Electrophotographic device and process cartridge

Abstract

To provide an electrophotographic device that can prevent the occurrence of a streak-like image defect even when used in a high temperature and high humidity environment.SOLUTION: An electrophotographic device has: an electrophotographic photoreceptor; developing means that has toner and is to develop an electrostatic latent image with the toner to form a toner image on a surface of the electrophotographic photoreceptor; and cleaning means that is to remove residual toner remaining on the surface of the electrophotographic photoreceptor after the toner image is transferred to a transfer material from the surface of the electrophotographic photoreceptor. The surface of the photoelectric photoreceptor is formed of amorphous silicon carbide. In a near-surface area (surface area A) from the surface of the electrophotographic photoreceptor to a depth of 100nm, the Si atom density is 1.0×1022 atom / cm3 or less. The toner includes toner particles containing a polyester resin having a polyethylene terephthalate segment, and inorganic fine particles.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to an electrophotographic apparatus using an electrophotographic photoreceptor having a surface formed of amorphous silicon carbide, and a process cartridge.

Background Art

[0002] Electrophotographic image forming methods (hereinafter also simply referred to as "image forming methods") and electrophotographic apparatuses using the same are widely and commonly used as copiers, facsimile apparatuses, and printers. In such an electrophotographic apparatus, the surface of an electrophotographic photoreceptor provided with a photoconductive layer is uniformly charged, and an electrostatic latent image is formed on the surface of the electrophotographic photoreceptor by exposing it with a laser or an LED according to image information. Then, a toner image is formed on the surface of the electrophotographic photoreceptor by attaching toner to the formed electrostatic latent image, and this is transferred to a transfer material such as paper to perform image formation. As an electrophotographic photoreceptor that can be suitably used in such an electrophotographic apparatus, an amorphous silicon electrophotographic photoreceptor using hydrogenated amorphous silicon in the photoconductive layer is known. Note that hydrogenated amorphous silicon is also abbreviated as "a-Si:H", the electrophotographic photoreceptor is abbreviated as "photoreceptor", and the amorphous silicon electrophotographic photoreceptor is abbreviated as "a-Si photoreceptor". The a-Si photoreceptor has a Vickers hardness of 1000 kgf / mm 2 or more, which is very hard, and is excellent in durability, heat resistance, and environmental stability. Therefore, it is preferably used in high-speed machines that particularly require high reliability.

[0003] On the other hand, since the a-Si photoreceptor has a small wear amount and a high surface friction resistance, abnormalities may occur in the output image due to defects in the cleaning process of the photoreceptor by the cleaning blade. In order to improve this, a technique for suppressing the occurrence of image defects by controlling the surface roughness of the a-Si photoreceptor is known. (Patent Document 1)

[0004] In recent years, in order to reduce the energy consumption of electrophotographic devices, technologies for fixing toner at low temperatures have been proposed. Patent Document 2 describes a technology related to a toner having, as one of the resin components, a polyester obtained by reacting a polyethylene terephthalate resin, an alcohol component, and a carboxylic acid component.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] As a result of investigations by the present inventors, it has been found that when an a-Si photoreceptor described in the prior art and a toner containing a polyester resin having a polyethylene terephthalate segment are used in combination, the following problems exist. When the usage environment is high temperature and high humidity, streak-like image defects, which are thought to be caused by toner leakage at the cleaned portion of the photoreceptor, may occur at the initial stage of use. Therefore, an object of the present disclosure is to provide an electrophotographic device in which the occurrence of streak-like image defects is suppressed even in a high temperature and high humidity usage environment when an a-Si photoreceptor and a toner containing a polyester resin having a polyethylene terephthalate segment are used in combination.

Means for Solving the Problems

[0007] The above object is achieved by the following present disclosure. That is, an electrophotographic apparatus having an electrophotographic photoreceptor, a charging means for charging the surface of the electrophotographic photoreceptor, an image exposure means for irradiating image exposure light onto the charged surface of the electrophotographic photoreceptor to form an electrostatic latent image on the surface of the electrophotographic photoreceptor, a developing means having toner for developing the electrostatic latent image with the toner to form a toner image on the surface of the electrophotographic photoreceptor, a transfer means for transferring the toner image from the surface of the electrophotographic photoreceptor to a transfer material, and a cleaning means for removing residual toner remaining on the surface of the electrophotographic photoreceptor after the toner image is transferred to the transfer material, wherein the surface of the electrophotographic photoreceptor is formed of amorphous silicon carbide, and the Si atom density in the surface vicinity region from the surface of the electrophotographic photoreceptor to a depth of 100 nm is 1.0×10 22 atoms / cm 3 or less, and the toner has toner particles containing a polyester resin having a polyethylene terephthalate segment and inorganic fine particles. The electrophotographic apparatus is characterized by this.

[0008] Further, a process cartridge integrally supporting an electrophotographic photoreceptor, toner, a developing means for developing an electrostatic latent image formed on the surface of the electrophotographic photoreceptor with the toner to form a toner image on the surface of the electrophotographic photoreceptor, and a cleaning means for removing residual toner remaining on the surface of the electrophotographic photoreceptor after the toner image is transferred from the surface of the electrophotographic photoreceptor to a transfer material, and being detachable from the electrophotographic apparatus main body, wherein the surface of the electrophotographic photoreceptor is formed of amorphous silicon carbide, and the Si atom density in the surface vicinity region from the surface of the electrophotographic photoreceptor to a depth of 100 nm is 1.0×10 22 atoms / cm 3 or less, and the toner has toner particles containing a polyester resin having a polyethylene terephthalate segment and inorganic fine particles. The process cartridge is characterized by this.

Advantages of the Invention

[0009] According to the present disclosure, when an a-Si photoreceptor is combined with a toner containing a polyester resin having a polyethylene terephthalate segment, an electrophotographic apparatus can be provided in which the occurrence of streak-like image defects is suppressed even in a high-temperature and high-humidity usage environment.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Embodiments for Carrying Out the Invention

[0011] The form of the electrophotographic apparatus according to the present disclosure is as follows. That is, an electrophotographic apparatus having an electrophotographic photoreceptor, a charging means for charging the surface of the electrophotographic photoreceptor, an image exposure means for irradiating image exposure light onto the charged surface of the electrophotographic photoreceptor to form an electrostatic latent image on the surface of the electrophotographic photoreceptor, a developing means having toner for developing the electrostatic latent image with the toner to form a toner image on the surface of the electrophotographic photoreceptor, a transfer means for transferring the toner image from the surface of the electrophotographic photoreceptor to a transfer material, and a cleaning means for removing residual toner remaining on the surface of the electrophotographic photoreceptor after transferring the toner image to the transfer material, wherein the surface of the electrophotographic photoreceptor is formed of amorphous silicon carbide, and the Si atom density in the surface vicinity region (hereinafter also referred to as surface region A) from the surface of the electrophotographic photoreceptor to a depth of 100 nm is 1.0×10 22 atoms / cm 3It is as follows, and the toner has toner particles containing a polyester resin having a polyethylene terephthalate segment and inorganic fine particles, and is an electrophotographic apparatus characterized by this.

[0012] The inventors of the present invention consider the mechanism by which the electrophotographic apparatus according to the present disclosure solves the problems as follows. Regarding the streak-like image defect that occurs when using an a-Si photoreceptor and a toner containing a polyester resin having a polyethylene terephthalate segment in a high-temperature and high-humidity usage environment, the inventors of the present invention speculate the cause as follows. Compared with the polyester resin generally used in toners, the toner containing a polyester resin having a polyethylene terephthalate segment tends to have a higher polarity by introducing the polyethylene terephthalate segment. Therefore, its affinity with water tends to increase. In particular, it is considered that the polyethylene terephthalate segment easily adsorbs moisture. Also, it is known that Si atoms present in the a-Si photoreceptor become Si-O by oxidation. This Si-O site is considered to easily adsorb moisture. When using an a-Si photoreceptor and a toner containing a polyester resin having a polyethylene terephthalate segment in a high-temperature and high-humidity environment, the polyethylene terephthalate segment of the toner and the Si-O site of the photoreceptor specifically interact via water. As a result, the adhesion force between the toner and the photoreceptor increases, and an effect occurs where the toner is difficult to clean. It is speculated that streak-like image defects occur when the toner slips through the cleaning blade.

[0013] In addition, it has been found that, particularly at the initial stage of use of the electrophotographic apparatus, the aforementioned streak-like image defects are likely to occur. In the present disclosure, the initial stage of starting the use of an electrophotographic apparatus means the period during which about several tens of images are output after starting image output. During this period, there are almost no inorganic fine particles supplied from the toner in the nip portion of the cleaning blade of the photoreceptor, and it is considered that the cleaning stability is low. Since the cleaning stability in the initial stage of starting the use of the electrophotographic apparatus is low, it is considered that streak-like image defects are particularly likely to occur.

[0014] As a result of intensive studies by the present inventors, when the Si atom density in the surface vicinity region (surface region A) from the surface of the a-Si photoreceptor to a depth of 100 nm is controlled to 1.0×10 22 atoms / cm 3 or less, it has been found that the occurrence of image defects in the initial stage of use can be suppressed even in a high-temperature and high-humidity use environment. The present inventors presume this mechanism as follows. That is, it is presumed that when Si atoms are oxidized to Si—O in the surface region A of the photoreceptor, the interaction with the polyethylene terephthalate segment of the toner described above becomes particularly strong, and greatly affects the cleaning stability of the toner. By controlling the Si atom density in the surface region A of the photoreceptor to be within a specified range or less, the amount of Si—O in the surface region A of the photoreceptor during image output decreases. As a result, it is considered that the interaction with the polyethylene terephthalate segment of the toner described above becomes smaller, and the occurrence of streak-like image defects is suppressed. An amorphous silicon photoreceptor whose surface is formed of amorphous silicon carbide has a very small wear amount. In the number of output sheets at which streak-like image defects occur / improve in the initial stage of using the electrophotographic apparatus, the surface of the photoreceptor is hardly worn, and it is presumed that the effect of the present disclosure is independent of the wear amount of the surface of the photoreceptor. Hereinafter, embodiments for carrying out the present disclosure will be described in detail.

[0015] [Electrophotographic apparatus] An image forming method by an electrophotographic apparatus using an a-Si photoreceptor in the present disclosure will be described with reference to FIG. 1. First, the electrophotographic photoreceptor 101 is rotated, and the surface of the electrophotographic photoreceptor 101 is uniformly charged by the charging means 102. Then, after irradiating the surface of the electrophotographic photoreceptor 101 with image exposure light by the image exposure means 103 to form an electrostatic latent image on the surface of the electrophotographic photoreceptor 101, development is performed using toner supplied from the developing means 104. As a result, a toner image is formed on the surface of the electrophotographic photoreceptor 101. Then, this toner image is transferred to the intermediate transfer member 105, secondarily transferred from the intermediate transfer member 105 to a transfer material (not shown), and the toner image is fixed to the transfer material by a fixing means (not shown). The toner remaining on the surface of the electrophotographic photoreceptor 101 to which the toner image has been transferred is removed by the cleaning means 106. The cleaning means 106 includes a rubbing roller 106a having an elastic sponge that rubs the electrophotographic photoreceptor 101, and a cleaning blade 106b. Then, the electrophotographic photoreceptor 101 is discharged by exposing the surface of the electrophotographic photoreceptor 101 by the pre-exposure means 107. By repeating this series of processes, image formation is continuously performed. The rubbing roller 106a is arranged to rub the surface of the electrophotographic photoreceptor 101 with an elastic sponge to actively remove discharge products generated by charging. Also, the cleaning blade 106b is arranged to contact the electrophotographic photoreceptor 101 to remove residual toner.

