JP2023072114A - Image formation method - Google Patents

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

The present invention relates to an image forming method using toner used in electrophotography.

In recent years, with the widespread use of electrophotographic full-color copiers, the demand for image forming devices capable of producing high-quality images over a long period of time has increased. Demand for longer life is also increasing.
As an electrophotographic photoreceptor for achieving high image quality, high speed, and long life, an electrophotographic apparatus using a photoreceptor using amorphous silicon for a photosensitive layer (hereinafter abbreviated as an a-Si photoreceptor) is known. ing.
In an image forming apparatus using such an a-Si photoreceptor, an image defect may occur in which characters are blurred in a high-humidity environment, or characters are not printed and white spots occur. . These image defects are hereinafter referred to as "image deletion".
There are various causes of image smearing. Discharge products are generated when the photoreceptor is charged, and the discharge products absorb moisture, reducing the resistance of the surface of the photoreceptor. Disturbance is known as a cause.
Conventionally, mainly two means have been studied for suppressing image smearing. One has been to heat the photoreceptor to reduce or remove moisture adsorbed on the surface of the photoreceptor. Various methods are known as means for heating such a 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. .
As another means, it has been studied to use an abrasive as an external additive for the toner, which has an effect of scraping off the generated discharge products. Japanese Patent Application Laid-Open No. 2002-201001 describes a toner in which specific inorganic fine particles, which are perovskite crystals having a cubic or rectangular parallelepiped shape, are used as an external additive for the toner and used as an abrasive for a photoreceptor.

JP 2017-15759 A JP 2006-285145 A

The method described in Japanese Patent Application Laid-Open No. 2002-200312 leads to an increase in the size of the image forming apparatus, and there is a problem that power consumption is required for heating.
On the other hand, the a-Si photoreceptor described in Patent Document 2 has a harder surface layer than the organic photoreceptor, so that discharge products are less likely to be scraped off. Therefore, the effect on image deletion was completely insufficient. In addition, there is a drawback that the fluidity and chargeability of the toner are lowered, making it difficult to obtain high-quality images.
The present invention provides an image forming method that solves the above problems. Specifically, even when a photoreceptor with an amorphous silicon photosensitive layer is used, image smearing in a high-humidity environment is suppressed, and stable, high-quality images can be obtained even after long-term durable printing. It is to provide a forming method.

The present invention comprises a charging step of charging an electrostatic charge image carrier with a charging member, an electrostatic latent image forming step of forming an electrostatic latent image on the charged electrostatic charge image carrier, and a developing step using toner. a developing step of forming a toner image on the electrostatic charge image carrier;
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 onto the recording medium;
a cleaning step of removing transfer residual toner remaining on the surface of the electrostatic charge image bearing member after the transfer step using a cleaning blade;
An image forming method comprising
the photosensitive layer of the electrostatic charge image carrier contains amorphous silicon;
the surface layer of the electrostatic charge image carrier contains amorphous silicon carbide or amorphous carbon;
The image forming method is characterized in that the toner comprises toner particles, silica particles and organosilicon polymer particles.

According to the present invention, even when a photoreceptor using amorphous silicon is used for the photosensitive layer of the electrostatic charge image carrier, image deletion in a high-humidity environment can be suppressed, and high image quality can be stably maintained even after long-term durable printing. It is possible to provide an image forming method capable of obtaining a high-quality image.

It is an example of the image forming method of the present invention. It is an example of the layer structure of the amorphous silicon photoreceptor of the electrostatic charge image carrier of the present invention. It is an example of a film forming apparatus for a photoreceptor of the present invention. 2 is an enlarged view of a nip portion between a cleaning blade and an electrostatic image bearing member of the present invention; FIG.

In the present invention, unless otherwise specified, the descriptions of "○○ or more and XX or less" and "○○ to XX", which represent numerical ranges, mean numerical ranges including the lower and upper limits that are endpoints.

According to the studies of the present inventors, in order to stably prevent the toner from passing through in the cleaning method using a blade, it is necessary to form a blocking layer with an external additive in the vicinity of the cleaning blade nip. thinking. The characteristics of the external additive are important for stably forming this blocking layer. If the external additive has too high lubricity, the external additive moves too fast, making it difficult to form a stable blocking layer. It is considered that cohesiveness, which suppresses mutual movement when external additives are gathered, is important for stable formation of an external additive blocking layer.

When attempting to suppress image smearing in a high-temperature, high-humidity environment without using conventionally known abrasives, we thought that it would be good if the discharge products could be scraped off by a blocking layer made of an external additive. In this case, the external additive-blocking layer is required to have stability to prevent the toner from slipping through, and to have abrasiveness to scrape off the discharge products.

The present inventors have found 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 in the vicinity of the cleaning blade nip. The inventors have found the present invention.

That is, the present invention comprises a charging step of charging an electrostatic charge image carrier with a charging member, an electrostatic latent image forming step of forming an electrostatic latent image on the charged electrostatic charge image carrier, and a toner. a developing step of developing to form a toner image on the electrostatic charge image carrier;
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 onto the recording medium;
a cleaning step of removing transfer residual toner remaining on the surface of the electrostatic charge image bearing member after the transfer step using a cleaning blade;
An image forming method comprising
the photosensitive layer of the electrostatic charge image carrier contains amorphous silicon;
the surface layer of the electrostatic charge image carrier contains amorphous silicon carbide or amorphous carbon;
The image forming method is characterized in that the toner comprises toner particles, silica particles and organosilicon polymer particles.

The organosilicon polymer particles used in the present invention have a lower Young's modulus than the a-Si photoreceptor and silica fine particles, and are easily deformed by an external force. It is thought that when organosilicon polymer fine particles having such characteristics are present in the external additive blocking layer, the organosilicon polymer fine particles in the blocking layer are deformed by pressure applied by the cleaning blade, and the density of the blocking layer increases. As a result, the density of the external additive blocking layer is increased, and the deformation energy of the organosilicon polymer particles is converted into the energy for scraping off the discharge products. It is believed that the effect of scraping off the discharge products is dramatically increased, and the effects of the present invention can be obtained. On the other hand, when the external additive-blocking layer is composed of organosilicon polymer particles alone, a stable blocking layer with high sliding property between particles is not formed, and the effect is not exhibited.

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

<<Image forming method>>
FIG. 1 shows an example of an image forming apparatus according to the present invention. This figure is a vertical cross-sectional view showing a schematic configuration of a digital copying machine.

The copier shown in FIG. 1 includes a drum-type electrophotographic photosensitive member 101 as an electrostatic charge image bearing member. The photosensitive member 101 is rotationally driven in the direction of the arrow by driving means (not shown). A charging roller 102 as a primary charging means, an exposure means 103, a developing device 104, a transfer charging device 105, and a cleaning device 107 having a cleaning blade are arranged around the photoreceptor 101 substantially in this order along its rotational direction. It is Further, a fixing device 106 is arranged downstream (left side in the figure) of the transfer charging device 105 in the conveying direction (arrow direction) of the transfer material 108 which is the recording medium.

The surface of the photoreceptor 101 is charged by the charging roller 102 . Next, the laser light emitted from the exposing means 103 removes electric charges from the laser light irradiated portion, thereby forming an electrostatic latent image. The electrostatic latent image on photoreceptor 101 is developed with charged toner in developing device 104 . The developed toner image on the photosensitive member 101 is transferred by a transfer charger 105 onto a transfer material 111 conveyed in the direction of the arrow. The transfer material 111 after the toner image has been transferred at the transfer unit is conveyed to a fixing device 106 where it is heated and pressurized to fix the toner image on its surface. A cleaning device 107 collects residual toner remaining on the photosensitive member after transfer.

<Electrostatic charge image carrier>
First, the layer structure of a photoreceptor, which is an electrostatic charge image carrier to which the present invention is applied, will be described.

FIG. 2A is a schematic diagram showing the layer structure of an a-Si photoreceptor. A withstand voltage layer 201 , a charge injection blocking layer 202 , a photosensitive layer 203 and a surface layer 204 are sequentially laminated on a substrate 200 . This layer structure is mainly applied to a-Si photoreceptors for positive charging.

FIG. 2B 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. As shown in FIG. By providing the intermediate layer 205 with a charge blocking ability, it can also be applied to an a-Si photosensitive member for negative charging.

FIG. 2C is a schematic diagram of a layer structure of an a-Si photoreceptor in which a plurality of intermediate layers 206 are provided between a photosensitive layer 203 and a surface layer 204. FIG. This configuration can also be applied to an a-Si photoreceptor for negative charging by imparting a charge blocking ability to any one of a plurality of intermediate layers 206 .

FIG. 2D is a schematic diagram of the layer structure of an a-Si photoreceptor in which a changeable layer 207 is provided between a photosensitive layer 203 and a surface layer 204. FIG. This configuration can also be applied to an a-Si photosensitive member for negative charging by imparting a charge blocking ability to a portion of the variable layer 207 .

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

The electrostatic charge image carrier of the present invention comprises a photosensitive layer made of amorphous silicon formed on a drum-shaped conductive substrate. A photosensitive layer made of amorphous silicon can be formed, for example, by vapor phase epitaxy such as glow discharge decomposition, sputtering, ECR, plasma CVD, vapor deposition, and ion plating. When forming a photosensitive layer made of amorphous silicon, the photosensitive layer can contain hydrogen or a halogen element.

In the present invention, it is preferred that the photosensitive layer contain atoms for controlling the conductivity, if necessary. Atoms for controlling conductivity include so-called impurities in the field of semiconductors. 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, a phosphorus atom (P) and an arsenic atom (As) are preferred.

