image quality, and the like.

  In recent years, in order to overcome the problems of the pulverization method, for example, Patent Document 1 discloses a method of producing toner base particles by a suspension polymerization method. At this time, the toner base particles obtained by the suspension polymerization method are spherical, but have a problem of poor cleaning properties. For this reason, when an image with a low image area ratio is formed, the amount of residual toner is small, and cleaning defects do not become a problem. However, when a photographic image with a high image area ratio is formed, In the case of a paper defect or the like, untransferred toner may be generated as a transfer residual toner on the photoconductor, and accumulation of the image causes background smearing. In addition, the charging roller or the like that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. Furthermore, the low-temperature fixability is not sufficient, and a lot of energy necessary for fixing is required.

  Patent Documents 2 and 3 disclose a method for obtaining base particles of an irregular shaped toner by associating resin fine particles obtained by an emulsion polymerization method. However, the toner base particles obtained by the emulsion polymerization method have a problem that a large amount of the surfactant remains not only on the surface of the particles but also in the interior even after the water washing step. For this reason, the environmental stability of charging of the toner is impaired, the distribution of the charge amount is widened, and scumming occurs. Further, the remaining surfactant may contaminate the photoconductor, the charging roller, the developing roller, and the like, so that the original charging ability cannot be exhibited.

  On the other hand, in a fixing process by a contact heating method using a heating member such as a heating roller, toner releasability (hereinafter sometimes referred to as offset resistance) to the heating member is required. Here, the offset resistance can be improved by allowing a release agent to be present on the surface of the toner base particles. On the other hand, Patent Documents 4 and 5 disclose a method of improving the offset resistance by causing the resin fine particles not only to exist inside the toner base particles but also to be unevenly distributed on the surface. However, this method has a problem that the minimum fixing temperature increases and the low-temperature fixability is not sufficient.

  In addition, in the method of assembling the resin fine particles obtained by the emulsion polymerization method to obtain the base particles of the irregular shaped toner, in order to improve the offset resistance, when the fine particles of the release agent are associated, There is a problem that fine particles are taken into the toner base particles. As a result, the offset resistance is not sufficiently improved. Resin fine particles, release agent fine particles, colorant fine particles, etc. are randomly fused to form toner base particles. Therefore, the composition (content ratio of constituent components) between the toners, the molecular weight of the constituent resin, etc. Variations occur. As a result, the surface characteristics differ between the toners, and a stable image cannot be formed over a long period of time. Furthermore, in a low-temperature fixing system that requires low-temperature fixability, there is a problem in that a fixing temperature range cannot be secured sufficiently because of inhibition of fixing due to resin fine particles unevenly distributed on the toner surface.

  On the other hand, the dissolution suspension method is a method of granulating from a polymer dissolved in an organic solvent or the like, while the suspension polymerization method forms particles from monomers, and expands the selection range of the resin, controls the polarity, etc. It is known that there are benefits. Another advantage is toner structure control (core / shell structure control). However, the shell is a resin-only layer intended to reduce the exposure of the pigment and wax to the surface, and the surface state is not particularly devised (see Non-Patent Document 1). Therefore, although it has a core / shell structure, the surface of the toner is an ordinary resin, and when aiming at low-temperature fixing, it is not sufficient in terms of heat-resistant storage stability and environmental charge stability.

  In addition, the suspension polymerization method, the emulsion polymerization method, and the dissolution suspension method all use a styrene / acrylic resin. When the polyester resin is formed into particles, the particle size and particle size distribution are used. , Shape control is difficult. Furthermore, there is a problem with low-temperature fixability.

  Therefore, Patent Document 6 discloses the use of a polyester modified with a urea bond as a toner binder for the purpose of heat-resistant storage and low-temperature fixability. However, this method is not sufficient in terms of environmental charging stability because the surface is not particularly devised.

  On the other hand, in the field of electrophotography, high image quality has been studied from various angles, and among them, the recognition that reducing the particle size and spheroidizing toner is extremely effective is increasing. However, when the particle size of the toner is reduced, the transfer property and the fixability tend to be lowered. On the other hand, it is known that transferability is improved by making the toner spherical (see Patent Document 7). Further, in the field of color copiers and color printers, further speeding up of image formation is desired. Note that the tandem method is effective for speeding up image formation (see Patent Document 8).

  The tandem method is a method for forming a full-color image on a transfer sheet by sequentially superimposing and transferring the image formed by the image forming unit on a single transfer sheet conveyed to a transfer belt. The tandem color image forming apparatus has many types of transfer paper that can be used, has high quality of full color images, and can form full color images at high speed. In particular, the ability to form a full-color image at a high speed is a unique property not found in other types of color image forming apparatuses.

In addition, attempts have been made to achieve high speed while improving image quality using spherical toner. For example, a spherical toner such as a chemical toner forms a visible image on a photoconductor so that a transfer pressure at the time of transfer is evenly applied to the toner layer. Compared to the above, there are few occurrences of transfer abnormalities such as a transfer rate and a lack of a transfer image. However, in long-term use, external additives added to improve transferability and impart fluidity are rapidly embedded in the toner surface compared to toner produced by the pulverization method. Changes in liquidity and fluidity. In particular, when an image with a small image area, that is, an image with a small amount of toner consumption is output continuously, the external additive in the toner is buried over time, and the effect of improving the fluidity cannot be obtained. There are problems such as fluctuations in image quality and unevenness on the image due to the fluctuations. In addition to these problems, the addition amount of the fluidity modifier tends to increase in order to maintain fluidity by reducing the particle size of the toner. However, when the addition amount is increased, the adhesive force between the toner base particles and the external additive is lowered, and the external additive existing free is increased. For this reason, there exists a problem that it becomes easy to transfer an external additive to a contact member, and causes filming.
Japanese Patent Laid-Open No. 9-43909 Japanese Patent No. 2537503 JP 2000-292773 A JP 2000-292978 A Japanese Patent No. 3141784 Japanese Patent Laid-Open No. 11-133667 JP 9-258474 A JP-A-5-341617 Takao Ishiyama and two others "Characteristics and future prospects of new toners" (The 4th Joint Symposium of the Imaging Society of Japan / Electrostatic Society (2000.7.29))

  The present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide a toner excellent in transferability, cleaning property, filming resistance and charging stability, and a method for producing the toner. Another object of the present invention is to provide a developer, a process cartridge, and an image forming method using the toner.

According to the first aspect of the present invention, a coating layer is formed on the surface of the toner base particles using a fluid in which a silicone resin that is a solid at least at normal temperature and pressure is dissolved in at least one of a supercritical fluid and a subcritical fluid. It has the process of forming, It is characterized by the above-mentioned. Thereby, it is possible to provide a method for producing a toner excellent in transferability, cleaning property, filming resistance and charging stability.

  According to a second aspect of the present invention, in the toner manufacturing method according to the first aspect, the binder resin constituting the toner base particles is at least one of the supercritical fluid and the subcritical fluid, and at least a silicone resin. It is characterized by being insoluble in a fluid in which is dissolved. Thereby, a toner having excellent transferability, cleaning property, filming resistance and charging stability can be obtained.

  According to a third aspect of the present invention, there is provided the toner manufacturing method according to the first or second aspect, wherein at least one of the supercritical fluid and the subcritical fluid is a fluid in which at least a silicone resin is dissolved. The coating layer is formed by spraying on the surface. Thereby, a toner having excellent transferability, cleaning property, filming resistance and charging stability can be obtained.

  According to a fourth aspect of the present invention, in the toner manufacturing method according to the first or second aspect, a fluid in which at least a silicone resin is dissolved in at least one of the supercritical fluid and the subcritical fluid, and base particles of the toner are provided. Then, the coating layer is formed by releasing pressure and rapidly expanding after mixing. Thereby, a toner having excellent transferability, cleaning property, filming resistance and charging stability can be obtained.

  According to a fifth aspect of the present invention, in the toner manufacturing method according to the first or second aspect, a fluid in which at least a silicone resin is dissolved in at least one of the supercritical fluid and the subcritical fluid, and base particles of the toner are provided. After coating, the coating layer is formed by changing at least one of pressure and temperature. Thereby, a toner having excellent transferability, cleaning property, filming resistance and charging stability can be obtained.

  The invention according to claim 6 is the toner production method according to any one of claims 1 to 5, wherein at least one of the supercritical fluid and the subcritical fluid contains carbon dioxide. To do. Thereby, a toner can be manufactured with a simple manufacturing process.

  The invention according to claim 7 is the toner manufacturing method according to any one of claims 1 to 6, wherein at least one of the supercritical fluid and the subcritical fluid contains an entrainer. To do. Thereby, the solubility of the silicone resin can be controlled.

  The invention according to claim 8 is the toner manufacturing method according to claim 7, wherein the ratio of the weight of the entrainer to the total weight of at least one of the supercritical fluid and the subcritical fluid and the entrainer is 0. .1 wt% or more and 10 wt% or less. Thereby, the solubility of the silicone resin can be controlled.

  The invention according to claim 9 is the toner manufacturing method according to claim 7 or 8, wherein the entrainer is a poor solvent for the toner base particles and the silicone resin under normal temperature and pressure. It is characterized by. Thereby, a coating layer can be formed favorable.

  According to a tenth aspect of the present invention, in the toner production method according to any one of the seventh to ninth aspects, the entrainer is at least one of methanol, ethanol, and propanol. Thereby, a coating layer can be formed favorable.

  According to an eleventh aspect of the present invention, in the toner manufacturing method according to any one of the first to tenth aspects, the silicone resin has a general formula.

で表される構造を有し、Ｒは、水素原子、水酸基、アルコキシル基、アルキル基又はアリール基であることを特徴とする。これにより、被覆層を良好に形成することができる。

Wherein R is a hydrogen atom, a hydroxyl group, an alkoxyl group, an alkyl group, or an aryl group. Thereby, a coating layer can be formed favorable.

According to a twelfth aspect of the present invention, in the toner production method according to any one of the first to eleventh aspects, the content of silanol groups in the silicone resin is 0.1 wt% or more and 10 wt% or less. It is characterized by being. Thereby, it can bridge | crosslink favorably.

According to a thirteenth aspect of the present invention, in the toner production method according to any one of the first to twelfth aspects, the silicone resin has a weight average molecular weight of 500 or more and 100,000 or less. Thereby, a coating layer can be formed favorable.

According to a fourteenth aspect of the present invention, a toner is manufactured using the toner manufacturing method according to any one of the first to thirteenth aspects. As a result, it is possible to provide a toner having excellent transferability, cleaning properties, filming resistance, and charging stability.

According to a fifteenth aspect of the present invention, in the toner according to the fourteenth aspect , the weight average particle diameter is 3 μm or more and 8 μm or less. Thereby, a high-resolution and high-quality image can be formed.

According to a sixteenth aspect of the present invention, the developer contains the toner according to the fourteenth or fifteenth aspect. Thereby, it is possible to provide a developer excellent in transferability, cleaning property, filming resistance and charge stability.

The invention described in claim 17 is the developer according to claim 16 , further comprising a carrier. Thereby, a two-component developer excellent in transferability, cleaning property, filming resistance and charging stability can be obtained.

According to an eighteenth aspect of the present invention, in the image forming method, using the developer according to the sixteenth or seventeenth aspect , a step of developing the electrostatic latent image formed on the photoconductor, the developer is developed with the developer. And a step of transferring the visible image onto the transfer medium and a step of fixing the visible image transferred onto the transfer medium by heat and pressure using a fixing device. Thereby, it is possible to provide an image forming method excellent in transferability, cleaning property, filming resistance and charging stability.