[0016] [Process Cartridge] The process cartridge according to the present disclosure integrally supports an electrophotographic photoreceptor, toner, developing means for developing an electrostatic latent image formed on the surface of the electrophotographic photoreceptor with the toner to form a toner image on the surface of the electrophotographic photoreceptor, and cleaning means for removing residual toner remaining on the surface of the electrophotographic photoreceptor after the toner image is transferred from the surface of the electrophotographic photoreceptor to a transfer material, and is detachable from the electrophotographic apparatus main body. The surface of the electrophotographic photoreceptor is formed of amorphous silicon carbide, and the Si atom density in the surface vicinity region (surface region A) from the surface of the electrophotographic photoreceptor to a depth of 100 nm is 1.0×10 22atoms / cm 3 is as follows, and the toner has toner particles containing a polyester resin having polyethylene terephthalate segments and inorganic fine particles, and is a process cartridge characterized by this. In addition, the process cartridge according to the present disclosure may further have a charging means for charging the surface of the electrophotographic photoreceptor in addition to the electrophotographic photoreceptor, developing means, and cleaning means described above.

[0017] FIG. 4 shows an example of a schematic configuration of an electrophotographic apparatus including a process cartridge having an electrophotographic photoreceptor. In FIG. 4, the cylindrical electrophotographic photoreceptor 401 is rotationally driven about the axis 402 with a predetermined peripheral speed in the direction of the arrow. In the rotation process of the electrophotographic photoreceptor 401, the surface (circumferential surface) thereof is charged positively or negatively by a charging means (primary charging means) 403. Next, the electrophotographic photoreceptor 401 is irradiated with exposure light (image exposure light) 404 output from an exposure means (image exposure means) (not shown). The exposure light 404 is intensity-modulated corresponding to the time-series electrical digital image signal of the target image information. Examples of the exposure means include slit exposure and laser beam scanning exposure. Thus, an electrostatic latent image corresponding to the target image information is formed on the surface of the electrophotographic photoreceptor 401. The electrostatic latent image formed on the surface of the electrophotographic photoreceptor 401 is then developed (normal development or reversal development) with toner accommodated in the developing means 415 to form a toner image. The toner image formed on the surface of the electrophotographic photoreceptor 401 is transferred to the transfer material 417 by the transfer means 406. Here, when the transfer material 417 is paper, it is taken out from a paper feeding unit (not shown) in synchronization with the rotation of the electrophotographic photoreceptor 401 and fed between the electrophotographic photoreceptor 401 and the transfer means 406. Further, a bias voltage having a polarity opposite to the charge held by the toner is applied to the transfer means 406 from a bias power supply (not shown). Also, the transfer means 406 may be an intermediate transfer type transfer means having a primary transfer member, an intermediate transfer body, and a secondary transfer member.

[0018] The transfer material 417 onto which the toner image has been transferred is separated from the surface of the electrophotographic photoreceptor 401, conveyed to the fixing means 408, and subjected to the fixing process of the toner image, and then printed out as an image formation (print, copy) outside the electrophotographic apparatus. The surface of the electrophotographic photoreceptor 401 after toner image transfer is cleaned by the cleaning means 409, and deposits such as residual transfer toner are removed. The residual transfer toner can also be recovered by the developing means 415 or the like. Further, if necessary, the surface of the electrophotographic photoreceptor 401 is discharged by irradiation with pre-exposure light 410 from a pre-exposure means (not shown), and then repeatedly used for image formation. Note that when the charging means 403 is a contact charging means using a roller-shaped charging member (charging roller) or the like, the pre-exposure means is not necessarily required. Among the components such as the electrophotographic photoreceptor 401, the charging means 403, the developing means 415, and the cleaning means 409, a plurality of elements are selected, housed in a container, and integrally supported as a process cartridge. This process cartridge may be configured to be detachable from the electrophotographic apparatus main body such as a copying machine or a laser beam printer. In FIG. 4, the electrophotographic photoreceptor 401, the charging means 403, the developing means 415, and the cleaning means 409 are integrally supported and formed into a cartridge. Then, it is used as a process cartridge 411 that is detachable from the electrophotographic apparatus main body using guiding means 412 such as rails of the electrophotographic apparatus main body.

[0019] [Electrophotographic photoreceptor] FIG. 2 is a schematic diagram showing an example of the layer structure of the a-Si photoreceptor used in the present disclosure. The photoreceptor 200 shown in FIG. 2 has a pressure-resistant layer 202, a charge injection blocking layer 203, a photoconductive layer 204, and a surface protection layer 205 on a conductive substrate 201. Next, the conductive substrate and each layer constituting the photoreceptor having the above-described layer structure will be described.

[0020] (Conductive substrate) The material of the conductive substrate is preferably a material that forms a Schottky junction with the pressure-resistant layer directly formed on the surface of the conductive substrate. For example, when applying hydrogenated amorphous silicon nitride (hereinafter also abbreviated as a-SiN:H) to the material of the pressure-resistant layer, an alloy mainly composed of aluminum can be cited as a suitable material. The surface of the conductive substrate may be roughened. The surface roughness Sa of the conductive substrate may be, for example, 80 nm or more and 120 nm or less after roughening. Thereby, for example, when forming a film by the plasma CVD method or the like, an electrophotographic photoreceptor having an arithmetic mean roughness Sa of the surface of the electrophotographic photoreceptor of 80 nm or more and 120 nm or less can be obtained, which is preferable. As a method for roughening the surface of the conductive substrate, for example, wet blasting, sputter etching, gas etching, polishing, turning, wet etching, galvanic corrosion, etc. may be used. In addition, if it is a drawn tube that satisfies the above surface roughness, it can be used as it is without performing a surface treatment for adjusting the surface shape.

[0021] (Pressure-resistant layer) In the electrophotographic process, a voltage of the opposite polarity to the charging polarity of the photoreceptor may be applied in the developing process, the transfer process, etc. The pressure-resistant layer is a layer that suppresses the dielectric breakdown of the photoreceptor when a voltage of the opposite polarity to the charging polarity of the photoreceptor is applied. The pressure-resistant layer is preferably formed of hydrogenated amorphous silicon nitride (a-SiN:H).

[0022] (Charge injection blocking layer) The charge injection blocking layer has a function of blocking the injection of electrons from the conductive substrate side to the photoconductive layer when the surface of the photoreceptor is positively charged. The charge injection blocking layer is preferably formed of hydrogenated amorphous silicon (a-Si:H). The material of the charge injection blocking layer contains relatively more atoms for controlling the conductivity of electrons than the photoconductive layer, based on the material constituting the photoconductive layer. In the photoreceptor used in the present disclosure, an atom belonging to Group 13 of the periodic table can be used as an atom contained in the charge injection blocking layer to control the conductivity of electrons. Among the atoms belonging to Group 13 of the periodic table, boron atoms (B), aluminum atoms (Al), and gallium atoms (Ga) are preferable. The content of the atom belonging to Group 13 of the periodic table contained in the charge injection blocking layer is 1×10 2 atomic ppm or more and 3×10 3 atomic ppm or less with respect to the content of silicon atoms (Si) contained in the charge injection blocking layer is preferable. The atoms belonging to Group 13 of the periodic table may be contained in a state of being uniformly distributed throughout the charge injection blocking layer, or there may be a portion contained in a non-uniform distribution state in the film thickness direction. In any case, it is preferable for the atoms for controlling the conductivity of electrons to be contained in the charge injection blocking layer in a uniform distribution in the in-plane direction parallel to the surface of the substrate in order to achieve uniform characteristics. Furthermore, by containing at least one kind of atom among carbon atoms, nitrogen atoms, and oxygen atoms in the charge injection blocking layer, the adhesion between the charge injection blocking layer and the withstand voltage layer can be improved.

[0023] (Photoconductive layer) The photoconductive layer is preferably formed of hydrogenated amorphous silicon (a-Si:H). Further, in order to compensate for the dangling bonds, it is preferable to contain hydrogen atoms in the photoconductive layer. In the present disclosure, it is preferable to contain atoms for controlling the conductivity of electrons in the photoconductive layer as needed. The atoms for controlling the conductivity of electrons may be contained in a state of being uniformly distributed throughout the photoconductive layer, or there may be a portion contained in a non-uniform distribution state in the film thickness direction. Examples of atoms for controlling the conductivity of electrons include so-called impurities in the semiconductor field. That is, an atom belonging to Group 13 of the periodic table that provides p-type conductivity or an atom belonging to Group 15 of the periodic table that provides n-type conductivity can be used. Among the atoms belonging to Group 13 of the periodic table, boron atoms (B), aluminum atoms (Al), and gallium atoms (Ga) are preferred. Among the atoms belonging to Group 15 of the periodic table, phosphorus atoms (P) and arsenic atoms (As) are preferred. The content of the atom for controlling the conductivity of the electrons contained in the photoconductive layer is preferably 1×10 -2 atomic ppm or more with respect to silicon atoms (Si). On the other hand, it is preferably 1×10 atomic ppm or less. Note that the photoconductive layer may be composed of a single layer or may be composed of a plurality of layers (for example, a charge generation layer and a charge transport layer).

[0024] (Surface protection layer) The surface protection layer is formed of amorphous silicon carbide (including hydrogenated amorphous silicon carbide). Amorphous silicon carbide is preferably hydrogenated (hereinafter, hydrogenated amorphous silicon carbide is referred to as a-SiC:H). In the photoreceptor for positive charging having the above layer structure, the surface protection layer also has a charge injection blocking function of preventing holes, which are charged charges, from being injected into the photoconductive layer. Also, the surface protection layer may have a multi-layer structure. In this case, as shown in FIG. 2, it is preferably the first region 205-1, the second region 205-2, and the third region 205-3 from the photoconductive layer side. In the first region, by changing the ratio of carbon atoms stepwise or continuously, the reflection of light generated at the interface between the photoconductive layer and the surface protection layer can be suppressed. In the second region, in order to increase the transmittance of the exposure light, the ratio of the number of carbon atoms to the total number of silicon atoms and carbon atoms [C / (Si+C)] is preferably 0.50 or more and 0.80 or less. The third region is the outermost surface region. From the perspective of durability, the film thickness of the third region is preferably 150 nm or more. In the present disclosure, the Si atom density in the surface-near region (surface region A) from the surface of the electrophotographic photoreceptor to a depth of 100 nm is 1.0×10 22 atoms / cm 3 or less. The Si atom density in the surface-near region (surface region A) from the surface of the electrophotographic photoreceptor to a depth of 100 nm can be 2.0×10 20 atoms / cm 3 or more. In addition, in the surface region A, it is preferable to contain hydrogen atoms in order to compensate for the unbonded hands.

[0025] (Manufacturing method of a-Si photoreceptor in the present disclosure) The manufacturing method of the a-Si photoreceptor in the present disclosure may be any method as long as it can form a layer that satisfies the above-described regulations. Specifically, a plasma CVD method, a vacuum evaporation method, a sputtering method, an ion plating method, etc. can be mentioned. Among these, the plasma CVD method is preferable in terms of ease of raw material supply and the like. Hereinafter, a manufacturing apparatus and a manufacturing method using the plasma CVD method will be described.