The content of atoms for controlling conductivity contained in the photosensitive layer is preferably 1×10 ⁻² atom ppm or more relative to silicon atoms (Si). On the other hand, it is preferably 1×10 atomic ppm or less.

Further, the electrostatic charge image bearing member 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. Amorphous carbon is more preferable from the viewpoints of lubricity with the external additive blocking layer in which organosilicon polymer particles are present and ease of scraping off discharge products adhering to the surface.

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

When the carrier blocking layer is provided, the injection of carriers into the photosensitive layer made of amorphous silicon is prevented during development, and the electrostatic contrast between the exposed and non-exposed areas is increased, thereby improving image density and reducing background fogging. can be achieved. Examples of materials for the carrier blocking layer include inorganic insulating materials such as amorphous silicon carbide, amorphous silicon oxide, amorphous silicon nitride, and amorphous silicon oxynitride, polyethylene terephthalate, polytetrafluoroethylene, polyimide, polyfluoroethylene propylene, and polyurethane. , epoxy resin, polyester, polycarbonate, and other organic insulating materials.

<Method for producing a-Si photoreceptor>
Any method for producing the a-Si photoreceptor may be used as long as it can form a layer that satisfies the above requirements. Specifically, the plasma CVD method, the vacuum deposition method, the sputtering method, the ion plating method, and the like can be mentioned. Among these, the plasma CVD method is preferable in terms of ease of supply of raw materials.

A manufacturing apparatus and manufacturing method using the plasma CVD method will be described below.

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

This deposition apparatus is roughly composed of a deposition apparatus 3100 having a reaction vessel 3110 , a source gas supply apparatus 3200 , and an exhaust system (not shown) for reducing the pressure in the reaction vessel 3110 .

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

The source gas supply device 3200 comprises source gas cylinders 3221-3227, valves 3231-3237, pressure regulators 3261-3267, inflow valves 3241-3247, and outflow valves 3251-3257. Furthermore, mass flow controllers 3211 to 3217 are provided. A cylinder containing each raw material gas is connected to the raw material gas introduction pipe 3114 in the reaction vessel 3110 via an auxiliary valve 3260 . 3116 is a gas pipe, 3117 is a leak valve, and 3121 is an insulating material.

Next, a method of forming a deposited film using this apparatus will be described. First, the substrate 3112 which has been degreased and washed in advance is placed in the reaction container 3110 via the cradle 3123 . Next, an exhaust system (not shown) is operated to exhaust the inside of the reaction vessel 3110 . While watching the display of the vacuum gauge 3119, when the pressure in the reaction vessel 3110 reaches a predetermined pressure of, for example, 1 Pa or less, electric power is supplied to the substrate heating heater 3113 to heat the substrate 3112 by, for example, 50 to 350 degrees Celsius. Heat to a given temperature of °C. At this time, an inert gas such as Ar or He can be supplied from the gas supply device 3200 to the reaction vessel 3110 to perform heating in an inert gas atmosphere.

Next, the gas used for depositing film formation is supplied to the reaction vessel 3110 from the gas supply device 3200 . That is, the valves 3231-3237, the inflow valves 3241-3247, and the outflow valves 3251-3257 are opened as necessary to set the flow rates in the mass flow controllers 3211-3217. When the flow rate of each mass flow controller is stabilized, the main valve 3118 is operated while observing the display of the vacuum gauge 3119 to adjust the pressure inside the reaction vessel 3110 to the desired pressure. When a 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 in the reaction vessel 3110 . After that, the high-frequency power is quickly adjusted to a desired power to form a deposited film.

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

This completes the formation of the deposited film. In the case of forming a plurality of deposited films, the above procedure may be repeated to form each layer. The bonding region can also be formed by changing the raw material gas flow rate, pressure, etc. to the conditions for forming the photosensitive layer at a constant time.

After all deposited films have been formed, the main valve 3118 is closed, inert gas is introduced into the reaction vessel 3110 to restore the atmospheric pressure, and then the substrate 3112 is taken out.

Silanes such as silane (SiH ₄ ) and disilane (Si ₂ H ₆ ) can be suitably used as source gases for supplying silicon atoms in the formation of the withstand voltage layer. Moreover, ammonia (NH ₃ ), nitrogen (N ₂ ), etc., can be suitably used as the raw material gas for supplying nitrogen atoms, for example. As the source gas for supplying oxygen atoms, oxygen (O ₂ ), nitrogen monoxide (NO), etc., can be suitably used in addition to the above source gases. In addition to the above source gas, for example, hydrogen (H ₂ ) can be suitably used as the source gas for supplying hydrogen atoms. In addition, when carbon atoms or the like are contained in the charge injection blocking layer in order to improve adhesion to the conductive substrate, a gaseous or easily gasifiable substance containing atoms to be contained may be appropriately used as the material. Just do it.

For the formation of the charge injection blocking layer, silanes such as silane (SiH ₄ ) and disilane (Si ₂ H ₆ ) can be suitably used as the source gas for supplying silicon atoms. Diborane (B ₂ H ₆ ), for example, can be suitably used as the raw material gas for supplying Group 13 atoms. In addition to the above source gases, hydrogen (H ₂ ), for example, can also be suitably used as the source gas for supplying hydrogen atoms. In addition, when carbon atoms, oxygen atoms, nitrogen atoms, or the like are contained in the charge injection blocking layer in order to improve adhesion with the breakdown voltage layer, gaseous or easily gasifiable substances containing these atoms are used. It may be used appropriately as a material.

In the formation of the photosensitive layer, silanes such as silane (SiH ₄ ) and disilane (Si ₂ H ₆ ) can be suitably used as source gas for supplying silicon atoms. In addition to the above-described silanes, hydrogen (H ₂ ), for example, can also be suitably used as the raw material gas for supplying hydrogen atoms. In addition, when the photosensitive layer contains the above-mentioned halogen atoms, atoms for controlling conductivity, carbon atoms, oxygen atoms, nitrogen atoms, etc., gaseous or easily gasifiable substances containing these atoms are used as materials. can be used as appropriate.

When amorphous silicon carbide is formed as the surface layer, silanes such as silane (SiH ₄ ) and disilane (Si ₂ H ₆ ) can be suitably used as source gases for supplying silicon atoms. As the source gas for supplying carbon atoms, for example, gases such as methane (CH ₄ ) and acetylene (C ₂ H ₂ ) can be suitably used. 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 (CH ₄ ) and acetylene (C ₂ H ₂ ) can be suitably used as source gases for supplying carbon atoms. Moreover, in either material, hydrogen (H ₂ ), for example, can be suitably used as the raw material gas for supplying hydrogen atoms.

<Cleaning blade>
In the present invention, the method for cleaning the toner on the electrophotographic photosensitive member is a cleaning blade method. In this method, a blade-shaped cleaning member made of an elastic material is pressed against the photoreceptor to dam up and collect the transfer residual toner on the photoreceptor.

As shown in FIG. 4, the external additive blocking layer 404, which is mainly formed by migrating the external additive fine particles contained in the toner, has the effect of scraping off the discharge products adhering to the surface of the photoreceptor. In addition, the external additive blocking layer 404 is also important for blocking the toner 403, maintaining lubricity between the cleaning blade 402 and the photoreceptor 401, and preventing toner from slipping through.

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

As the material for the cleaning blade, a rubber material is suitable from the viewpoint of followability to the surface of the photoreceptor and resistance to scratching. Among them, polyurethane rubber is most suitable from the physical and chemical aspects, and the rubber hardness is preferably from 60 degrees to 90 degrees in International Rubber Hardness (IRHD).

"toner"
The toner of the present invention is characterized by comprising toner particles, silica particles and organosilicon polymer particles.

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 or more and 300 nm or less. When the thickness is 40 nm or more, the rate of slipping through the cleaning blade is suppressed, and a stable blocking layer is easily formed. When it is 300 nm or less, it is easy to uniformly externally add to the surface of the toner, and it becomes easy to obtain good durability stability.

More preferably, both Da and Db are in the range of 50 nm or more and 200 nm or less. particles are more likely to come into contact with each other. Therefore, the density and deformation energy of the external additive-blocking layer are increased, and the effect of scraping off discharge products is enhanced, and the effect of suppressing image deletion is improved.

The Young's modulus Ea of the organosilicon polymer particles is preferably in the range of 1.0 GPa or more and 30.0 GPa or less. By setting it within this range, the bulk density of the external additive blocking layer at the cleaning blade nip is increased, and the effect of scraping off discharge products is easily obtained. The Young's modulus of the organosilicon polymer particles can be controlled by changing the structure of the Si-bonded functional groups of the constituent compounds. Specifically, it can be controlled by changing the abundance ratio of each constituent compound of the M unit structure (S1), D unit structure (S2), T unit structure (S3), and Q unit structure (S4).

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 and the Young's modulus of the silica particles are largely different, so that the bulk density of the external additive-blocking layer in the cleaning blade nip increases, and the effect of suppressing image deletion is likely to be obtained. More preferably, Ea/Eb≦0.40, still more preferably Ea/Eb≦0.20.

The Young's modulus Ed of the surface of the electrostatic charge image bearing member and the Young's modulus Ea of the organosilicon polymer particles preferably have a relationship of Ea/Ed≦0.20. Within this range, the organosilicon polymer particles are easily deformed on the surface of the electrostatic charge image bearing member, the bulk density of the external additive blocking layer at the cleaning blade nip is increased, and the effect of suppressing image deletion is easily obtained. Ea/Ed≦0.10 is more preferred, and Ea/Ed≦0.05 is even more preferred.

The amount of organosilicon polymer 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 the above range, excellent blade cleaning properties and durability stability can be obtained. By setting the addition amount to 0.2% by mass or more, the amount of the external additive necessary for forming the blocking layer can be reliably secured. Further, when the content is within 10.0% by mass, contamination of members by the external additive can be suppressed, and good durability stability can be obtained.

