Image formation methods

Abstract

To provide an image formation method which can suppress image deletion in a high-humidity environment even when using an electrostatic charge image carrier using amorphous silicon in a photosensitive layer and stably obtain a high-quality image after durable printing for a long period of time.SOLUTION: An image formation method comprises: an electrification step of electrifying an electrostatic charge image carrier with an electrification member; an electrostatic latent image formation step of forming an electrostatic latent image on the electrified electrostatic charge image carrier; a development step of forming a toner image on the electrostatic charge image carrier by performing development using toner; a transfer step of transferring the toner image onto a recording medium; a fixation step of fixing the toner image transferred onto the recording medium to the recording medium; and a cleaning step of removing transfer residual toner left on the surface of the electrostatic charge image carrier after the transfer step using a cleaning blade. A photosensitive layer of the electrostatic charge image carrier contains amorphous silicon. A surface layer of the electrostatic charge image carrier contains amorphous silicon carbide or amorphous carbon. The toner contains toner particles, silica particles and organic silicon polymer particles.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an image forming method using a toner used in an electrophotographic system. [Background technology]

[0002] In recent years, as electrophotographic full-color copying machines have become more widespread, there has been an increasing demand for image forming apparatuses that can produce high-quality images over a long period of time. At the same time, there has also been an increasing demand for longer-lasting consumable parts in order to reduce the frequency of maintenance and lower running costs. As an electrophotographic photoreceptor for achieving high image quality, high speed, and long life, an electrophotographic device using a photoreceptor with amorphous silicon in the photosensitive layer (hereinafter abbreviated as a-Si photoreceptor) is known. In image forming devices using such a-Si photoreceptors, image defects such as blurred characters or blank spaces where characters are not printed may occur in high-humidity environments. These image defects will be referred to as "image deletion" below. There are various causes of image deletion, but one known cause is that when the photosensitive member is charged, discharge products are generated, and when these discharge products adsorb moisture, the resistance of the photosensitive member surface decreases, disrupting the latent image charge on the photosensitive member surface. Two main methods have been considered to suppress image deletion. One method involves heating the photoreceptor to reduce or remove moisture adsorbed on the surface of the photoreceptor. Various methods are known for heating the photoreceptor. For example, Patent Document 1 describes a method in which a heater is provided outside the photoreceptor to heat the photoreceptor from the outside. Another approach being considered is to use an abrasive, which has the effect of scraping off the generated discharge products, as an external additive to the toner. Patent Document 2 describes a toner in which specific inorganic fine particles, which are perovskite crystals with a cubic or rectangular parallelepiped shape, are used as an external additive to the toner and as an abrasive for the photoreceptor. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-15759 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-285145 Summary of the Invention [Problem to be solved by the invention]

[0004] The method described in Patent Document 1 has the problem that it leads to an increase in the size of the image forming apparatus and requires power consumption for heating. On the other hand, the a-Si photoconductor described in Patent Document 2 has a harder surface than organic photoconductors, making it difficult to scrape off discharge products. As a result, its effectiveness against image deletion was completely insufficient. It also had the drawback of reducing the fluidity and charging properties of the toner, making it difficult to obtain high-quality images. The present invention provides an image forming method that solves the above-mentioned problems. Specifically, it aims to provide an image forming method that suppresses image deletion in a high-humidity environment and that can stably obtain high-quality images even after long-term endurance printing, even when a photoreceptor using amorphous silicon in the photosensitive layer is used. [Means for solving the problem]

[0005] The present invention includes a charging step of charging an electrostatic image bearing member with a charging member, an electrostatic latent image forming step of forming an electrostatic latent image on the charged electrostatic image bearing member, and a developing step of developing the electrostatic image bearing member with a toner to form a toner image on the electrostatic image bearing member. a transfer step of transferring the toner image onto a recording medium; a fixing step of fixing the toner image transferred onto the recording medium; a cleaning step of removing residual toner remaining on the surface of the electrostatic image bearing member after the transfer step using a cleaning blade; An image forming method comprising: the photosensitive layer of the electrostatic image bearing member contains amorphous silicon; the surface layer of the electrostatic image bearing member contains amorphous silicon carbide or amorphous carbon; The toner comprises toner particles, silica particles, and organosilicon polymer particles. death, When the toner is subjected to a water washing treatment, the amount of the organosilicon polymer particles that migrate from the toner is A (mass %), and the amount of the silica particles that migrate from the toner is B (mass %), based on the mass of the toner. When A and B are: 0.50≦A+B≦4.00 0.20≦B / A≦2.00 Fulfilling the number average diameter Da of the primary particles of the migrated organosilicon polymer particles is 50 nm or more and 200 nm or less; the number average particle diameter Db of the primary particles of the transferred silica particles is 50 nm or more and 200 nm or less; is The image forming method is characterized by the above. [Effects of the Invention]

[0006] According to the present invention, even when a photoreceptor using amorphous silicon is used in the photosensitive layer of an electrostatic image carrier, it is possible to provide an image forming method that suppresses image deletion in a high-humidity environment and that can stably obtain high-quality images even after long-term endurance printing. [Brief explanation of the drawings]

[0007] [Figure 1] This is an example of the image forming method of the present invention. [Figure 2] 1 is an example of a layer structure of an amorphous silicon photosensitive member of an electrostatic image bearing member of the present invention. [Figure 3] 1 is an example of a film forming apparatus for a photoreceptor according to the present invention. [Figure 4] FIG. 2 is an enlarged view of a nip portion between the cleaning blade of the present invention and the electrostatic image bearing member. DETAILED DESCRIPTION OF THE INVENTION

[0008] In the present invention, unless otherwise specified, the expressions "xx or more and xx or less" and "xx to xx" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints.

[0009] According to the inventors' investigations, in order to stably prevent toner slip-through in a blade cleaning method, it is necessary to form a blocking layer of external additives near the cleaning blade nip. The properties of the external additives are important for stably forming this blocking layer. External additives with too high slipperiness move too quickly, making it difficult to form a stable blocking layer. The inventors believe that the cohesion properties that suppress the mutual movement of external additives when they come together are important for forming a stable external additive blocking layer.

[0010] In order to prevent image deletion in high-temperature, high-humidity environments without using conventional abrasives, we thought it would be sufficient to scrape off discharge products using a blocking layer made of external additives. In this case, the external additive blocking layer is required to have stability that prevents toner from slipping through, as well as abrasiveness that can scrape off discharge products.

[0011] The present inventors have discovered that in an image forming method using an a-Si photoreceptor, image deletion can be specifically suppressed when silica fine particles and an organosilicon polymer are mixed in the external additive blocking layer near the cleaning blade nip, leading to the present invention.

[0012] That is, the present invention provides a method for producing an electrostatic latent image by a charging step of charging an electrostatic image carrier with a charging member, an electrostatic latent image forming step of forming an electrostatic latent image on the charged electrostatic image carrier, and a developing step of developing an electrostatic latent image on the electrostatic image carrier with a toner, a transfer step of transferring the toner image onto a recording medium; a fixing step of fixing the toner image transferred onto the recording medium; a cleaning step of removing residual toner remaining on the surface of the electrostatic image bearing member after the transfer step using a cleaning blade; An image forming method comprising: the photosensitive layer of the electrostatic image bearing member contains amorphous silicon; the surface layer of the electrostatic image bearing member contains amorphous silicon carbide or amorphous carbon; The toner is an image forming method characterized by having toner particles, silica particles, and organosilicon polymer particles.

[0013] The organosilicon polymer particles used in this invention have a lower Young's modulus than a-Si photoreceptors and silica microparticles, and are therefore more susceptible to deformation under external force.When organosilicon polymer microparticles with these properties are present in the external additive blocking layer, it is believed that the pressure applied by the cleaning blade causes the organosilicon polymer microparticles in the blocking layer to deform, increasing the density of the blocking layer.As a result, the density of the external additive blocking layer increases, and the deformation energy of the organosilicon polymer particles is converted into energy for scraping off discharge products, so the scraping effect of discharge products is dramatically improved compared to when the external additive blocking layer is made of silica particles alone, and it is believed that this is how the effects of this invention are achieved.On the other hand, if the external additive blocking layer is made of organosilicon polymer particles alone, the particles do not have high slip properties and a stable blocking layer is not formed, and the effect is not achieved.

[0014] An example of an embodiment of the present invention will be described below.

[0015] 《Image forming method》 An example of an image forming apparatus according to the present invention is shown in Fig. 1. The figure is a vertical cross-sectional view showing the schematic configuration of a digital copying machine.

[0016] The copying machine shown in FIG. 1 has a drum-shaped electrophotographic photosensitive member 101 as an electrostatic image carrier. This photosensitive member 101 is driven to rotate in the direction of the arrow by a driving means (not shown). Around the photosensitive member 101, and arranged in approximately the same order along the direction of rotation, are a charging roller 102 as a primary charging means, an exposure means 103, a developing unit 104, a transfer charger 105, and a cleaning device 107 equipped with a cleaning blade. Furthermore, a fixing unit 106 is arranged downstream (on the left side in the figure) of the transfer charger 105 in the transport direction (direction of the arrow) of a transfer material 108 as a recording medium.

[0017] The surface of the photoreceptor 101 is charged by a charging roller 102. Next, a laser beam emitted from an exposure means 103 removes the charge from the laser beam irradiated portion, forming an electrostatic latent image. The electrostatic latent image on the photoreceptor 101 is developed with charged toner in a developing device 104. The developed toner image on the photoreceptor 101 is transferred by a transfer charger 105 to a transfer material 111 being transported in the direction of the arrow. After the toner image has been transferred in the transfer section, the transfer material 111 is transported to a fixing device 106, where it is heated and pressed to fix the toner image to the surface. Residual toner remaining on the photoreceptor after transfer is collected by a cleaning device 107.

[0018] <Electrostatic image carrier> First, the layer structure of the photosensitive member, which is an electrostatic image bearing member to which the present invention is applied, will be described.

[0019] 2(A) is a schematic diagram showing the layer structure of an a-Si photoconductor. A voltage-resistant layer 201, a charge injection blocking layer 202, a photosensitive layer 203, and a surface layer 204 are sequentially stacked on a substrate 200. This layer structure is mainly applied to a-Si photoconductors for positive charging.

[0020] 2(B) is a schematic diagram showing the layer structure of an a-Si photoreceptor in which an intermediate layer 205 is provided between a photosensitive layer 203 and a surface layer 204. By imparting charge blocking capability to the intermediate layer 205, it can also be used as a negatively charged a-Si photoreceptor.

[0021] 2(C) is a schematic diagram of the layer structure of an a-Si photoconductor in which multiple intermediate layers 206 are provided between the photosensitive layer 203 and the surface layer 204. This structure can also be applied to a negatively charged a-Si photoconductor by imparting charge blocking capability to one of the multiple intermediate layers 206.

[0022] 2(D) is a schematic diagram of the layer structure of an a-Si photosensitive member in which a change layer 207 is provided between the photosensitive layer 203 and the surface layer 204. This structure can also be applied to a negatively charged a-Si photosensitive member by imparting charge blocking capability to a portion of the change layer 207.