[0026] FIG. 3 is a diagram schematically showing an example of a deposition apparatus by an RF plasma CVD method using a high-frequency power source, which can be used for manufacturing the a-Si photoreceptor in the present disclosure. This deposition apparatus is roughly composed of a deposition apparatus 3100 having a reaction vessel 3110, a raw material gas supply apparatus 3200, and an exhaust apparatus (not shown) for reducing the pressure inside the reaction vessel 3110. Inside the reaction vessel 3110 in the deposition apparatus 3100, a substrate 3112 connected to the ground, a substrate heating heater 3113, and a raw material gas introduction pipe 3114 are installed. Further, a high-frequency power source 3120 is connected to the cathode electrode 3111 via a high-frequency matching box 3115. The raw material gas supply device 3200 is composed of raw material gas cylinders 3221 to 3227, valves 3231 to 3237, pressure regulators 3261 to 3267, inlet valves 3241 to 3247, and outlet valves 3251 to 3257. Furthermore, it is equipped with mass flow controllers 3211 to 3217. The raw material gas cylinders 3221 to 3227 filled with each raw material gas are connected to the raw material gas introduction pipe 3114 in the reaction vessel 3110 via the auxiliary valve 3260. 3116 is a gas pipe, 3117 is a leak valve, and 3121 is an insulating material.

[0027] Next, a method for forming a deposited film using this device will be described. First, a substrate 3112 that has been degreased and cleaned in advance is placed in the reaction vessel 3110 via the receiving base 3123. Next, an exhaust device (not shown) is operated to evacuate the inside of the reaction vessel 3110. While observing the display of the vacuum gauge 3119, when the pressure inside the reaction vessel 3110 reaches a predetermined pressure, for example, 1 Pa or less, power is supplied to the substrate heating heater 3113 to heat the substrate 3112 to a predetermined temperature, for example, 50 to 350 °C. At this time, an inert gas such as Ar or He can be supplied from the raw material gas supply device 3200 to the reaction vessel 3110 to perform heating in an inert gas atmosphere.

[0028] Next, the gas used for forming the deposited film is supplied from the raw material gas supply device 3200 to the reaction vessel 3110. That is, the valves 3231 to 3237, the inlet valves 3241 to 3247, and the outlet valves 3251 to 3257 are opened as necessary, and the mass flow controllers 3211 to 3217 are set for the flow rate. When the flow rate of each mass flow controller has stabilized, while observing the display of the vacuum gauge 3119, the main valve 3118 is operated to adjust the pressure inside the reaction vessel 3110 to the desired pressure. When the desired pressure is obtained, high-frequency power is applied from the high-frequency power supply 3120, and at the same time, the high-frequency matching box 3115 is operated to generate plasma discharge inside the reaction vessel 3110. Then, the high-frequency power is quickly adjusted to the desired power to form the deposited film. When the formation of the specified deposited film is completed, the application of high-frequency power is stopped, valves 3231 to 3237, inlet valves 3241 to 3247, outlet valves 3251 to 3257, and auxiliary valve 3260 are closed, and the supply of the source gas is terminated. At the same time, main valve 3118 is fully opened, and the inside of reaction vessel 3110 is evacuated to a pressure of 1 Pa or less.

[0029] Thus, the formation of the deposited film is completed. When forming a plurality of deposited films, the above procedure may be repeated to form each layer. The formation of the bonding region can also be performed by changing the source gas flow rate, pressure, etc. over a certain period in accordance with the conditions for forming, for example, a photoconductive layer. After all the deposited films are formed, main valve 3118 is closed, an inert gas is introduced into reaction vessel 3110 to return to atmospheric pressure, and then substrate 3112 is taken out.

[0030] In the formation of the pressure-resistant layer, as the source gas for supplying silicon atoms, for example, silanes such as silane (SiH4) and disilane (Si2H6) can be preferably used. As the source gas for supplying nitrogen atoms, for example, ammonia (NH3), nitrogen (N2), etc. can be preferably used. When containing oxygen atoms, in addition to the above source gas, for example, oxygen (O2), nitric oxide (NO), etc. can be preferably used as the source gas for supplying oxygen atoms. When containing hydrogen atoms, in addition to the above source gas, for example, hydrogen (H2) can be preferably used as the source gas for supplying hydrogen atoms. When containing carbon atoms or the like in the pressure-resistant layer to improve the adhesion to the conductive substrate, a gaseous substance containing the atoms to be contained or a substance that can be easily gasified may be appropriately used as the material.

[0031] In the formation of the charge injection blocking layer, as the raw material gas for supplying silicon atoms, silanes such as silane (SiH4) and disilane (Si2H6) can be preferably used as in the above case. Further, as the raw material gas for supplying group 13 atoms, for example, diborane (B2H6) and the like can be preferably used. In addition, as the raw material gas for supplying hydrogen atoms, in addition to the above raw material gases, for example, hydrogen (H2) can also be preferably used. Further, when carbon atoms, oxygen atoms, nitrogen atoms, etc. are contained in the charge injection blocking layer to improve the adhesion to the pressure-resistant layer, gaseous substances containing each atom or substances that can be easily gasified can be appropriately used as materials.

[0032] In the formation of the photoconductive layer, as the raw material gas for supplying silicon atoms, silanes such as silane (SiH4) and disilane (Si2H6) can be preferably used as in the above case. In addition, as the raw material gas for supplying hydrogen atoms, in addition to the above silanes, for example, hydrogen (H2) can also be preferably used. Further, when atoms for controlling the conductivity of electrons, carbon atoms, oxygen atoms, nitrogen atoms, etc. are contained in the photoconductive layer, gaseous substances containing each atom or substances that can be easily gasified can be appropriately used as materials.

[0033] When forming a-SiC:H as the surface protection layer, as the raw material gas for supplying silicon atoms, silanes such as silane (SiH4) and disilane (Si2H6) can be preferably used as in the above case. Further, as the raw material gas for supplying carbon atoms, for example, gases such as methane (CH4) and acetylene (C2H2) can be preferably used. As the raw material gas for supplying hydrogen atoms, for example, hydrogen (H2) can also be preferably used. The composition and atomic density of each layer can be changed depending on the type of source gas, etc. The amount of gas containing atoms that adjust the atomic density and component ratio can be reduced, and the atomic density and component ratio within the layer can be decreased accordingly. In addition, with regard to film formation parameters other than the type of source gas, there are the substrate temperature, the applied high-frequency power, the addition of dilution gas, the film formation pressure, and the film formation rate. To form a surface protective layer made of amorphous silicon carbide, the above-described gas containing silicon atoms and the gas containing carbon atoms (in the case of hydrogenated amorphous silicon carbide, a gas containing hydrogen atoms such as H2 described above) may be used for forming the deposited film of the surface protective layer.

[0034] <Toner and developer> The toner used in the electrophotographic apparatus of the present disclosure is a toner having toner particles containing a polyester resin having a polyethylene terephthalate segment and inorganic fine particles. Hereinafter, the toner according to the present disclosure will be described.

[0035] <Polyester resin having a polyethylene terephthalate segment> The structure of the polyester resin included in the toner in the present disclosure has the structure of polyethylene terephthalate. Examples of the components constituting the polyester resin having a polyethylene terephthalate segment include a polyethylene terephthalate segment, a dihydric or higher alcohol monomer component, and an acid monomer component such as a dihydric or higher carboxylic acid, a dihydric or higher carboxylic acid anhydride, and / or a dihydric or higher carboxylic acid ester.

[0036] <Polyethylene terephthalate segment> The polyethylene terephthalate segment of the present disclosure has a structure in which the structural unit of polyethylene terephthalate (C 10 H8O4) is repeated. The polyethylene terephthalate segments of the present disclosure can use those produced according to conventional methods by a condensation reaction or transesterification reaction of ethylene glycol and terephthalic acid, dimethyl terephthalate, etc. Also, recycled polyethylene terephthalate resin can be used. Polyethylene terephthalate resin is used in various products such as containers and films, and it is preferable to recycle and reuse it from the perspective of environmental protection. The recycled polyethylene terephthalate resin does not contain impurities that affect toner properties or reactions in the manufacturing process, and its type is not limited as long as it has an appropriate purity.

[0037] <Divalent or higher alcohol monomer component> Examples of the divalent or higher alcohol monomer component include alkylene oxide adducts of bisphenol A such as polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(3.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2.0)-polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(6)-2,2-bis(4-hydroxyphenyl)propane; ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, neopentyl glycol, polyethylene glycol, polypropylene glycol, etc.

[0038] <Acid monomer component> On the other hand, examples of the acid monomer component such as divalent or higher carboxylic acids, divalent or higher carboxylic anhydrides, and divalent or higher carboxylic acid esters include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or their anhydrides; alkyldicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid or their anhydrides, etc.

[0039] <Method for Producing Polyester Resin Having Polyethylene Terephthalate Segments> The polyester resin having polyethylene terephthalate segments of the present disclosure can be produced according to a normal polyester synthesis method. For example, after subjecting a carboxylic acid monomer and an alcohol monomer to an esterification reaction or a transesterification reaction, a desired polyester resin can be obtained by carrying out a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method.

[0040] <Amorphous Resin A, Crystalline Polyester Resin C, and Phosphorus Compound> Furthermore, it is more preferable because the low-temperature fixability and scratch resistance can be improved by using a toner as shown below. A toner having toner particles containing a binder resin, wherein the binder resin contains an amorphous resin A and a crystalline polyester resin C, The amorphous resin A is a polyester resin, and the amorphous resin A has, as a structure forming a polyester skeleton, (i) a polyethylene terephthalate segment, and (ii) at least one structure selected from the group consisting of a structure represented by the following formula (1), a structure represented by the following formula (2), a structure represented by the following formula (3), and a structure represented by the following formula (4).

Chemical formula

Chemical formula

[0041] Hereinafter, the reasons for the improvement of low-temperature fixability and scratch resistance will be explained. As a result of the study by the present inventors, it has been found that in a toner having the following characteristics, good low-temperature fixability is exhibited while improving scratch resistance. (i) It can flexibly deform the three-dimensional structure in the direction of the applied external force. (ii) When the external force is removed, it can return to the original three-dimensional structure. Such a toner can be achieved by the above-described configuration.

[0042] The amorphous resin A in the present disclosure has at least one structure selected from the group consisting of the structure represented by formula (1), the structure represented by formula (2), the structure represented by formula (3), and the structure represented by formula (4), and the SP values of the amorphous resin A and the crystalline polyester resin C are controlled. Thereby, the amorphous resin A has an affinity with the crystalline polyester resin C. Therefore, in the fixed image, the amorphous resin A is affected by the crystalline polyester resin C and becomes flexible. And this structure can flexibly deform the three-dimensional structure in the direction in which the external force is received without breaking the molecular chain in order to disperse the given external force.

[0043] In addition, since the amorphous resin A contains a polyethylene terephthalate segment, it has a repeating structure of a condensate of terephthalic acid and ethylene glycol in the polyester skeleton. The structure derived from ethylene glycol of the polyethylene terephthalate segment has ester groups at a very close molecular distance for two carbon atoms because both ends of ethylene glycol have undergone an ester reaction. Therefore, the amorphous resin A has ester groups localized in the resin.

[0044] In addition, the phosphorus compound in which three non-bonding electron pairs in the outermost shell have reacted also has a bonding point at a very close molecular distance. Therefore, the amorphous resin A can interact with the localized ester groups in the amorphous resin A around the phosphorus element of the phosphorus compound to form a three-dimensional crosslinked structure. By having this structure, when the applied external force is removed, it can return from the deformed state to the original three-dimensional structure. As described above, it is considered that by adopting the configuration of the present disclosure, excellent low-temperature fixability and scratch resistance can be obtained.