Further, when the theoretical BET specific surface area of the organosilicon polymer particles is X (m ² /g) and the actually measured BET specific surface area of the organosilicon polymer particles is Y (m ² /g), X and Y and
3.0≤Y/X≤8.0
It is preferable to

An increase in the value of Y/X means that the surface has fine irregularities (increase in pores). In the present invention, image deletion can be further suppressed by setting this value to 3.0 or more. It is believed that this is because the minute irregularities on the surface can adsorb a large amount of discharge products and moisture, which are factors of image deletion. On the other hand, if it exceeds 8.0, the number of pores will increase too much, and the moisture adsorption will increase, which is not preferable from the viewpoint of the charging stability of the toner.

As a method for controlling the value of Y/X, each constituent compound of the M unit structure (S1), D unit structure (S2), T unit structure (S3), and Q unit structure (S4) of the organosilicon polymer fine particles can be controlled by changing the abundance ratio of , changing the reaction rate during production, and the like.

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 the above range, excellent blade cleaning properties and durability stability can be obtained. By setting the addition amount to 0.2% by mass or more, the amount of the external additive necessary for forming the blocking layer can be reliably secured. Further, when the content is 10.0% by mass or less, contamination of members by the external additive can be suppressed, and good durability stability can be obtained.

In the toner of the present invention, the transfer amount of the organosilicon polymer particles from the toner is A (% by mass) based on the weight of the toner when the toner is washed with water, and the transfer amount of the silica particles from the toner is When is B (mass%), the A and the B are
0.50≤A+B≤4.00
0.20≤B/A≤2.00
is preferably satisfied. A (% by mass) is the amount of the organosilicon polymer particles transferred from the toner, and B (% by mass) is the amount of the silica particles transferred from the toner when the toner is washed with water by the method described later. If there is a relationship, the effect of suppressing image deletion and the effect of suppressing image defects during long-term printing are easily compatible, which is preferable. When A+B is 0.50 or more, a sufficient amount of the external additive for forming the external additive blocking layer can be ensured. When A+B is 4.00 or less, it is possible to suppress contamination of the member due to the external additive during endurance printing, and to suppress image defects caused by the contamination of the member. When B/A is within the above range, the bulk density of the external additive blocking layer at the cleaning blade nip is highly effective in suppressing image deletion, which is preferable.

The migration amounts A and B are controlled by changing the production conditions in the external addition process during toner production, adding a process such as thermal fixation after the external addition process, and changing the amount of presence in the toner. Is possible.

<Organosilicon polymer particles>
The method for producing the organosilicon polymer particles is not particularly limited. For example, particles can be formed through hydrolysis and polycondensation reaction of a silicon compound (silane monomer) by a sol-gel method. Specifically, 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 is hydrolyzed and polycondensed. The particles can be formed by polymerizing with.

The method for producing the organosilicon polymer particles is not particularly limited. For example, the silane compound may be added dropwise to water, hydrolyzed and condensed with a catalyst, and the resulting suspension may be filtered and dried. In addition, the particle size can be controlled by the type of catalyst, compounding ratio, reaction initiation temperature, dropping time, and the like. Acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid and nitric acid, and basic catalysts include ammonia water, sodium hydroxide, potassium hydroxide and the like, but are not limited to these.

Organosilicon polymer particles are preferably produced by the following method. Specifically, a first step of obtaining a hydrolyzate of a silicon compound, a second step of mixing the hydrolyzate with an alkaline aqueous medium and subjecting the hydrolyzate to a polycondensation reaction, a polycondensation reaction product and an aqueous solution are mixed to form particles. In some cases, a hydrophobizing agent may be added to the organosilicon polymer particle dispersion to obtain hydrophobized organosilicon polymer particles.

In the first step, a silicon compound and a catalyst are brought into contact with each other 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. A known catalyst can be suitably used as the catalyst. Specifically, acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, and basic catalysts include aqueous ammonia, sodium hydroxide, potassium hydroxide, and the like.

The amount of catalyst to be used may be appropriately adjusted depending on the type of silicon compound and catalyst. Preferably, it is selected in the range of 1×10 ⁻³ to 1 part by mass with respect to 100 parts by mass of water used for hydrolyzing the silicon compound.

If the amount of the catalyst used is 1×10 ⁻³ parts by mass or more, the reaction will proceed sufficiently. On the other hand, when the amount of the catalyst used is 1 part by mass or less, the concentration of impurities remaining in the fine particles becomes low, and hydrolysis is facilitated. The amount of water used is preferably 2 mol or more and 15 mol or less per 1 mol of the silicon compound. When the amount of water is 2 mol or more, the hydrolysis reaction proceeds sufficiently, and when it is 15 mol or less, productivity improves.

The reaction temperature is not particularly limited, and may be carried out at normal temperature or in a heated state, but since the hydrolyzate can be obtained in a short time and the partial condensation reaction of the produced hydrolyzate can be suppressed, it is kept at 10 to 60 ° C. It is preferable to carry out the reaction in such a state. The reaction time is not particularly limited, and may be appropriately selected in consideration of the reactivity of the silicon compound used, the composition of the reaction solution prepared by mixing the silicon compound, acid and water, and the productivity.

In the method for producing silicon polymer particles, in the second step, the raw material solution obtained in the first step and an alkaline aqueous medium are mixed to cause a polycondensation reaction of the particle precursors. Thus, a polycondensation reaction liquid is obtained. Here, the alkaline aqueous medium is a liquid obtained by mixing an alkaline component, water, and, if necessary, an organic solvent or the like.

The alkaline component used in the alkaline aqueous medium is one whose aqueous solution exhibits basicity, and acts as a neutralizing agent for the catalyst used in the first step and as a catalyst for the polycondensation reaction in the second step. It is something to do. Examples of such alkali components include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonia; and organic amines such as monomethylamine and dimethylamine.

The amount of the alkaline component used is an amount that neutralizes the acid and acts effectively as a catalyst for the polycondensation reaction. Therefore, it is usually selected in the range of 0.01 parts by mass or more and 12.50 parts by mass or less.

In the second step, in addition to the alkaline component and water, an organic solvent may be used to prepare the alkaline aqueous medium. 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 suitable.

Specifically, 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; ethylene glycol monoethyl ether, ethers such as acetone, diethyl ether, tetrahydrofuran and diacetone alcohol; and amide compounds such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.

Among the organic solvents listed above, alcoholic solvents such as methanol, ethanol, 2-propanol and butanol are preferred. Furthermore, from the viewpoint of hydrolysis and dehydration condensation reaction, it is more preferable to select the same alcohol as the alcohol to be eliminated as the organic solvent.

In the third step, the polycondensation reaction product obtained in the second step is mixed with an aqueous solution to form particles. As the aqueous solution, water (tap water, pure water, etc.) can be suitably used. Further may be added. The temperature of the polycondensation reaction solution and the aqueous solution when mixed is not particularly limited, and a range of 5 to 70° C. is preferably selected in consideration of their composition, productivity and the like.

As a method for recovering the silicon polymer particles, any known method can be used without particular limitation. For example, the floating powder can be scooped out, and a filtering method may be employed, and the filtering method is preferable because the operation is simple. The filtration method is not particularly limited, and a known device such as vacuum filtration, centrifugal filtration, pressure filtration, or the like may be selected. Filter papers, filters, filter cloths, and the like used for filtration are not particularly limited as long as they are industrially available, and may be appropriately selected according to the device to be used.

The silane monomer to be used can be appropriately selected depending on compatibility with solvents and catalysts, hydrolyzability, and the like.

Examples of tetrafunctional silanes include tetramethoxysilane, tetraethoxysilane, tetraisocyanatesilane, and the like.

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

Bifunctional silanes include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, diethyldimethoxysilane and the like.

Among the above, tetraethoxysilane is preferable as the tetrafunctional silane, trimethoxymethylsilane as the trifunctional silane, and dimethyldimethoxysilane as the bifunctional silane.

Also, these polyfunctional monomers can be used alone or in combination. Although the detailed reason is unknown, when the amount of the trifunctional monomer used is less than the total amount of the tetrafunctional monomer and the bifunctional monomer used, the effects of the present invention are likely to appear more remarkably, which is preferable.

The organosilicon polymer particles may be surface-treated with a 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, 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. preferably. When the degree of hydrophobicity is 35 or more, the effect of suppressing image deletion is enhanced, which is preferable.

<Silica particles>
As the silica particles of the present invention, fine silica particles produced by any method such as a wet method, a flame fusion method and a vapor phase method are preferably used.

As a wet method, alkoxysilane is added dropwise to an organic solvent containing water, hydrolysis and condensation reactions are carried out using a catalyst, the solvent is removed from the obtained silica sol suspension, and sol-gel silica is obtained by drying. A sol-gel method is mentioned.

In the flame melting method, a silicon compound that is gaseous or liquid at room temperature is gasified in advance, and then a combustible gas composed of hydrogen and/or hydrocarbons and oxygen are supplied to form an outer flame, A method of obtaining fine silica particles (fused silica) by decomposing and melting the silicon compound may be mentioned.

In the flame fusion method, silica fine particles are generated from the silicon compound in an external flame, and at the same time, the silica fine particles are fused and coalesced so as to have a desired particle size and shape, and then cooled to form a bag filter. etc. can be collected. The silicon compound used as a raw material is not particularly limited as long as it is gaseous or liquid at room temperature. siloxanes such as octamethyltrisiloxane; alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane or dimethyldimethoxysilane; organosilane compounds such as tetramethylsilane, diethylsilane or hexamethyldisilazane; Silicon halides such as chlorosilane, trichlorosilane or tetrachlorosilane; and inorganic silicon such as monosilane or disilane.