[0023] Next, each layer and substrate constituting the photoreceptor having the above-described layer structure will be described.

[0024] The electrostatic image carrier of the present invention has a photosensitive layer made of amorphous silicon formed on a drum-shaped conductive substrate. The photosensitive layer made of amorphous silicon can be formed by a vapor phase growth method such as glow discharge decomposition, sputtering, ECR, plasma CVD, vapor deposition, or ion plating. When forming the photosensitive layer made of amorphous silicon, hydrogen or a halogen element can be incorporated into the photosensitive layer.

[0025] In the present invention, it is preferable to incorporate atoms for controlling conductivity into the photosensitive layer as needed. Examples of atoms for controlling conductivity include so-called impurities in the semiconductor field. That is, atoms belonging to Group 13 of the periodic table that provide p-type conductivity or atoms belonging to Group 15 of the periodic table that provide n-type conductivity can be used. Among the atoms belonging to Group 13 of the periodic table, boron atoms (B), aluminum atoms (Al), and gallium atoms (Ga) are preferred. Among the atoms belonging to Group 15 of the periodic table, phosphorus atoms (P) and arsenic atoms (As) are preferred.

[0026] The content of atoms for controlling conductivity contained in the photosensitive layer is 1 × 10 relative to silicon atoms (Si). -2 It is preferably 1×10 atomic ppm or more, while it is preferably 1×10 atomic ppm or less.

[0027] The electrostatic image carrier of the present invention is characterized in that a surface layer is provided on the photosensitive layer, and the surface layer is made of amorphous silicon carbide or amorphous carbon. From the viewpoints of lubricity with the external additive blocking layer containing organosilicon polymer particles and ease of scraping off discharge products adhering to the surface, amorphous carbon is more preferred.

[0028] The photosensitive layer may be formed on a carrier blocking layer formed on a conductive substrate.

[0029] When a carrier blocking layer is provided, during development, the injection of carriers into the photosensitive layer made of amorphous silicon is blocked, and the electrostatic contrast between the exposed part and the unexposed part is enhanced, thereby improving the density of the image and reducing the background fog. Examples of the material for the carrier blocking layer include inorganic insulating materials such as amorphous silicon carbide, amorphous silicon oxide, amorphous silicon nitride, and amorphous silicon oxynitride, and organic insulating materials such as polyethylene terephthalate, polytetrafluoroethylene, polyimide, ethylene-propylene fluoride copolymer, polyurethane, epoxy resin, polyester, and polycarbonate.

[0030] <Manufacturing Method of a-Si Photoconductor> The manufacturing method of the a-Si photoconductor may be any method as long as it can form a layer satisfying the above-mentioned conditions. Specifically, examples include the plasma CVD method, vacuum evaporation method, sputtering method, ion plating method, etc. Among these, the plasma CVD method is preferable in terms of ease of raw material supply and the like.

[0031] Hereinafter, a manufacturing apparatus and a manufacturing method using the plasma CVD method will be described.

[0032] FIG. 3 is a diagram schematically showing an example of a deposition apparatus for an electrophotographic photoreceptor by an RF plasma CVD method using a high-frequency power source for manufacturing the a-Si photoreceptor of the present invention.

[0033] This deposition apparatus is roughly composed of a deposition apparatus 3100 having a reaction vessel 3110, a raw material gas supply apparatus 3200, and an exhaust apparatus (not shown) for reducing the pressure inside the reaction vessel 3110.

[0034] Inside the reaction vessel 3110 in the deposition apparatus 3100, a substrate 3112 connected to the ground, a substrate heating heater 3, and a raw material gas introduction pipe 3114 are installed. Further, a high-frequency power source 3120 is connected to the cathode electrode 3111 via a high-frequency matching box 3115.

[0035] The source gas supply device 3200 is composed of source gas cylinders 3221 to 3227, valves 3231 to 3237, pressure regulators 3261 to 3267, inlet valves 3241 to 3247, and outlet valves 3251 to 3257. It also has mass flow controllers 3211 to 3217. The gas cylinders containing the respective source gases are connected to source gas inlet pipes 3114 in the reaction vessel 3110 via auxiliary valves 3260. 3116 is a gas pipe, 3117 is a leak valve, and 3121 is an insulating material.

[0036] Next, a method for forming a deposited film using this apparatus will be described. First, a substrate 3112 that has been degreased and cleaned in advance is placed in the reaction vessel 3110 via a receiving stand 3123. Next, an exhaust device (not shown) is operated to evacuate the reaction vessel 3110. While watching the display of the vacuum gauge 3119, when the pressure inside the reaction vessel 3110 reaches a predetermined pressure, for example, 1 Pa or less, power is supplied to the substrate heater 3113, and the substrate 3112 is heated to a predetermined temperature, for example, 50 to 350°C. At this time, an inert gas such as Ar or He can be supplied to the reaction vessel 3110 from the gas supply device 3200, and heating can also be performed in an inert gas atmosphere.

[0037] Next, gas used for forming the deposited film is supplied to the reaction vessel 3110 from the gas supply device 3200. That is, valves 3231 to 3237, inlet valves 3241 to 3247, and outlet valves 3251 to 3257 are opened as necessary, and the flow rates are set in the mass flow controllers 3211 to 3217. Once the flow rates of the mass flow controllers have stabilized, the main valve 3118 is operated while watching the display of the vacuum gauge 3119, and the pressure inside the reaction vessel 3110 is adjusted to the desired pressure. Once the desired pressure is obtained, high-frequency power is applied from the high-frequency power supply 3120, and at the same time, the high-frequency matching box 3115 is operated to generate plasma discharge inside the reaction vessel 3110. Thereafter, the high-frequency power is quickly adjusted to the desired power, and the deposition film is formed.

[0038] When the formation of a predetermined deposited film is completed, the application of high frequency power is stopped, and the valves 3231 to 3237, inlet valves 3241 to 3247, outlet valves 3251 to 3257, and auxiliary valve 3260 are closed to terminate the supply of source gas. At the same time, the main valve 3118 is fully opened, and the inside of the reaction vessel 3110 is evacuated to a pressure of 1 Pa or less.

[0039] This completes the formation of the deposited film, but if multiple deposited films are to be formed, the above procedure can be repeated to form each layer. The bonded region can also be formed by changing the source gas flow rate, pressure, etc. to the conditions for forming the photosensitive layer over a certain period of time.

[0040] After all the deposition films have been formed, the main valve 3118 is closed, an inert gas is introduced into the reaction vessel 3110 to return the pressure to atmospheric pressure, and then the substrate 3112 is taken out.

[0041] In forming the voltage-resistant layer, silanes such as silane (SiH4) and disilane (Si2H6) can be suitably used as the source gas for supplying silicon atoms. Furthermore, ammonia (NH3) and nitrogen (N2) can be suitably used as the source gas for supplying nitrogen atoms. Furthermore, in addition to the above-mentioned source gases, oxygen (O2) and nitric oxide (NO) can be suitably used as the source gas for supplying oxygen atoms. Furthermore, in addition to the above-mentioned source gases, hydrogen (H2) can be suitably used as the source gas for supplying hydrogen atoms. Furthermore, when carbon atoms or the like are contained in the charge injection blocking layer to improve adhesion to the conductive substrate, a gaseous or easily gasifiable substance containing the atoms to be contained can be used as the material.

[0042] Similarly, when forming the charge injection blocking layer, silanes such as silane (SiH4) and disilane (Si2H6) can be suitably used as a source gas for supplying silicon atoms. Furthermore, diborane (B2H6), for example, can be suitably used as a source gas for supplying Group 13 atoms. Furthermore, in addition to the above-mentioned source gases, hydrogen (H2) can also be suitably used as a source gas for supplying hydrogen atoms. Furthermore, when carbon atoms, oxygen atoms, nitrogen atoms, etc. are to be contained in the charge injection blocking layer to improve adhesion with the voltage-resistant layer, a gaseous or easily gasifiable substance containing the respective atoms can be used as the material.

[0043] Similarly, when forming the photosensitive layer, silanes such as silane (SiH4) and disilane (Si2H6) can be suitably used as a source gas for supplying silicon atoms. Furthermore, in addition to the above-mentioned silanes, hydrogen (H2) can also be suitably used as a source gas for supplying hydrogen atoms. Furthermore, when the photosensitive layer contains the above-mentioned halogen atoms, atoms for controlling conductivity, carbon atoms, oxygen atoms, nitrogen atoms, or the like, a gaseous or easily gasifiable substance containing the respective atoms can be used as the material.

[0044] When amorphous silicon carbide is formed as the surface layer, silanes such as silane (SiH4) and disilane (Si2H6) can be suitably used as the source gas for supplying silicon atoms. Furthermore, gases such as methane (CH4) and acetylene (C2H2) can be suitably used as the source gas for supplying carbon atoms. The C / (Si+C) of amorphous silicon carbide can be adjusted by adjusting the mixing ratio of these source gases. On the other hand, when amorphous carbon is formed as the surface layer, gases such as methane (CH4) and acetylene (C2H2) can be suitably used as the source gas for supplying carbon atoms. For either material, hydrogen (H2) can also be suitably used as the source gas for supplying hydrogen atoms.

[0045] <Cleaning blade> In the present invention, the cleaning method for cleaning the toner on the electrophotographic photosensitive member is a cleaning blade method, in which a blade-shaped cleaning member made of an elastic material is pressed against the photosensitive member to catch and collect the residual toner, etc., on the photosensitive member.

[0046] 4, the external additive blocking layer 404, which is formed mainly by the migration of external additive particles contained in the toner, has the effect of scraping off discharge products that have adhered to the surface of the photoreceptor. The external additive blocking layer 404 is also important in preventing toner 403 and maintaining the lubrication between the cleaning blade 402 and the photoreceptor 401, thereby preventing toner from slipping through.

[0047] In order to realize the effect of scraping off discharge products by the external additive blocking layer, it is important that the toner has the characteristics described below.

[0048] Rubber materials are suitable for cleaning blades because they conform well to the photoreceptor surface and are less likely to scratch it. Among these, polyurethane rubber is the most suitable from both a physical and chemical standpoint, and the rubber hardness should preferably be between 60 and 90 degrees on the International Rubber Hardness Scale (IRHD).

[0049] "toner" The toner of the present invention is characterized by having toner particles, silica particles, and organosilicon polymer particles.

[0050] The number-average diameter Da of the primary particles of the organosilicon polymer particles and the number-average diameter Db of the primary particles of the silica particles are preferably in the range of 40 nm to 300 nm. A diameter of 40 nm or greater reduces the percentage of particles that slip through the cleaning blade, making it easier to form a stable blocking layer. A diameter of 300 nm or less makes it easier to apply the particles uniformly to the toner surface, making it easier to achieve good durability and stability.