[0045] The amorphous resin A of the present disclosure has, as a structure forming a polyester skeleton, at least one structure selected from the group consisting of the structure represented by formula (1), the structure represented by formula (2), the structure represented by formula (3), and the structure represented by formula (4). The structure of the long-chain hydrocarbon group such as an alkyl group or an alkenyl group contained in each of the above structures is a relatively low-polarity structure compared to the structure derived from ethylene glycol of the polyethylene terephthalate segment described above. Therefore, the structure of the long-chain hydrocarbon group such as an alkyl group or an alkenyl group contained in each structure becomes flexible due to the increased affinity with the crystalline polyester resin C. And this structure can flexibly deform the three-dimensional structure in the direction of the applied external force without breaking the molecular chain in order to disperse the given external force. As a result, excellent scratch resistance is obtained by realizing an improvement in elastic deformation.

[0046] Also, the SP of the amorphous resin A of the present disclosure A (cal / cm 3 ) 0.5 and the SP of the crystalline polyester resin C C (cal / cm 3 ) 0.5 satisfy the above formula (C). When SP A - SP C satisfies the above formula (C), the amorphous resin A and the crystalline polyester resin C are easily compatible, so the crystalline polyester resin C can act on the structure having a long-chain hydrocarbon group such as an alkyl group or an alkenyl group of the amorphous resin A without delay. Therefore, this structure becomes flexible due to the increased affinity with the crystalline polyester resin C. And its structure can flexibly deform the three-dimensional structure in the direction of the applied external force without breaking the molecular chain in order to disperse the given external force. As a result, excellent scratch resistance is obtained by realizing an improvement in elastic deformation characteristics.

[0047] Furthermore, the toner of the present disclosure contains a phosphorus element derived from a phosphorus compound, and W P ​​​​(Mass ppm) satisfies the above formula (D). When the content of phosphorus element in the toner satisfies the above formula (D), it indicates that there is a sufficient amount of phosphorus element that interacts with the localized ester groups in the amorphous resin A around the phosphorus element and forms a three-dimensional cross-linked structure. That is, it is the minimum amount of phosphorus element that can flexibly change the three-dimensional structure in the direction of the external force received without breaking the molecular chain to disperse the given external force, and the maximum amount of phosphorus element that can ensure a certain plastic deformation to guarantee low-temperature fixability.

[0048] <Amorphous resin A> The amorphous resin A is a polyester resin and has the following (i) and (ii) as the structure forming the polyester backbone. (i) Polyethylene terephthalate segment (ii) At least one structure selected from the group consisting of the structure represented by formula (1), the structure represented by formula (2), the structure represented by formula (3), and the structure represented by formula (4)

[0049] The polyethylene terephthalate segment used in the amorphous resin A is obtained by polycondensing ethylene glycol and terephthalic acid.

[0050] And the synthesis of the amorphous resin A can be carried out in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and further, if necessary, in the presence of an esterification cocatalyst, a polymerization inhibitor, etc., preferably at a temperature of 180 °C or higher and 250 °C or lower.

[0051] Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin(II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropylate bistriethanolamineate. Among these, tin compounds such as tin(II) 2-ethylhexanoate are preferred. The amount of the esterification catalyst used is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, preferably 1.5 parts by mass or less, and more preferably 1.0 part by mass or less with respect to 100 parts by mass of the raw material monomers (alcohol component, carboxylic acid component, and PET). Examples of the esterification cocatalyst include gallic acid. The amount of the esterification cocatalyst used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.5 part by mass or less, more preferably 0.1 part by mass or less with respect to 100 parts by mass of the raw material monomers. Examples of the polymerization inhibitor include tert-butylcatechol. The amount of the polymerization inhibitor used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.5 part by mass or less, more preferably 0.1 part by mass or less with respect to 100 parts by mass of the raw material monomers.

[0052] In the synthesis of the amorphous resin A, polyethylene terephthalate may be present from the start of the polycondensation reaction or added to the reaction system during the polycondensation reaction. In order for the polyethylene terephthalate segment to be incorporated into the main skeleton of the amorphous resin A in a somewhat blocky form, the addition time of polyethylene terephthalate is preferably at a stage where the reaction rate of the alcohol component and the carboxylic acid component is 10% or less, and more preferably 5% or less. Here, the reaction rate refers to the value of (mol of generated reaction water amount) / (mol of theoretical generated water amount)×100.

[0053] In addition, used polyethylene terephthalate (so-called recycled PET) can be used as the polyethylene terephthalate segment contained in the amorphous resin A. Reusing polyethylene terephthalate is preferable from the environmental viewpoint.

[0054] The used PET is recovered, and the recovered PET is washed, sorted so that no other materials or garbage are mixed, and after removing labels, etc., it is pulverized into flakes or the like. The pulverized material can be used as it is, or the pulverized material can be kneaded and coarsely pulverized and then used. When chemical substances adsorbed on the surface of the PET bottle cannot be sufficiently removed by normal washing, alkali washing may be carried out. When a part of the pulverized material is hydrolyzed by alkali washing, in order to restore the reduced degree of polymerization, it is preferable to melt the washed pulverized material and subject the pelletized product to solid-phase polymerization. The solid-phase polymerization step can be carried out by continuously solid-phase polymerizing the washed flakes or the flakes melted and extruded into pellets in an inert gas such as nitrogen gas or rare gas at 180 to 245 °C, preferably 200 to 240 °C. Also, the washed pulverized material may be decomposed into monomer units by depolymerization and then resynthesized and used. Further, the recycled PET is not limited to the above-mentioned used PET, and fiber scraps or pellets of off-spec PET discharged from the factory may be used.

[0055] In addition, in order to incorporate at least one structure selected from the group consisting of the structure represented by formula (1), the structure represented by formula (2), the structure represented by formula (3), and the structure represented by formula (4) into the amorphous resin A, the following monomers can be used. 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, dodecenyl succinic acid, n-octyl succinic acid, isododecenyl succinic acid, dodecyl succinic acid, isooctenyl succinic acid, hexadecyl succinic acid, etc.

[0056] Among the above structures, it is preferable that the amorphous resin A contains a structure represented by the formula (1) or a structure represented by the formula (2). The branching of an alkyl group or alkenyl group having 6 to 16 carbon atoms from the main chain of the polyester skeleton increases the affinity with the release agent and further enhances the dispersibility of the release agent.

[0057] In addition, as components for obtaining the amorphous resin A, in addition to the above-described structures and monomers, other polyhydric alcohols (di- or higher-valent alcohols), polyvalent carboxylic acids (di- or higher-valent carboxylic acids), their acid anhydrides, or their lower alkyl esters may be used.

[0058] As the polyhydric alcohol monomer, the following polyhydric alcohol monomers can be used. As the dihydric alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol represented by the following formula (F) and its derivatives, and diols represented by the following formula (G) can be mentioned.

Chemical formula

Chemical formula

[0059] Examples of the alcohol component having three or more valences include sorbitol, 1,2,3,6 - hexanetetrol, 1,4 - sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4 - butanetriol, 1,2,5 - pentanetriol, glycerol, 2 - methylpropanetriol, 2 - methyl - 1,2,4 - butanetriol, trimethylolethane, trimethylolpropane, 1,3,5 - trihydroxymethylbenzene. Among these, glycerol, trimethylolpropane, and pentaerythritol are preferably used.

[0060] These divalent alcohols and alcohols having three or more valences can be used alone or in combination of two or more.

[0061] Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, azelaic acid, malonic acid, anhydrides of these acids, and lower alkyl esters of these acids. Among these, maleic acid, fumaric acid, and terephthalic acid are preferably used.

[0062] Examples of the carboxylic acid having three or more valences, its acid anhydride, or its lower alkyl ester include 1,2,4 - benzenetricarboxylic acid, 2,5,7 - naphthalenetricarboxylic acid, 1,2,4 - naphthalenetricarboxylic acid, 1,2,4 - butanetricarboxylic acid, 1,2,5 - hexanetricarboxylic acid, 1,3 - dicarboxyl - 2 - methyl - 2 - methylenecarboxypropane, 1,2,4 - cyclohexanetricarboxylic acid, tetra(methylene carboxyl)methane, 1,2,7,8 - octanetetracarboxylic acid, pyromellitic acid, Empol trimer acid, acid anhydrides of these acids, or lower alkyl esters of these acids. Among these, 1,2,4 - benzenetricarboxylic acid, that is, trimellitic acid or its derivatives are preferably used because they are inexpensive and the reaction control is easy. These divalent carboxylic acids, etc. and carboxylic acids having three or more valences can be used alone or in combination of two or more.

[0063] The method for producing the amorphous resin A is not particularly limited, and known methods can be used. For example, the aforementioned alcohol monomer and carboxylic acid monomer are charged simultaneously, and polymerized through an esterification reaction or transesterification reaction, and a condensation reaction to produce the amorphous resin A. The polymerization temperature is not particularly limited, but a range of 180°C or higher and 290°C or lower is preferable. When polymerizing the polyester unit, for example, polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide can be used. In particular, it is more preferable that the amorphous resin A is a polyester resin polymerized using a tin-based catalyst.

[0064] The amorphous resin A may be a polyester resin having a vinyl resin part. As a method for obtaining a polyester resin bonded with a vinyl resin, a method using a monomer component capable of reacting with both the vinyl resin and the polyester unit is preferable. Such monomers are preferably monomers having an unsaturated double bond and a carboxy group or a hydroxy group. Examples include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, itaconic acid or their anhydrides, and acrylic acid or methacrylic acid esters.

[0065] Also, from the viewpoint of low-temperature fixability and the like, it is preferable that the peak molecular weight of the amorphous resin A is 3500 or more and 20000 or less. The glass transition temperature is preferably 40°C to 70°C.

[0066] In addition to the amorphous resin A, various resins conventionally known as binder resins can be used in combination as the amorphous resin. Examples of such resins include phenol resins, natural resin-modified phenol resins, natural resin-modified maleic resins, acrylic resins, methacrylic resins, polyvinyl acetate resins, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral resins, terpene resins, coumarone-indene resins, petroleum resins, and the like.

[0067] <Crystalline polyester resin C> As monomers used in the polyester unit of the crystalline polyester resin C used in the toner of the present disclosure, polyhydric alcohols (diols or higher polyhydric alcohols), polyvalent carboxylic acids (divalent or higher polyvalent carboxylic acids), their acid anhydrides or their lower alkyl esters are used.

[0068] As the polyhydric alcohol monomer used in the polyester unit of the crystalline polyester resin C, the following polyhydric alcohol monomers can be used. The polyhydric alcohol monomer is not particularly limited, but is preferably a chain (more preferably a linear) aliphatic diol. For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2 - propylene glycol, 1,3 - propylene glycol, 1,6 - hexanediol, dipropylene glycol, 1,4 - butanediol, 1,4 - butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol can be mentioned. Among these, in particular, linear aliphatic α,ω - diols such as ethylene glycol, diethylene glycol, 1,4 - butanediol, and 1,6 - hexanediol are preferably exemplified.