Vapor phase processes include fumed processes in which silicon tetrachloride is produced by burning it at high temperatures with a mixture of oxygen, hydrogen and a diluent gas such as nitrogen, argon and carbon dioxide.

The silica particles are preferably surface-treated for the purpose of hydrophobizing the surface and improving charging stability. A silane coupling agent or silicone oil is preferably used as the surface treatment agent at this time.

Silane coupling agents include, for example, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilamen, dimethyldiethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, or having 2 to 12 siloxane units per molecule, Examples include dimethylpolysiloxanes each containing a silicon-bonded hydroxyl group in each terminal unit.

Examples of the silicone oil used for treating the silica particles used 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 those having the above formula. The silicone oil preferably has a viscosity of 50 mm ² /s or more and 1000 mm ² /s or less at a temperature of 25°C. If it is less than 50 mm ² /s, it is partially volatilized by the application of heat, tending to deteriorate charging characteristics. If it exceeds 1000 mm ² /s, it tends to be difficult to handle in processing operations. A known technique can be used as a method of silicone oil treatment. For example, silicic acid fine powder and silicone oil are mixed using a mixer; silicone oil is sprayed into silicic acid fine powder using a sprayer; or after dissolving silicone oil in a solvent, silicic acid fine powder A method of mixing bodies is included. The processing method is not limited to this.

In particular, the silica particles of the present invention preferably use hexamethyldisilazane or silicone oil as a surface treatment agent.

<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.

For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene, and substituted products thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer , styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl Styrenic copolymers such as ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, 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, petroleum-based resins, and the like can be used. Among them, polyester resins are preferable from the viewpoint of durability stability and charging stability.

<Colorant>
A colorant may be used in the toner of the present invention, if necessary. Colorants include the following.

Examples of black colorants include carbon black; black toned by using a yellow colorant, a magenta colorant and a cyan colorant. A pigment may be used alone as a coloring agent, but it is more preferable to use a dye and a pigment in combination to improve the definition from the viewpoint of image quality of a full-color image.

Examples of magenta toner pigments include the following. C. I. 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; I. Pigment Violet 19; C.I. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

Dyes for magenta toner include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. disperse thread 9;C. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of cyan toner pigments include the following. C. I. Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment having a phthalocyanine skeleton substituted with 1 to 5 phthalimidomethyl groups.

As dyes for cyan toners, C.I. I. There is Solvent Blue 70.

Examples of yellow toner pigments include the following. C. I. 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; I. Bat Yellow 1, 3, 20.
As a yellow toner dye, C.I. I. There is Solvent Yellow 162.

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.

<Wax>
Wax may be used in the toner of the present invention, if necessary. Examples of wax include the following.

Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; fatty acid esters such as carnauba wax as a main component; Waxes that deoxidize partially or wholly deoxidized fatty acid esters such as deoxidized carnauba wax.

Furthermore, the following are mentioned. Saturated straight-chain fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid and valinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol and ceryl alcohol , saturated alcohols such as mericyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid and montanic acid; Esters with alcohols such as ceryl alcohol and melicyl alcohol; Fatty acid amides such as linoleic acid amide, oleic acid amide and lauric acid amide; Methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amides, saturated fatty acid bisamides such as hexamethylenebisstearic acid amide; unsaturated fatty acid amides; aromatic bisamides such as m-xylene bisstearic acid amide and N,N' distearyl isophthalic acid amide; fats such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate group metal salts (generally called metal soaps); waxes obtained by grafting vinyl monomers such as styrene and acrylic acid to aliphatic hydrocarbon waxes; Partial esters of hydric alcohols; methyl ester compounds with hydroxyl groups obtained by hydrogenation of vegetable oils and fats.

The wax content 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. Waxes may be used alone, or may be used in combination of multiple types.

<Charge control agent>
The toner of the present invention may also contain a charge control agent, if desired. As the charge control agent contained in the toner, a known charge control agent can be used, but it is particularly preferable to use a positive charge control agent when combined with the photoreceptor of the present invention.

Examples of positive charge control agents include azine compounds, azine dyes, nigrosine dyes, quaternary ammonium salts, resins containing quaternary ammonium cationic groups, triaminotriphenylmethane compounds and imidazole compounds.

Negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylic acid compounds, polymeric compounds having sulfonic acid or carboxylic acid side chains, and sulfonate or sulfonate ester side chain compounds. Polymeric compounds, polymeric compounds having carboxylates or carboxylic acid esters in side chains, boron compounds, urea compounds, silicon compounds, and calixarene can be mentioned.

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, more preferably 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

<Inorganic fine particles>
In the toner of the present invention, in addition to the external additive for toner described above, other inorganic fine particles may be used in combination, if necessary, as long as the effects of the present invention are not impaired.

As the external additive, inorganic fine particles having a specific surface area of 50 m ² /g or more and 400 m ² /g or less are preferable. Fine adjustment of fluidity and chargeability can be achieved by using together inorganic fine particles having a specific surface area within the above range. When combined with the electrostatic charge image bearing member of the present invention, fine particles having a primary particle number average diameter smaller than that of the organosilicon polymer particles and silica particles and having a low resistance are used. This is preferable because excessive charging is suppressed and a stable external additive blocking layer is easily formed. 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 particles have a number average diameter of less than 40 nm.

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 with respect to 100 parts by mass of the toner particles.

<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 recommended to mix it with a magnetic carrier and use it as a two-component developer to obtain stable images over a long period of time. It is preferable in that Furthermore, it is possible to suppress the extent to which the external additive particles of the toner migrate into the developing machine, and to form an appropriate external additive blocking layer on the surface of the electrostatic charge image bearing member. That is, it is a two-component developer containing a toner and a magnetic carrier, and the toner is preferably the toner of the present invention.

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

<Method for producing toner particles>
The method for producing the toner particles is not particularly limited, and conventionally known production methods such as a suspension polymerization method, an emulsion aggregation method, a melt-kneading method, and a dissolution suspension method can be employed.

Fine particles containing organosilicon polymer fine particles and silica fine particles of the present invention are mixed with the obtained toner particles to obtain a toner. Toner particles, inorganic fine particles, and other external additives can be mixed with a double-con mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, Mechanohybrid (manufactured by Nippon Coke Kogyo Co., Ltd.), Nobilta ( (manufactured by Hosokawa Micron Corporation) or the like can be used. The organosilicon polymer fine particles and silica fine particles of the present invention may be added to the toner particles at the same time, or one of them may be mixed with the toner particles and then the other may be added.

In addition, after mixing, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mechanofusion system (manufactured by Hosokawa Micron Corporation), a faculty (manufactured by Hosokawa Micron Corporation), and a Meteor Rainbow MR Type (manufactured by Nippon Pneumatic Co., Ltd.) are used to mechanically or thermally By performing such a treatment, it is possible to control the fixation rate of the organosilicon polymer fine particles and silica fine particles on the surface of the toner particles.

《Method of measuring physical properties》
The method for measuring physical properties according to the present invention is described below.

<Method for Identifying Organosilicon Polymer Particles>
A method for identifying the organosilicon polymer particles contained in the toner can be carried out by combining shape observation by SEM and elemental analysis by EDS.

Using a scanning electron microscope “S-4800” (trade name; manufactured by Hitachi Ltd.), the toner is observed in a field magnified up to 50,000 times. The external additive is observed by focusing on the toner particle surface. EDS analysis is performed on each particle of the external additive, and it is determined whether or not the analyzed particles are organosilicon polymer fine particles based on the presence or absence of Si element peaks.

When the toner contains both organosilicon polymer fine particles and silica fine particles, the ratio (Si/O ratio) of the element contents (atomic %) of Si and O can be compared with that of a sample. Identification of organosilicon polymer microparticles.

An EDS analysis is performed under the same conditions on samples of each of the organosilicon polymer fine particles and the silica fine particles to obtain the element content (atomic %) of each of Si and O.

Let A be the Si/O ratio of the organosilicon polymer fine particles, and B be the Si/O ratio of the silica fine particles. Select a measurement condition under which A is significantly greater than B.

Specifically, the sample is measured 10 times under the same conditions, and the arithmetic mean values of A and B are obtained. Measurement conditions are selected such that the obtained average value is A/B>1.1.

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

Tospar 120A (Momentive Performance Materials Japan LLC) is used as a sample of organosilicon polymer particles, and HDK V15 (Asahi Kasei) is used as a sample of silica fine particles.

<Method for Measuring the Number Average Particle Diameter of Primary Particles of Organosilicon Polymer Particles and Silica Particles>
A scanning electron microscope “S-4800” (trade name; manufactured by Hitachi, Ltd.) used for toner preparation and elemental analysis by energy dispersive X-ray spectroscopy (EDS) are combined.

In a field of view enlarged up to 50,000 times, the above-described elemental analysis method by EDS is also used, and fine particles are photographed at random.

100 organosilicon polymer fine particles and silica fine particles are randomly selected from the photographed image, the major diameters of the primary particles of the target fine particles are measured, and the arithmetic mean value is taken as the number average particle diameter.

The observation magnification is appropriately adjusted according to the sizes of the organosilicon polymer fine particles and the silica fine particles.

<Method for Quantifying Organosilicon Polymer Particles or Silica Particles Contained in Toner>
1 g of toner is placed in a vial, dissolved in 31 g of chloroform, and dispersed. For dispersion, an ultrasonic homogenizer is used for 30 minutes to prepare a dispersion.

After that, centrifugation is used to separate the organosilicon polymer fine particles and the silica fine particles according to the difference in specific gravity to obtain each sample, and the content of the organosilicon polymer fine particles or the silica fine particles is determined.