[0051] It is even more preferable that both Da and Db are in the range of 50 nm to 200 nm. In this range, the particle sizes of the organosilicon polymer particles and silica particles in the external additive blocking layer are close to each other, increasing the probability of contact between the two particles. This increases the density and deformation energy of the external additive blocking layer, improving the scraping effect of discharge products and improving the suppression of image deletion.

[0052] The Young's modulus Ea of the organosilicon polymer particles is preferably in the range of 1.0 GPa to 30.0 GPa. This range increases the bulk density of the external additive blocking layer in the cleaning blade nip, making it easier to scrape off discharge products. The Young's modulus of the organosilicon polymer particles can be controlled by changing the structure of the functional groups bonded to Si in the constituent compounds. Specifically, this can be controlled by changing the abundance ratio of the constituent compounds: M unit structure (S1), D unit structure (S2), T unit structure (S3), and Q unit structure (S4).

[0053] [ka]

[0054] [ka]

[0055] [ka]

[0056] [ka]

[0057] The Young's modulus Eb of the silica particles and the Young's modulus Ea of the organosilicon polymer particles preferably satisfy the relationship Ea / Eb≦0.60. Within this range, the Young's modulus of the organosilicon polymer particles differs significantly from that of the silica particles, increasing the bulk density of the external additive blocking layer at the cleaning blade nip and making it easier to suppress image deletion. More preferably, Ea / Eb≦0.40, and even more preferably, Ea / Eb≦0.20.

[0058] The Young's modulus Ed of the electrostatic image carrier surface and the Young's modulus Ea of the organosilicon polymer particles preferably satisfy the relationship Ea / Ed≦0.20. Within this range, the organosilicon polymer particles are more likely to deform on the electrostatic image carrier surface, increasing the bulk density of the external additive blocking layer at the cleaning blade nip and making it easier to suppress image deletion. More preferably, Ea / Ed≦0.10, and even more preferably, Ea / Ed≦0.05.

[0059] The amount of organosilicon polymer particles added is preferably 0.2% by weight or more and 10.0% by weight or less, based on the weight of the toner. By maintaining this range, excellent blade cleaning performance and durability can be achieved. By maintaining the amount at 0.2% by weight or more, the amount of external additives necessary for forming the blocking layer can be reliably secured. Furthermore, by maintaining the amount at 10.0% by weight or less, component contamination by external additives can be suppressed, and good durability and stability can be achieved.

[0060] Also, the theoretical BET specific surface area of ​​the organosilicon polymer particles is defined as X (m 2 / g), and the measured BET specific surface area of ​​the organosilicon polymer particles is defined as Y(m 2 / g), X and Y are 3.0≦Y / X≦8.0 It is preferable to set the following.

[0061] A larger Y / X value means that the surface has minute irregularities (more pores). In the present invention, image deletion can be further suppressed by setting this value to 3.0 or more. This is thought to be because the minute irregularities on the surface can adsorb large amounts of discharge products and moisture, which are the causes of image deletion. On the other hand, if the value exceeds 8.0, the number of pores will be too large, which will increase moisture adsorption and is undesirable from the perspective of toner charging stability.

[0062] The value of Y / X can be controlled by varying the abundance ratio of each of the constituent compounds of the organosilicon polymer microparticles, namely the M unit structure (S1), the D unit structure (S2), the T unit structure (S3), and the Q unit structure (S4), or by changing the reaction rate during production.

[0063] The amount of silica particles added is preferably 0.2% by mass or more and 10.0% by mass or less based on the mass of the toner. By setting the amount within this range, excellent blade cleaning performance and durability stability can be obtained. By setting the amount to 0.2% by mass or more, the amount of external additives necessary for forming the blocking layer can be reliably secured. Furthermore, by setting the amount to 10.0% by mass or less, contamination of components by external additives can be suppressed and good durability stability can be obtained.

[0064] In the toner of the present invention, when the amount of the organosilicon polymer particles that migrate from the toner is A (mass %) and the amount of the silica particles that migrate from the toner is B (mass %), based on the mass of the toner when the toner is washed with water, A and B are 0.50≦A+B≦4.00 0.20≦B / A≦2.00 It is preferable to satisfy the above relationship. When the toner is subjected to a water washing treatment using the method described below, the amount of the organosilicon polymer particles that migrate from the toner, A (mass %), and the amount of the silica particles that migrate from the toner, B (mass %), satisfy the above relationship, as this facilitates both image deletion prevention and image defect prevention during endurance printing. When A+B is 0.50 or more, sufficient external additives can be secured to form an external additive blocking layer. When A+B is 4.00 or less, component contamination by external additives during endurance printing can be suppressed, and image defects caused by component contamination can be suppressed. When B / A is in the above range, this is preferable because it results in a bulk density of the external additive blocking layer in the cleaning blade nip that is highly effective at suppressing image deletion.

[0065] The migration amounts A and B can be controlled by changing the manufacturing conditions in the external addition step during toner manufacturing, adding a step such as thermal fixation after the external addition step, changing the amount present in the toner, etc.

[0066] <Organosilicon polymer particles> The method for producing organosilicon polymer particles is not particularly limited, but for example, particles can be formed by hydrolysis of silicon compounds (silane monomers) by the sol-gel method and polycondensation reaction.Specifically, particles can be formed by polymerizing a mixture of a bifunctional silane having two siloxane bonds, a trifunctional silane having three siloxane bonds, and a tetrafunctional silane having four siloxane bonds through hydrolysis and polycondensation reaction.

[0067] The method for producing organosilicon polymer particles is not particularly limited. For example, a silane compound can be added dropwise to water, hydrolyzed and condensed in the presence of a catalyst, and the resulting suspension can then be filtered and dried to obtain the particles. Furthermore, the particle size can be controlled by the type of catalyst, the compounding ratio, the reaction initiation temperature, the dropwise addition time, etc. Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include, but are not limited to, aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0068] Organosilicon polymer particles are preferably produced by the following method. Specifically, the process preferably comprises a first step of obtaining a hydrolysate of a silicon compound, a second step of mixing the hydrolysate with an alkaline aqueous medium and subjecting the hydrolysate to a polycondensation reaction, and a third step of mixing the polycondensation reaction product with an aqueous solution to form particles. In some cases, a hydrophobizing agent may be further added to the organosilicon polymer particle dispersion to obtain hydrophobicized organosilicon polymer particles.

[0069] In the first step, a silicon compound is contacted with a catalyst by stirring, mixing, or the like in an aqueous solution in which an acidic or alkaline substance serving as a catalyst is dissolved in water. Known catalysts can be suitably used. Specific examples of acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while basic catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0070] The amount of catalyst used may be adjusted appropriately depending on the type of silicon compound and catalyst. Preferably, the amount of catalyst used is 1×10 -3 The amount is selected from the range of 1 part by mass or more and 1 part by mass or less.

[0071] The amount of catalyst used is 1×10 -3 If the amount of catalyst used is 1 part by mass or more, the reaction proceeds sufficiently. On the other hand, if the amount of catalyst used is 1 part by mass or less, the concentration of impurities remaining in the fine particles will be low, making hydrolysis easier. The amount of water used is preferably 2 to 15 moles per mole of silicon compound. If the amount of water is 2 moles or more, the hydrolysis reaction will proceed sufficiently, and if it is 15 moles or less, productivity will be improved.

[0072] The reaction temperature is not particularly limited and may be carried out at room temperature or under heating, but it is preferable to carry out the reaction at a temperature maintained at 10 to 60° C., as this allows a hydrolysate to be obtained in a short time and prevents a partial condensation reaction of the produced hydrolysate. The reaction time is not particularly limited and may be appropriately selected taking into consideration the reactivity of the silicon compound used, the composition of the reaction liquid obtained by mixing the silicon compound, acid, and water, and productivity.

[0073] In the second step of the method for producing silicon polymer particles, the raw material solution obtained in the first step is mixed with an alkaline aqueous medium to polycondense the particle precursor, thereby obtaining a polycondensation reaction solution. Here, the alkaline aqueous medium is a liquid obtained by mixing an alkaline component, water, and, if necessary, an organic solvent.

[0074] The alkaline component used in the alkaline aqueous medium is one whose aqueous solution is basic and acts as a neutralizer for the catalyst used in step 1 and as a catalyst for the polycondensation reaction in step 2. Examples of such alkaline components include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia; and organic amines such as monomethylamine and dimethylamine.

[0075] The amount of the alkali component used is an amount that neutralizes the acid and effectively acts as a catalyst for the polycondensation reaction. For example, when ammonia is used as the alkali component, the amount is usually selected in the range of 0.01 parts by mass or more and 12.50 parts by mass or less per 100 parts by mass of the mixture of water and the organic solvent.

[0076] In the second step, in order to prepare an alkaline aqueous medium, an organic solvent may be used in addition to the alkaline component and water. The organic solvent is not particularly limited as long as it is compatible with water, but an organic solvent that dissolves 10 g or more of water per 100 g at room temperature and normal pressure is preferred.

[0077] Specific examples include alcohols such as methanol, ethanol, n-propanol, 2-propanol, and butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; ethers such as ethylene glycol monoethyl ether, acetone, diethyl ether, tetrahydrofuran, and diacetone alcohol; and amide compounds such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0078] Among the organic solvents listed above, alcohol solvents such as methanol, ethanol, 2-propanol, butanol, etc. are preferred. Furthermore, from the viewpoint of hydrolysis and dehydration condensation reactions, it is more preferred to select as the organic solvent the same alcohol as the alcohol produced by elimination.

[0079] In the third step, the polycondensation reaction product obtained in the second step is mixed with an aqueous solution to form particles. Water (tap water, pure water, etc.) is preferably used as the aqueous solution, but components compatible with water, such as salts, acids, alkalis, organic solvents, surfactants, and water-soluble polymers, may also be added to the water. The temperatures of the polycondensation reaction liquid and the aqueous solution when mixed are not particularly limited, and are preferably selected in the range of 5 to 70°C, taking into consideration the composition, productivity, etc.

[0080] The method for recovering the silicon polymer particles can be any known method without any particular limitations. For example, floating powder can be scooped out or a filtration method can be used, with filtration being preferred due to its simple operation. The filtration method is not particularly limited, and known devices such as vacuum filtration, centrifugal filtration, and pressure filtration can be selected. The filter paper, filters, filter cloth, etc. used for filtration are not particularly limited as long as they are industrially available, and can be selected appropriately depending on the device used.

[0081] The silane monomer to be used can be appropriately selected depending on its compatibility with the solvent and catalyst, its hydrolysis property, and the like.

[0082] Examples of tetrafunctional silanes include tetramethoxysilane, tetraethoxysilane, and tetraisocyanate silane.

[0083] Trifunctional silanes include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, and methyldiethoxyhydroxysilane. silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

[0084] Examples of bifunctional silanes include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, and diethyldimethoxysilane.

[0085] Of the above, the preferred tetrafunctional silane is tetraethoxysilane, the preferred trifunctional silane is trimethoxymethylsilane, and the preferred difunctional silane is dimethyldimethoxysilane.