[0069] In the present disclosure, polyhydric alcohol monomers other than the above polyhydric alcohol can also be used. Among the polyhydric alcohol monomers, examples of the dihydric alcohol monomers include aromatic alcohols such as polyoxyethylenated bisphenol A and polyoxypropylenated bisphenol A; and 1,4-cyclohexanedimethanol. Further, among the polyhydric alcohol monomers with three or more hydroxyl groups, examples of the polyhydric alcohol monomers include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; aliphatic alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin element, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

[0070] As the polycarboxylic acid monomer used in the polyester unit of the crystalline polyester resin C, the following polycarboxylic acid monomers can be used. The polycarboxylic acid monomer is not particularly limited, but is preferably a chain (more preferably linear) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, and also include those obtained by hydrolyzing acid anhydrides or lower alkyl esters thereof.

[0071] In the present disclosure, polycarboxylic acids other than the above polycarboxylic acid monomers can also be used. Among other polycarboxylic acid monomers, examples of the divalent carboxylic acid include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecyl succinic acid and n-dodecenyl succinic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, and acid anhydrides or lower alkyl esters thereof are also included. Among other carboxylic acid monomers, examples of the polycarboxylic acid having a trivalent or higher valence include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromellitic acid, and aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, and derivatives such as acid anhydrides or lower alkyl esters thereof are also included.

[0072] Further, the crystalline polyester resin C is preferably a modified crystalline polyester resin having a structure in which the hydroxy group at the main chain terminal is end-capped with an aliphatic monocarboxylic acid having 16 to 31 carbon atoms, or a modified crystalline polyester resin having a structure in which the carboxy group at the main chain terminal is end-capped with an aliphatic monoalcohol having 15 to 30 carbon atoms.

[0073] Examples of the aliphatic monocarboxylic acid monomer having 16 to 31 carbon atoms include palmitic acid (hexadecanoic acid), margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), nonadecylic acid, arachidic acid (eicosanoic acid), heneicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid, and triacontanoic acid.

[0074] Examples of aliphatic monohydric alcohols having 15 to 30 carbon atoms include cetyl alcohol, palmityl alcohol (hexadecanol), margaryl alcohol (heptadecanol), stearyl alcohol (octadecanol), nonadecanol, arachidyl alcohol (icosanol), heneicosanol, behenyl alcohol, lignoceryl alcohol, cerol alcohol, 1-heptacosanol, montanyl alcohol, 1-nonacosanol, and myristyl alcohol.

[0075] Crystalline polyester resin C can be produced according to a conventional polyester synthesis method. For example, after subjecting the above-described carboxylic acid monomer and alcohol monomer to an esterification reaction or a transesterification reaction, a crystalline polyester resin can be obtained by performing a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. Thereafter, by further adding the above aliphatic compound and performing an esterification reaction, a desired crystalline polyester resin can be obtained.

[0076] The above esterification or transesterification reaction can be carried out using a conventional esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, or magnesium acetate, as necessary.

[0077] Also, the above polycondensation reaction can be carried out using a known catalyst such as a conventional polymerization catalyst, for example, titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, or germanium dioxide. The polymerization temperature and the amount of catalyst are not particularly limited and may be determined as appropriate.

[0078] In the esterification or transesterification reaction or the polycondensation reaction, a method of charging all the monomers at once may be used to increase the strength of the obtained crystalline polyester resin. Also, a method such as reacting a divalent monomer first and then adding and reacting a trivalent or higher-valent monomer may be used to reduce low molecular weight components.

[0079] The melting point of the crystalline polyester resin C is preferably 70°C to 110°C, more preferably 80°C to 100°C from the viewpoint of low-temperature fixability. In the toner of the present disclosure, the crystalline polyester resin C is preferably used in an amount of 3 parts by mass or more and 20 parts by mass or less per 100 parts by mass of the amorphous resin from the viewpoints of low-temperature fixability, rub resistance, and charge retention in a high-temperature and high-humidity environment.

[0080] <Phosphorus compound> Examples of the phosphorus compound used in the toner of the present disclosure include trisodium phosphate, trimethyl phosphate, triethyl phosphate, tri-2-ethylhexyl phosphate, tris(isopropylphenyl) phosphate, triphenyl phosphate, tributyl phosphate, trimethyl phosphite, tributyl phosphite, triphenyl phosphite, and the like. Among them, trivalent phosphorus compounds that easily form three-dimensional crosslinks are preferred.

[0081] The optimal W for forming a three-dimensional crosslinked structure P is as described above. Further, when the used toner contains polyethylene terephthalate (so-called recycled PET), blocks of polyethylene terephthalate are likely to be formed, so ester groups with close molecular distances aggregate more, and a strong three-dimensional crosslinked structure can be formed. This structure can return to its original three-dimensional structure when the applied external force is removed.

[0082] <Inorganic fine particles> The toner contains inorganic fine particles. When the toner contains inorganic fine particles, during repeated use of the electrophotographic apparatus, the inorganic fine particles are supplied to the nip portion between the cleaning blade and the portion to be cleaned of the photoreceptor, and the cleaning is stabilized, thereby suppressing the occurrence of streak-like image defects. Examples of the inorganic fine particles include fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, or composite oxide fine particles thereof. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferred for improving fluidity and charge uniformity. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, a silicone oil, or a mixture thereof.

[0083] <Release agent> The toner particles may contain wax as a release agent. Examples of the wax include polyethylene wax, polypropylene wax, polypropylene copolymer wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, carnauba wax, rice wax, candelilla wax, montan wax, and the like.

[0084] <Colorant> The toner may contain a colorant. Examples of the colorant include known organic pigments or oil dyes, magnetic materials, and the like. Examples of the colorant include carbon black, phthalocyanine blue, permanent brown FG, brilliant fast scarlet, pigment red 122, pigment green B, rhodamine-B base, solvent red 49, solvent red 146, solvent blue 35, quinacridone, carmine 6B, isoindoline, disazo yellow, benzidine yellow, monoazo dyes, disazo dyes, and the like.

[0085] <Charge control agent> The toner particles may contain a charge control agent as needed. Known charge control agents can be used, but particularly when combined with the photoreceptor used in the present disclosure, it is preferable to use a positive charge control agent. Examples of the positive charge control agent include quaternary ammonium salt compounds, triphenylmethane compounds, imidazole compounds, nigrosine dyes, and the like. Examples of the negative charge control agent include metal salicylate compounds, metal naphthenate compounds, metal dicarboxylate compounds, polymer compounds having a sulfonic acid or carboxylic acid in the side chain, polymer compounds having a sulfonate or sulfonic acid esterified product in the side chain, polymer compounds having a carboxylate or carboxylic acid esterified product in the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0086] <External additive> As the external additive, in addition to the above inorganic fine particles, organic fine particles such as melamine resin fine particles and polytetrafluoroethylene resin fine particles may be used.

[0087] From the viewpoint of improving fluidity, the median diameter (D 50 ) of the external additive in terms of the number of particles is preferably 10 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, and even more preferably 90 nm or less.

[0088] The content of the external additive is preferably 0.1 part by mass to 10.0 parts by mass with respect to 100 parts by mass of the toner particles. Mixing of the toner particles and the external additive can be performed using a known mixer such as a Henschel mixer.

[0089] <Method for producing toner particles> The method for producing toner particles is not particularly limited, and known methods such as a pulverization method, a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and a dispersion polymerization method can be used. Among them, from the viewpoint of controlling the wax on the toner particle surface, the pulverization method is preferable. That is, the toner particles are preferably pulverized toner particles. Hereinafter, the toner production procedure by the pulverization method will be described.

[0090] The pulverization method includes, for example, a raw material mixing step of mixing a crystalline polyester resin C, an amorphous resin A, a phosphorus compound, and, if necessary, other amorphous resins, waxes, colorants, charge control agents, and other components as a binder resin, a step of melt-kneading the mixed raw materials to obtain a resin composition, and a step of pulverizing the obtained resin composition to obtain toner particles.

[0091] In the raw material mixing step, as materials constituting toner particles, for example, a binder resin, wax, and other components such as a colorant and a charge control agent as required are weighed in predetermined amounts, blended, and mixed. Examples of mixing devices include a double cone mixer, V-type mixer, drum-type mixer, super mixer, Henschel mixer, Nauta mixer, and mechano hybrid (manufactured by Nippon Coke & Engineering Co., Ltd.).

[0092] Next, the mixed materials are melt-kneaded to disperse the materials in the binder resin. In the melt-kneading step, a batch kneader such as a pressure kneader or Banbury mixer, or a continuous kneader can be used. Due to the advantage of continuous production, single-screw or twin-screw extruders are the mainstream. For example, KTK type twin-screw extruder (manufactured by Kobe Steel, Ltd.), TEM type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikegai Iron Works), twin-screw extruder (manufactured by K.C.K. Co., Ltd.), co-kneader (manufactured by Buss Co., Ltd.), and Neodeck (manufactured by Nippon Coke & Engineering Co., Ltd.) can be mentioned. Furthermore, the resin composition obtained by melt-kneading may be rolled with a two-roll mill or the like and cooled with water or the like in the cooling step.

[0093] Then, the cooled resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization step, first, it is roughly pulverized with a pulverizer such as a crusher, hammer mill, or feather mill. Then, it is finely pulverized with a fine pulverizer such as a Cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), Turbo Mill (manufactured by Turbo Industries), or an air jet type fine pulverizer.

[0094] Thereafter, if necessary, it is classified using a classifier or sieve such as an elbow jet of the inertial classification method (manufactured by Nippon Steel Mining Co., Ltd.), turbo plex of the centrifugal classification method (manufactured by Hosokawa Micron Corporation), TSP separator (manufactured by Hosokawa Micron Corporation), and Faculty (manufactured by Hosokawa Micron Corporation).

[0095] After that, if necessary, an external additive such as silica fine particles is externally added to the surface of the toner particles to obtain a toner. Examples of the apparatus for external addition treatment include mixing apparatuses such as a double cone mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke & Engineering Co., Ltd.), and a Nobiltra (manufactured by Hosokawa Micron Corporation).

[0096] The measurement methods for various physical properties will be described below. (Separation method of each material from the toner) Each material contained in the toner can be separated from the toner by utilizing the difference in solubility of each material in a solvent or GPC. Using the separated materials, the following various physical properties can be measured. First separation: Dissolve the toner in methyl ethyl ketone (MEK) at 23°C to separate the soluble components (amorphous resin A, other amorphous resins, crystalline polyester resin C, phosphorus compound) and the insoluble components (wax, colorant, inorganic fine particles, etc.). Second separation: Dissolve the soluble components (amorphous resin A, other amorphous resins, crystalline polyester resin C, phosphorus compound) obtained in the first separation in tetrahydrofuran (THF) at 23°C to separate the soluble components (amorphous resin A, other amorphous resins, phosphorus compound) and the insoluble component (crystalline polyester resin C). Third separation: Dissolve the insoluble components (wax, colorant, inorganic fine particles, etc.) obtained in the first separation in MEK at 100°C to separate the soluble component (wax) and the insoluble components (colorant, inorganic fine particles, etc.). Fourth separation: Dissolve the soluble components (amorphous resin A, other amorphous resins, phosphorus compound) obtained in the second separation in tetrahydrofuran (THF) at 23°C, and separate amorphous resin A, other amorphous resins, and the phosphorus compound by preparative GPC.

[0097] <Method for confirming the attribution and measuring the content ratio of various monomer units in amorphous resin and crystalline polyester resin> The confirmation of the attribution and the measurement of the content ratio of various monomer units in the amorphous resin and the crystalline polyester resin are carried out by 1H-NMR under the following conditions. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measuring frequency: 400 MHz Pulse condition: 5.0 μs Frequency range: 10500 Hz Number of integrations: 64 times Measuring temperature: 30 °C Sample: 50 mg of the measurement sample is placed in a sample tube with an inner diameter of 5 mm, and deuterated chloroform (CDCl3) is added as a solvent, and this is dissolved in a constant temperature bath at 40 °C for preparation.