First, the pressed toner is measured with fluorescent X-rays, and the content of silicon in the toner is obtained by analytical processing such as the calibration curve method or the FP method.

Next, for each constituent compound forming the organosilicon polymer fine particles and, if necessary, the silica fine particles, the structure is specified using solid-state ²⁹ Si-NMR, pyrolysis GC/MS, etc., and the Obtain the silicon content in the silica fine particles. From the relationship between the silicon content in the toner determined by fluorescent X-rays and the silicon content in the organosilicon polymer fine particles and silica fine particles determined by solid ²⁹ Si-NMR and pyrolysis GC/MS, the toner was calculated. The content of organosilicon polymer fine particles or silica fine particles is determined.

<Amount Transferred from Toner Particles and Particle Size of Transferred Organosilicon Polymer Particles or Silica Particles by Water Washing of Organosilicon Polymer Particles or Silica Particles>
(Washing process)
Pre-wash toner:
Using various toners produced as they are, the amount of silicon in the silicon compound present on the surfaces of the toner particles before washing is determined by the following method.

Post-wash toner:
Add 500 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) to 250 mL of ion-exchanged water and dissolve in a hot water bath to prepare a concentrated sucrose solution. In a centrifugation tube (capacity: 50 mL), 31 g of the concentrated sucrose solution and Contaminon N (a pH 7 neutral detergent for cleaning precision measuring instruments consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) were added. 6 mL of a mass % aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion. 1.0 g of toner is added to this dispersion, and clumps of toner are loosened with a spatula or the like.

The centrifuge tube is shaken on a shaker at 350 spm (strokes per min) for 20 minutes. By this operation, the organosilicon polymer or the silica particles migrate from the toner particles to the dispersion liquid side depending on the state of fixation of the organosilicon polymer or silica particles to the toner particles. After shaking, the solution is replaced in a swing rotor glass tube (capacity 50 mL) and separated in a centrifuge (H-9R manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 minutes. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the separated toner on the uppermost layer is collected with a spatula or the like. After the collected aqueous solution containing the toner is filtered with a vacuum filter, it is dried with a dryer for 1 hour or longer. The dried product is pulverized with a spatula, washed, and used as a toner.

If the toner is a magnetic toner containing a magnetic material, the supernatant liquid containing the organosilicon polymer or silica fine particles is separated while the toner is constrained by a neodymium magnet instead of being centrifuged, and washed with pure water. After repeating, the magnetic toner may be collected by filtration.
The organosilicon polymer fine particles or silica fine particles that have migrated into the aqueous solution are sedimented by centrifugation, the supernatant is removed, and the sediment is collected after repeated washing with pure water.

Next, using a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Co., Ltd.), the toner not subjected to the water washing process (toner before washing) and the toner obtained through the water washing process Take a picture of the washed toner (washed toner).

Then, the photographed toner surface image is analyzed using image analysis software Image-Pro Plus ver. 5.0 (Nippon Roper Co., Ltd.) to analyze and calculate the coverage.

The imaging conditions for the S-4800 are as follows.

(1) Sample Preparation A sample stage (aluminum sample stage 15 mm×6 mm) is thinly coated with conductive paste, and toner is sprayed thereon. Further, air blowing is performed to remove excess toner from the sample stage, and the sample stage is sufficiently dried. A sample stage is set on the sample holder, and the height of the sample stage is adjusted to 36 mm using the sample height gauge.

(2) S-4800 Observation Condition Setting When measuring the coverage rate, an elemental analysis is performed in advance by the energy dispersive X-ray spectroscopy (EDS) described above, and the organosilicon polymer fine particles or silica fine particles on the surface of the toner particles are distinguished. Measure with

The anti-contamination trap attached to the S-4800 housing is flooded with liquid nitrogen and left for 30 minutes. Start the "PC-SEM" of the S-4800 and perform flushing (cleaning of the FE chip, which is the electron source). Click the acceleration voltage display part of 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. Confirm that the emission current due to flashing is 20 to 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.

Click the acceleration voltage display to open the HV setting dialog, and set the acceleration 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 [ L. A. 100] to set the mode for observing backscattered electron images. Similarly, 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 on the acceleration voltage display section of the control panel to apply the acceleration voltage.

(3) Calculation of number-average particle diameter (D1) of toner Drag within the magnification display area of the control panel to set the magnification to 5000 (5k) times. Rotate the focus knob [COARSE] on the operation panel, and adjust the aperture alignment when the focus is achieved to some extent. Click [Align] in 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 circle. Next, select [Aperture] and turn the STIGMA/ALIGNMENT knobs (X, Y) one by one to stop or minimize the movement of the image. Close the aperture dialog and focus with autofocus. Repeat this operation two more times to adjust the focus.

After that, the particle size of 300 toner particles is measured to obtain the number average particle size (D1). Note that the particle diameter of each particle is the maximum diameter when the toner particles are observed.

(4) Focus adjustment For particles with a number average particle diameter (D1) of ± 0.1 μm obtained in (3) above, the middle point of the maximum diameter is aligned with the center of the measurement screen. to set the magnification to 10000 (10k) times.

Rotate the focus knob [COARSE] on the operation panel, and adjust the aperture alignment when the focus is achieved to some extent. Click [Align] in 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 circle. Next, select [Aperture] and turn the STIGMA/ALIGNMENT knobs (X, Y) one by one to stop or minimize the movement of the image. Close the aperture dialog and focus with autofocus. After that, the magnification is set to 50,000 (50k) times, the focus is adjusted using the focus knob and the STIGMA/ALIGNMENT knob in the same manner as above, and the focus is adjusted by autofocus again. Repeat this operation again to adjust the focus. Here, if the tilt angle of the observation surface is large, the coverage rate measurement accuracy tends to be low. and analyze.

(5) Save image Adjust the brightness in ABC mode, take a picture with a size of 640×480 pixels, and save it. The following analysis is performed using this image file. One photograph is taken for one toner, and an image is obtained for 25 particles of toner.

(6) Image Analysis Using the following analysis software, the coverage is calculated by binarizing the image obtained by the above method. At this time, the one screen is divided into 12 squares and each of them is analyzed.

Image analysis software Image-Pro Plus ver. 5.0 analysis conditions are as follows. However, in the divided section, there are organosilicon polymer fine particles with a particle size of less than 30 nm and over 300 nm (when measuring the coverage of the organosilicon polymer fine particles), silica fine particles with a particle size of less than 100 nm and over 300 nm (silica When measuring the coverage rate of fine particles), the calculation of the coverage rate is not performed in that section.
Software Image-ProPlus5.1J

Select "Measurement" from the toolbar, then "Count/Size" and then "Options" to set the binarization conditions. Select 8-connected among the object extraction options and set the smoothing to 0. In addition, preselect, fill holes, do not select comprehensive lines, and set "exclude border" to "none". Select "measurement item" from "measurement" on the toolbar, and enter 2 to 107 in the area sorting range.

The calculation of coverage is performed by enclosing a square area. At this time, the area (C) of the region is set to 24,000 to 26,000 pixels. "Treatment"-binarization automatically binarizes, and the total area (D) of the regions without organosilicon polymer fine particles or silica fine particles is calculated.

From the area C of the square regions and the total area D of the regions without the organosilicon polymer fine particles or silica fine particles, the coverage is obtained by the following formula.
Coverage (%) = 100 - (D/C x 100)

The arithmetic average value of all data obtained is taken as the coverage.

Then, the coverage ratios of the toner before washing and the toner after washing are calculated,
[Toner coverage after washing with water]/[Toner coverage before washing with water]×100 is defined as the “fixing rate” of the present invention.

The "migration amount" of the present invention is obtained by (1-"adhesion rate") x fine particle content.

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

<Young's Modulus of Surface of Electrostatic Charge Image Bearing Member>
A surface film physical property test (Fischer Scope H100V, manufactured by Fischer Instruments) was performed to determine the Young's modulus Ed of the surface of the electrostatic charge image bearing member.

The measurement conditions at this time were a maximum indentation depth of 1 μm, 60 measurement points in the depth direction, and the measurement was performed in a constant environment (room temperature 23° C., humidity 50% RH). In the measurement of the Young's modulus E in the surface film physical property test, a diamond indenter 11 having a square pyramid shape and a facing angle defined to be 136° is used, and a set load is applied stepwise to the surface of the photosensitive drum 9 to a specific depth. After it is pushed into the film up to the point where it is pulled out, the depth of pushing in with a load applied is electrically detected and read.

<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 obtained from a microcompression test using a Hygitron PI 85L picodenter (manufactured by BRUKER).

Young's modulus (MPa) is calculated from the slope of the profile (load-displacement curve) of displacement (nm) and test force (μN) obtained by measurement.
・Equipment/jig base system: Hysitron PI-85L
Measurement indenter: 1 μm flat end indenter used SEM: Thermo Fisher Versa 3D
SEM conditions: -10° tilt, 13 pA at 10 keV
・Measurement conditions Measurement mode: Displacement control Maximum displacement: 30 nm
Displacement rate: 1 nm/sec Retention time: 2 sec Unloading rate: 5 nm/sec ・Analysis method Hertz analysis was applied to the obtained load-displacement curve when compressed from 0 nm to 10 nm, and the Young's modulus of the fine particles was calculated. calculate.
・Sample preparation A silicon wafer on which fine particles are adhered.