According to a nineteenth aspect of the present invention, in the image forming method according to the eighteenth aspect , the photoconductor is an organic photoconductor or an amorphous silicon photoconductor. Thereby, durability can be improved.

According to a twentieth aspect of the present invention, in the image forming method according to the eighteenth or nineteenth aspect , the fixing device includes a heating body provided with a heating element, a film in contact with the heating body, and the film via the film. A pressure member that is in pressure contact with the heating member, and the material to be transferred onto which the visible image has been transferred is passed between the film and the pressure member to fix the heat and pressure. . Thereby, an unfixed image can be fixed satisfactorily.

The invention of claim 21 is the image forming method according to any one of claims 18 to 20, when developing the electrostatic latent image formed on the photosensitive member, applying an alternating electric field It is characterized by that. Thereby, a high-quality image can be formed.

According to a twenty-second aspect of the present invention, in the process cartridge, the developing device having the developer according to the sixteenth or seventeenth aspect and the photosensitive member are supported at least integrally, and are detachable from the main body of the image forming apparatus. To do. Accordingly, it is possible to provide a process cartridge that is excellent in transferability, cleaning property, filming resistance, and charging stability.

  According to the present invention, it is possible to provide a toner excellent in transferability, cleanability, filming resistance and charging stability, and a method for producing the toner. In addition, according to the present invention, a developer, a process cartridge, and an image forming method using the toner can be provided.

  Next, the best mode for carrying out the present invention will be described.

  The method for producing a toner of the present invention includes a step of forming a coating layer on the surface of the toner base particles using a fluid in which at least a silicone resin is dissolved in at least one of a supercritical fluid and a subcritical fluid. The method for forming the coating layer is not particularly limited as long as a fluid in which a silicone resin is dissolved is used as at least one of the supercritical fluid and the subcritical fluid, and can be appropriately selected according to the purpose.

  In the first embodiment of the toner production method of the present invention, a coating layer is formed by spraying at least one of a supercritical fluid and a subcritical fluid on a toner base particle with a fluid in which at least a silicone resin is dissolved. To do.

  In a second embodiment of the method for producing a toner of the present invention, at least one of a supercritical fluid and a subcritical fluid is mixed with a fluid in which at least a silicone resin is dissolved and toner base particles, and then the pressure is released. A coating layer is formed by rapid expansion. At this time, the silicone resin can be deposited around the toner base particles by releasing the pressure and rapidly expanding.

  In the third embodiment of the toner manufacturing method of the present invention, after mixing at least one of a supercritical fluid and a subcritical fluid with a fluid in which at least a silicone resin is dissolved and toner base particles, the pressure and temperature are mixed. The coating layer is formed by changing at least one of them. At this time, the solubility of the silicone resin can be lowered by changing at least one of the pressure and the temperature, and as a result, the silicone resin can be deposited around the toner base particles.

  Here, the apparatus used for forming the coating layer is not particularly limited and can be appropriately selected according to the purpose. For example, a pressure vessel for dissolving at least a silicone resin, and a supercritical fluid And a device including a pressurizing pump for supplying at least one of the subcritical fluid. As a processing method using this apparatus, at least a silicone resin is charged in a pressure vessel, and at least one of a supercritical fluid and a subcritical fluid is supplied into the pressure vessel by a pressure pump to dissolve the silicone resin. Is used to form a coating layer on the surface of the toner base particles. At this time, if carbon dioxide is used as at least one of the supercritical fluid and subcritical fluid, it will become a gas when it is returned to room temperature and normal pressure, so that it is not necessary to remove the solvent. Wastewater is no longer necessary, reducing the environmental burden. In addition, normal temperature normal pressure means 25 degreeC and 1 atmosphere.

  At least one of the supercritical fluid and the subcritical fluid can be present at the time of mixing at least one of the supercritical fluid and the subcritical fluid with the fluid in which at least the silicone resin is dissolved and the toner base particles. There are no particular restrictions as long as the conditions are appropriate, and it can be appropriately selected according to the purpose, but it is preferably 0 to 100 ° C, more preferably 20 to 80 ° C. When this temperature exceeds 100 ° C., the toner base particles may be dissolved.

  At least one of the supercritical fluid and the subcritical fluid can exist as the pressure when mixing the toner base particles with the fluid in which at least the silicone resin is dissolved in at least one of the supercritical fluid and the subcritical fluid. There are no particular limitations as long as the conditions are appropriate, and it can be appropriately selected according to the purpose, but it is preferably 1 to 60 MPa.

  Supercritical fluid has properties that are intermediate between gas and liquid, and has properties such as fast mass transfer and heat transfer and low viscosity, and by changing temperature and pressure, its density, dielectric constant, It means a fluid capable of continuously changing the solubility parameter, free volume and the like. Furthermore, since the supercritical fluid has an extremely small interfacial tension as compared with an organic solvent, it can follow and be wet even if there is a minute undulation on the surface.

  In the present invention, the supercritical fluid is not particularly limited as long as it is a non-condensable high-density fluid that exists in a temperature and pressure region exceeding the limit (critical point) at which a gas and a liquid can coexist. Although it can be selected, those having a low critical temperature and critical pressure are preferred. Further, the subcritical fluid is not particularly limited as long as it is a high-pressure liquid existing in a temperature and pressure region near the critical point, and can be appropriately selected according to the purpose. Examples of the supercritical fluid or subcritical fluid include carbon monoxide, carbon dioxide, ammonia, nitrogen, water, methanol, ethanol, ethane, propane, 2,3-dimethylbutane, benzene, chlorotrifluoromethane, and dimethyl ether. Of these, carbon dioxide is preferred. Since carbon dioxide has a critical pressure of 7.3 MPa and a critical temperature of 31 ° C., it is easy to be in a supercritical state, and is nonflammable and highly safe. Supercritical carbon dioxide vaporizes when it is returned to room temperature and normal pressure, so it can be easily recovered and reused, and the toner obtained in supercritical carbon dioxide does not need to be dried. Does not occur. The supercritical fluid or subcritical fluid may be used alone or in combination of two or more.

  The critical temperature and critical pressure of the supercritical fluid are not particularly limited and may be appropriately selected according to the purpose. The critical temperature is preferably −273 to 300 ° C., more preferably 0 to 200 ° C. . Moreover, the lower the critical pressure, the more advantageous in terms of, for example, apparatus load, equipment cost, operating energy, etc., but it is preferably 1 to 100 MPa, and more preferably 1 to 50 MPa.

  In the toner production method of the present invention, a coating layer can be formed on the surface of the toner base particles by positively utilizing the properties of the supercritical fluid or subcritical fluid. In addition, since the supercritical fluid can be easily separated from the product and can be recovered and reused, a conventional low-impact toner production method that does not use water or organic solvents can be used. Can be realized.

  In the present invention, in addition to at least one of the supercritical fluid and the subcritical fluid, other fluids can be used in combination. Such a fluid is preferably one that can easily control the solubility of the material constituting the toner. Specific examples include methane, ethane, propane, ethylene and the like.

  In addition to at least one of the supercritical fluid and the subcritical fluid, an entrainer (azeotropic agent) may be added. By adding an entrainer, the solubility of the silicone resin can be controlled. The entrainer is not particularly limited and can be appropriately selected according to the purpose, but is preferably a polar organic solvent. Examples of the polar organic solvent include methanol, ethanol, propanol, butanol, hexane, toluene, ethyl acetate, chloroform, dichloromethane, ammonia, melamine, urea, thioethylene glycol, and the like.

  In the present invention, the entrainer is preferably a poor solvent for the toner base particles and the silicone resin under normal temperature and normal pressure. At this time, the toner base particles and the silicone resin are insoluble or slightly swollen in the entrainer. The difference in solubility parameter (SP value) between the entrainer and the silicone resin is preferably 1.0 or more, and more preferably 2.0 or more. As such an entrainer, it is preferable to use methanol, ethanol, n-propanol or the like having a high SP value or n-hexane, n-heptane or the like having a low SP value. When the difference in SP value is greater than 5, the wettability of the toner in the fluid in which at least the silicone resin is dissolved in at least one of the supercritical fluid and the subcritical fluid may be reduced. Further, it may be difficult to dissolve the silicone resin in at least one of the supercritical fluid and the subcritical fluid.

  Further, the content of the entrainer in the mixed fluid of at least one of the supercritical fluid and the subcritical fluid and the entrainer is preferably 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight. . If the content of the entrainer is less than 0.1% by weight, it may be difficult to obtain the effect of the entrainer. If the content exceeds 10% by weight, the properties of the entrainer become too strong and supercritical. The state or subcritical state may be difficult to obtain.

  In the present invention, the silicone resin used for forming the coating layer on the surface of the toner base particles is not particularly limited and can be appropriately selected from generally known silicone resins according to the purpose. it can. In addition, as a silicone resin, you may synthesize | combine suitably and may use a commercial item. For example, as a straight silicone resin, KR271, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2406, SR2410, 217 Flakes Resin, 220 Flakes Resin, 233 Flakes Resin, 249 Flakes Resin, Z-6018 Intermediate ( As mentioned above, examples of the modified silicone resin include KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) (Shin-Etsu Chemical Co., Ltd.). SR2115 (epoxy modification), SR2110 (alkyd modification) (above, manufactured by Toray Dow Corning), and the like. Above all, general formula

で表される構造を有することが好ましい。式中、Ｒは、水素原子、水酸基、アルコキシル基、アルキル基又はアリール基である。アルコキシル基としては、メトキシル基、エトキシル基等が挙げられ、アルキル基としては、メチル基、エチル基、プロピル基等が挙げられ、アリール基としては、フェニル基、トリル基、キシリル基等が挙げられる。なお、シリコーン樹脂は、単独で用いることも可能であるが、架橋反応する成分、帯電量を調整する成分等と共に用いることも可能である。

It preferably has a structure represented by In the formula, R is a hydrogen atom, a hydroxyl group, an alkoxyl group, an alkyl group or an aryl group. Examples of the alkoxyl group include a methoxyl group and an ethoxyl group. Examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. Examples of the aryl group include a phenyl group, a tolyl group, and a xylyl group. . The silicone resin can be used alone, but can also be used together with a component that undergoes a crosslinking reaction, a component that adjusts the charge amount, and the like.

  There is no restriction | limiting in particular in the weight average molecular weight of a silicone resin, Although it can select suitably according to the objective, It is preferable that it is 500-100000, and 1000-10000 are more preferable.

  Moreover, since the silicone resin is excellent in handleability, film formability, and film thickness controllability, it is preferable that the silicone resin be solid at normal temperature and pressure.

  In the present invention, it is preferable to crosslink the silicone resin when forming the coating layer. The content of silanol groups in the silicone resin is preferably 0.1 to 10% by weight, more preferably 0.2 to 9% by weight, and 0.3 to 8% by weight in order to crosslink the silicone resin after film formation. Is particularly preferred. If the silanol group content exceeds 10% by weight, the crosslinked film may be hard and brittle, or unreacted silanol groups may reduce the environmental stability of the toner charge amount. In addition, when a silicone resin is crosslinked, a conventionally known catalyst used for crosslinking a silanol group can be used.