[0086] These polyfunctional monomers can be used alone or in combination. Although the detailed reason is unclear, it is preferable that the amount of the trifunctional monomer used is less than the total amount of the tetrafunctional monomer and the bifunctional monomer used, because the effects of the present invention are more likely to be exhibited.

[0087] The organosilicon polymer particles may be surface-treated with known means such as a silane coupling agent or silicone oil to adjust the degree of hydrophobicity. In particular, when the silica fine particles are hydrophobized in the present invention, it is preferable that the organosilicon polymer particles are also hydrophobized in order to further improve the cohesive force between the silica fine particles and the organosilicon polymer particles in the external additive blocking layer. A hydrophobicity of 35 or more is preferable because it enhances the effect of suppressing image deletion.

[0088] <Silica particles> As the silica particles of the present invention, silica fine particles produced by any method such as a wet method, a flame fusion method, or a gas phase method are preferably used.

[0089] An example of a wet method is a sol-gel method in which an alkoxysilane is dropped into an organic solvent in the presence of water, hydrolysis and condensation reaction are carried out in the presence of a catalyst, and then the solvent is removed from the resulting silica sol suspension, followed by drying to obtain sol-gel silica.

[0090] The flame fusion method involves first converting a silicon compound, which is gaseous or liquid at room temperature, into a gaseous state, and then supplying a flammable gas consisting of hydrogen and / or hydrocarbon, and oxygen, to form an outer flame, whereby the silicon compound is decomposed and melted to obtain silica fine particles (fused silica).

[0091] In the flame fusion method, silica fine particles are produced from the silicon compound in an outer flame, and simultaneously, the silica fine particles are fused and coalesced together to form a desired particle size and shape, after which they can be cooled and collected using a bag filter, etc. The silicon compound used as a raw material is not particularly limited as long as it is gaseous or liquid at room temperature, and examples thereof include cyclic siloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane; siloxanes such as hexamethyldisiloxane and octamethyltrisiloxane; alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, and dimethyldimethoxysilane; organic silane compounds such as tetramethylsilane, diethylsilane, and hexamethyldisilazane; silicon halides such as monochlorosilane, dichlorosilane, trichlorosilane, and tetrachlorosilane; and inorganic silicon compounds such as monosilane and disilane.

[0092] Examples of the gas phase method include a fumed method in which silicon tetrachloride is produced by burning it at high temperature together with a mixed gas of oxygen, hydrogen, and a diluent gas (for example, nitrogen, argon, carbon dioxide, etc.).

[0093] The silica particles are preferably subjected to a surface treatment to make the surface hydrophobic and improve the charging stability, and a silane coupling agent or silicone oil is preferably used as the surface treatment agent.

[0094] Examples of silane coupling agents include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilyl mercaptan, and Examples of the silyl mercaptan include ethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilamene, dimethyldiethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane having 2 to 12 siloxane units per molecule and containing a hydroxyl group bonded to a silicon atom in each of the terminal units.

[0095] Examples of silicone oils used in the treatment of silica particles in the present invention include dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil. The silicone oil is not limited to the above formula. The silicone oil has a viscosity of 50 mm at a temperature of 25°C. 2 / s or more 1000mm 2 / s or less is preferable. 50mm 2 At temperatures below 1000mm / s, some of the charge tends to volatilize due to the application of heat, resulting in deterioration of charging characteristics. 2 When the viscosity exceeds 1 / s, handling tends to be difficult during processing. As a method for silicone oil processing, known techniques can be used. For example, mixing silicic acid fine powder and silicone oil using a mixer; spraying silicone oil into silicic acid fine powder using a sprayer; or dissolving silicone oil in a solvent and then mixing with silicic acid fine powder. The processing method is not limited to these.

[0096] In particular, the silica particles of the present invention are preferably those which use hexamethyldisilazane or silicone oil as a surface treatment agent.

[0097] <Binder resin> The binder resin used in the toner of the present invention is not particularly limited, and the following polymers or resins can be used.

[0098] Examples of suitable materials include homopolymers of styrene and its substituted derivatives, such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-α-chloromethyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, and styrene-acrylonitrile-indene copolymers; and polyvinyl chloride, phenolic resins, naturally modified phenolic resins, naturally modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethanes, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, and petroleum-based resins. Among these, polyester resins are preferred from the viewpoints of durability and charging stability.

[0099] <Coloring agent> The toner of the present invention may contain a colorant, if necessary. Examples of the colorant include the following.

[0100] Examples of black colorants include carbon black and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment in combination to improve the clarity from the viewpoint of the image quality of a full-color image.

[0101] Examples of pigments for magenta toner include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0102] Dyes for magenta toner include solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; and CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0103] Examples of pigments for cyan toner include CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; CI Vat Blue 6; and CI Acid Blue 45, and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

[0104] An example of a dye for cyan toner is CI Solvent Blue 70.

[0105] Yellow toner pigments include the following: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Vat Yellow 1, 3, 20. An example of a yellow toner dye is CI Solvent Yellow 162.

[0106] The content of the colorant is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0107] <Wax> The toner of the present invention may contain wax, if necessary. Examples of wax include the following.

[0108] Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or their block copolymers; waxes whose main component is fatty acid esters such as carnauba wax; partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

[0109] Further examples include saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and valinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene Saturated fatty acid bisamides such as bisstearamide; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacamide; aromatic bisamides such as m-xylene bisstearamide and N,N'-distearyl isophthalamide; fatty metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats.

[0110] The content of the wax is preferably 2.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin. The wax may be used alone or in combination of two or more kinds.

[0111] <Charge control agent> The toner of the present invention may contain a charge control agent, if necessary. Known charge control agents can be used as the charge control agent contained in the toner, but it is preferable to use a positive charge control agent, particularly when combined with the photoreceptor of the present invention.

[0112] Examples of the positive charge control agent include azine compounds, azine dyes, nigrosine dyes, quaternary ammonium salts, resins containing quaternary ammonium cationic groups, triaminotriphenylmethane compounds, and imidazole compounds.

[0113] Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate salts or sulfonate esters on the side chain, polymeric compounds having carboxylate salts or carboxylate esters on the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0114] The charge control agent may be added internally or externally to the toner particles. The content of the charge control agent is preferably 0.2 parts by mass or more and 10.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, relative to 100 parts by mass of the binder resin.

[0115] <Inorganic fine particles> In addition to the external additives for toner described above, other inorganic fine particles may also be used in combination with the toner of the present invention, if necessary, within the range that does not impair the effects of the present invention.

[0116] As an external additive, 2 / g or more 400m 2 / g or less are preferred. By using inorganic fine particles with a specific surface area within the above range in combination, it is possible to finely adjust the fluidity and chargeability. When combined with the electrostatic image carrier of the present invention, it is preferable to use fine particles with a smaller number-average primary particle diameter and lower resistance than the organosilicon polymer particles or silica particles, as this prevents excessive charging of the particles within the external additive blocking layer, making it easier to form a stable external additive blocking layer. Examples of such fine particles include titania fine particles and various fine particles whose surfaces are coated with a conductive film such as titania or tin oxide, and whose primary particle number-average diameter is less than 40 nm.

[0117] The inorganic fine particles are preferably used in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of toner particles.

[0118] <Developer> The toner of the present invention can be used as a one-component developer, but in order to further improve dot reproducibility, it is preferable to mix it with a magnetic carrier and use it as a two-component developer, in that stable images can be obtained over a long period of time.Furthermore, it is also preferable in that the degree to which external additive particles of the toner migrate into the developing machine can be suppressed and an appropriate external additive blocking layer can be formed on the surface of the electrostatic image carrier.In other words, it is preferable that the toner is the toner of the present invention, which is a two-component developer containing a toner and a magnetic carrier.

[0119] Examples of magnetic carriers that can be used include generally known magnetic carriers such as surface-oxidized iron powder, unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, oxide particles, and magnetic materials such as ferrite, and magnetic material-dispersed resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state.

[0120] <Method of manufacturing toner particles> The method for producing toner particles is not particularly limited, and any of the conventionally known production methods such as suspension polymerization, emulsion aggregation, melt-kneading, and dissolution suspension methods can be used.

[0121] The resulting toner particles are mixed with the organosilicon polymer microparticles of the present invention and microparticles containing silica microparticles to obtain a toner. The toner particles, inorganic microparticles, and other external additives can be mixed using a mixing device such as a double con mixer, V-type mixer, drum mixer, Super Mixer, Henschel mixer, Nauta mixer, Mechano Hybrid (manufactured by Nippon Coke & Engineering Co., Ltd.), or Nobilta (manufactured by Hosokawa Micron Corporation). The organosilicon polymer microparticles of the present invention and silica microparticles may be added to the toner particles simultaneously, or one may be mixed with the toner particles and then the other added.

[0122] In addition, after mixing, mechanical or thermal treatment can be performed using a Hybridization System (manufactured by Nara Machinery Works), Mechanofusion System (manufactured by Hosokawa Micron Corporation), Faculty (manufactured by Hosokawa Micron Corporation), or Meteor Rainbow MR Type (manufactured by Nippon Pneumatic Co., Ltd.) to control the adhesion rate of the organosilicon polymer microparticles and silica microparticles on the surface of the toner particles.

[0123] <<Method of measuring physical properties>> The methods for measuring physical properties according to the present invention will be described below.

[0124] <Method for Identifying Organosilicon Polymer Particles> The organosilicon polymer particles contained in the toner can be identified by a combination of shape observation using an SEM and elemental analysis using EDS.

[0125] Using a scanning electron microscope "S-4800" (trade name; manufactured by Hitachi, Ltd.), the toner is observed at a maximum magnification of 50,000 times. The focus is adjusted to the surface of the toner particles, and the external additives are observed. EDS analysis is performed on each particle of the external additive, and based on the presence or absence of a Si element peak, it is determined whether the analyzed particle is an organosilicon polymer microparticle.

[0126] When a toner contains both organosilicon polymer particles and silica particles, the organosilicon polymer particles are identified by comparing the ratio of the elemental content (atomic %) of Si and O (Si / O ratio) with that of a standard sample.

[0127] EDS analysis is performed under the same conditions on samples of organosilicon polymer microparticles and silica microparticles to obtain the elemental contents (atomic %) of Si and O.

[0128] The Si / O ratio of the organosilicon polymer microparticles is designated as A, and the Si / O ratio of the silica microparticles is designated as B. Measurement conditions are selected such that A is significantly greater than B.

[0129] Specifically, the standard is measured 10 times under the same conditions, and the arithmetic mean values ​​for A and B are obtained. The measurement conditions are selected so that the obtained mean value A / B>1.1.

[0130] If the Si / O ratio of the particles to be judged is on the A side of [(A+B) / 2], the particles are judged to be organosilicon polymer particles.

[0131] Tospearl 120A (Momentive Performance Materials Japan, LLC) was used as a sample of organosilicon polymer particles, and HDK V15 (Asahi Kasei) was used as a sample of silica microparticles.