<Method for Measuring Hydrophobicity of External Additive Particles for Toner>
The degree of hydrophobicity of the external additive particles for toner of the present invention is calculated by a methanol titration method. Specifically, it is measured by the following procedure. 0.5 g of external toner additive particles are added to 50 ml of RO water, and methanol is added dropwise from a burette while stirring the mixed liquid until the entire amount of the external additive particles for toner is wetted. . Whether or not the entire amount has been wetted is determined by whether or not all the toner external additive particles floating on the surface of the water are submerged in the liquid and suspended in the liquid. At this time, the percentage value of methanol with respect to the total amount of the mixed liquid and the dropped methanol at the end of dropping is defined as the degree of hydrophobicity. Higher hydrophobicity values indicate higher hydrophobicity.

<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 according to the BET method (preferably the BET multipoint method). For example, using a specific surface area measuring device (trade name: Gemini 2375 Ver.5.0, manufactured by Shimadzu Corporation), nitrogen gas is adsorbed on the surface of the sample, and the BET multipoint method is used for measurement. BET specific surface area Y (m ² /g) can be calculated.

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

As the value of density (cm ³ /g) required for calculation, the value of true density measured using a dry density meter Accupic 1330 (manufactured by Shimadzu Corporation) is used.

<Method for Measuring Weight Average Particle Diameter (D4) of Toner Particles and Particle Size Distribution>
The weight-average particle diameter (D4) of the toner particles was measured using a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube. Using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting conditions and analyzing measurement data, the number of effective measurement channels is 25,000. is analyzed and calculated.

As the electrolytic aqueous solution used for measurement, a solution obtained by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used.

Before performing measurement and analysis, the dedicated software is set as follows.

In the "change standard measurement method (SOM) screen" of the dedicated software, set the total count number in control mode to 50000 particles, set the number of measurements to 1, and set the Kd value to "standard particle 10.0 μm" (Beckman Coulter (manufactured by Co., Ltd.) is used to set the value obtained. By pressing the threshold/noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flash of aperture tube after measurement.

In the "pulse-to-particle size conversion setting screen" of the dedicated software, 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.

A specific measuring method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is placed in a 250 ml round-bottom glass beaker exclusively for Multisizer 3, set on a sample stand, and stirred with a stirrer rod counterclockwise at 24 rotations/second. Then, remove the dirt and air bubbles inside the aperture tube using the dedicated software's "Flush Aperture Tube" function.
(2) About 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat-bottomed glass beaker, and "Contaminon N" (a nonionic surfactant, an anionic surfactant, and an organic builder consisting of an organic builder) is used as a dispersing agent in the beaker. About 0.3 ml of a diluent obtained by diluting a 10% by mass aqueous solution of a neutral detergent for washing ware (manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water three times by mass is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with a phase shift of 180 degrees, and an ultrasonic disperser with an electrical output of 120 W "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) in a water tank. A predetermined amount of ion-exchanged water is put into the water tank, and about 2 ml of the contaminon N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker in (4) above is being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water in the water tank is appropriately adjusted to 10°C or higher and 40°C or lower.
(6) The electrolytic aqueous solution of (5), in which toner is dispersed, is dripped into the round-bottom beaker of (1) set in the sample stand using a pipette, and the measured concentration is adjusted to about 5%. . The measurement is continued until the number of measured particles reaches 50,000.
(7) Analyze the measurement data with the dedicated software attached to the apparatus, and calculate the weight average particle size (D4). The weight average particle diameter (D4) is the "average diameter" on the analysis/volume statistics (arithmetic mean) screen when graph/vol% is set using dedicated software.

The present invention will be specifically described by way of examples shown below. However, these do not limit the present invention at all. Unless otherwise specified, "parts" in the following prescriptions are all based on mass.

<Production example of organosilicon polymer particles 1>
1. Hydrolysis Step 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 was added as a silane monomer and stirred for 1.5 hours to obtain a raw material solution.

2. Condensation Polymerization Step 70.0 g of RO water, 340.0 g of methanol and 2.0 g of 25% aqueous ammonia were placed in a 1000 ml beaker and stirred at 30° C. to prepare an alkaline aqueous medium. The raw material solution obtained in the hydrolysis step was added dropwise to this alkaline aqueous medium over a period of 1 minute. The mixed solution after dropping the raw material solution was stirred for 1.5 hours while being kept at 30° C. to proceed the polycondensation reaction and obtain a polycondensation reaction solution.

3. Particulation Step 700 g of RO water was put into a 2000 ml beaker, and the polycondensation reaction liquid obtained in the condensation polymerization step 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. to obtain a dispersion containing silicon polymer particles having siloxane bonds.

4. Hydrophobization Step To the dispersion containing silicon polymer particles having siloxane bonds obtained in the above particle formation step, 23 g of hexamethyldisilazane was added as a hydrophobizing agent, and the mixture was stirred at 60° C. for 2.5 hours. After allowing to stand for 5 minutes, the powder 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 additive particles 1 for toner.

The number average particle diameter of the primary particles of the obtained external additive particles 1 for toner measured by SEM was 105 nm. Table 1 shows the physical properties of the organosilicon polymer particles 1.

<Production example of organosilicon polymer particles 2>
Organosilicon polymer particles 2 were prepared in the same manner as in the production example of organosilicon polymer particles 1, except that 28.0 g of trimethoxymethylsilane and 24.0 g of tetraethoxysilane were used as silane monomers in the hydrolysis step. Obtained. Table 1 shows the physical properties of the obtained particles.

<Production example of organosilicon polymer particles 3>
Organosilicon polymer particles 3 were prepared in the same manner as in the production example of organosilicon polymer particles 1, except that 30.0 g of trimethoxymethylsilane and 22.0 g of tetraethoxysilane were used as silane monomers in the hydrolysis step. Obtained. Table 1 shows the physical properties of the obtained particles.

<Production example of organosilicon polymer particles 4>
Organosilicon polymer particles 4 were prepared in the same manner as in the production example of organosilicon polymer particles 1, except that 42.0 g of trimethoxymethylsilane and 10.0 g of tetraethoxysilane were used as silane monomers in the hydrolysis step. Obtained. Table 1 shows the physical properties of the obtained particles.

<Production example of organosilicon polymer particles 5>
Organosilicon polymer particles 5 were prepared in the same manner as in the production example of organosilicon polymer particles 1, except that 48.0 g of trimethoxymethylsilane and 4.0 g of tetraethoxysilane were used as silane monomers in the hydrolysis step. Obtained. Table 1 shows the physical properties of the obtained particles.

<Production example of organosilicon polymer particles 6>
Organosilicon polymer particles 6 were prepared in the same manner as in the production example of organosilicon polymer particles 1, except that 26.0 g of tetramethoxymethylsilane and 28.0 g of dimethyldimethoxysilane were used as silane monomers in the hydrolysis step. Obtained. Table 1 shows the physical properties of the obtained particles.

<Production example of organosilicon polymer particles 7>
Organosilicon polymer particles 7 were prepared in the same manner as in the production example of organosilicon polymer particles 1, except that 44.0 g of trimethoxymethylsilane and 8.0 g of dimethyldimethoxysilane were used as silane monomers in the hydrolysis step. Obtained. Table 1 shows the physical properties of the obtained particles.

<Production Example of Organosilicon Polymer Particles 8>
Organosilicon polymer particles 8 were prepared in the same manner as in the production example of organosilicon polymer particles 1, except that 48.0 g of trimethoxymethylsilane and 4.0 g of dimethyldimethoxysilane were used as silane monomers in the hydrolysis step. Obtained. Table 1 shows the physical properties of the obtained particles.

<Production Example of Organosilicon Polymer Particles 9>
In the polycondensation step, the stirring temperature of the mixed solution after dropping the raw material solution was changed to 35°C, and in the particle formation step, the same procedure as in the production example of organosilicon polymer particles 1 was carried out, except that the stirring temperature was changed to 45°C. to obtain organosilicon polymer particles 9. Table 1 shows the physical properties of the obtained particles.

<Production Example of Organosilicon Polymer Particles 10>
Organosilicon polymer particles 9 were obtained in the same manner as in the production example of organosilicon polymer particles 1, except that in the polycondensation step, the stirring temperature of the mixture after dropping the raw material solution was changed to 35°C. Table 1 shows the physical properties of the obtained particles.

<Production Example of Organosilicon Polymer Particles 11>
In the polycondensation step, the stirring temperature of the mixed solution after dropping the raw material solution was changed to 25°C, and in the particle formation step, the same procedure as in the production example of organosilicon polymer particles 1 was carried out, except that the stirring temperature was changed to 30°C. to obtain organosilicon polymer particles 11. Table 1 shows the physical properties of the obtained particles.

<Production Example of Organosilicon Polymer Particles 12>
In the polycondensation step, the stirring temperature of the mixed solution after dropping the raw material solution was changed to 20°C, and in the particle formation step, the same procedure as in the production example of organosilicon polymer particles 1 was performed except that the stirring temperature was changed to 25°C. to obtain organosilicon polymer particles 12. Table 1 shows the physical properties of the obtained particles.

<Production Example of Organosilicon Polymer Particles 13>
Organosilicon polymer particles 13 were obtained in the same manner as in the production example of organosilicon polymer particles 1 except that the amount of 28% aqueous ammonia added was changed to 1.0 g in the polycondensation step. Table 1 shows the physical properties of the obtained particles.

<Production Example of Organosilicon Polymer Particles 14>
Organosilicon polymer particles 14 were obtained in the same manner as in the production example of organosilicon polymer particles 1 except that the amount of 28% aqueous ammonia added was changed to 1.4 g in the polycondensation step. Table 1 shows the physical properties of the obtained particles.

<Production Example of Organosilicon Polymer Particles 15>
Organosilicon polymer particles 15 were obtained in the same manner as in the production example of organosilicon polymer particles 1 except that the amount of 28% aqueous ammonia added was changed to 1.7 g in the polycondensation step. Table 1 shows the physical properties of the obtained particles.