  In the present invention, the unreacted silanol group of the silicone resin after the crosslinking reaction is hydrophobized using, for example, hexamethyldisilazane (HMDS), so that the flow characteristics and charging characteristics are deteriorated even under high humidity. Can be suppressed. Other hydrophobizing agents include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modification agents Silicone oil etc. are mentioned. The hydrophobizing agent is preferably added in an amount of 1 to 40% by weight, more preferably 3 to 25% by weight, based on the silicone resin.

  These hydrophobically treated toners preferably have a degree of hydrophobicity of 30 to 80% as shown by wettability with methanol. The degree of hydrophobicity can be calculated using a powder wettability tester WET-100P (Resca). Specifically, 50 ml of pure water was put in a 300 ml beaker, 0.05 g of toner was floated on this, methanol was added dropwise at 1 ml / min while stirring with a stirrer, and the methanol when the permeability reached 50%. Is calculated as the degree of hydrophobicity.

  In the present invention, the coating layer may contain a cleaning property improving agent in order to remove the transferred developer remaining on the photoreceptor or the primary transfer medium. Examples of the cleaning property improving agent include fatty acid metal salts such as zinc stearate and calcium stearate, polymer particles produced by soap-free emulsion polymerization such as polymethyl methacrylate particles and polystyrene particles, and the like. At this time, the polymer particles preferably have a relatively narrow particle size distribution and a weight average particle size of 0.01 to 1 μm. The coating layer can contain a fluidity improver, a magnetic material, a metal soap, and the like.

Here, the amount of the coated silicone resin can be calculated using a fluorescent X-ray analyzer. Specifically, a predetermined amount of silicone resin is added in advance (for example, 0.1%, 0.3%, 0.6%, 1.2%, 2.4%, and 4.8%). A spherical pellet having a diameter of 40 mm is prepared by adding 3 g to the base particles and molding each 3 g at a pressure of 6 t / cm ² for 1 minute. This sample is analyzed with a wavelength dispersive X-ray fluorescence analyzer RIX3000 (manufactured by Rigaku Corporation), and a calibration curve for the X-ray intensity of Si element and the amount of silicone resin added is prepared. The amount of the coated silicone resin can be calculated with a fluorescent X-ray analyzer by preparing pellets in the same manner.

  In the present invention, the toner base particles contain a binder resin and a colorant, and can further contain a release agent, a charge control agent and the like.

  The method for producing the toner base particles is not particularly limited and may be appropriately selected depending on the intended purpose. However, the toner base particles are obtained by emulsifying, suspending or agglomerating the oil phase in an aqueous medium. The emulsion polymerization method, suspension polymerization method, polymer suspension method and the like that form a polymer are exemplified, and the emulsion polymerization method, suspension polymerization method, and polymer suspension method are particularly preferable.

  There is no restriction | limiting in particular as binder resin, According to the objective, it can select suitably according to the objective, For example, styrene, such as a polystyrene, poly (p-chlorostyrene), polyvinyltoluene, and its substituted single Polymer, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-methacrylic acid Copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, Styrene-vinyl methyl ether copolymer, styrene-vinyl methyl keto Copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene copolymers such as styrene-maleic acid ester copolymers, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyacetic acid Vinyl, polyethylene, polyester, polyurethane, epoxy resin, polyvinyl butyral, polyacrylic acid, rosin, modified rosin, terpene resin, phenol resin, aliphatic or aromatic hydrocarbon resin, aromatic petroleum resin, etc. Two or more kinds can be mixed and used.

  The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu , Permanent red 4R, para red, Vishay Red, p-Chloro-o-Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B , Rhodamine lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil red Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, indanthrene blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Examples thereof include a ceramic, a malachite green lake, a phthalocyanine green, an anthraquinone green, a titanium oxide, a zinc white, and a ritbon, and can be used alone or in combination of two or more.

  The content of the colorant in the toner base particles is preferably 1 to 15% by weight, and more preferably 3 to 10% by weight.

  The colorant may be used as a master batch combined with a resin. Such a resin is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, a homopolymer of styrene or a substituted product thereof, a styrene copolymer, polymethyl methacrylate, Polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin , Alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffins and the like, and may be used alone or in combination of two or more.

  There is no restriction | limiting in particular in a mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. can be used. Examples of waxes include carbonyl group-containing waxes, polyolefin waxes, long-chain hydrocarbons, and the like, and these can be used alone or in combination of two or more. Among these, a wax having a carbonyl group is preferable.

  Examples of the wax having a carbonyl group include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, etc. Among them, polyalkanoic acid esters are particularly preferable. Examples of polyalkanoic acid esters include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol. Examples include distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid, distearyl maleate, and the like. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of dialkyl ketones include distearyl ketone.

  Examples of the polyolefin wax include polyethylene wax and polypropylene wax.

  Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

  The melting point of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 40 to 160 ° C, more preferably 50 to 120 ° C, and particularly preferably 60 to 90 ° C. When the melting point is less than 40 ° C., the release agent may adversely affect the heat-resistant storage stability, and when it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.

  The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the release agent. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving the hot offset resistance and the low-temperature fixability may not be obtained.

  The content of the release agent in the toner base particles is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 1 to 40% by weight, and more preferably 3 to 30% by weight. When the content exceeds 40% by weight, the fluidity of the toner may be lowered.

  The charge control agent is not particularly limited, and a positive or negative charge control agent can be appropriately selected and used depending on whether the charge charged on the photoreceptor is positive or negative.

  As the negative charge control agent, for example, a resin or compound having an electron-donating functional group, an azo dye, a metal complex of an organic acid, or the like can be used. Specifically, Bontron (product numbers: S-31, S-32, S-34, S-36, S-37, S-39, S-40, S-44, E-81, E-82, E -84, E-86, E-88, A, 1-A, 2-A, 3-A) (above, manufactured by Orient Chemical Industry Co., Ltd.), Kaya Charge (part numbers: N-1, N-2), Kaya Set black (product number: T-2, 004) (above, Nippon Kayaku Co., Ltd.)), Eisenspiron black (T-37, T-77, T-95, TRH, TNS-2) (above, Hodogaya Chemical Industry Co., Ltd.), FCA-1001-N, FCA-1001-NB, FCA-1001-NZ (manufactured by Fujikura Kasei Co., Ltd.) and the like can be used alone or in combination.

  As the positive charge control agent, for example, basic compounds such as nigrosine dyes, cationic compounds such as quaternary ammonium salts, metal salts of higher fatty acids, and the like can be used. Specifically, Bontron (part numbers: N-01, N-02, N-03, N-04, N-05, N-07, N-09, N-10, N-11, N-13, P -51, P-52, AFP-B) (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415, TP-4040 (above, manufactured by Hodogaya Chemical Co., Ltd.), Copy Blue PR, Copy Charge ( Product number: PX-VP-435, NX-VP-434) (manufactured by Hoechst), FCA (product number: 201, 201-B-1, 201-B-2, 201-B-3, 201-PB, 201-PZ, 301) (above, manufactured by Fujikura Kasei Co., Ltd.), PLZ (part numbers: 1001, 2001, 6001, 7001) (above, manufactured by Shikoku Kasei Kogyo Co., Ltd.) and the like. can do.

  The addition amount of the charge control agent is determined by the method of manufacturing the toner base particles including the type of the binder resin and the dispersion method, and is not uniquely limited. On the other hand, it is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight. When the addition amount exceeds 10% by weight, the chargeability of the toner is too high, the effect of the charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, the image The concentration may decrease. On the other hand, if the addition amount is less than 0.1% by weight, the charge rising property and the charge amount are not sufficient, and the toner image may be easily affected.

  Next, a pulverization method will be described as a method for producing toner base particles. First, a mixture in which toner base particle materials are mixed is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. Specifically, a KTK type twin screw extruder (Kobe Steel Co., Ltd.), a TEM type extruder (Toshiba Machine Co., Ltd.), a twin screw extruder (Cay Kay), a PCM type twin screw extruder (Ikegai Iron Works) And Kneader (manufactured by Busus). The melt kneading is preferably performed under appropriate conditions so that the molecular chain of the binder resin is not broken. Specifically, if the melt-kneading temperature is too high above the softening point of the binder resin, cutting may become severe, and if it is too low, melt-kneading may not proceed.

  Next, the kneaded material obtained by melt kneading is pulverized. When the kneaded product is pulverized, it is preferable that the kneaded product is coarsely pulverized and then finely pulverized. Specifically, a method of pulverizing by colliding with a collision plate in a jet stream, a method of pulverizing particles by colliding with each other in a jet stream, or a method of pulverizing with a narrow gap between a mechanically rotating rotor and a stator are used. It is preferable.

  Furthermore, the pulverized pulverized product is classified to adjust the particle size within a predetermined range. In classification, for example, fine particles are removed by a cyclone, a decanter, a centrifugal separator, or the like. Further, toner base particles can be obtained by removing coarse particles and aggregated particles using a sieve of 250 mesh or more.

  The shape, size, etc. of the toner of the present invention are not particularly limited and can be appropriately selected according to the purpose. The average circularity, the weight average particle diameter with respect to the number average particle diameter, and the like are as follows. It is preferable to have a ratio of

  The average circularity of the toner of the present invention is preferably 0.900 to 0.980, and more preferably 0.950 to 0.975. Furthermore, it is preferable that the particles having an average circularity of less than 0.94 is 15% by weight or less. The circularity is a value obtained by dividing the circumference of a circle having the same area as the projected area of the particle by the circumference of the particle. When the average circularity is less than 0.900, the transferability may be deteriorated and a high-quality image without dust may not be obtained. When the average circularity exceeds 0.980, an image forming system employing blade cleaning or the like is adopted. In a case where a defective cleaning of a photosensitive member, a transfer belt, etc. occurs and an image is formed with an untransferred image due to a poor paper feed or the like in the case of image formation with a high image area ratio such as a photographic image. May cause smudges in the image accumulated on the photoreceptor as transfer residual toner. In addition, a charging roller for contacting and charging the photosensitive member may be contaminated, and the original charging ability may not be exhibited.

  The average circularity can be measured by using an optical detection band method in which a suspension containing toner is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.).

  The weight average particle size of the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 to 8 μm, and more preferably 3 to 7 μm. When the weight average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. In the case of the agent, the toner filming on the developing roller or the toner layer is thinned, so that toner fusion to a member such as a blade is likely to occur. Further, if the weight average particle diameter exceeds 8 μm, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle diameter may increase. is there.

  In the toner of the present invention, the ratio of the weight average particle diameter to the number average particle diameter is preferably 1.00 to 1.25, more preferably 1.00 to 1.20, and 1.10 to 1.15. Particularly preferred. Thereby, since the particle size distribution of the toner is relatively sharp, the fixing property can be improved. If this ratio exceeds 1.25, the two-component developer may cause the toner to fuse to the surface of the carrier during long-term agitation in the developing device, thereby reducing the chargeability of the carrier or reducing the cleaning properties. There is. In addition, with a one-component developer, filming of the toner on the developing roller and toner fusion to a member such as a blade for thinning the toner may easily occur, and high resolution and high image quality may occur. When the balance of the toner in the developer is made, it is sometimes difficult to obtain an image of the toner.

  The particle size of the toner can be measured using a particle size measuring device Coulter Counter TAII (manufactured by Coulter Electronics).

  The toner of the present invention can be at least one selected from black toner, cyan toner, magenta toner, and yellow toner, and each color toner can be obtained by appropriately selecting the type of colorant.