[0132] <Method for measuring the number average particle size of primary particles of organosilicon polymer particles and silica particles> This is performed using a scanning electron microscope "S-4800" (product name: manufactured by Hitachi, Ltd.) used in toner production in combination with elemental analysis using energy dispersive X-ray analysis (EDS).

[0133] In a field of view magnified up to 50,000 times, the fine particles are randomly photographed using the elemental analysis method using EDS described above.

[0134] From the captured image, 100 organosilicon polymer microparticles and silica microparticles are randomly selected, the major axis of the primary particles of the target microparticles is measured, and the arithmetic mean value is taken as the number-average particle size.

[0135] The magnification for observation is adjusted appropriately depending on the size of the organosilicon polymer fine particles and silica fine particles.

[0136] <Method for quantifying organosilicon polymer particles or silica particles contained in toner> 1 g of toner is placed in a vial and dissolved in 31 g of chloroform, and dispersed in an ultrasonic homogenizer for 30 minutes to produce a dispersion.

[0137] The organosilicon polymer particles and silica particles are then separated by centrifugation based on the difference in specific gravity to obtain samples, and the content of organosilicon polymer particles or silica particles is determined.

[0138] First, the pressed toner is measured using fluorescent X-rays, and the silicon content in the toner is determined by performing analytical processing such as the calibration curve method or FP method.

[0139] Next, the components that form the organosilicon polymer microparticles and, if necessary, the silica microparticles are subjected to solidification. 29 The structure is identified using Si-NMR and pyrolysis GC / MS, and the silicon content in the organosilicon polymer particles and silica particles is determined. The silicon content in the toner determined by fluorescent X-rays and the solid 29 The content of organosilicon polymer particles or silica particles in the toner is calculated from the relationship between the silicon content in the organosilicon polymer particles and the silica particles determined by Si-NMR and pyrolysis GC / MS.

[0140] <Amount of organosilicon polymer particles or silica particles transferred from toner particles and particle size of transferred organosilicon polymer particles or silica particles by water washing method> (Water washing process) Before cleaning the toner: The various toners thus produced are used as they are to determine the amount of silicon in the silicon compound present on the surface of the toner particles before washing by the method described below.

[0141] After cleaning the toner: Add 500 g of sucrose (Kishida Chemical) to 250 mL of ion-exchanged water and dissolve in a hot water bath to prepare a concentrated sucrose solution. Place 31 g of the above concentrated sucrose solution and 6 mL of Contaminon N (a 10% by weight aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) in a 50 mL centrifuge tube to prepare a dispersion. Add 1.0 g of toner to this dispersion and break up any clumps of toner with a spatula or similar.

[0142] The centrifuge tube is shaken at 350 strokes per minute (spm) for 20 minutes. Depending on the adhesion of the organosilicon polymer or silica particles to the toner particles, this operation may result in the organosilicon polymer or silica particles migrating from the toner particles to the dispersion liquid. After shaking, the solution is transferred to a glass tube (50 mL capacity) for a swing rotor and separated in a centrifuge (H-9R, manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 minutes. Visually confirm that the toner and aqueous solution have been sufficiently separated, and collect the separated toner at the top with a spatula. The collected aqueous solution containing the toner is filtered through a vacuum filter and then dried in a dryer for at least 1 hour. The dried product is crushed with a spatula and washed to produce toner.

[0143] In the case of a magnetic toner containing a magnetic substance, instead of using a centrifuge, the toner can be restrained by a neodymium magnet, and the supernatant liquid containing the organosilicon polymer or silica fine particles can be separated. After repeated washing with pure water, the magnetic toner can be recovered by filtration. The organosilicon polymer particles or silica particles that have migrated into the aqueous solution are allowed to settle by centrifugation, the supernatant liquid is removed, and the particles are washed repeatedly with pure water before being recovered.

[0144] Next, a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation) is used to photograph the toner that has not been subjected to the above-mentioned washing process (toner before washing) and the toner obtained through the above-mentioned washing process (toner after washing).

[0145] The photographed toner surface image is then analyzed using image analysis software Image-Pro Plus ver. 5.0 (Nippon Roper Co., Ltd.) to calculate the coverage.

[0146] The imaging conditions for the S-4800 are as follows:

[0147] (1) Sample preparation Apply a thin layer of conductive paste to a sample stage (aluminum sample stage 15 mm x 6 mm), then spray toner onto it. Then, use air to remove excess toner from the sample stage and allow it to dry thoroughly. Place the sample stage in the sample holder and adjust the sample stage height to 36 mm using the sample height gauge.

[0148] (2) S-4800 observation condition setting When measuring the coverage, elemental analysis by the energy dispersive X-ray analysis (EDS) described above is carried out in advance to distinguish between organosilicon polymer fine particles and silica fine particles on the toner particle surface before measurement.

[0149] Pour liquid nitrogen into the anti-contamination trap attached to the S-4800 housing until it overflows and leave it for 30 minutes. Start the S-4800's "PC-SEM" and perform flushing (cleaning the FE chip, which is the electron source). Click the accelerating voltage display area on the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2 and execute it. Confirm that the emission current due to flushing is 20-40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.

[0150] Click the accelerating voltage display to open the HV setting dialog, and set the accelerating voltage to [1.1 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select [Upper (U)] and [+BSE] for the SE detector, and select [LA100] in the selection box to the right of [+BSE] to set the mode for observation using backscattered electron images. Also in the [Basic] tab of the operation panel, set the probe current in the electron optical system condition block to [Normal], the focus mode to [UHR], and the WD to [4.5 mm]. Press the [ON] button in the accelerating voltage display on the control panel to apply the accelerating voltage.

[0151] (3) Calculation of the number average particle size (D1) of the toner Drag within the magnification display area on the control panel to set the magnification to 5000 (5k). Rotate the focus knob [COARSE] on the operation panel to achieve a certain degree of focus, then adjust the aperture alignment. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture], and rotate the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the image movement or adjust it so that it moves as little as possible. Close the aperture dialog, and use autofocus to adjust the focus. Repeat this operation twice more to adjust the focus.

[0152] Thereafter, the particle diameters of 300 toner particles are measured to determine the number average particle diameter (D1). The particle diameter of each particle is the maximum diameter observed when the toner particles are observed.

[0153] (4) Focus adjustment For the particles with a number average particle diameter (D1) of ±0.1 μm obtained in (3) above, align the midpoint of the maximum diameter with the center of the measurement screen, and drag within the magnification display section of the control panel to set the magnification to 10,000 (10k) times.

[0154] Rotate the focus knob [COARSE] on the control panel until the image is in focus to some extent, then adjust the aperture alignment. Click [Align] on the control panel to display the alignment dialog and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the control panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture] and rotate the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the image movement or minimize its movement. Close the aperture dialog and use autofocus to adjust the focus. Then, set the magnification to 50,000 (50k)x and adjust the focus using the focus knob and STIGMA / ALIGNMENT knob as above, then use autofocus to adjust the focus again. Repeat this process to adjust the focus. Here, if the tilt angle of the observation surface is large, the accuracy of measuring the coverage rate tends to be low, so when adjusting the focus, select an object that can simultaneously bring the entire observation surface into focus, and then select an object with as little surface tilt as possible for analysis.

[0155] (5) Save image Adjust the brightness in ABC mode, take a photo at a size of 640 x 480 pixels, and save it. Use this image file for the following analysis. Take one photo for each toner, and obtain images for 25 toner particles.

[0156] (6) Image analysis The image obtained using the above method is binarized using the following analysis software to calculate the coverage. At this time, the above screen is divided into 12 squares and each is analyzed.

[0157] The analysis conditions for the image analysis software Image-Pro Plus ver.5.0 are as follows: However, if a divided section contains organosilicon polymer microparticles with particle sizes of less than 30 nm and more than 300 nm (when measuring the coverage of organosilicon polymer microparticles), or silica microparticles with particle sizes of less than 100 nm and more than 300 nm (when measuring the coverage of silica microparticles), the coverage will not be calculated for that section. Software Image-ProPlus5.1J

[0158] From the "Measure" menu on the toolbar, select "Count / Size" and then "Options" to set the binarization conditions. Select 8 connectivity in the object extraction options and set smoothing to 0. In addition, do not select pre-sort, fill holes, or encompass lines, and set "Exclude boundaries" to "None." From the "Measure" menu on the toolbar, select "Measurement Items" and enter 2 to 107 in the area selection range.

[0159] The coverage rate is calculated by enclosing a square area. The area (C) of the area should be 24,000 to 26,000 pixels. Automatic binarization is performed using "Processing" - Binarization, and the total area of ​​areas without organosilicon polymer microparticles or silica microparticles (D) is calculated.

[0160] The coverage rate can be calculated using the following formula from the area C of the square region and the total area D of the region free of organosilicon polymer fine particles or silica fine particles. Coverage rate (%)=100-(D / C×100)

[0161] The arithmetic mean value of all the data obtained is taken as the coverage rate.

[0162] Then, the coverage of the toner before and after washing is calculated, [Toner coverage rate after washing] / [Toner coverage rate before washing]×100 is defined as the "adhesion rate" in the present invention.

[0163] The "transfer amount" of the present invention is calculated by (1-"adhesion rate") x fine particle content.

[0164] The particle size Da of the migrated organosilicon polymer particles or the particle size Db of the migrated silica particles is measured for the recovered particles in the same manner as for measuring the number average particle size of primary particles described above.

[0165] <Young's modulus of the electrostatic image carrier surface> A surface film physical property test was carried out using a surface film physical property tester (Fisherscope H100V, manufactured by Fisher Instruments) to determine the Young's modulus Ed of the surface of the electrostatic image bearing member.

[0166] The measurement conditions were a maximum indentation depth of 1 μm, 60 measurement points in the depth direction, and measurements were taken in a constant environment (room temperature 23°C, humidity 50% RH). To measure Young's modulus E in the surface film physical property test, a diamond indenter 11 with a square pyramid shape and a facing angle of 136° was used, and a set load was applied in stages to the surface of the photosensitive drum 9, pressing it into the film to a specific depth, and then the indentation depth while the load was being applied was electrically detected and read as it was pulled out.

[0167] <Method for measuring Young's modulus of organosilicon polymer particles and silica particles> The Young's modulus Ea of the organosilicon polymer particles and the Young's modulus Eb of the silica particles are determined by a microcompression test using a Hysitron PI 85L pico-indenter (manufactured by BRUKER).

[0168] The Young's modulus (MPa) is calculated from the slope of the profile (load-displacement curve) of the displacement (nm) and test force (μN) obtained in the measurement. Equipment and fixtures Base system: Hysitron PI-85L Measuring indenter: 1 μm flat-end indenter SEM used: Thermo Fisher Versa 3D SEM conditions: -10°tilt, 13pA at 10keV Measurement conditions Measurement mode: Displacement control Maximum displacement: 30nm Displacement speed: 1 nm / sec Hold time: 2 seconds Unloading speed: 5nm / sec ·Analysis method Hertz analysis is applied to the curve obtained when compressed from 0 nm to 10 nm in the load-displacement curve, and the Young's modulus of the fine particles is calculated. Sample preparation Fine particles adhered to a silicon wafer.