[0098] Obtained 1 From the 1H-NMR chart, the structures of various monomer units are specified, and the integral values S1, S2, S3, ··· S of the peaks attributed to each monomer unit n are calculated.

[0099] The content ratios of various monomer units are obtained as follows using the above integral values S1, S2, S3 and S n Note that n1, n2, n3 ··· n n are the number of hydrogens in each monomer unit. Content ratio (mol%) of various monomer units = {(S n / n n ) / ((S1 / n1) + (S2 / n2) + (S3 / n3) ··· + (S n / n n ))} × 100 Change the numerator term of the same operation and calculate the content ratio (mol%) of various monomer units respectively. Note that when a polymerizable monomer containing no hydrogen atom is used for various monomer units, 13 Use 13C-NMR to measure the nuclei 13 as 13C and perform the measurement in single pulse mode, 1 and calculate in the same manner as in 1H-NMR.

[0100] <Method for calculating SP value of amorphous resin A and crystalline polyester resin C> The SP values of amorphous resin A and crystalline polyester resin C are calculated according to the calculation method proposed by Fedors. Specifically, the evaporation energy (Δei), molar volume (Δvi), and molar ratio (j) in the resin are determined for each monomer unit. Using these values, the SP value is calculated from the following formula. SP value (cal / cm 3 ) 0.5 ={(Σj × ΣΔei) / (Σj × ΣΔvi)} 0.5 For the evaporation energy (Δei) and molar volume (Δvi) of atoms or atomic groups in the monomer unit, the values described in "polym.Eng.Sci., 14(2), 147 - 154(1974)" are used.

[0101] <Content W of phosphorus element in toner P Measurement method> The content W of phosphorus element in toner P (in mass ppm) is measured using a multi - element simultaneous ICP emission spectrometer Vista - PRO (manufactured by Hitachi High - Technologies Corporation). Sample: 50 mg Solvent: 6 mL of nitric acid Weigh the above, and perform a decomposition treatment using a microwave sample pretreatment device ETHOS UP (manufactured by Milestone General). Temperature: Heat up from 20°C to 230°C and hold at 230°C for 30 min After passing the decomposition solution through filter paper (5C), transfer it to a 50 - mL volumetric flask and make up to 50 mL with ultrapure water. By measuring the aqueous solution in the volumetric flask with a multi - element simultaneous ICP emission spectrometer Vista - PRO under the following conditions, the content of phosphorus element in the toner can be quantified. The quantification of the content is carried out by creating a calibration curve using a standard sample of the element to be quantified and calculating based on that calibration curve. Conditions: RF power 1.20 kW Ar gas: Plasma flow 15.0 L / min Auxiliary flow: 1.50 L / min MFC: 1.50 L / min Nebulizer flow: 0.90 L / min Liquid delivery pump speed: 15 rpm Measurement repetition: 3 times Measurement time: 1.0 s

[0102] <Developer> The toner can be used as a one-component developer, but in order to further improve dot reproducibility and supply stable images over a long period, it is preferably used as a two-component developer by mixing with a magnetic carrier. As the magnetic carrier, generally known materials such as metal particles such as iron, cobalt, and nickel, and magnetic materials such as ferrite can be used.

Examples

[0103] Hereinafter, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to these examples. In addition, the parts in the following formulations are all based on mass unless otherwise specified.

[0104] [Manufacturing Examples of Electrophotographic Photoreceptors 1 to 16] As a cylindrical conductive substrate, an aluminum alloy base tube (outer diameter: 84 mm, length: 370 mm) was prepared. The outer peripheral surface of the prepared conductive substrate was subjected to mirror finishing and wet blasting, and then washed. First, as the mirror finishing of the surface of the conductive substrate, while holding the conductive substrate at both ends and rotating it at a high speed of 1500 to 8000 rpm, a diamond bit was pressed against it, and vanishing processing was performed at a feed rate of 0.08 / second to 0.5 mm / second. That is, a smooth finish was obtained by pressing the finish surface of the diamond bit having a depth in the workpiece rotation direction against the surface of the conductive substrate. After such mirror finishing, the conductive substrate was subjected to degreasing and cleaning. Next, as wet blasting, a hard abrasive such as alumina and water were stirred, mixed and accelerated with compressed air, and projected onto the surface of the mirror-finished conductive substrate to roughen it. In this method, since the conductive substrate is processed while being rotated, a processed surface with excellent uniformity can be formed in a short time. Specifically, as the conditions for wet blasting, conductive substrates having different surface roughnesses were prepared by adjusting the following parameters. Abrasive material quality and particle size: A (Aluminum oxide, brown fused alumina) #320 - #4000 Abrasive material concentration: 10 - 18% Projection air pressure: 0.10 - 0.35 MPa Projection distance (distance between the work center and the blast head): 20 - 300 mm Projection time: 1 - 60 seconds Work rotation speed: 120 - 180 rpm Note that the surface roughness was adjusted by changing the abrasive material quality and particle size, concentration, projection air pressure, projection distance, and projection time. And after performing wet blasting, the conductive substrate was prepared by washing and removing the residue remaining on the surface. Using the deposition apparatus shown in Figure 3, the conductive substrate prepared in this way was used to form each layer on the surface of the conductive substrate under the film formation conditions shown in Table 1 and Table 2 so as to have the layer structure shown in Figure 2, and an a-Si photoreceptor was fabricated. Note that for the first region of the surface protection layer, film formation was performed by changing the flow rate of the source gas and the high-frequency power as described in Table 1 so that the number of carbon atoms changed continuously. Also, the flow rate of the source gas, reaction pressure, high-frequency power, and substrate temperature during the formation of the third region of the surface protection layer were set to the conditions shown in Table 2.

[0105]

Table 1

[0106]

Table 2

[0107] For the electrophotographic photoreceptors 1 - 16 obtained as described above, the surface shape was measured. The measurement was carried out using a Keyence laser microscope VK-X100 to evaluate the surface shape with three-dimensional roughness parameters conforming to ISO25178. As measurement conditions, a lens with a magnification of 100 times was used for measurement. Since the measurement object was cylindrical, curvature correction was performed in the two-dimensional direction, and the arithmetic mean roughness Sa was calculated. The measurement was performed at a total of 28 locations, including 7 locations (center, ±50 mm, ±100 mm, ±150 mm) in the axial direction and 4 locations (every 90°) in the circumferential direction of the electrophotographic photoreceptor, and the average value was taken as the arithmetic mean roughness Sa of the electrophotographic photoreceptor. The results are shown in Table 3.

[0108] Also, the Si atomic density in the surface vicinity region (surface region A) from the surface of the electrophotographic photoreceptor to a depth of 100 nm was determined by the following method. The film thickness information of the surface layer was measured by spectroscopic ellipsometry using the method described in JP-A-2010-49241. Next, the number of Si atoms was determined by Rutherford backscattering spectrometry using the method described in JP-A-2010-49241, and by combining with the above-described film thickness information of the surface layer, the Si atomic density in surface region A was determined. The obtained results are shown in Table 3.

[0109]

Table 3

[0110] [Production Example 1 of Toner] <Measurement Method of Softening Point of Resin> The measurement of the softening point of the resin is carried out using a capillary rheometer of the constant load extrusion type (trade name: Flow Characteristic Evaluation Flow Tester CFT-500D, manufactured by Shimadzu Corporation) in accordance with the manual attached to the apparatus. In this apparatus, while applying a constant load from above the measurement sample by a piston, the measurement sample filled in the cylinder is heated to melt, and the melted measurement sample is extruded from the die at the bottom of the cylinder, and a flow curve showing the relationship between the piston descent amount and the temperature at this time can be obtained. The softening point is defined as the "melting temperature in the 1 / 2 method" described in the manual attached to the Flow Property Evaluation Flow Tester CFT-500D. The melting temperature in the 1 / 2 method is calculated as follows. First, find 1 / 2 of the difference between the piston descent amount (Smax) at the end of the outflow and the piston descent amount (Smin) at the start of the outflow (let this be X. X = (Smax - Smin) / 2). Then, the temperature at which the piston descent amount in the flow curve becomes the sum of X and Smin is the melting temperature in the 1 / 2 method. As the measurement sample, about 1.0 g of resin is compression molded at about 10 MPa for about 60 seconds using a tablet molding compression machine (e.g., NT-100H, manufactured by NPE System Co., Ltd.) in an environment of 25°C to form a cylindrical shape with a diameter of about 8 mm. The measurement conditions of the CFT-500D are as follows. Test mode: Heating rate method Start temperature: 50°C Reach temperature: 200°C Measurement interval: 1.0°C Heating rate: 4.0°C / min Piston cross-sectional area: 1.000 cm 2 Test load (piston load): 10.0 kgf / cm 2 (0.9807 MPa) Preheating time: 300 seconds Diameter of die hole: 1.0 mm Length of die: 1.0 mm

[0111] <Manufacturing Example of Resin 1> The following materials were charged into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. · 100 parts by mass of a propylene oxide adduct of bisphenol A (average addition mole number: 2.2 moles) · 21 parts by mass of recycled polyethylene terephthalate resin (diethylene glycol content = 1.3% by mass) · 0.08 parts by mass of dibutyltin oxide While stirring the inside of the reaction vessel at 200 rpm, it was heated to 230 °C and reacted for 7 hours. Subsequently, it was cooled to 180 °C, 30 parts by mass of fumaric acid and 0.08 parts by mass of hydroquinone were added, and it was heated to 210 °C over 4 hours. Then, the pressure was reduced to 8 kPa and reacted until the softening point reached 103 °C to obtain Resin 1.

[0112] <Production Example of Resin 2> In a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, the following materials were charged under a nitrogen atmosphere. · 100 parts by mass of propylene oxide adduct of bisphenol A (average number of moles of addition: 2.2 moles) · 40 parts by mass of ethylene oxide adduct of bisphenol A (average number of moles of addition: 2.2 moles) · 13 parts by mass of dodecenyl succinic anhydride · 37 parts by mass of terephthalic acid · 12 parts by mass of trimellitic anhydride · 0.5 parts by mass of dibutyltin oxide While stirring the inside of the reaction vessel at 200 rpm, it was heated to 235 °C and reacted for 4 hours. Then, the pressure was reduced to 8 kPa and reacted until the softening point reached 146 °C to obtain Resin 2.

[0113] <Production Example of Toner Particles 1> · 70 parts by mass of Resin 1 · 30 parts by mass of Resin 2 · 7 parts by mass of carbon black R330R (manufactured by Cabot Corporation) · 0.5 parts by mass of charge control agent Bontron P-51 (manufactured by Orient Chemical Industries Co., Ltd.) · 4 parts by mass of release agent carnauba wax No. 1 (manufactured by Kato Yoko Co., Ltd.) Using a Henschel mixer (FM-75 type, manufactured by Nippon Coke Industry Co., Ltd.), the above materials were rotated at 20 s -1, it was mixed for 5 minutes of rotation time. Then, it was kneaded at a discharge temperature of 135°C using a twin-screw kneader (PCM-30 type, manufactured by Ikegai Corporation) set at a temperature of 120°C and a screw rotation speed of 200 rpm. The obtained kneaded material was cooled at a cooling rate of 15°C / min and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The obtained coarsely pulverized product was finely pulverized using a mechanical pulverizer (T-250, manufactured by Freund Turbo Co., Ltd.). Furthermore, classification was performed using a Faculity F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions were a classifier rotor rotation speed of 130 s -1 , a dispersion rotor rotation speed of 120 s -1 .