  The developer of the present invention may be either a one-component developer composed of the toner of the present invention or a two-component developer composed of the toner of the present invention and a carrier, such as a high-speed printer corresponding to an improvement in information processing speed. In the case of use in the two-component developer, it is preferable to use a two-component developer from the viewpoint of life. The mixing ratio of the toner and the carrier in the two-component developer is preferably 1 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier.

  When the toner of the present invention is used as a one-component developer, even if the balance of the toner is performed, there is little fluctuation in the particle size of the toner, the filming of the toner on the developing roller, and a blade for thinning the toner The toner is not fused to such a member, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the toner balance for a long period of time is performed, the fluctuation of the toner particle size in the developer is small, and it is good even for long-term stirring in the developing device. And stable developability can be obtained.

  There is no restriction | limiting in particular in a carrier, Although it can select suitably according to the objective, It is preferable to have a core material and the resin layer which coat | covers a core material.

  The core material is not particularly limited and can be appropriately selected from known materials. For example, 50 to 90 emu / g manganese-strontium (Mn-Sr) -based material, manganese-magnesium (Mn-Mg) A high-magnetization material such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) is preferable from the viewpoint of securing image density. In addition, it is possible to weaken the hitting of the toner that is in a spiked state to the photosensitive member, and it is advantageous in improving the image quality. From the viewpoint of improving the image quality, a copper-zinc (Cu—Zn) system (30 to 80 emu / g) or the like. The weakly magnetized material is preferred. These can be used individually or in mixture of 2 or more types.

  The weight average particle diameter of the core material is preferably 10 to 200 μm, and more preferably 40 to 100 μm. When the weight average particle diameter is less than 10 μm, the fine powder component of the carrier increases, and the magnetization per particle may be lowered and carrier scattering may occur. When the weight average particle diameter exceeds 200 μm, the specific surface area decreases, and the toner May occur, and the reproducibility of the solid portion may be deteriorated particularly in a full color having many solid portions.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyester resins Resin, polycarbonate resin, polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer weight of vinylidene fluoride and vinyl fluoride Examples thereof include fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride, and non-fluorinated monomers, silicone resins, and the like, which can be used alone or in combination of two or more.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral. Examples of the polystyrene resin include polystyrene and styrene-acrylic copolymer. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester-based resin include polyethylene terephthalate and polybutylene terephthalate.

  You may add conductive powder etc. to a resin layer as needed. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle size of the conductive powder is preferably 1 μm or less. When the average particle size exceeds 1 μm, it may be difficult to control the electric resistance.

  The resin layer is formed by, for example, preparing a coating solution by dissolving a silicone resin or the like in a solvent, then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. can do. Examples of the application method include a dipping method, a spray method, and a brush coating method.

  The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, and butyl acetate.

  The baking is not particularly limited and may be either an external heating method or an internal heating method. For example, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, or the like, The method to use etc. are mentioned.

  The content of the resin layer in the carrier is preferably 0.01 to 5.0% by weight. If the content is less than 0.01% by weight, the resin layer may not be uniformly formed on the surface of the core material. If the content exceeds 5.0% by weight, the resin layer becomes too thick and the carriers are Granulation may occur.

  The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

  The developer of the present invention can be made into a container containing a developer by being accommodated in the container.

  There is no restriction | limiting in particular in a container, It can select suitably from well-known things, For example, the thing etc. which have a container main body and a cap are mentioned.

  The size, shape, structure, material, etc. of the container body is not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical, and the inner circumference In particular, a spiral-shaped unevenness is formed on the surface, and the developer as a content can be transferred to the discharge port side by rotating the surface, and a part or all of the spiral part has a bellows function, etc. preferable.

  The material of the container body is not particularly limited, and those having good dimensional accuracy are preferable, for example, resin, among which polyester, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylic acid, polycarbonate, ABS resin, polyacetal Examples thereof include resins.

  Such a developer-containing container is easy to store and transport, and has excellent handling properties. Therefore, as a member of a process cartridge, an image forming apparatus, etc., it can be detachably attached and used to replenish the developer. Can do.

  The process cartridge of the present invention at least integrally supports a photosensitive member on which an electrostatic latent image is formed and a developing device that develops the electrostatic latent image formed on the photosensitive member using the developer of the present invention. The image forming apparatus main body is detachable. It should be noted that the process cartridge of the present invention may further support other means appropriately selected as needed.

  The developing device has at least a developer-containing container in which the developer of the present invention is accommodated, and a developer carrier that carries and conveys the developer contained in the developer-containing container. It may further include a layer thickness regulating member for regulating the layer thickness of the developer carried on the substrate.

  FIG. 1 shows an example of the process cartridge of the present invention. The process cartridge includes a photoreceptor 10 and includes a charging device 20, an exposure device 30, a developing device 40, a cleaning device 60, and a transfer device 80. These members can be the same as those used in the image forming apparatus described later.

  The image forming method of the present invention has at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, and a recycling step. Further, a control process or the like may be included.

  The image forming apparatus used in the present invention includes at least a photoconductor, a charging device, an exposure device, a developing device, a transfer device, and a fixing device, and other means appropriately selected as necessary, for example, a static elimination device, a cleaning device. You may further have an apparatus, a recycling apparatus, a control apparatus, etc.

  The electrostatic latent image forming step is a step of forming an electrostatic latent image on the photoreceptor. The electrostatic latent image is formed, for example, by charging the surface of the photosensitive member uniformly by applying a voltage using a charging device and then exposing it like an image using an exposure device. Can do.

  The material, shape, structure, size and the like of the photoreceptor are not particularly limited and can be appropriately selected from known ones, but the shape is preferably a drum shape. Examples of the photoreceptor include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors (OPC) such as polysilane and phthalopolymethine. Amorphous silicon photoreceptors are preferable in terms of long life. .

  The charging device is not particularly limited and can be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roll, brush, film, rubber blade, Examples thereof include a non-contact charger using corona discharge such as corotron and scorotron. The charging device is preferably arranged in contact or non-contact with the photoreceptor, and charges the surface of the photoreceptor by applying a DC voltage and an AC voltage in a superimposed manner. The charging device is a charging roller that is disposed in close proximity to the photoconductor via a gap tape, and charges the surface of the photoconductor by applying a DC voltage and an AC voltage superimposed on the charging roller. Those that do are preferred.

  The exposure apparatus is not particularly limited as long as it can image-wise expose the surface of the photoreceptor charged by the charging apparatus, and can be appropriately selected according to the purpose. Examples thereof include a rod lens array system, a laser optical system, and a liquid crystal shutter optical system. In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of a photoreceptor.

  The developing step is a step of forming a visible image by developing the electrostatic latent image with the developer of the present invention using a developing device.

  The developing device is not particularly limited as long as it can be developed using the developer of the present invention, and can be appropriately selected from known ones. For example, the developing device accommodates the developer of the present invention and is electrostatically charged. Examples include those having at least a developer-carrying body capable of applying a developer to a latent image in a contact or non-contact manner, and preferably including a developer-containing container in a detachable manner. The developing device may be either a dry developing method or a wet developing method, and may be either a single color developing device or a multicolor developing device. For example, the developer is charged by friction stirring. Examples include a stirrer and a rotatable magnet roller. In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. Since the magnet roller is disposed in the vicinity of the photoconductor, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the photoconductor by an electric attractive force. As a result, the electrostatic latent image is developed with toner, and a visible image is formed on the surface of the photoreceptor. Note that an alternating electric field is preferably applied when the toner is moved to the surface of the photoreceptor.

  The transfer process is a process in which a visible image is transferred to a transfer target using a transfer device. After the primary transfer of the visible image onto the intermediate transfer member using the intermediate transfer member, the visible image is transferred to the transfer target. A mode in which secondary transfer is performed on a transfer body is preferred. In addition, a primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer member using two or more colors, preferably full color toner, as the toner, and the composite transfer image on the transfer target An embodiment having a secondary transfer step of transferring is preferable. The visible image can be transferred by charging the photoconductor using, for example, a transfer charger.

  The transfer device preferably has a primary transfer device that transfers a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer device that transfers the composite transfer image onto a transfer target. The transfer device (primary transfer device, secondary transfer device) preferably has at least a transfer device that peels and charges the visible image formed on the photosensitive member toward the transfer target. There may be one transfer device or two or more transfer devices. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

  The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. Examples thereof include a transfer belt.

  The transfer target is not particularly limited and can be appropriately selected from known recording media (recording paper).

  The fixing step is a step of fixing the visible image transferred to the transfer target using a fixing device, and may be fixed for each color toner each time it is transferred to the transfer target. The toners may be fixed simultaneously at the same time in a state where the toners are laminated.

  The fixing device is not particularly limited and may be appropriately selected according to the purpose. However, a fixing device that is heat-pressed and fixed using a known fixing member is preferable. The fixing member is preferably in the form of a roller or a belt, and examples thereof include a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller and an endless belt. At this time, it is preferable that heating temperature is 80-200 degreeC normally.

  In the present invention, the fixing device includes a heating body having a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film. It is possible to use means for heating and press-fixing by passing the transfer body on which the received image is formed.

  Depending on the purpose, for example, a known optical fixing device may be used together with the fixing device or instead of the fixing device.

  The neutralization step is a step of performing neutralization by applying a neutralization bias to the photoconductor using a neutralization device.

  The neutralization device is not particularly limited, and may be any one as long as it can apply a neutralization bias to the photosensitive member, and can be appropriately selected from known neutralization devices. Examples thereof include a neutralization lamp.

  The cleaning step is a step of removing toner remaining on the photoreceptor using a cleaning device.

  The cleaning device is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected from known cleaners. For example, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller A cleaner, a blade cleaner, a brush cleaner, a web cleaner, etc. are mentioned.

  The recycling process is a process in which the toner removed in the cleaning process is recycled to the developing device using a recycling apparatus.

  There is no restriction | limiting in particular in a recycling apparatus, For example, a well-known conveyance means etc. are mentioned.

  A control process is a process of controlling each process using a control device.

  The control device is not particularly limited as long as the movement of each step can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  Next, the image forming method of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 2 includes a photosensitive member 10, a charging device 20, an exposure device 30, a developing device 40, an intermediate transfer member 50, a cleaning device 60 having a cleaning blade, a charge eliminating device 70, a transfer device. A device 80 is provided. Note that a charging roller is used as the charging device 20, a static elimination lamp as the static elimination device 70, and a transfer roller as the transfer device 80.

  The intermediate transfer member 50 is an endless belt, and is designed to be stretched by three support rollers 51 arranged on the inner side thereof so as to be movable in the arrow direction. A part of the three support rollers 51 also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer member 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof. Further, a transfer device 80 capable of applying a secondary transfer bias for transferring a visible image (secondary transfer) to the transfer target 95 is disposed opposite to the transfer device 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the visible image on the intermediate transfer member 50 is in contact with the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. And the contact portion between the intermediate transfer body 50 and the transfer body 95. Note that transfer paper is used as the transfer target 95.

  The developing device 40 includes a developing belt 41 as a developer carrier, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. ing. The developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K, and the developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The developing unit 45M includes a developer accommodating portion 42M, a developer supply roller 43M, and a developing roller 44M. The developing unit 45C includes a developer accommodating portion 42C, the developer supplying roller 43C, and the developing roller 44C. Yes. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In this image forming apparatus, after the charging device 20 uniformly charges the photoconductor 10, the exposure device 30 performs imagewise exposure on the photoconductor 10 to form an electrostatic latent image. Next, the developing device 40 supplies the developer to the electrostatic latent image formed on the photoconductor 10 and develops it to form a visible image. The visible image is transferred (primary transfer) onto the intermediate transfer body 50 by the voltage applied from the support roller 51 and further transferred (secondary transfer) onto the transfer body 95. As a result, a transfer image is formed on the transfer target 95. The toner remaining on the photoconductor 10 is removed by the cleaning device 60, and the charge of the photoconductor 10 is removed by the charge eliminating lamp 70.