[0169] <Method for measuring the hydrophobicity of toner external additive particles> The hydrophobicity of the toner external additive particles of the present invention is calculated by the methanol titration method. Specifically, it is measured by the following procedure. In a mixed solution prepared by adding 0.5 g of toner external additive particles to 50 ml of RO water, methanol is added dropwise from a burette while stirring the mixed solution until all of the toner external additive particles are wetted. Whether all of the particles are wetted is determined by whether all of the toner external additive particles floating on the water surface are submerged and suspended in the liquid. At this time, the percentage of methanol relative to the total amount of the mixed solution and the added methanol at the end of the dropwise addition is taken as the hydrophobicity. A higher hydrophobicity value indicates higher hydrophobicity.

[0170] <Measurement of BET specific surface area of ​​fine particles> The BET specific surface area S can be determined by a low-temperature gas adsorption method using a dynamic constant pressure method in accordance with the BET method (preferably the BET multipoint method). For example, a specific surface area measuring device (trade name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation) is used to adsorb nitrogen gas onto the surface of a sample, and measurement is performed using the BET multipoint method to determine the BET specific surface area Y (m 2 / g) can be calculated.

[0171] In addition, the theoretical BET specific surface area X (m 2 / g) is calculated by the following formula, assuming that the particles are spherical. Theoretical BET specific surface area X = (4 × π × number average particle size) 2 ) / (4 / 3×π×number average particle size A 3 / density)×1000

[0172] Density (cm) required for calculation 3 The value of true density measured using a dry density meter Accupyc 1330 (manufactured by Shimadzu Corporation) is used as the value of the density (density).

[0173] <Method for measuring weight-average particle size (D4) and particle size distribution of toner particles> The weight-average particle size (D4) of the toner particles is measured with an effective number of 25,000 measurement channels using a precision particle size distribution measuring device equipped with a 100 μm aperture tube and using the narrow-pore electrical resistance method, the Coulter Counter Multisizer 3 (registered trademark, manufactured by Beckman Coulter, Inc.), and the accompanying dedicated software for setting measurement conditions and analyzing measurement data, the Beckman Coulter Multisizer 3 Version 3.51 (manufactured by Beckman Coulter, Inc.), and the measurement data is analyzed and calculated.

[0174] The aqueous electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, such as "ISOTON II" (manufactured by Beckman Coulter).

[0175] Before carrying out the measurement and analysis, the dedicated software is set up as follows.

[0176] In the "Change Standard Measurement Method (SOM)" screen of the dedicated software, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement."

[0177] In the dedicated software's "Pulse to particle size conversion setting screen," set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less.

[0178] The specific measurement method is as follows. (1) Pour approximately 200 ml of the electrolyte solution into a 250 ml round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture tube flush" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Approximately 30 ml of the above-mentioned aqueous electrolyte solution is placed in a 100 ml flat-bottom glass beaker, and approximately 0.3 ml of a dilution obtained by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added as a dispersant. (3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser, "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.), which has two built-in oscillators with an oscillation frequency of 50 kHz and a phase difference of 180 degrees and an electrical output of 120 W, and approximately 2 ml of the Contaminon N is added to this water tank. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, approximately 10 mg of toner is added little by little to the electrolyte solution and dispersed. The ultrasonic dispersion process is then continued for another 60 seconds. During the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C. (6) Using a pipette, the electrolytic solution (5) containing the dispersed toner is dropped into the round-bottom beaker (1) placed in the sample stand, and the measurement concentration is adjusted to approximately 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software provided with the device, and the weight-average particle size (D4) is calculated. Note that when the dedicated software is set to Graph / Volume %, the "Average diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen is the weight-average particle size (D4). [Example]

[0179] The present invention will be explained in more detail with reference to the following examples, which, however, are not intended to limit the scope of the present invention. Examples 14, 15, 20, 25, 31 and 32 are reference examples. Unless otherwise specified, all "parts" in the following formulations are by mass.

[0180] <Production Example of Organosilicon Polymer Particles 1> 1. Hydrolysis process A 200 ml beaker was charged with 43.0 g of RO water and 0.008 g of acetic acid as a catalyst, and stirred at 45° C. 52.0 g of trimethoxymethylsilane as a silane monomer was added thereto, and the mixture was stirred for 1.5 hours to obtain a raw material solution.

[0181] 2. Polycondensation process An alkaline aqueous medium was prepared by adding 70.0 g of RO water, 340.0 g of methanol, and 2.0 g of 25% aqueous ammonia to a 1000 ml beaker and stirring at 30°C. The raw material solution obtained in the hydrolysis step was added dropwise to this alkaline aqueous medium over 1 minute. The mixture after the dropwise addition of the raw material solution was stirred for 1.5 hours while maintaining the temperature at 30°C, allowing the polycondensation reaction to proceed and obtaining a polycondensation reaction liquid.

[0182] 3.Particleization process 700 g of RO water was placed in a 2000 ml beaker, and the polycondensation reaction liquid obtained in the polycondensation step above was added dropwise over 10 minutes while stirring at 25°C. The mixture was heated to 40°C and stirred for 1.0 hour while maintaining the temperature at 40°C, yielding a dispersion containing silicon polymer particles having siloxane bonds.

[0183] 4. Hydrophobization process 23 g of hexamethyldisilazane as a hydrophobizing agent was added to the dispersion containing the silicon polymer particles having siloxane bonds obtained in the above-mentioned particulation step, and the mixture was stirred for 2.5 hours at 60° C. After leaving the mixture to stand for 5 minutes, the powder that precipitated at the bottom of the solution was collected by suction filtration and dried under reduced pressure at 120° C. for 24 hours to obtain external toner additive particles 1.

[0184] The number average particle size of the primary particles of the resulting toner external additive particles 1 measured by SEM was 105 nm. The physical properties of organosilicon polymer particles 1 are shown in Table 1.

[0185] <Production Example of Organosilicon Polymer Particles 2> Organosilicon polymer particles 2 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that in the hydrolysis step, 28.0 g of trimethoxymethylsilane and 24.0 g of tetraethoxysilane were used as silane monomers. The physical properties of the resulting particles are shown in Table 1.

[0186] <Production Example of Organosilicon Polymer Particles 3> Organosilicon polymer particles 3 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that in the hydrolysis step, the silane monomers were changed to 30.0 g of trimethoxymethylsilane and 22.0 g of tetraethoxysilane. The physical properties of the obtained particles are shown in Table 1.

[0187] <Production Example of Organosilicon Polymer Particles 4> Organosilicon polymer particles 4 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that in the hydrolysis step, 42.0 g of trimethoxymethylsilane and 10.0 g of tetraethoxysilane were used as silane monomers. The physical properties of the resulting particles are shown in Table 1.

[0188] <Production Example of Organosilicon Polymer Particles 5> Organosilicon polymer particles 5 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the silane monomers used in the hydrolysis step were changed to 48.0 g of trimethoxymethylsilane and 4.0 g of tetraethoxysilane. The physical properties of the resulting particles are shown in Table 1.

[0189] <Production Example of Organosilicon Polymer Particles 6> Organosilicon polymer particles 6 were obtained in the same manner as in the preparation example for organosilicon polymer particles 1, except that the silane monomers used in the hydrolysis step were changed to 26.0 g of tetramethoxymethylsilane and 28.0 g of dimethyldimethoxysilane. The physical properties of the resulting particles are shown in Table 1.

[0190] <Production Example of Organosilicon Polymer Particles 7> Organosilicon polymer particles 7 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the silane monomers used in the hydrolysis step were changed to 44.0 g of trimethoxymethylsilane and 8.0 g of dimethyldimethoxysilane. The physical properties of the resulting particles are shown in Table 1.

[0191] <Production Example of Organosilicon Polymer Particles 8> Organosilicon polymer particles 8 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the silane monomers used in the hydrolysis step were changed to 48.0 g of trimethoxymethylsilane and 4.0 g of dimethyldimethoxysilane. The physical properties of the resulting particles are shown in Table 1.

[0192] <Production Example of Organosilicon Polymer Particles 9> Organosilicon polymer particles 9 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the stirring temperature of the mixture after dropwise addition of the raw material solution in the condensation polymerization step was changed to 35°C, and the stirring temperature in the particulation step was changed to 45°C. The physical properties of the resulting particles are shown in Table 1.

[0193] <Production Example of Organosilicon Polymer Particles 10> Organosilicon polymer particles 9 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that in the condensation polymerization step, the stirring temperature of the mixture after dropwise addition of the raw material solution was changed to 35°C. The physical properties of the resulting particles are shown in Table 1.

[0194] <Production Example of Organosilicon Polymer Particles 11> Organosilicon polymer particles 11 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that in the condensation polymerization step, the stirring temperature of the mixture after dropwise addition of the raw material solution was changed to 25°C, and in the particulation step, the stirring temperature was changed to 30°C. The physical properties of the resulting particles are shown in Table 1.

[0195] <Production Example of Organosilicon Polymer Particles 12> Organosilicon polymer particles 12 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that in the condensation polymerization step, the stirring temperature of the mixed solution after dropwise addition of the raw material solution was changed to 20°C, and in the particulation step, the stirring temperature was changed to 25°C. The physical properties of the resulting particles are shown in Table 1.

[0196] <Production Example of Organosilicon Polymer Particles 13> Organosilicon polymer particles 13 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the amount of 28% aqueous ammonia added in the condensation polymerization step was changed to 1.0 g. The physical properties of the resulting particles are shown in Table 1.

[0197] <Production Example of Organosilicon Polymer Particles 14> Organosilicon polymer particles 14 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the amount of 28% aqueous ammonia added in the condensation polymerization step was changed to 1.4 g. The physical properties of the resulting particles are shown in Table 1.

[0198] <Production Example of Organosilicon Polymer Particles 15> Organosilicon polymer particles 15 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the amount of 28% aqueous ammonia added in the condensation polymerization step was changed to 1.7 g. The physical properties of the resulting particles are shown in Table 1.

[0199] <Production Example of Organosilicon Polymer Particles 16> Organosilicon polymer particles 16 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the amount of 28% aqueous ammonia added in the condensation polymerization step was changed to 2.5 g. The physical properties of the resulting particles are shown in Table 1.

[0200] <Production Example of Organosilicon Polymer Particles 17> Organosilicon polymer particles 17 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the amount of 28% aqueous ammonia added in the condensation polymerization step was changed to 2.8 g. The physical properties of the resulting particles are shown in Table 1.

[0201] <Production Example of Organosilicon Polymer Particles 18> Organosilicon polymer particles 18 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the amount of 28% aqueous ammonia added in the condensation polymerization step was changed to 3.2 g. The physical properties of the resulting particles are shown in Table 1.

[0202] <Production Example of Organosilicon Polymer Particles 19> Organosilicon polymer particles 19 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that hexamethyldisilazane was not added in the hydrophobization step. The physical properties of the resulting particles are shown in Table 1.