[0114] [Production Example of Toner 1] The following materials were mixed using a Henschel mixer FM-10C type (manufactured by Nippon Coke Industry Co., Ltd.) at a rotation speed of 30 s -1 and a rotation time of 10 minutes to obtain toner 1. · 100 parts by mass of toner particles 1 · 2.1 parts by mass of silica fine particles surface-treated with hexamethyldisilazane having an average particle size of 130 nm · 0.7 parts by mass of silica fine particles surface-treated with hexamethyldisilazane having an average particle size of 20 nm

[0115] [Production Example of Magnetic Carrier] [Production Example of Magnetic Carrier Core Particles] · 62.7 parts by mass of Fe2O3 · 29.5 parts by mass of MnCO3 · 6.8 parts by mass of Mg(OH)2 · 1.0 parts by mass of SrCO3 The ferrite raw materials were weighed so as to have the above composition ratio. Then, it was pulverized and mixed for 5 hours using a dry vibration mill using stainless steel beads. The obtained pulverized product was made into pellets of about 1 mm square using a roller compactor. The pellets were sieved with a vibrating sieve having a mesh size of 3 mm to remove coarse powder, and then sieved with a vibrating sieve having a mesh size of 0.5 mm to remove fine powder. After that, using a burner-type firing furnace, firing was carried out at a temperature of 1000 °C for 4 hours in a nitrogen atmosphere (oxygen concentration: 0.01% by volume) to produce calcined ferrite. After the above calcined ferrite was crushed to about 0.3 mm with a crusher, using zirconia beads, 30 parts by mass of water was added to 100 parts by mass of the calcined ferrite, and it was pulverized with a wet ball mill for 1 hour. Further, the obtained slurry was pulverized with a wet ball mill for 4 hours to obtain a ferrite slurry (a finely pulverized product of the calcined ferrite). To the above ferrite slurry, 1.0 part by mass of ammonium polycarboxylate as a dispersant and 2.0 parts by mass of polyvinyl alcohol as a binder were added based on 100 parts by mass of the calcined ferrite, and granulation was carried out into spherical particles with a spray dryer (manufacturer: Okawara Chemical Machinery Co., Ltd.). After adjusting the particle size of the obtained particles, heating was carried out at 650 °C for 2 hours using a rotary kiln to remove the organic components of the dispersant and the binder. In order to control the firing atmosphere, in an electric furnace under a nitrogen atmosphere (oxygen concentration: 1.00% by volume), the temperature was raised from room temperature to 1300 °C in 2 hours, and then firing was carried out at a temperature of 1150 °C for 4 hours. Then, the temperature was lowered to 60 °C over 4 hours, the atmosphere was returned from nitrogen to air, and it was taken out at a temperature of 40 °C or lower. After crushing the aggregated particles, low-magnetic products were cut by magnetic separation, and sieving was carried out with a sieve having a mesh size of 250 μm to remove coarse particles, and magnetic carrier core particles having a volume-based 50% particle size (D50) of 37.0 μm were obtained.

[0116] <Production Example of Magnetic Carrier 1> As the first coating step, a thermosetting silicone resin solution (methyl silicone resin) was applied to the magnetic carrier core particles. The amount of the coating resin was made 0.20 part by mass with respect to 100 parts by mass of the magnetic carrier core particles. At the time of coating, a coating device provided with a rotary bottom plate disk and stirring blades in a fluidized bed to form a swirling flow was used for coating. The above resin solution was sprayed from a direction perpendicular to the moving direction in the device of the fluidized bed. Next, the following materials were prepared. · Fluororesin solution (copolymer of tetrafluoroethylene and hexafluoropropylene (FEP)) (1.91 parts by mass based on 100 parts by mass of magnetic carrier core particles as solid content) · Thermosetting melamine resin solution (0.09 parts by mass based on 100 parts by mass of magnetic carrier core particles as solid content) These were thoroughly stirred and mixed to prepare a carrier coating solution. This carrier coating solution was applied to the magnetic carrier core particles as the second coating step. At the time of application, a coating device was used in which a rotary bottom plate disk and stirring blades were provided in a fluidized bed to form a swirling flow during coating. 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.

[0117] [Production Example of Developer 1] The following materials were mixed using a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain Developer 1. · Toner 1 8 parts by mass · Magnetic carrier 1 92 parts by mass

[0118] [Example 1] As an electrophotographic apparatus, a modified machine of a Canon copier image Press C800 was prepared. More specifically, it was modified so that the charging method became positive charging. Also, in order to make it an electrophotographic apparatus having the configuration shown in FIG. 1, the configuration of the cleaning means was modified to a configuration having a rubbing roller that rubs the electrophotographic photoreceptor with an elastic sponge and a cleaning blade. Also, the cleaning blade was adjusted to contact at a contact pressure of 40 g / cm, and the rubbing roller of the cleaner and the cleaning blade were replaced with new parts in order to reproduce the state at the initial stage of use of the electrophotographic apparatus. The electrophotographic photoreceptor 1 was set on the black station of the prepared electrophotographic apparatus, and Developer 1 was set in the developing device as the developer.

[0119] (Evaluation of Image) The image evaluation was performed in an environment of 32 ° C / 85% RH. As evaluation images, after outputting 30 consecutive prints of a halftone image with a pixel density of 5% on A4 size, one halftone image with a pixel density of 25% on A4 size was output. Furthermore, after outputting 200 consecutive prints of a halftone image with a pixel density of 5% on A4 size, one halftone image with a pixel density of 25% on A4 size was output. Regarding streak-like image defects, evaluation was performed according to the following evaluation criteria. The results are shown in Table 4. (Evaluation Criteria) A: No image defects are observed in all images. B: Images in which image defects are suspected are obtained in some images, but it remains at a level where it cannot be determined whether they are clear image defects. C: Slightly minor image defects at a level that causes no practical problems occurred in some images. D: Clear image defects have occurred on the image.

[0120] [Examples 2 to 13, Comparative Examples 1 to 3] As Examples 2 to 13 and Comparative Examples 1 to 3, evaluation was performed in the same manner as in Example 1 for the combinations of electrophotographic photoreceptors and developers shown in Table 4. The evaluation results are shown in Table 4.

[0121]

Table 4

[0122] [Production Example 2 of Toner] [Preparation of Amorphous Resin A1] · Polyethylene terephthalate (molecular weight: 2000, intrinsic viscosity: 0.1): 20.9 parts by mass (42.0 mol%) · Propylene oxide adduct of bisphenol A (average number of added moles 2.0 mol): 47.4 parts by mass (29.0 mol%) · Terephthalic acid: 15.8 parts by mass (18.3 mol%) · Dodecenyl succinic anhydride: 15.8 parts by mass (10.6 mol%) · Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass · Gallic acid (co-catalyst): 0.1 part by mass The above materials were weighed into a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen inlet pipe, and a thermocouple. The molar ratio of polyethylene terephthalate is a value based on the total number of units derived from ethylene glycol units and terephthalic acid units. Next, after replacing the inside of the flask 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.

[0123] Furthermore, the pressure inside the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 5 hours while maintaining the temperature at 200 °C. After confirming that the weight average molecular weight reached 6700, the temperature was lowered to stop the reaction, and an amorphous resin A1 having a polyethylene terephthalate segment in the molecule was obtained. The physical properties of the amorphous resin A1 obtained by the above-described measurement method are shown in Table 4.

[0124] <Preparation of Amorphous Resins A2 to A11> In the preparation of the amorphous resin A1, the reaction was carried out in the same manner except that the types and amounts of the polyethylene terephthalate and the polymerizable monomers were changed as shown in Tables 5-1 to 5-2. Thereby, amorphous resins A2 to A11 having a polyethylene terephthalate segment in the molecule were obtained. The physical properties of the amorphous resins A2 to A11 obtained by the above-described measurement method are shown in Tables 5-1 to 5-2.

[0125]

Table 5-1

[0126]

Table 5-2

[0127] <Production of Amorphous Resin B1> · Polyethylene terephthalate (molecular weight: 2000, intrinsic viscosity: 0.1): 4.1 parts by mass (9.8 mol%) · Propylene oxide adduct of bisphenol A (average number of added moles 2.0 mol): 57.8 parts by mass (42.8 mol%) · Terephthalic acid: 29.9 parts by mass (41.9 mol%) · Trimellitic acid: 7.0 parts by mass (4.5 mol%) · Stearic acid: 1.2 parts by mass (1.0 mol%) · Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass · Gallic acid (promoter): 0.1 parts by mass The above materials were weighed into a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen inlet pipe, and a thermocouple. Next, after replacing the inside of the flask 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.

[0128] Furthermore, the pressure inside the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 5 hours while maintaining the temperature at 200°C. After confirming that the weight-average molecular weight reached 1000, the temperature was lowered to stop the reaction, and amorphous resin B1 was obtained. The physical properties of amorphous resin B1 obtained by the measurement method described above were such that the SP value was 11.54 (cal / cm 3 ) 0.5 It was.

[0129] <Production of Crystalline Polyester Resin C1> · Ethylene glycol: 10.2 parts by mass (48.2 mol%) · Tetradecanedioic acid: 81.3 parts by mass (48.3 mol%) · Behenic acid: 8.5 parts by mass (3.5 mol%) · Titanium tetrabutoxide (esterification catalyst): 0.5 parts by mass The above materials were weighed into a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen inlet pipe, and a thermocouple. Next, after replacing the inside of the flask 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.

[0130] Furthermore, the pressure in the reaction vessel was reduced to 8.3 kPa and the temperature was maintained at 200 °C. After reacting for 5 hours, the temperature was lowered to stop the reaction, and crystalline polyester resin C1 was obtained. The physical properties of crystalline polyester resin C1 obtained by the above-described measurement method were such that the SP value was 10.09 (cal / cm 3 ) 0.5 .

[0131] <Production Example of Toner 2> · Amorphous resin A1: 66 parts by mass · Amorphous resin B1: 34 parts by mass · Crystalline polyester resin C1: 10 parts by mass · Fischer-Tropsch wax (peak temperature of the maximum endothermic peak: 100 °C): 5 parts by mass · Carbon black: 5 parts by mass · Sodium phosphate: 0.03 parts by mass · Charge control agent Bontron P-51 (manufactured by Orient Chemical Industries Co., Ltd.): 0.5 parts by mass The above materials were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 1500 rpm for 5 minutes, and then kneaded using a twin-screw kneader (PCM-30 type, manufactured by Ikegai Corporation) set at a temperature of 130 °C. The obtained kneaded product was cooled and roughly pulverized to 1 mm or less using a hammer mill to obtain a rough pulverized product. The obtained rough pulverized product was finely pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Industry Co., Ltd.). Further, classification was performed using a Faculity (F-300, manufactured by Hosokawa Micron Corporation) to obtain toner particles 2. The operating conditions were a classification rotor rotation speed of 11000 rpm and a dispersion rotor rotation speed of 7200 rpm.

[0132] · Toner particles 2: 95 parts · Inorganic fine particles with large particle size: Fumed silica surface-treated with hexamethyldisilazane (Median diameter (D50) on a number basis is 120 nm) 4 parts by mass · Inorganic fine particles with small particle size: Titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (Median diameter (D50) on a number basis is 10 nm) 1 part by mass The above materials were mixed in a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotation speed of 1900 rpm for 10 minutes to obtain Toner 2 exhibiting positive chargeability. The physical properties of Toner 2 obtained by the above-described measurement method are shown in Table 6.