  Next, another aspect of the image forming method of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 3 has a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan around the photosensitive member 10, instead of the developing device 40 in the image forming apparatus shown in FIG. The developing unit 45C has the same configuration as that of the image forming apparatus shown in FIG. In FIG. 3, the same components as those of the image forming apparatus shown in FIG. The same applies to FIGS. 4 and 5 described later.

  Next, another aspect of the image forming method of the present invention will be described with reference to FIG. The image forming apparatus shown in FIG. 4 is a tandem type color image forming apparatus. The image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

  The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can rotate clockwise in FIG. A cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched by the support roller 14 and the support roller 15 has four image forming units 18 of yellow, cyan, magenta, and black facing each other along the conveying direction. A means 120 is arranged. An exposure device 30 is disposed in the vicinity of the image forming unit 120. The secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the image forming unit 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of support rollers 23, and the recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 are mutually connected. It is possible to touch. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt and a pressure roller 27 that is pressed against the fixing belt 26. A reversing device 28 for reversing the recording paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25 in order to form images on both sides of the recording paper.

  Next, formation of a full-color image (color copy) using the image forming unit 120 will be described. First, an original document is set on the document table 130 of the automatic document feeder (ADF) 400 or the automatic document feeder 400 is opened, and the original document is set on the contact glass 32 of the scanner 300. Close.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. When this happens, the scanner 300 is immediately driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33, and reflected light from the document surface is reflected by a mirror in the second traveling body 34. Further, the image is received by the reading sensor 36 through the imaging lens 35, and the original is read to obtain image information of black, yellow, magenta and cyan. Next, each image information is transmitted to each image forming unit 18 in the image forming means 120, and a visible image of each color of black, yellow, magenta and cyan is formed.

  As shown in FIG. 5, the image forming unit 18 includes a photoconductor 10, a charging device 20 that uniformly charges the photoconductor 10, and an exposure device 30, based on each image information. A developing device 61 that develops the electrostatic latent image formed by exposing the toner 10 with each toner (black toner, yellow toner, magenta toner, and cyan toner) to form a visible image with each toner; A transfer charger 62 for transferring a visible image onto the intermediate transfer member 50, a cleaning device 60, and a charge eliminating device 70 are provided, and a visible image of each color can be formed based on each image information. is there. Next, the visible images of the respective colors are sequentially transferred (primary transfer) onto the intermediate transfer body 50 that is rotated and moved by the support rollers 14, 15 and 16, and the visible images of the respective colors are superimposed to form a composite transfer image. It is formed.

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed the recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller 142 is rotated to feed out the recording paper on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual paper feed path 53, and abutted against the registration roller 49 and stopped. The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the recording paper. Then, the registration roller 49 is rotated in synchronization with the composite transfer image formed on the intermediate transfer member 50, and the recording paper is sent between the intermediate transfer member 50 and the secondary transfer device 22, so that the secondary transfer device. By transferring the composite transfer image onto the recording paper (secondary transfer) by 22, a color image is formed on the recording paper. The toner remaining on the intermediate transfer member 50 is removed by the cleaning device 17.

  The recording paper on which the color image is formed is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the composite transfer image is heated and pressed and fixed on the recording paper. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the discharge tray 57. Alternatively, it is switched by the switching claw 55 and reversed by the reversing device 28 and led to the transfer position again. After an image is formed also on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In addition, the part in an Example means a weight part unless there is particular notice. Further, although the silicone resin was dissolved in the supercritical fluid used in the examples, the binder resin constituting the toner base particles was insoluble.
(Manufacture of base particle 1)
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of Eleminol RS-30 (manufactured by Sanyo Chemical Industries), which is a sodium salt of sulfate of ethylene oxide adduct of methacrylic acid, 83 parts of styrene, methacrylic acid When 83 parts of acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. This was heated to raise the temperature inside the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% by weight aqueous ammonium persulfate solution was added and aged at 75 ° C. for 5 hours to obtain an aqueous vinyl resin copolymer dispersion (resin dispersion 1).

  It was 105 nm when the weight average particle diameter of resin contained in the resin dispersion 1 was measured by a particle size distribution measuring apparatus LA-920 (manufactured by Horiba, Ltd.) using a laser light scattering method. Further, when a part of the resin dispersion 1 was dried to isolate the resin, the glass transition temperature was 59 ° C. and the weight average molecular weight was 150,000.

  By mixing and stirring 990 parts of water, 83 parts of resin dispersion 1, 37 parts of 48.5% by weight sodium dodecyl diphenyl ether sodium disulfonate aqueous solution Eleminol MON-7 (manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate, Aqueous phase 1 was obtained.

  In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts of an ethylene oxide 2-mole adduct of bisphenol A, 529 parts of a propylene oxide 3-mole adduct of bisphenol A, 208 parts of terephthalic acid, 46 parts of adipic acid and dibutyltin 2 parts of oxide was charged and reacted at 230 ° C. (normal pressure) for 8 hours. Next, after making it react at 10-15 mmHg for 5 hours, 44 parts of trimellitic anhydride was put into a reaction vessel and reacted at 180 ° C. (normal pressure) for 2 hours to obtain low molecular weight polyester 1. Low molecular weight polyester 1 had a glass transition temperature of 45 ° C., a weight average molecular weight of 5800, a number average molecular weight of 2600, and an acid value of 24 mgKOH / g.

  In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 Parts and 2 parts of dibutyltin oxide were prepared, reacted at 230 ° C. (normal pressure) for 8 hours, and then reacted at 10 to 15 mmHg for 5 hours to obtain an intermediate polyester 1. The intermediate polyester 1 has a number average molecular weight of 2100, a weight average molecular weight of 9500, a glass transition temperature of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g. It was.

  Next, 410 parts of intermediate polyester 1, 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. (normal pressure) for 5 hours. By doing so, Prepolymer 1 was obtained. The content of free isocyanate groups in Prepolymer 1 was 1.74% by weight.

  In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. (normal pressure) for 5 hours to obtain a ketimine compound 1. The amine value of ketimine compound 1 was 418 mgKOH / g.

  Henschel mixer (Mitsui) (Mine company). The obtained mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer to obtain a master batch 1.

  In a reaction vessel equipped with a stir bar and a thermometer, 300 parts of low molecular weight polyester 1, 90 parts of carnauba wax, 10 parts of rice wax and 1000 parts of ethyl acetate were charged and dissolved at 79 ° C. with stirring. Quenched to 4 ° C. This is filled with 80% by volume of zirconia beads having a particle size of 0.5 mm in a bead mill, Ultra Visco Mill (manufactured by Imex Co., Ltd.), and dispersed under conditions of a liquid feed speed of 1 kg / hour, a disk peripheral speed of 6 m / second, and three passes. As a result, a wax dispersion having a weight average particle diameter of 0.6 μm was obtained.

  Next, 500 parts of masterbatch 1 and 640 parts of a 70% by weight ethyl acetate solution of low molecular weight polyester 1 are added and mixed for 10 hours, then 5 passes through the bead mill described above, and ethyl acetate is added to obtain a solid content concentration of 50. The oil phase 1 was obtained by adjusting to weight%.

  73.2 parts of oil phase 1, 6.8 parts of prepolymer 1 and 0.48 parts of ketimine compound 1 are charged into a container and mixed well, then 120 parts of water phase 1 is added, and 1 is added with a homomixer. Emulsified slurry 1 was obtained by mixing for 1 minute and converging while stirring with a paddle for 1 hour.

The emulsion slurry 1 was desolvated at 30 ° C. for 1 hour, aged at 60 ° C. for 5 hours, washed with water, filtered and dried, and then sieved with a 75 μm mesh, so that the weight average particle diameter was 6.1 μm. Black base particles 1 having a number average particle size of 5.4 μm and an average circularity of 0.987 were obtained.
(Manufacture of base particle 2)
100 parts of a polyester resin having a weight average molecular weight of 12,000, 2 parts of a copper phthalocyanine pigment, and a structural formula

で表される帯電制御剤２部を、熱ロールを用いて１２０℃で混練した。次に、冷却、固化した後、粉砕、分級することにより、重量平均粒径７．１μｍ、個数平均粒径５．０μｍ、平均円形度０．９２１のシアンの母体粒子２を得た。
（母体粒子３の製造）
重量平均分子量１２０００のポリエステル樹脂１００部、カーボンブラック５部及び構造式

2 parts of the charge control agent represented by the formula was kneaded at 120 ° C. using a hot roll. Next, after cooling and solidifying, pulverization and classification were performed to obtain cyan base particles 2 having a weight average particle diameter of 7.1 μm, a number average particle diameter of 5.0 μm, and an average circularity of 0.921.
(Manufacture of base particle 3)
100 parts of a polyester resin having a weight average molecular weight of 12,000, 5 parts of carbon black and a structural formula

で表される含クロムアゾ染料２部を、熱ロールを用いて１２０℃で混練した。次に、冷却、固化した後、粉砕、分級することにより、重量平均粒径７．３μｍ、個数平均粒径５．１μｍ、平均円形度０．９１７のブラックの母体粒子３を得た。
（参考例１）
図６に示す装置において、コート剤溶解タンク（内容積２００ｍｌ）に、化学構造式

2 parts of a chromium-containing azo dye represented by the formula (1) was kneaded at 120 ° C. using a hot roll. Next, after cooling and solidifying, pulverization and classification were performed to obtain black base particles 3 having a weight average particle diameter of 7.3 μm, a number average particle diameter of 5.1 μm, and an average circularity of 0.917.
( Reference Example 1)
In the apparatus shown in FIG. 6, the chemical structural formula is added to the coating agent dissolution tank (internal volume 200 ml).