[0203] [Table 1]

[0204] <Production example of silica particles 1> Oxygen gas was supplied to the burner, and the ignition burner was ignited. Hydrogen gas was then supplied to the burner to form a flame, and the raw material silicon tetrachloride was added to this and gasified to obtain silica microparticles. The obtained silica microparticles were transferred to an electric furnace, spread out in a thin layer, and then heat-treated at 900°C for sintering. Subsequently, the surface was treated with hexamethyldisilazane to make them hydrophobic, yielding silica particles 1. The physical properties are shown in Table 2.

[0205] <Production Examples of Silica Particles 2 to 7> Silica particles 2 to 7 were obtained by adjusting the amount of silicon tetrachloride, amount of oxygen gas, amount of hydrogen gas, silica concentration, residence time, sintering conditions, and surface treatment agent in the production example of silica particles 1. Table 2 shows their physical properties.

[0206] [Table 2]

[0207] <Production Example of Polyester Resin A1> 76.9 parts (0.167 moles) of polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane Terephthalic acid (TPA) 25.0 parts (0.145 moles) Adipic acid 8.0 parts (0.054 moles) Titanium tetrabutoxide 0.5 parts The above materials were placed in a 4-liter, four-necked glass flask, fitted with a thermometer, stirring rod, condenser, and nitrogen inlet tube, and placed in a mantle heater. The atmosphere in the flask was then replaced with nitrogen gas, and the temperature was gradually raised with stirring until the mixture was allowed to react for 4 hours at 200°C. Subsequently, 1.2 parts (0.006 mol) of trimellitic anhydride (TMA) was added, and the mixture was allowed to react for 1 hour at 180°C, yielding polyester resin A1. The softening point of this polyester resin A1 was 90°C.

[0208] <Production Example of Polyester Resin A2> 71.3 parts (0.155 moles) of polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane Terephthalic acid 24.1 parts (0.145 moles) Titanium tetrabutoxide 0.6 parts The above materials were placed in a 4-liter, four-necked glass flask, fitted with a thermometer, stirring rod, condenser, and nitrogen inlet tube, and placed in a mantle heater. The atmosphere in the flask was then purged with nitrogen gas, and the temperature was gradually raised with stirring. The mixture was allowed to react for 2 hours at 200°C while stirring. 5.8 parts (0.030 mol%) of trimellitic anhydride was then added, and the mixture was allowed to react for 10 hours at 180°C, yielding polyester resin A2. The softening point of this polyester resin A2 was 130°C.

[0209] <Production Example of Toner Particle 1> Polyester resin A1 70.0 parts Polyester resin A2 30.0 parts Fischer-Tropsch wax (maximum endothermic peak temperature 78°C) 5.0 parts CI Pigment Blue 15:3 5.0 parts 1-Naphthol 4-sulfonic acid benzyltributylammonium salt 0.5 parts The raw materials shown in the above recipe were mixed in a Henschel mixer (FM-75, manufactured by Nippon Coke and Engineering Co., Ltd.) at a rotation speed of 20 s -1 After mixing for 5 minutes, the mixture was kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 125°C and a rotation speed of 300 rpm. The resulting kneaded mixture was cooled and coarsely pulverized using a hammer mill to obtain a coarsely pulverized product with a diameter of 1 mm or less. The coarsely pulverized product was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Freund Turbo Corporation). Further, classification was carried out using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were a classification rotor rotation speed of 50.0 s -1 The resulting toner particles 1 had a weight average particle size (D4) of 6.2 μm.

[0210] <Toner 1 manufacturing example> 96.5 parts toner particles 1.5 parts of organosilicon polymer particles Silica particles 1 2.0 parts Titania particles 1 (primary particle number average diameter 30 nm; surface coated with antimony-doped tin oxide) 0.5 parts The above materials were put into a Henschel mixer FM-10C (manufactured by Mitsui Miike Chemical Engineering Co., Ltd.). Then, the rotation speed was 65 s -1 This cycle was repeated 10 times to obtain Toner 1. The physical properties of Toner 1 are shown in Table 4.

[0211] <Production examples of toners 2 to 36> Toners 2 to 36 were obtained in the same manner as in the production example of Toner 1, except that the types, amounts added, and external addition conditions of the toner particles, organosilicon polymer particles, silica particles, and titania particles were changed to those shown in Table 3. The physical properties of each toner are shown in Table 4.

[0212] [Table 3]

[0213] [Table 4]

[0214] <Production example of magnetic carrier core particles> ·Fe2O362.7 parts ·MnCO329.5 parts ·Mg(OH)26.8 parts ·SrCO31.0 parts The ferrite raw materials were weighed so that the above materials had the above composition ratio.

[0215] The mixture was then pulverized and mixed for 5 hours in a dry vibration mill using stainless steel beads, and the resulting pulverized material was then made into pellets of approximately 1 mm square in a roller compactor.

[0216] The pellets were passed through a vibrating sieve with 3 mm openings to remove coarse particles, and then through a vibrating sieve with 0.5 mm openings to remove fine particles. After that, the pellets were fired in a burner-type firing furnace at 1000°C for 4 hours in a nitrogen atmosphere (oxygen concentration 0.01% by volume) to produce calcined ferrite.

[0217] The calcined ferrite was crushed to about 0.3 mm using a crusher, and then 30 parts of water was added to 100 parts of the calcined ferrite using zirconia beads, followed by pulverization in a wet ball mill for 1 hour. The resulting slurry was further crushed in the wet ball mill for 4 hours to obtain a ferrite slurry (finely crushed calcined ferrite).

[0218] To the ferrite slurry, 1.0 part of ammonium polycarboxylate as a dispersant and 2.0 parts of polyvinyl alcohol as a binder were added per 100 parts of calcined ferrite, and the mixture was granulated into spherical particles using a spray dryer (manufacturer: Okawahara Kakoki Co., Ltd.). After adjusting the particle size of the resulting particles, the mixture was heated in a rotary kiln at 650°C for 2 hours to remove the organic components of the dispersant and binder.

[0219] To control the firing atmosphere, the material was heated from room temperature to 1300°C in a nitrogen atmosphere (oxygen concentration 1.00% by volume) in an electric furnace over two hours, and then fired at 1150°C for four hours. The material was then cooled to 60°C over four hours, returned from the nitrogen atmosphere to the air, and removed at a temperature of 40°C or below.

[0220] After crushing the agglomerated particles, low magnetic particles were removed by magnetic separation, and coarse particles were removed by sieving through a sieve with 250 μm openings, yielding magnetic carrier core particles with a volume-based 50% particle size (D50) of 37.0 μm.

[0221] <Magnetic Carrier 1 Manufacturing Example> In the first coating step, a thermosetting silicone resin solution (methyl silicone resin) was applied to the magnetic carrier core particles using a coating device that was equipped with a rotary bottom plate disk and stirring blades in a fluidized bed to form a swirling flow so that the amount of coating resin was 0.20 parts per 100 parts of the magnetic carrier core particles. The resin solution was sprayed from a direction perpendicular to the direction of movement of the fluidized bed within the device.

[0222] Next, in the second coating step, a fluororesin solution (a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP)) (1.91 parts solids per 100 parts magnetic carrier core particles) and a thermosetting melamine resin solution (0.09 parts solids per 100 parts magnetic core particles) were mixed with sufficient stirring to prepare a carrier coating solution. This coating solution was applied to the magnetic carrier core particles using a coating device equipped with a rotating bottom disk and stirring blades in a fluidized bed to form a swirling flow while coating. The resulting carrier was then dried in the fluidized bed at 280°C for 1 hour to remove the solvent, and magnetic carrier 1 was obtained.

[0223] <Manufacturing example of two-component developer 1> To 92.0 parts of magnetic carrier 1, 8.0 parts of toner 1 were added and mixed in a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain two-component developer 1.

[0224] <Production examples of two-component developers 2 to 36> Two-component developers 2 to 36 were obtained by carrying out the same production procedure as in the production example of two-component developer 1, except that the toner was changed as shown in Table 5.

[0225] [Table 5]

[0226] <Photoreceptor 1 manufacturing example> An aluminum alloy tube (outer diameter 84 mm, inner diameter 78 mm, length 370 mm) was prepared as a cylindrical conductive substrate. The outer surface of the conductive substrate was polished to a mirror finish and wet blasted, and then cleaned.

[0227] First, to mirror-finish the surface of the conductive substrate, the conductive substrate was held at both ends and rotated at a high speed of 1500-8000 rpm, and a diamond bit was pressed against it, and burnishing was performed at a feed rate of 0.08-0.5 mm. That is, a diamond bit with a depth in the workpiece rotation direction on the finishing surface of the bit was pressed against the surface of the conductive substrate, thereby obtaining a smooth finished surface.

[0228] After such mirror finishing, the conductive substrate was degreased and washed.

[0229] Next, a wet blasting process was performed in which a high-hardness abrasive such as alumina was mixed with water, mixed with compressed air, accelerated, and projected onto the surface of the mirror-finished conductive substrate to roughen it. This method allows for the formation of a highly uniform surface in a short time, as the conductive substrate is rotated during processing.

[0230] Specifically, the following parameters were adjusted as conditions for wet blasting to prepare conductive substrates having different surface roughnesses. Abrasive material and particle size: A (alundum (brown fused alumina)) #320~#4000 Abrasive concentration: 10~18% Projection air pressure: 0.10~0.35MPa Throw distance (distance between workpiece center and blast head): 20-300mm Projection time: 1 to 60 seconds Workpiece rotation speed: 120-180 rpm

[0231] The surface roughness was adjusted by changing the abrasive material, particle size, concentration, projection air pressure, projection distance, and projection time.

[0232] After wet blasting, residue remaining on the surface was removed by cleaning, thereby preparing a conductive substrate.

[0233] The conductive substrate thus prepared was subjected to the plasma CVD apparatus shown in Figure 3 to form layers on the surface of the conductive substrate under the film formation conditions shown in Tables 6 and 7, thereby producing Photoreceptor 1 having an amorphous carbon surface layer. The Young's modulus of the surface of Photoreceptor 1 was 200 GPa.

[0234] The flow rate of the source gas, reaction pressure, high frequency power, and substrate temperature during the formation of the third region of the surface layer were set under the conditions shown in Table 7.

[0235] <Production example of photoreceptor 2> Photoreceptor 2, whose surface layer was made of amorphous silicon carbide, was obtained by carrying out production in the same manner as in Production Example 1 of Photoreceptor 1, except that the film formation conditions for the surface layer (third region) were changed to those in Table 7. The Young's modulus of the surface of Photoreceptor 2 was 270 GPa.

[0236] [Table 6]

[0237] [Table 7]

[0238] Example 1 [Image evaluation] A modified version of the Canon Inc. digital electrophotographic device "Image Press C800" (product name) was used. This device uses a cleaning blade to clean excess toner from the electrostatic image carrier. The modification involved applying primary charging and developing bias from an external power source.