<Production Example of Organosilicon Polymer Particles 16>
Organosilicon polymer particles 16 were obtained in the same manner as in the production example of organosilicon polymer particles 1 except that the amount of 28% aqueous ammonia added was changed to 2.5 g in the polycondensation step. Table 1 shows the physical properties of the obtained particles.

<Production Example of Organosilicon Polymer Particles 17>
Organosilicon polymer particles 17 were obtained in the same manner as in the production example of organosilicon polymer particles 1 except that the amount of 28% aqueous ammonia added was changed to 2.8 g in the polycondensation step. Table 1 shows the physical properties of the obtained particles.

<Production example of organosilicon polymer particles 18>
Organosilicon polymer particles 18 were obtained in the same manner as in the production example of organosilicon polymer particles 1 except that the amount of 28% aqueous ammonia added was changed to 3.2 g in the polycondensation step. Table 1 shows the physical properties of the obtained particles.

<Production Example of Organosilicon Polymer Particles 19>
Organosilicon polymer particles 19 were obtained in the same manner as in the production example of organosilicon polymer particles 1, except that hexamethyldisilazane was not added in the hydrophobizing step. Table 1 shows the physical properties of the obtained particles.

<Production example of silica particles 1>
After oxygen gas was supplied to the burner and the ignition burner was ignited, hydrogen gas was supplied to the burner to form a flame, and silicon tetrachloride as a raw material was added to the flame and gasified to obtain fine silica particles. . The obtained silica fine particles were transferred to an electric furnace, spread in a thin layer, and then heat-treated at 900° C. for sintering. Thereafter, silica particles 1 were obtained by surface-treating with hexamethyldisilazane as a hydrophobizing treatment. Physical properties are shown in Table 2.

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

<Production example of polyester resin A1>
· Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 76.9 parts (0.167 mol)
- Terephthalic acid (TPA) 25.0 parts (0.145 mol)
- Adipic acid 8.0 parts (0.054 mol)
- Titanium tetrabutoxide 0.5 parts The above materials were placed in a 4-liter glass flask with four necks, equipped with a thermometer, a stirring bar, a condenser and a nitrogen inlet tube, and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200°C. Then, 1.2 parts (0.006 mol) of trimellitic anhydride (TMA) was added and reacted at 180° C. for 1 hour to obtain polyester resin A1. The softening point of this polyester resin A1 was 90°C.

<Production example of polyester resin A2>
· Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane 71.3 parts (0.155 mol)
- Terephthalic acid 24.1 parts (0.145 mol)
- Titanium tetrabutoxide 0.6 part The above materials were placed in a 4-liter four-necked glass flask, equipped with a thermometer, a stirring bar, a condenser and a nitrogen inlet tube, and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200°C. Then, 5.8 parts (0.030 mol %) of trimellitic anhydride was added and reacted at 180° C. for 10 hours to obtain polyester resin A2. The softening point of this polyester resin A2 was 130°C.

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

<Production Example of Toner 1>
・Toner particles 1 96.5 parts ・Organosilicon polymer particles 1 1.5 parts ・Silica particles 1 2.0 parts ・Titania particles 1 (the number average diameter of the primary particles is 30 nm; the surface is coated with antimony-doped tin oxide Material) 0.5 parts The above materials were charged into a Henschel mixer FM-10C (manufactured by Mitsui Miike Kakoki Co., Ltd.). After that, a step of mixing at a rotation speed of 65 s ⁻¹ and a rotation time of 1 minute and then standing for 1 minute was defined as one cycle. Table 4 shows the physical properties of Toner 1.

<Manufacturing Examples of Toners 2 to 36>
Toner 1 was produced in the same manner as in Production Example of Toner 1, except that the types of toner particles, organosilicon polymer particles, silica particles, and titania particles, addition amounts, and external addition conditions were changed to those shown in Table 3. Toners 2-36 were obtained. Table 4 shows the physical properties of each toner.

<Production example of magnetic carrier core particles>
62.7 parts of Fe ₂ O ₃ 29.5 parts of MnCO ₃ 6.8 parts of Mg(OH) ₂ 1.0 part of SrCO ₃ Ferrite raw materials were weighed so as to obtain the above composition ratio.

After that, it was pulverized and mixed for 5 hours in a dry vibration mill using stainless steel beads. The pulverized material thus obtained was made into pellets of about 1 mm square by a roller compactor.

Coarse powder was removed from the pellets with a vibrating sieve with an opening of 3 mm, and then fine powder was removed with a vibrating sieve with an opening of 0.5 mm. 01% by volume) and fired at a temperature of 1000° C. for 4 hours to prepare a calcined ferrite.

After crushing the calcined ferrite to about 0.3 mm with a crusher, 30 parts of water was added to 100 parts of calcined ferrite using zirconia beads, and the mixture was crushed with a wet ball mill for 1 hour. Further, the resulting slurry was pulverized in a wet ball mill for 4 hours to obtain a ferrite slurry (finely pulverized calcined ferrite).

To the ferrite slurry, 1.0 parts of ammonium polycarboxylate as a dispersant and 2.0 parts of polyvinyl alcohol as a binder are added to 100 parts of calcined ferrite, and a spray dryer (manufacturer: Okawara Kakoki ) to granulate into spherical particles. After adjusting the particle size of the obtained particles, they were heated at 650° C. for 2 hours using a rotary kiln to remove the organic components of the dispersant and binder.

In order to control the sintering atmosphere, the temperature was raised from room temperature to 1300° C. in 2 hours in an electric furnace under a nitrogen atmosphere (oxygen concentration 1.00% by volume), and then sintered at 1150° C. for 4 hours. After that, the temperature was lowered to 60° C. over 4 hours, the nitrogen atmosphere was returned to the air, and the temperature was 40° C. or less and taken out.

After crushing the aggregated particles, the low magnetic force products are cut by magnetic separation, sieved with a sieve with an opening of 250 μm to remove coarse particles, and the 50% volume-based particle size (D50) is 37.0 μm. Magnetic carrier core particles were obtained.

<Manufacturing Example of Magnetic Carrier 1>
In the first coating step, a thermosetting silicone resin solution (methylsilicone resin) was placed in the fluidized bed in such a manner that the coating resin amount was 0.20 parts per 100 parts of the magnetic carrier core particles. The magnetic carrier core particles were coated using a coating apparatus that was provided to perform coating while forming a swirling flow. The resin solution described above was sprayed in a direction perpendicular to the moving direction of the fluidized bed in the apparatus.

Next, in the second coating step, a fluororesin solution (coalescing of tetrafluoroethylene and hexafluoropropylene (FEP)) (1.91 parts as solid content per 100 parts of the magnetic carrier core particles) and a thermosetting melamine resin solution (0.09 part as a solid content with respect to 100 parts of the magnetic core particles) were thoroughly stirred and mixed to prepare a carrier coating solution. This coating solution was applied to the magnetic carrier core particles using a coating apparatus in which a rotating bottom plate disk and stirring blades were provided in a fluidized bed to form a swirling flow. Thereafter, the obtained carrier was dried in a fluidized bed at a temperature of 280° C. for 1 hour to remove the solvent, and magnetic carrier 1 was obtained.

<Production example of two-component developer 1>
Two-component developer 1 was obtained by adding 8.0 parts of toner 1 to 92.0 parts of magnetic carrier 1 and mixing them with a V-type mixer (V-20, manufactured by Seishin Enterprises).

<Production Examples of Two-Component Developers 2 to 36>
Two-component developers 2 to 36 were obtained in the same manner as in the production example of two-component developer 1, except that the toner was changed as shown in Table 5.

<Production Example of Photoreceptor 1>
An aluminum alloy tube (outer diameter 84 mm, inner diameter 78 mm, length 370 mm) was prepared as a cylindrical conductive substrate. The outer peripheral surface of the prepared conductive substrate was mirror-finished and wet-blasted, and then washed.

First, as mirror finishing of the surface of the conductive substrate, the conductive substrate is held at both ends and rotated at a high speed of 1500 to 8000 rpm. processed. That is, a smooth finished surface was obtained by pressing a diamond cutting tool having a depth in the rotating direction of the workpiece against the surface of the conductive substrate.

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

Next, as wet blasting, a high-hardness abrasive such as alumina and water are stirred, mixed with compressed air, accelerated, and projected onto the mirror-finished surface of the conductive substrate to roughen the surface. rice field. In this method, since the conductive substrate is processed while being rotated, a highly uniform processed surface can be formed in a short period of time.

Specifically, conductive substrates having different surface roughnesses were prepared by adjusting the following parameters as wet blasting conditions.
Abrasive material/particle size: A (alundum (brown dissolved alumina)) #320 to #4000
Abrasive concentration: 10-18%
Projection air pressure: 0.10 to 0.35 MPa
Projection distance (distance between work center and blast head): 20-300mm
Projection time: 1 to 60 seconds Work rotation speed: 120 to 180 rpm

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

Then, after performing wet blasting, a conductive substrate was prepared by washing and removing the residue remaining on the surface.

Using the plasma CVD apparatus shown in FIG. 3, each layer was formed on the surface of the conductive substrate prepared in this manner under the film forming conditions shown in Tables 6 and 7. A photoreceptor 1 made of amorphous carbon was produced. The Young's modulus of the surface of the photoreceptor 1 was 200 GPa.

The conditions shown in Table 7 were used for the flow rate of the raw material gas, the reaction pressure, the high-frequency power, and the substrate temperature during the formation of the third region of the surface layer.

<Manufacturing Example of Photoreceptor 2>
Photoreceptor 1 was manufactured in the same manner as in Photoreceptor 1, except that the surface layer (third region) film formation conditions were changed to those shown in Table 7, and the surface layer was amorphous silicon carbide. Photoreceptor 2 was obtained. The Young's modulus of the surface of the photoreceptor 2 was 270 GPa.