で表される構造を有する重量平均分子量約４０００のシリコーン樹脂ａ（ＳＲ−２１３（東レ・ダウコーニング社製）の脱溶剤品）２００部及び１０部の化学構造式
Ｓｎ（ＣＨ_３）_２（ＯＣＯＣＨ_３）_２
で表される触媒ｂを仕込み、トナー処理タンク（内容積４００ｍｌ）に、５００部の母体粒子１を仕込み、コート剤溶解タンク内及びトナー処理タンク内は、それぞれ攪拌子及びスターラーを用いて攪拌した。この状態で、バルブ３及びバルブ６を開け、加圧ポンプ１で純度９９．５％の二酸化炭素（太田酸素社製）を供給し、コート剤溶解タンク内及びトナー処理タンク内を２５ＭＰａ、８０℃にした後、バルブ６を閉じた。次に、バルブ５、バルブ７及びバルブ８を開け、減圧弁１を調整し、トナー処理タンク内が２５ＭＰａ、８０℃を維持するように内圧を制御しながら、常圧下における１Ｌ／分に相当する流量で超臨界二酸化炭素を１時間流通させた。さらに、バルブ３を閉じ、減圧弁１で１５分かけて常圧に戻した。得られたシリコーン樹脂が被覆された母体粒子１を、８０℃で４８時間加熱し、架橋させることにより、トナーを得た。なお、使用されなかったコート剤は、コート剤溶解タンクと原料回収タンクから回収することができ、再利用することができた。
（参考例２）
図７に示す装置において、コート剤溶解タンク（内容積１００ｍｌ）に、２００部のシリコーン樹脂ａ及び１０部の触媒ｂを仕込み、トナー処理カラム（内容積１２５ｍｌ）には、５００部の母体粒子１を仕込み、コート剤溶解タンク内は、攪拌子及びスターラーを用いて攪拌した。この状態で、バルブ３及びバルブ６を開け、加圧ポンプ１で純度９９．５％の二酸化炭素（太田酸素社製）を供給し、コート剤溶解タンク内及びトナー処理カラム内を２５ＭＰａ、６０℃にした後、バルブ６を閉じた。次に、バルブ５、バルブ７及びバルブ８を開け、減圧弁１を調整し、トナー処理カラム内が２５ＭＰａ、６０℃を維持するように内圧を制御しながら、常圧下における１Ｌ／分に相当する流量で超臨界二酸化炭素を１時間流通させた。さらに、バルブ３を閉じ、減圧弁１で２時間かけて常圧に戻した。得られたシリコーン樹脂が被覆された母体粒子１を、６０℃で７２時間加熱し、架橋させることにより、トナーを得た。なお、使用されなかったコート剤は、コート剤溶解タンクと原料回収タンクから回収することができ、再利用することができた。
（参考例３）
図８に示す装置において、コート剤溶解タンク（内容積５００ｍｌ）に、１００部のシリコーン樹脂ａ及び５部の触媒ｂを仕込み、バルブ３を開け、加圧ポンプ１で純度９９．５％の二酸化炭素（太田酸素社製）を供給し、コート剤溶解タンク内を３５ＭＰａ、４０℃にして、攪拌羽根で攪拌することにより、塗布流体ｃを作製した。

200 parts and 10 parts of chemical structural formula Sn (CH ₃ ) ₂ (OCOCH) with a weight average molecular weight of about 4000 (SR-213 (made by Toray Dow Corning)) ₃ ) ₂
In the toner processing tank (internal volume 400 ml), 500 parts of the base particles 1 were charged, and the coating agent dissolution tank and the toner processing tank were stirred using a stirrer and a stirrer, respectively. . In this state, the valve 3 and the valve 6 are opened, and carbon dioxide having a purity of 99.5% (manufactured by Ota Oxygen Co., Ltd.) is supplied by the pressure pump 1, and the inside of the coating agent dissolution tank and the toner processing tank is 25 MPa, 80 ° C. After that, the valve 6 was closed. Next, the valve 5, the valve 7 and the valve 8 are opened, the pressure reducing valve 1 is adjusted, and the internal pressure is controlled so that the inside of the toner processing tank is maintained at 25 MPa and 80 ° C., which corresponds to 1 L / min under normal pressure. Supercritical carbon dioxide was allowed to flow for 1 hour at a flow rate. Further, the valve 3 was closed, and the pressure reducing valve 1 was returned to normal pressure over 15 minutes. The obtained base particles 1 coated with the silicone resin were heated at 80 ° C. for 48 hours to be crosslinked to obtain a toner. In addition, the coating agent that was not used could be recovered from the coating agent dissolution tank and the raw material recovery tank and reused.
( Reference Example 2)
In the apparatus shown in FIG. 7, 200 parts of silicone resin a and 10 parts of catalyst b are charged in a coating agent dissolution tank (internal volume 100 ml), and 500 parts of base particles 1 are placed in a toner processing column (internal volume 125 ml). The inside of the coating agent dissolution tank was stirred using a stirrer and a stirrer. In this state, the valve 3 and the valve 6 are opened, and carbon dioxide having a purity of 99.5% (manufactured by Ota Oxygen Co., Ltd.) is supplied by the pressure pump 1, and the inside of the coating agent dissolution tank and the toner processing column is 25 MPa, 60 ° C. After that, the valve 6 was closed. Next, the valve 5, the valve 7 and the valve 8 are opened, the pressure reducing valve 1 is adjusted, and the internal pressure is controlled so as to maintain the inside of the toner processing column at 25 MPa and 60 ° C., which corresponds to 1 L / min under normal pressure. Supercritical carbon dioxide was allowed to flow for 1 hour at a flow rate. Further, the valve 3 was closed and the pressure reducing valve 1 was returned to normal pressure over 2 hours. The obtained base particles 1 coated with the silicone resin were heated at 60 ° C. for 72 hours to be crosslinked to obtain a toner. In addition, the coating agent that was not used could be recovered from the coating agent dissolution tank and the raw material recovery tank and reused.
( Reference Example 3)
In the apparatus shown in FIG. 8, 100 parts of silicone resin a and 5 parts of catalyst b are charged into a coating agent dissolution tank (internal volume 500 ml), valve 3 is opened, and pressurizing pump 1 is used to produce 99.5% pure CO 2. Carbon (manufactured by Ota Oxygen Co., Ltd.) was supplied, the inside of the coating agent dissolution tank was set to 35 MPa and 40 ° C., and the mixture was stirred with a stirring blade to prepare a coating fluid c.

Next, 500 parts of the base particles 1 are charged into a toner processing tank (internal volume 1000 ml), the valve 6 is opened, the inside of the toner processing tank is set to 3 MPa and 40 ° C., the valve 6 is closed, and then the valve 5 and the valve 7 and the valve 8 were opened, the pressure reducing valve 1 was adjusted, and the coating fluid c was applied for about 40 minutes while stirring with a stirring blade while controlling the internal pressure so that the inside of the toner processing tank did not become 7 MPa or more. . The obtained base particles 1 coated with the silicone resin were heated at 50 ° C. for 120 hours to be crosslinked to obtain a toner. In addition, the coating agent that was not used could be recovered from the coating agent dissolution tank and the raw material recovery tank and reused.
( Reference Example 4)
In the apparatus shown in FIG. 9, 50 parts of silicone resin a and 2.5 parts of catalyst b are charged in a coating agent dissolution tank (internal volume of 500 ml), and 500 parts of base particles in a toner processing tank (internal volume of 1000 ml). 1 and the valve 3 and the valve 5 are opened, carbon dioxide (made by Ota Oxygen Co., Ltd.) having a purity of 99.5% is supplied by the pressure pump 1, and the inside of the coating agent dissolution tank and the toner processing tank is 15 MPa, 65 ° C. Then, a toner dispersion fluid d was prepared by stirring with a stirring blade. The inside of the spray tank was set to 30 ° C. (normal pressure), and the toner dispersion fluid d was ejected (rapid expansion) from the nozzle. The obtained base particles 1 coated with the silicone resin were heated at 50 ° C. for 120 hours to be crosslinked to obtain a toner. The coating agent that was not used could be recovered from the coating agent dissolution tank and the toner processing tank and reused.
( Reference Example 5)
The same procedure as in Reference Example 1 was performed except that epoxy-modified silicone resin SR2115 (manufactured by Dow Corning Toray) was used instead of silicone resin a, and the pressure and temperature conditions during treatment were 30 MPa and 70 ° C. A toner was obtained.
( Reference Example 6)
Instead of the silicone resin a, a silicone resin KR271 (from Shin-Etsu Chemical Co., Ltd.), the pressure during the treatment, the temperature conditions, 35 MPa, except for using 90 ° C., using the same method as in Reference Example 1, the toner Obtained.
(Example 7)
Silicone resin 249 Flask Resin (made by Toray Dow Corning Co., Ltd.) having a silanol group content of 5% by weight, a crosslinking degree of 71%, a silicon dioxide content of% by weight, and a molecular weight of 2000 to 4000 instead of silicone resin a The toner was obtained in the same manner as in Reference Example 1 except that the pressure and temperature conditions during the treatment were 20 MPa and 60 ° C.
(Example 8)
A toner was obtained in the same manner as in Example 7 except that the pressure and temperature conditions during the treatment were 30 MPa and 80 ° C.
Example 9
Instead of silicone resin a, silicone resin 233 Flakes Resin (Toray Dow Corning Co., Ltd.) having a silanol group content of 5% by weight, a crosslinking degree of 71%, a silicon dioxide content of 52% by weight, and a molecular weight of 2000 to 4000 The toner was obtained in the same manner as in Reference Example 1 except that the pressure and temperature conditions during the treatment were 25 MPa and 65 ° C.
( Reference Example 10)
In the coating agent dissolution tank, the chemical structural formula NH ₂ (CH ₂ ) ₃ Si (OCH ₃ ) ₃
A toner was obtained in the same manner as in Reference Example 1 except that 2.5 parts of an aminosilane coupling agent represented by
(Example 11)
Silicone resin 217 Flask Resin (Toray Dow Corning Co., Ltd.) having a silanol group content of 6% by weight, a crosslinking degree of 75%, a silicon dioxide content of 46% by weight and a molecular weight of 1500 to 2500 instead of silicone resin a The ethanol is charged into the entrainer tank, the valve 4 is opened, and 0.5% by weight (about 5 g / L per volume) of ethanol with respect to the total weight of carbon dioxide and ethanol by the pressure pump 2 Was added and a toner was obtained in the same manner as in Reference Example 4 except that the inside of the spray tank was set to 50 ° C. (normal pressure).
(Example 12)
Instead of silicone resin 217 Flakes Resin, silicone resin 220 Flakes Resin (Toray Dow) having a silanol group content of 6% by weight, a crosslinking degree of 70%, a silicon dioxide content of 51% by weight and a molecular weight of 2000 to 4000 Example 11 except that methanol was charged into the entrainer tank, the valve 4 was opened, and 5% by weight of methanol was added to the total weight of carbon dioxide and methanol by the pressure pump 2 using Corning). The toner was obtained in the same manner as described above.
(Example 13)
Instead of the silicone resin 217 Flakes Resin, the silicone resin 233 Flakes Resin is used, propanol is charged into the entrainer tank, the valve 4 is opened, and the pressurizing pump 2 makes 1 wt% of the total weight of carbon dioxide and propanol. A toner was obtained in the same manner as in Example 11 except that propanol was added.
( Reference Example 14)
A toner was obtained in the same manner as in Reference Example 1 except that the base particle 2 was used instead of the base particle 1.
( Reference Example 15)
A toner was obtained in the same manner as in Reference Example 1 except that the base particles 3 were used instead of the base particles 1.
(Comparative Example 1)
For 100 parts of base particles 1, 1.5 parts of hydrophobic silica having a surface treatment with hexamethyldisilazane of 65%, an average primary particle diameter of 12 nm, and a BET specific surface area of 150 m ² / g The mixture was added and mixed using a Henschel mixer for 5 minutes at a peripheral speed of 8 m / sec. Next, the coarse powder was removed by sieving with a mesh having an opening of 100 μm to obtain a toner.
(Comparative Example 2)
To 100 parts of base particles 2, 1.5 parts of hydrophobic silica having a surface treatment with hexamethyldisilazane of 65%, an average primary particle diameter of 12 nm, and a BET specific surface area of 150 m ² / g The mixture was added and mixed using a Henschel mixer for 5 minutes at a peripheral speed of 8 m / sec. Next, the coarse powder was removed by sieving with a mesh having an opening of 100 μm to obtain a toner.
(Comparative Example 3)
With respect to 100 parts of base particles 1, 1.5 parts of hydrophobic silica having a surface treatment with hexamethyldisilazane of 65%, an average primary particle size of 12 nm, and a BET specific surface area of 150 m ² / g, Then, 0.5 part of hydrophobic titanium oxide surface-treated with isobutyltrimethoxysilane having a hydrophobization degree of 70%, an average primary particle diameter of 15 nm, and a BET specific surface area of 58 m ² / g was added, and a Henschel mixer was used. The mixture was mixed for 10 minutes at a peripheral speed of 8 m / sec. Next, the coarse powder was removed by sieving with a mesh having an opening of 100 μm to obtain a toner.
(Comparative Example 4)
To 100 parts of the base particles 3, 1.5 parts of hydrophobic silica having a surface treatment with hexamethyldisilazane of 65%, an average primary particle diameter of 12 nm, and a BET specific surface area of 150 m ² / g Then, using a hybridization system (manufactured by Nara Machinery Co., Ltd.), mixing was performed for 1 minute at a peripheral speed of 200 m / sec. Next, 0.5 parts of hydrophobic titanium oxide surface-treated with isobutyltrimethoxysilane having a hydrophobization degree of 70%, an average primary particle diameter of 15 nm, and a BET specific surface area of 58 m ² / g was added to the hybridization system. Was mixed for 1 minute at a peripheral speed of 200 m / sec. Next, the coarse powder was removed by sieving with a mesh having an opening of 100 μm to obtain a toner.
(Carrier production)
200 parts of toluene, 200 parts of silicone resin SR2400 (made by Toray Dow Corning) with a nonvolatile content of 50% by weight, 7 parts of aminosilane SH6020 (made by Toray Dow Corning), and 4 parts of carbon black were dispersed with a stirrer for 10 minutes. Then, a coating layer coating solution was prepared.