[0239] The prepared photoreceptor 1 was mounted in the black station, and two-component developer 1 was set in the developing unit, and toner 1 was set in the toner bottle. The primary current for primary charging and grid voltage were adjusted with the wire and grid so that the dark surface potential of the photoreceptor was 500 V. Next, image exposure was performed while the photoreceptor was charged under the previously set charging conditions, and the exposure energy was adjusted to set the potential at the developing unit position to 150 V.

[0240] (Image flow resistance) To evaluate image flow resistance, an A3 character chart (4pt, print rate 4%) image was printed before the continuous paper feed test under a high temperature and humidity environment (32°C / 85%RH). The evaluation paper was plain paper for color copiers and printers, GF-C081 (A4, 81.0 g / m 2) (sold by Canon Marketing Japan Inc.) was used. The test was also carried out with the photosensitive drum heater turned on.

[0241] After the image output before the continuous paper feed test, the continuous paper feed test was conducted under the condition that the photosensitive drum heater was always turned off while the electrophotographic device was operating and while the electrophotographic device was stopped.

[0242] Specifically, 10,000 sheets of A4 test pattern with a print rate of 1% were printed per day, and then the printer was left in a high-temperature, high-humidity environment for one day. This cycle was repeated 10 times over 20 days, for a total of 100,000 sheets. After the paper printing test, the printer was left in a high-temperature, high-humidity environment for 72 hours.

[0243] After that, the evaluation machine was started up with the photosensitive heater turned off, and an A3 character chart image (4pt, print rate 4%) was output. The images output before and after the continuous paper feed test were digitized into PDF files at 300 dpi and binary conditions.

[0244] The digitized image was edited using Adobe Photoshop (product name), and the image ratio of the image area of ​​one circumference of the electrophotographic photosensitive member was measured. Next, the ratio of the image output after the continuous paper feed test to the image output before the continuous paper feed test was calculated, and the image flow during the test was evaluated.

[0245] When high-humidity bleeding occurs, characters become blurred across the entire image, or characters are not printed and instead leave blank spaces, resulting in a lower output image ratio compared to a normal image before the continuous paper feed test. Therefore, assuming that the normal image ratio before the continuous paper feed test is 100%, the closer the output image ratio after the continuous paper feed test is to 100%, the better the resistance to image bleeding. Evaluation was performed using the following criteria. The evaluation results are shown in Table 8. A rank of C or higher is considered to be a level at which the effects of the present invention are achieved. A: The image ratio output after the continuous paper feed test is 95% or more but less than 110% of the image ratio before the continuous paper feed test. B: The image ratio output after the continuous paper feed test is 90% or more but less than 95% of the image ratio before the continuous paper feed test. C: The image ratio output after the continuous paper feed test is 80% or more but less than 90% of the image ratio before the continuous paper feed test. D: The image ratio output after the continuous paper feed test is less than 80% of the image ratio before the continuous paper feed test.

[0246] (Evaluation of component contamination resistance) The following evaluations were carried out in a room temperature, low humidity environment (23°C / 5%RH) using the same evaluation machine and evaluation paper as used in the image deletion evaluation above. If external additives migrate from the toner to the components and contaminate them, this can cause density changes. The evaluation was carried out with the photoreceptor heater turned off.

[0247] The pattern image to be output was a pattern image in which 2 mm wide strip-shaped solid areas and 18 mm wide strip-shaped white areas were repeatedly arranged in a direction parallel to the paper feed direction. The amount of toner on the solid areas of the pattern image was 0.45 mg / cm. 2 FFh is the 256 gradations expressed in hexadecimal, with 00h being the first gradation of the 256 gradations (white background) and FF being the 256th gradation of the 256 gradations (solid area).

[0248] When the pattern image had been output on 10,000 sheets, the output was stopped once, and then an image in which the entire surface of the paper was halftone (80h) was output.

[0249] The image density of the entire solid image was measured at 20 random locations using an X-Rite color reflection densitometer ("500 Series", manufactured by X-Rite Corporation), and the image density was evaluated using the difference between the maximum and minimum values ​​of the image density (image density difference). The evaluation results are shown in Table 8. A rank of C or higher was determined to indicate that the effects of the present invention were achieved. A: Image density difference is less than 0.04 B: Image density difference is 0.04 or more and less than 0.07 C: Image density difference is 0.07 or more and less than 0.10 D: Image density difference is 0.10 or more

[0250] (Change in charge retention rate) The toner on the electrostatic image bearing member was collected by suction using a metal cylindrical tube and a cylindrical filter, and the amount of triboelectric charge of the toner was calculated.

[0251] Specifically, the amount of triboelectric charge of the toner on the electrostatic latent image carrier was measured using a Faraday cage. A Faraday cage is a coaxial double cylinder with an insulated inner and outer cylinder. If a charged body with a charge Q is placed inside this inner cylinder, electrostatic induction will create the same effect as if a metal cylinder with a charge Q were present. This induced charge was measured using an electrometer (Kesley 6517A, manufactured by Kesley), and the amount of charge Q (mC) divided by the mass M (kg) of the toner in the inner cylinder (Q / M) was determined as the amount of triboelectric charge of the toner. Toner triboelectric charge (mC / kg) = Q / M

[0252] First, an evaluation image used in the image defect evaluation was formed on an electrostatic image carrier, and before the image was transferred to the intermediate transfer member, the rotation of the electrostatic image carrier was stopped, and the toner on the electrostatic image carrier was suction-collected using a metal cylindrical tube and a cylindrical filter, and the [initial Q / M] was measured.

[0253] The developer was then left in the evaluation machine for one week in a high-temperature, high-humidity environment (32°C, 85% RH), and the same procedures were then repeated to measure the charge amount Q / M (mC / kg) per unit mass on the electrostatic image carrier after leaving it. The Q / M per unit mass on the electrostatic image carrier before leaving it was defined as [initial Q / M], and the Q / M per unit mass on the electrostatic image carrier after leaving it was defined as [Q / M after leaving it]. The retention rate was calculated as ([Q / M after leaving it] / [initial Q / M] x 100) and evaluated according to the following criteria. The evaluation results are shown in Table 8. A rating of C or higher was considered to be a level at which the effects of the present invention were obtained.

[0254] (Evaluation criteria) A: Retention rate is over 90% B: Retention rate is between 85% and 90% C: Retention rate is between 80% and 85% D: Retention rate is less than 80%

[0255] Example 2 In Example 1, the same evaluation was carried out except that the photoreceptor 1 was replaced with the photoreceptor 2. The evaluation results are shown in Table 8.

[0256] [Examples 3 to 35, Comparative Examples 1 and 2] In Example 1, the two-component developer 1 was changed to the two-component developer shown in Table 8, and the same evaluation was carried out. The evaluation results are shown in Table 8.

[0257] [Table 8] [Explanation of symbols]

[0258] 101: electrostatic charge image carrier (electrophotographic photosensitive member), 102: charging roller, 103: exposure means, 104: developing device, 105: transfer charger, 106: fixing device, 107: cleaning device, 108: recording medium (transfer paper), 200: substrate, 201: pressure-resistant layer, 202: charge injection blocking layer, 203: photosensitive layer, 204: surface layer, 205: intermediate layer, 206: multiple intermediate layers, 207: change layer, 3100: deposition device, 3110: reaction vessel, 3200: raw material gas supply device, 3111: cathode electrode, 3112: substrate, 3113: heater for heating substrate, 3114: raw material gas introduction pipe, 3115 : High frequency matching box, 3116: Gas piping, 3117: Leak valve, 3118: Main valve, 3119: Vacuum gauge, 3120: High frequency power supply, 3121: Insulating material, 3123: Receiving stand, 3221 to 3225: Raw material gas cylinder, 3231 to 3235: Valve, 3261 to 3265: Pressure regulator, 3241 to 3245: Inlet valve, 3251 to 3255: Outlet valve, 3211 to 3215: Mass flow controller, 3260: Auxiliary valve, 401: Photosensitive member (rotation direction), 402: Cleaning blade edge, 403: Toner, 404: External additive blocking layer

Claims

1. a charging step of charging an electrostatic image bearing member with a charging member, an electrostatic latent image forming step of forming an electrostatic latent image on the charged electrostatic image bearing member, and a developing step of developing the electrostatic image bearing member with toner to form a toner image on the electrostatic image bearing member; a transfer step of transferring the toner image onto a recording medium; a fixing step of fixing the toner image transferred onto the recording medium; a cleaning step of removing residual toner remaining on the surface of the electrostatic image bearing member after the transfer step using a cleaning blade; An image forming method comprising: the photosensitive layer of the electrostatic image bearing member contains amorphous silicon; the surface layer of the electrostatic image bearing member contains amorphous silicon carbide or amorphous carbon; The toner comprises toner particles, silica particles, and organosilicon polymer particles; When the toner is subjected to a water washing treatment, the amount of the organosilicon polymer particles that migrate from the toner is A (mass %), and the amount of the silica particles that migrate from the toner is B (mass %), based on the mass of the toner. When A and B are: 0.50≦A+B≦4.00 0.20≦B / A≦2.00 Fulfilling the number average diameter Da of the primary particles of the transferred organosilicon polymer particles is 50 nm or more and 200 nm or less; the number average particle diameter Db of the primary particles of the transferred silica particles is 50 nm or more and 200 nm or less; An image forming method characterized by:

2. 2. The image forming method according to claim 1, wherein the organosilicon polymer particles have a Young's modulus Ea of 1.0 GPa or more and 30.0 GPa or less.

3. The theoretical BET specific surface area of ​​the organosilicon polymer particles is defined as X (m 2 / g), and the measured BET specific surface area of ​​the organosilicon polymer particles is defined as Y(m 2 3. The image forming method according to claim 1, wherein X and Y satisfy the relationship 3.0≦Y / X≦8.0 when the ratio of X to Y is 1.0 / g.

4. 4. The image forming method according to claim 1, wherein the Young's modulus of the organosilicon polymer particles is Ea and the Young's modulus of the silica particles is Eb, and the relationship Ea / Eb≦0.20 is satisfied.

5. 5. The image forming method according to claim 1, wherein the Young's modulus of the electrostatic image carrier is defined as Ed, and the Young's modulus of the organosilicon polymer particles is defined as Ea / Ed≦0.

05.

6. When the toner is subjected to a water washing treatment, the amount of the organosilicon polymer particles that migrate from the toner is A (mass %), and the amount of the silica particles that migrate from the toner is B (mass %), based on the mass of the toner, and A and B are: 0.50≦A+B≦2.50 0.20≦B / A≦2.00 Fulfilling the organosilicon polymer particles are hydrophobically treated particles, When the Young's modulus of the electrostatic image bearing member is Ed, the Young's modulus of the organosilicon polymer particles, Ea, is expressed as follows: Ea / Ed≦0.05 6. The image forming method according to claim 1, wherein the above formula (1) is satisfied.

7. The image forming method according to claim 6, wherein the toner comprises titania particles in addition to the toner particles, the silica particles, and the organosilicon polymer particles.

8. 8. The image forming method according to claim 1, wherein the surface layer of the electrostatic image bearing member contains amorphous carbon.

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