[0133] <Production Examples of Toners 3 to 19> In the production example of Toner 2, the same operations as in the production example of Toner 2 were carried out except that the types and parts by mass of the amorphous resin A and the additives were changed as shown in Table 6 to obtain Toners 3 to 19. The physical properties of Toners 3 to 19 obtained by the above-described measurement method are shown in Table 6.

[0134]

Table 6

[0135] <Production Examples of Developers 2 to 19> In the production example of Developer 1, the same operations were carried out except that the changes were made as shown in Table 7 to obtain Developers 2 to 19.

[0136]

Table 7

[0137] [Examples 14 to 31] The electrophotographic apparatus was evaluated in the same manner as in Example 1 except that the types of the electrophotographic photoreceptor and the developer were changed as shown in Table 8. Also, the evaluation of scratch resistance and low-temperature fixability was carried out by the methods shown below. The evaluation results are shown in Table 8.

[0138] [Evaluation of Scratch Resistance / Low-Temperature Fixability] As an image forming apparatus, a modified machine of the Canon digital commercial printer imagePress C800 for black station was used. The electrophotographic photoreceptor 1 was set on the black station, and each developer was put into the developing device. As the modification points of the apparatus, the fixing temperature, the process speed, the DC voltage V of the developer carrier DC , the charging voltage V of the electrophotographic photoreceptor D , and the laser power were changed so that they could be freely set. For the image output evaluation, an FFh image (solid image) with a desired image ratio was output, and V was adjusted so that the toner loading amount on the FFh image on the paper became desired DC , V D , and the laser power were adjusted to evaluate the scratch resistance and low-temperature fixability described later. FFh is a value representing 256 gradations in hexadecimal notation. 00h is the first gradation (blank part) of 256 gradations, and FFh is the 256th gradation (solid part) of 256 gradations.

[0139] [Evaluation of Scratch Resistance] Paper: UPM FINESSE GLOSS 300GSM Toner loading amount on paper: 0.05mg / cm 2 (2Fh image) (The toner loading amount is adjusted by the DC voltage V of the developer carrier DC , the charging voltage V of the electrophotographic photoreceptor D , and the laser power. The charging voltage V of the electrophotographic photoreceptor D was set as positive charging.) Evaluation image: A 3 cm × 15 cm image was placed at the center of the above A4 paper Fixing test environment: Normal temperature and humidity environment (temperature 23°C / humidity 50%RH (hereinafter N / N)) Fixing temperature: 180°C Process speed: 377 mm / sec The above evaluation image was output and the scratch resistance was evaluated. Specifically, using a surface property tester HEIDON TYPE14FW manufactured by Shinto Kagaku Co., Ltd., a 200 g weight was placed, and scratching was performed with a needle having a diameter of 0.75 mm at a speed of 60 mm / min and a length of 30 mm, and the evaluation was made based on the scratches generated on the image. The area ratio of the toner peeling was obtained by binarizing the area where the toner peeling occurred with respect to the scratched area by image processing. (Evaluation Criteria) A: 0.0% B: 0.1% or more and less than 1.1% C: 1.1% or more

[0140] [Evaluation of Low Temperature Fixing Property] Paper: GFC-081 (81.0 g / m 2 )(Sold by Canon Marketing Japan Inc.) Toner loading amount on paper: 0.50 mg / cm 2 (The toner loading amount is adjusted by the DC voltage V of the developer carrier DC , the charging voltage V of the electrophotographic photoreceptor D , and the laser power. The charging voltage V of the electrophotographic photoreceptor D was set to positive charging.) Evaluation image: A 2 cm × 5 cm image was placed at the center of the above A4 paper Test environment: Low temperature and low humidity environment: Temperature 15°C / Humidity 10% RH (hereinafter referred to as "L / L") Fixing temperature: 150°C Process speed: 630 mm / sec The above evaluation image was output and the low temperature fixing property was evaluated. The value of the reduction rate of the image density was used as an evaluation index for the low temperature fixing property.

[0141] Using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), first, the image density at the center was measured. Next, a load of 4.9 kPa (50 g / cm 2 ) was applied to the fixed image with a silicone paper by friction (5 reciprocations) with respect to the part where the image density was measured, and the image density was measured again. Then, the reduction rate of the image density before and after friction was calculated using the following formula. The obtained reduction rate of the image density was evaluated according to the following evaluation criteria. If the evaluation was A to C, it was judged to be good. Reduction rate of image density (%) = (Image density before friction - Image density after friction) / Image density before friction × 100 (Evaluation criteria) A: Reduction rate of image density less than 3% B: Reduction rate of image density 3% or more and less than 10% C: Reduction rate of image density 10% or more

[0142]

Table 8

[0143] The toner used in the electrophotographic apparatus of the present disclosure can use polyethylene terephthalate regenerated from used PET bottles, etc. as the toner material, so the technology described in this specification can contribute to the realization of a sustainable society such as a decarbonized / circular society.

Explanation of symbols

[0144] 101... Electrophotographic photoreceptor 102... Charging means 103... Image exposure means 104... Developing means 105... Intermediate transfer body 106... Cleaning means 106a... Rubbing roller 106b... Cleaning blade 107... Pre-exposure means

Claims

1. An electrophotographic photosensitive member, charging means for charging the surface of the electrophotographic photosensitive member, image exposure means for irradiating image exposure light onto the charged surface of the electrophotographic photosensitive member to form an electrostatic latent image on the surface of the electrophotographic photosensitive member, developing means having toner for developing the electrostatic latent image with the toner to form a toner image on the surface of the electrophotographic photosensitive member, transfer means for transferring the toner image from the surface of the electrophotographic photosensitive member to a transfer material, cleaning means for removing residual toner remaining on the surface of the electrophotographic photosensitive member after the toner image has been transferred to the transfer material, An electrophotographic apparatus comprising: The surface of the electrophotographic photosensitive member is formed of amorphous silicon carbide, The Si atom density in the surface-near region from the surface of the electrophotographic photoreceptor to a depth of 100 nm is 1.0×10 ２２ atoms / cm ３ or less, The toner has toner particles containing a polyester resin having polyethylene terephthalate segments and inorganic fine particles, An electrophotographic apparatus characterized by the above.

2. The electrophotographic apparatus according to claim 1, wherein the arithmetic mean roughness Sa of the surface of the electrophotographic photosensitive member is 80 nm or more and 120 nm or less.

3. An electrophotographic photosensitive member, developing means having toner for developing an electrostatic latent image formed on the surface of the electrophotographic photosensitive member with the toner to form a toner image on the surface of the electrophotographic photosensitive member, cleaning means for removing residual toner remaining on the surface of the electrophotographic photosensitive member after the toner image has been transferred from the surface of the electrophotographic photosensitive member to a transfer material, A process cartridge integrally supporting the above and being detachable from the electrophotographic apparatus main body, The surface of the electrophotographic photosensitive member is formed of amorphous silicon carbide, The Si atom density in the surface vicinity region from the surface of the electrophotographic photoreceptor to a depth of 100 nm is 1.0×10 ２２ atoms / cm ３ or less, The toner has toner particles containing a polyester resin having polyethylene terephthalate segments and inorganic fine particles, A process cartridge characterized by the above.

4. The toner particles contain a binder resin, and the binder resin contains an amorphous resin A and a crystalline polyester resin C, The amorphous resin A is a polyester resin, and the amorphous resin A has, as a structure forming a polyester skeleton, (i) a polyethylene terephthalate segment, and (ii) at least one structure selected from the group consisting of a structure represented by the following formula (1), a structure represented by the following formula (2), a structure represented by the following formula (3), and a structure represented by the following formula (4), 【Chemical 1】 (In formula (1), R １ represents an alkyl group having 6 to 16 carbon atoms or an alkenyl group having 6 to 16 carbon atoms, A represents a hydrocarbon group, * represents a bonding part in the polyester skeleton, m represents an integer of 2 or more. ) [Chemical Formula 2] (In formula (2), R ２ represents an alkyl group having 6 to 16 carbon atoms or an alkenyl group having 6 to 16 carbon atoms, B represents a hydrocarbon group, * represents a bonding part in the polyester skeleton, n represents an integer of 2 or more. ) 【Chemical Formula 3】 (In formula (3), * represents a bonding part in the polyester skeleton, x represents an integer of 6 to 16. ) 【Chemical 4】 (In formula (4), * represents a bonding part in the polyester skeleton, y represents an integer of 6 to 16. ) Let the SP value of the amorphous resin A be SP Ａ (cal / cm ３ ) ０．５ , and when the SP value of the crystalline polyester resin C is SP Ｃ (cal / cm ３ ), ０．５ then the SP Ａ and the SP Ｃ satisfy the following formula (C), 1.00 ≤ SP Ａ -SP Ｃ ≤ 1.35... (C) The toner contains phosphorus element derived from a phosphorus compound, When the content of the phosphorus element in the toner is W (ppm) based on the mass of the toner, Ｐ the electrophotographic apparatus according to claim 1 or 2, wherein the W Ｐ satisfies the following formula (D). 5 ≤ W Ｐ ≤ 500... (D)

5. Said W Ｐ The electrophotographic apparatus according to claim 4, wherein said W satisfies the following formula (E). 20 ≤ W Ｐ ≤ 500... (E)

6. The toner particles contain a binder resin, and the binder resin contains an amorphous resin A and a crystalline polyester resin C. The amorphous resin A is a polyester resin, and the amorphous resin A has, as a structure forming the polyester skeleton, (i) a polyethylene terephthalate segment, and (ii) at least one structure selected from the group consisting of a structure represented by the following formula (1), a structure represented by the following formula (2), a structure represented by the following formula (3), and a structure represented by the following formula (4). [Chemical Formula 5] (In formula (1), R １ represents an alkyl group having 6 to 16 carbon atoms or an alkenyl group having 6 to 16 carbon atoms, A represents a hydrocarbon group, * represents a bonding part in the polyester skeleton, m represents an integer of 2 or more. ) 【Chemical Formula 6】 (In formula (2), R ２ represents an alkyl group having 6 to 16 carbon atoms or an alkenyl group having 6 to 16 carbon atoms, B represents a hydrocarbon group, * represents a bonding part in the polyester skeleton, n represents an integer of 2 or more. ) 【Chemical Formula 7】 (In formula (3), * represents a bonding part in the polyester skeleton, x represents an integer of 6 to 16. ) 【Chemical Formula 8】 (In formula (4), * represents a bonding part in the polyester skeleton, y represents an integer of 6 to 16. ) When the SP value of the amorphous resin A is SP Ａ (cal / cm ３ ) ０．５ and the SP value of the crystalline polyester resin C is SP Ｃ (cal / cm ３ ) ０．５ , when the SP Ａ and the SP Ｃ satisfy the following formula (C), 1.00 ≤ SP Ａ -SP Ｃ ≤ 1.35... (C) The toner contains phosphorus element derived from a phosphorus compound, When the content of the phosphorus element in the toner is W (ppm) based on the mass of the toner, Ｐ the W Ｐ satisfies the following formula (D), and the process cartridge according to claim 3 is characterized in that. 5 ≤ W Ｐ ≤ 500... (D)

7. Said W Ｐ The process cartridge according to claim 6, wherein 20 ≤ W Ｐ ≤ 500... (E)

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