A coating apparatus for coating 5000 parts of Mn ferrite particles having a weight average particle diameter of 35 μm as a coating layer coating liquid and a core material with a rotating bottom plate disk and stirring blades in a fluidized bed and forming a swirling flow The coating solution for coating layer was applied on the core material. The obtained coated product was baked in an electric furnace at 250 ° C. for 2 hours to obtain a carrier.
(Evaluation of two-component developer)
7 parts of toner and 100 parts of carrier were uniformly mixed and charged using a tumbler mixer in which the container was rolled and stirred to prepare a two-component developer.

  The obtained two-component developer was loaded into an image forming apparatus IPSio Color 8100 (manufactured by Ricoh Company), an image was output, and evaluation was performed as follows. The results are shown in Table 1.

（一成分現像剤の評価）
トナーを１成分現像剤として、画像形成装置ＩＰＳｉｏ Ｃｏｌｏｒ ２０００に装填し、画像を出力して、以下のようにして評価した。結果を表２に示す。

(Evaluation of one-component developer)
The toner was loaded into the image forming apparatus IPSio Color 2000 as a one-component developer, and an image was output and evaluated as follows. The results are shown in Table 2.

＜画像濃度＞
普通紙の転写紙タイプ６２００（リコー社製）に、０．３±０．１ｍｇ／ｃｍ^２の低付着量でベタ画像を出力した後、画像濃度をＸ−Ｒｉｔｅ（Ｘ−Ｒｉｔｅ社製）により測定することにより、画像濃度を評価した。なお、画像濃度が１．４以上であるものを○、１．３５以上１．４未満であるものを△、１．３５未満であるものを×として、判定した。
＜クリーニング性＞
画像面積率が９５％のチャートを１０００枚出力した後のクリーニング工程を通過した感光体上の転写残トナーをスコッチテープ（住友スリーエム社製）で白紙に移し、それをマクベス反射濃度計ＲＤ５１４型で測定することにより、クリーニング性を評価した。なお、ブランクとの差が０．００５未満であるものを◎、０．００５以上０．０１未満であるものを○、０．０１以上０．０２未満であるものを△、０．０２以上であるものを×として、判定した。
＜転写性＞
画像面積率が２０％のチャートを感光体から紙に転写した後、クリーニングの直前における感光体上の転写残トナーをスコッチテープで白紙に移し、それをマクベス反射濃度計ＲＤ５１４型で測定することにより、転写性を評価した。なお、ブランクとの差が０．００５未満であるものを◎、０．００５以上０．０１未満であるものを○、０．０１以上０．０２未満であるものを△、０．０２以上であるものを×として、判定した。
＜トナー飛散＞
４０℃、９０％ＲＨの環境下で、画像形成装置ＩＰＳｉＯ Ｃｏｌｏｒ８１００（リコー社製）をオイルレス定着方式に改造してチューニングした評価機を用いて、画像面積率が５％のチャートを連続１０万枚出力する耐久試験を実施した後の画像形成装置内のトナーによる汚染状態を目視することにより、トナー飛散を評価した。なお、トナー汚れが全く観察されず、良好な状態であるものを◎、わずかに汚れが観察される程度であり、問題とならないものを○、少し汚れが観察される程度であるものを△、非常に汚れがあり、問題となるものを×として、判定した。
＜帯電安定性＞
画像面積率が１２％の文字画像パターンを連続１０万枚出力する耐久試験を実施し、スリーブ上から現像剤を少量採取し、ブローオフ法で帯電量の変化を測定することにより、帯電安定性を評価した。なお、帯電量の変化が５μＣ／ｇ未満であるものを○、５μＣ／ｇ以上１０μＣ／ｇ未満であるものを△、１０μＣ／ｇ以上であるものを×として、判定した。
＜耐フィルミング性＞
画像面積率が１００％、７５％及び５０％の帯チャートを１０００枚出力した後の現像ローラ及び感光体上のフィルミングを観察することにより、耐フィルミング性を評価した。なお、全くフィルミングが発生していないものを◎、うっすらとフィルミングの発生を確認できるものを○、スジ状にフィルミングが発生しているものを△、全面にフィルミングが発生しているものを×として、判定した。
＜粒径の測定法＞
重量平均粒径及び個数平均粒径は、コールターカウンター法による粒度分布測定装置コールターカウンターＴＡ−ＩＩ、コールターマルチサイザーＩＩ（以上、コールター社製）を用いて、測定した。まず、電解液１００〜１５０ｍｌ中に、分散剤として、界面活性剤のアルキルベンゼンスルホン酸塩０．１〜５ｍｌ加えた。ここで、電解液とは、約１重量％の１級塩化ナトリウムの水溶液であり、ＩＳＯＴＯＮ−ＩＩ（コールター社製）を使用した。次に、測定試料を２〜２０ｍｇ加え、超音波分散器で約１〜３分間分散処理を行い、１００μｍのアパーチャーを用いて、粒子の体積及び個数を測定することにより、体積分布及び個数分布を算出し、重量平均粒径及び個数平均粒径を求めた。なお、チャンネルとしては、２．００μｍ以上２．５２μｍ未満、２．５２μｍ以上３．１７μｍ未満、３．１７μｍ以上４．００μｍ未満、４．００μｍ以上５．０４μｍ未満、５．０４μｍ以上６．３５μｍ未満、６．３５μｍ以上８．００μｍ未満、８．００μｍ以上１０．０８μｍ未満、１０．０８μｍ以上１２．７０μｍ未満、１２．７０μｍ以上１６．００μｍ未満、１６．００μｍ以上２０．２０μｍ未満、２０．２０μｍ以上２５．４０μｍ未満、２５．４０μｍ以上３２．００μｍ未満及び３２．００μｍ以上４０．３０μｍ未満の１３チャンネルを使用し、粒径が２．００μｍ以上４０．３０μｍ未満の粒子を測定対象とした。
＜分子量の測定法＞
樹脂の数平均分子量、重量平均分子量は、ＧＰＣ（ｇｅｌ ｐｅｒｍｅａｔｉｏｎ ｃｈｒｏｍａｔｏｇｒａｐｈｙ）を用いて測定した。具体的には、０．０５〜０．６重量％の試料を０．１ｍｌ注入し、測定温度を４０℃とし、流速を１．０ｍｌ／分として、測定した。なお、ＧＰＣ測定装置としては、ＧＰＣ−１５０Ｃ（ウォーターズ社製）、カラムとしては、ＫＦ８０１〜８０７（ショウデックス社製）、溶媒としては、ＴＨＦ（テトラヒドロフラン）を用いた。以上の条件で測定された樹脂の分子量分布と、単分散ポリスチレン標準試料により作成した分子量校正曲線を使用して、樹脂の数平均分子量、重量平均分子量を算出した。
＜シラノール基の含有量の測定方法＞
シラノール基の含有量は、日本工業規格（ＪＩＳ）Ｋ００６８「化学製品の水分測定法」に記載されているカールフィッシャー（Ｋａｒｌ−Ｆｉｓｃｈｅｒ）滴定法を用いて測定した。なお、試料量や滴定溶媒の調整等も全てこれに準ずる。具体的には、メタノール−クロロホルム混合溶媒を用いて、シラノール基と水の含有量を測定した後に、ピリジン−エチレングリコール混合溶媒を用いて、水の含有量を測定した。これらの差からシラノール基の含有量が求められる。
＜ガラス転移温度の測定法＞
ガラス転移温度を測定する装置としては、ＴＧ−ＤＳＣシステムＴＡＳ−１００（理学電機社製）を使用した。まず、試料約１０ｍｇをアルミ製試料容器に入れ、それをホルダユニットにのせ、電気炉中にセットする。次に、室温から昇温速度１０℃／分で１５０℃まで加熱した後、１５０℃で１０分間放置し、室温まで冷却して１０分間放置した。さらに、窒素雰囲気下で昇温速度１０℃／分で１５０℃まで再度加熱してＤＳＣ測定を行った。ガラス転移温度は、ＴＡＳ−１００システム中の解析システムを用いて、ガラス転移温度近傍の吸熱カーブの接線とベースラインとの接点から算出した。
＜平均円形度の測定法＞
平均円形度を測定する装置としては、フロー式粒子像分析装置ＦＰＩＡ−２０００（東亜医用電子社製）を用いた。まず、フィルターを通して微細なごみを取り除き、１０^−３ｃｍ^３の水中に、円相当径０．６０μｍ以上１５９．２１μｍ未満の粒子数が２０個以下の水１０ｍｌ中にノニオン系界面活性剤コンタミノンＮ（和光純薬社製）を数滴加えた。さらに、測定試料を５ｍｇ加え、超音波分散器ＵＨ−５０（ＳＴＭ社製）を用いて、２０ｋＨｚ、５０Ｗ／１０ｃｍ^３の条件で１分間分散処理を行った後、合計５分間の分散処理を行った。得られた測定試料の円相当径範囲内の粒子の濃度が４０００〜８０００個／１０^−３ｃｍ^３の試料分散液を用いて、０．６０〜１５９．２１μｍの円相当径を有する粒子の粒度分布を測定した。