[Example 1]
[Image evaluation]
A modified digital electrophotographic apparatus "image Press C800" (trade name) manufactured by Canon Inc. was used. This device uses a cleaning blade to clean excess toner on the electrostatic charge image bearing member. The content of the modification was to apply the primary charging and developing bias from an external power source.

Photoreceptor 1 thus produced was mounted in a black station, two-component developer 1 was set in a developing device, and toner 1 was set in a toner bottle. The primary charging current and grit voltage were set so that the dark area surface potential of the photoreceptor was 500 V by adjusting the wire and grit. Next, while being charged under the previously set charging conditions, image exposure was applied, and the potential at the position of the developing device was set to 150 V by adjusting the irradiation energy.

(Resistant to image deletion)
For the evaluation of image deletion resistance, an image of an A3 character chart (4pt, printing rate 4%) was output before the continuous paper feed test under a high-temperature and high-humidity environment (32° C./85% RH). Plain paper for color copiers and printers "GF-C081 (A4, 81.0 g/m ² )" (available from Canon Marketing Japan Inc.) was used as evaluation paper. Also, the photoreceptor heater was turned on.

After the image output before the continuous paper feed test, the continuous paper feed test was performed. The continuous paper feed test was conducted under the condition that the photoreceptor heater was always turned off while the electrophotographic apparatus was in operation and the continuous paper feed test was performed and while the electrophotographic apparatus was stopped.

Specifically, 10,000 sheets of A4 size test pattern with a print rate of 1% were passed in a day, and then left in a high-temperature, high-humidity environment for one day. This cycle was repeated 10 times for 20 days, and a total of 100,000 sheets of paper were fed. After completion of the paper threading test, it was left for 72 hours under a high temperature and high humidity environment.

After that, the evaluation machine was started up with the photoreceptor heater turned off, and an image of an A3 character chart (4pt, printing rate 4%) was output. The image output before the continuous paper feeding test and the image output after the continuous paper feeding test were digitized into a PDF file under a binary condition of 300 dpi.

Using the image editing software “Adobe Photoshop” (trade name) from Adobe, the image ratio of the image area for one rotation of the electrophotographic photosensitive member was measured for the computerized image. Next, the ratio of the image output after the continuous paper-feeding test to the image output before the continuous paper-feeding test was obtained, and the durability running was evaluated.

When high-humidity bleeding occurs, characters are blurred over the entire image, or characters are not printed and white spots appear, so the output image ratio decreases when compared to the 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 image ratio output after the continuous paper feed test is to 100%, the better the image smear resistance. Evaluation was made according to the following criteria. Table 8 shows the evaluation results. If it is C rank or higher, it is regarded as a level at which the effect of the present invention is obtained.
A: The output image ratio after the continuous paper feeding test is 95% or more and less than 110% with respect to the image ratio before the continuous paper feeding test. B: The image ratio after the continuous paper feeding test is higher than the image ratio before the continuous paper feeding test. 90% or more and less than 95% C: Output image ratio after continuous paper feeding test is 80% or more and less than 90% with respect to image ratio before continuous paper feeding test D: Continuous paper feeding test with respect to image ratio before continuous paper feeding test Later output image ratio is less than 80%

(Member contamination resistance evaluation)
Using the evaluation machine and evaluation paper used for the above image deletion evaluation, the following evaluation was performed in a normal temperature and low humidity environment (23° C./5% RH). When the external additive migrates from the toner to the member and contaminates it, it becomes a factor of density change. Evaluation was performed with the photoreceptor heater turned off.

As the pattern image to be output, a pattern image was used in which a 2 mm-wide band-shaped solid portion and an 18 mm-wide band-shaped white background portion were repeatedly arranged in a direction parallel to the paper passing direction. The amount of toner applied on the paper in the solid portion of the pattern image was adjusted to 0.45 mg/cm ² . FFh is a value representing 256 gradations in hexadecimal, where 00h is the 1st gradation (white background portion) of 256 gradations, and FF is the 256th gradation (solid portion) of 256 gradations.

When the pattern image was output on 10,000 sheets, the output was temporarily stopped, and then an image in which the entire surface of the paper was halftone (80h) was output.

Using an X-Rite color reflection densitometer ("500 series", manufactured by X-Rite), the image density of the entire solid image was measured at 20 random points, and the maximum and minimum values of the image density were obtained. The difference (image density difference) was used for evaluation. Table 8 shows the evaluation results. It was judged that the effects of the present invention were obtained for C rank or higher.
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

(Charge retention rate change)
The triboelectrification amount of the toner was calculated by sucking and collecting the toner on the electrostatic charge image carrier using a metal cylindrical tube and a cylindrical filter.

Specifically, the triboelectric charge amount of the toner on the electrostatic latent image bearing member was measured by a Faraday-Cage. A Faraday cage is a coaxial double cylinder in which the inner and outer cylinders are insulated. If a charged body with an electric charge of Q is placed in this inner cylinder, it will be as if a metal cylinder with an electric charge of Q exists due to electrostatic induction. The amount of this induced charge was measured with an electrometer (Kesley 6517A, manufactured by Kessley). Quantity.
Triboelectric charge amount of toner (mC/kg)=Q/M

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

Subsequently, after leaving the developing device in the evaluation machine for one week in a high-temperature and high-humidity environment (32° C., 85% RH), the same operation as before leaving was performed, and the electrostatic charge image bearing member after leaving was treated. A charge amount Q/M (mC/kg) per unit mass was measured. The Q/M per unit mass on the electrostatic charge image bearing member before standing is defined as [initial Q/M], and the Q/M per unit mass on the electrostatic charge image bearing member after standing is defined as [After standing]. and ([Q/M after leaving]/[initial Q/M]×100) was calculated as a retention rate, and judged according to the following criteria. Table 8 shows the evaluation results. If it is C rank or higher, it is regarded as a level at which the effect of the present invention is obtained.

(Evaluation criteria)
A: Maintenance rate is 90% or more B: Maintenance rate is 85% or more and less than 90% C: Maintenance rate is 80% or more and less than 85% D: Maintenance rate is less than 80%

[Example 2]
In Example 1, the photoreceptor 1 was changed to the photoreceptor 2, and the same evaluation was performed. Table 8 shows the evaluation results.

[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 performed. Table 8 shows the evaluation results.

101: electrostatic charge image bearing member (electrophotographic photosensitive member), 102: charging roller, 103: exposure means, 104: developing device, 105: transfer charging device, 106: fixing device, 107: cleaning device, 108: recording medium ( Transfer paper), 200: Substrate, 201: Withstand voltage layer, 202: Charge injection blocking layer, 203: Photosensitive layer, 204: Surface layer, 205: Intermediate layer, 206: Multiple intermediate layers, 207: Changeable layer, 3100: Deposition Apparatus 3110: Reaction vessel 3200: Source gas supply device 3111: Cathode electrode 3112: Substrate 3113: Substrate heating heater 3114: Source gas introduction pipe 3115: High frequency matching box 3116: Gas pipe 3117: Leak valve, 3118: Main valve, 3119: Vacuum gauge, 3120: High frequency power supply, 3121: Insulating material, 3123: Cradle, 3221 to 3225: Source gas cylinder, 3231 to 3235: Valve, 3261 to 3265: Pressure regulator, 3241 3245: inflow valve, 3251 to 3255: outflow valve, 3211 to 3215: mass flow controller, 3260: auxiliary valve, 401: photoreceptor (rotating direction), 402: cleaning blade edge, 403: toner, 404: external additive blocking layer

Claims (8)

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 developing with toner to form the electrostatic charge. a developing step of forming a toner image on an image carrier;
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 onto the recording medium;
a cleaning step of removing transfer residual toner remaining on the surface of the electrostatic charge image bearing member after the transfer step using a cleaning blade;
An image forming method comprising
the photosensitive layer of the electrostatic charge image carrier contains amorphous silicon;
the surface layer of the electrostatic charge image carrier contains amorphous silicon carbide or amorphous carbon;
An image forming method, wherein the toner comprises toner particles, silica particles and organosilicon polymer particles. When the toner is washed with water, A (% by mass) is the amount of the organosilicon polymer particles transferred from the toner, and B (% by mass) is the amount of the silica particles transferred from the toner, based on the weight of the toner. % by mass), the A and the B are
0.50≤A+B≤4.00
0.20≤B/A≤2.00
The image forming method according to claim 1, wherein: 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 diameter Db of the primary particles of the migrated silica particles is 50 nm or more and 200 nm or less,
3. The image forming method according to claim 2. The image forming method according to any one of claims 1 to 3, wherein the Young's modulus Ea of the organosilicon polymer particles is 1.0 GPa or more and 30.0 GPa or less. Let X (m ² /g) be the theoretical BET specific surface area of the organosilicon polymer particles, and Y (m ² /g) be the actually measured BET specific surface area of the organosilicon polymer particles. 5. The image forming method according to claim 1, wherein Y satisfies 3.0≦Y/X≦8.0. 6. The image formation according to claim 1, wherein the relationship Ea/Eb≦0.20 is satisfied, where Ea is the Young's modulus of the organosilicon polymer particles and Eb is the Young's modulus of the silica particles. Method. 7. The method according to any one of claims 1 to 6, wherein Ea/Ed≦0.05 is satisfied in relation to the Young's modulus Ea of the organosilicon polymer particles, where Ed is the Young's modulus of the electrostatic charge image bearing member. The described imaging method. The image forming method according to any one of claims 1 to 7, wherein the surface layer of the electrostatic charge image bearing member contains amorphous carbon.

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