<Image density>
After outputting a solid image with a low adhesion amount of 0.3 ± 0.1 mg / cm ^{2 on} plain paper transfer paper type 6200 (manufactured by Ricoh), the image density was measured by X-Rite (manufactured by X-Rite). The image density was evaluated by measuring. In addition, it judged as (circle), that whose image density is 1.4 or more, (triangle | delta) for what is 1.35 or more and less than 1.4, and x which is less than 1.35.
<Cleanability>
The transfer residual toner on the photosensitive member that has passed through the cleaning process after outputting 1,000 charts with an image area ratio of 95% is transferred to white paper with Scotch tape (manufactured by Sumitomo 3M), and is transferred to a Macbeth reflection densitometer RD514 type. The cleaning property was evaluated by measuring. In addition, it is (double-circle) what is the difference with a blank less than 0.005, (circle), 0.005 or more and less than 0.01, (triangle | delta) which is 0.01 or more and less than 0.02, 0.02 or more. Some were judged as x.
<Transferability>
After transferring the chart with an image area ratio of 20% from the photoconductor to the paper, the transfer residual toner on the photoconductor immediately before cleaning is transferred to a white paper with a scotch tape, and measured with a Macbeth reflection densitometer RD514 type The transferability was evaluated. In addition, it is (double-circle) what is the difference with a blank less than 0.005, (circle), 0.005 or more and less than 0.01, (triangle | delta) which is 0.01 or more and less than 0.02, 0.02 or more. Some were judged as x.
<Toner scattering>
In an environment of 40 ° C. and 90% RH, an image forming apparatus IPSiO Color 8100 (manufactured by Ricoh) was remodeled into an oil-less fixing method and tuned, and a chart with an image area ratio of 5% was continuously displayed for 100,000. The toner scattering was evaluated by visually observing the state of contamination by the toner in the image forming apparatus after the durability test for sheet output. In addition, the toner stains are not observed at all, and those in a good state are marked with ◎, the stains are slightly observed with ○, those with no problem are marked with ○, and those with slight stains observed with Δ, Judgment was made as x where there was a very dirty and problematic.
<Charging stability>
Durability test that continuously outputs 100,000 character image patterns with an image area ratio of 12% is carried out, a small amount of developer is collected from the sleeve, and the change in charge amount is measured by the blow-off method. evaluated. The case where the change in the charge amount was less than 5 μC / g was evaluated as ◯, the case where the change was 5 μC / g or more and less than 10 μC / g was evaluated as Δ, and the case where it was 10 μC / g or more was evaluated as x.
<Film resistance>
Filming resistance was evaluated by observing the filming on the developing roller and the photoconductor after outputting 1,000 band charts with image area ratios of 100%, 75%, and 50%. It should be noted that the filming does not occur at all, ◎, the filming that can be confirmed a little filming, ◯ that the filming is streaked △, filming has occurred on the entire surface The thing was judged as x.
<Measuring method of particle size>
The weight average particle size and the number average particle size were measured using a particle size distribution measuring device Coulter Counter TA-II and Coulter Multisizer II (manufactured by Coulter, Inc.) by a Coulter counter method. First, 0.1 to 5 ml of a surfactant alkylbenzene sulfonate was added as a dispersant to 100 to 150 ml of the electrolytic solution. Here, the electrolytic solution is an aqueous solution of about 1% by weight of primary sodium chloride, and ISOTON-II (manufactured by Coulter, Inc.) was used. Next, 2 to 20 mg of a measurement sample is added, the dispersion treatment is performed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number distribution of particles are measured by measuring the volume and number of particles using a 100 μm aperture. The weight average particle diameter and the number average particle diameter were calculated. The channel is 2.00 μm or more and less than 2.52 μm, 2.52 μm or more and less than 3.17 μm, 3.17 μm or more and less than 4.00 μm, 4.00 μm or more and less than 5.04 μm, 5.04 μm or more and less than 6.35 μm. 6.35 μm to less than 8.00 μm, 8.00 μm to less than 10.08 μm, 10.08 μm to less than 12.70 μm, 12.70 μm to less than 16.00 μm, 16.00 μm to less than 20.20 μm, 20.20 μm or more 13 channels of less than 25.40 μm, 25.40 μm or more and less than 32.00 μm and 32.00 μm or more and less than 40.30 μm were used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm were measured.
<Measurement method of molecular weight>
The number average molecular weight and weight average molecular weight of the resin were measured using GPC (gel permeation chromatography). Specifically, 0.1 ml of a 0.05 to 0.6% by weight sample was injected, the measurement temperature was 40 ° C., and the flow rate was 1.0 ml / min. Note that GPC-150C (manufactured by Waters) was used as the GPC measuring apparatus, KF801-807 (manufactured by Shodex) was used as the column, and THF (tetrahydrofuran) was used as the solvent. The number average molecular weight and the weight average molecular weight of the resin were calculated using the molecular weight distribution of the resin measured under the above conditions and the molecular weight calibration curve prepared from the monodisperse polystyrene standard sample.
<Method for measuring content of silanol group>
The content of the silanol group was measured using a Karl-Fischer titration method described in Japanese Industrial Standard (JIS) K0068 “Method of Measuring Moisture of Chemical Products”. In addition, all adjustments of sample amount and titration solvent, etc. are based on this. Specifically, after measuring the content of silanol groups and water using a methanol-chloroform mixed solvent, the content of water was measured using a pyridine-ethylene glycol mixed solvent. From these differences, the silanol group content is determined.
<Measuring method of glass transition temperature>
As an apparatus for measuring the glass transition temperature, a TG-DSC system TAS-100 (manufactured by Rigaku Corporation) was used. First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. Next, after heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the mixture was left at 150 ° C. for 10 minutes, cooled to room temperature, and left for 10 minutes. Further, DSC measurement was performed by heating again to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. The glass transition temperature was calculated from the contact point between the tangent line and the base line of the endothermic curve near the glass transition temperature using an analysis system in the TAS-100 system.
<Measuring method of average circularity>
As an apparatus for measuring the average circularity, a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.) was used. First, fine dust is removed through a filter, and nonionic surfactant Contaminone N (in 10 ^-3 cm ³ of water having 10 or less particles with an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is 20 or less. A few drops of Wako Pure Chemical Industries, Ltd.) were added. Further, 5 mg of a measurement sample was added, and after performing a dispersion treatment for 1 minute under the conditions of 20 kHz and 50 W / 10 cm ³ using an ultrasonic dispersing device UH-50 (manufactured by STM), a dispersion treatment was performed for a total of 5 minutes. It was. The particle size of particles having an equivalent circle diameter of 0.60 to 159.21 μm using a sample dispersion having a concentration of particles in the equivalent circle diameter range of the obtained measurement sample of 4000 to 8000 pieces / 10 ⁻³ cm ^3. Distribution was measured.

  The sample dispersion is passed through a flow path extending along the flow direction of a flat and flat transparent flow cell having a thickness of about 200 μm. In order to form an optical path that crosses and passes through the thickness direction of the flow cell, a strobe and a CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area can be calculated as the equivalent circle diameter. Thereby, the equivalent circle diameter of 1200 or more particles can be measured in about 1 minute, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter are measured. Can do. The result can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (30 channels for one octave). In the actual measurement, particles were measured in the range where the equivalent circle diameter was 0.60 to 159.21 μm.

It is a figure which shows an example of the process cartridge of this invention. It is a figure which shows an example of the image forming apparatus used by this invention. It is a figure which shows the other example of the image forming apparatus used by this invention. It is a figure which shows the other example of the image forming apparatus used by this invention. FIG. 5 is a partially enlarged view of the image forming apparatus in FIG. 4. 2 is a diagram illustrating an apparatus used when toner is manufactured in Embodiment 1. FIG. 6 is a diagram illustrating an apparatus used when manufacturing toner in Example 2. FIG. 6 is a diagram illustrating an apparatus used when toner is manufactured in Example 3. FIG. FIG. 6 is a diagram illustrating an apparatus used when manufacturing toner in Example 4.

Explanation of symbols

10, 10K, 10Y, 10M, 10C Photoconductors 14, 15, 16 Support roller 17 Cleaning device 18 Image forming unit 20 Charging device 22 Secondary transfer device 23 Support roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure Roller 28 Reversing device 30 Exposure device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K, 42Y, 42M, 42C Developer accommodating portion 43K, 43Y, 43M, 43C Developer supply roller 44K, 44Y, 44M, 44C Development roller 45K, 45Y, 45M, 45C Development unit 49 Registration roller 50 Intermediate transfer member 51 Support roller 52 Separating roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona charger 60 Cleaning device 61 Development device 62 Transfer charger 70 Static elimination device 80 Transfer roller 90 Cleaning device 95 Transfer target 120 Image forming means 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation Roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Claims (22)

And a step of forming a coating layer on the surface of the toner base particles using a fluid in which a silicone resin that is solid at least at normal temperature and pressure is dissolved in at least one of a supercritical fluid and a subcritical fluid. Toner manufacturing method.   2. The binder resin constituting the toner base particles is insoluble in at least one of the supercritical fluid and subcritical fluid in a fluid in which at least a silicone resin is dissolved. Toner production method.   3. The coating layer according to claim 1, wherein the coating layer is formed by spraying at least one of the supercritical fluid and the subcritical fluid on a base particle of the toner with a fluid in which at least a silicone resin is dissolved. A method for producing the toner according to the description.   Forming at least one of the supercritical fluid and the subcritical fluid with a fluid in which at least a silicone resin is dissolved and the base particles of the toner, and then releasing the pressure and rapidly expanding to form the coating layer. The method for producing a toner according to claim 1, wherein the toner is a toner.   The coating layer is formed by changing at least one of pressure and temperature after mixing at least one of the supercritical fluid and subcritical fluid with at least a silicone resin-dissolved fluid and the toner base particles. The method for producing a toner according to claim 1, wherein the toner is a toner.   The method for producing a toner according to claim 1, wherein at least one of the supercritical fluid and the subcritical fluid contains carbon dioxide.   The method for producing a toner according to claim 1, wherein at least one of the supercritical fluid and the subcritical fluid contains an entrainer.   The toner according to claim 7, wherein a ratio of the weight of the entrainer to the total weight of at least one of the supercritical fluid and the subcritical fluid and the entrainer is 0.1% or more and 10% or less. Manufacturing method.   9. The method for producing a toner according to claim 7, wherein the entrainer is a poor solvent for the toner base particles and the silicone resin under normal temperature and pressure.   The method for producing a toner according to claim 7, wherein the entrainer is at least one of methanol, ethanol, and propanol. The silicone resin has a general formula

Having a structure represented by
The method for producing a toner according to claim 1, wherein R is a hydrogen atom, a hydroxyl group, an alkoxyl group, an alkyl group, or an aryl group. The content of silanol groups of the silicone resin, method for producing a toner according to any one of claims 1 to 11, characterized in that at most 10% by weight 0.1% by weight or more. The weight average molecular weight of the silicone resin, method for producing a toner according to any one of claims 1 to 12, characterized in that 500 to 100,000. Toner characterized in that it is manufactured using the method for producing a toner according to any one of claims 1 to 13. The toner according to claim 14 , wherein the toner has a weight average particle diameter of 3 μm or more and 8 μm or less. A developer comprising the toner according to claim 14 or 15 . The developer according to claim 16 , further comprising a carrier. A step of developing an electrostatic latent image formed on a photoreceptor using the developer according to claim 16 or 17 ,
A step of transferring a visible image developed with the developer onto a transfer target; and a step of heat-pressing and fixing the visible image transferred onto the transfer target using a fixing device. Image forming method. The image forming method according to claim 18 , wherein the photoconductor is an organic photoconductor or an amorphous silicon photoconductor. The fixing device includes a heating body provided with a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film,
20. The image forming method according to claim 18 or 19 , wherein the image-transferred member to which the visible image has been transferred is passed between the film and the pressure member so as to perform heat and pressure fixing. Wherein when developing the electrostatic latent image formed on the photosensitive member, an image forming method according to any one of claims 18 to 20, characterized in that applying an alternating electric field. A process cartridge, wherein claim 16 or a developing device and a photoreceptor having a developer according to 17 at least are integrally supported, is detachable to the image forming apparatus main body.

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