JP7224910B2 - Process cartridge and image forming apparatus - Google Patents

Description

The present invention relates to an electrophotographic image forming apparatus. Here, an electrophotographic image forming apparatus (hereinafter also simply referred to as an "image forming apparatus") forms an image on a recording material (recording medium) using an electrophotographic image forming method. Examples of image forming apparatuses include copiers, printers (laser beam printers, LED printers, etc.), facsimile machines, word processors, and multifunction machines (multifunction printers).

2. Description of the Related Art Conventionally, organic photoreceptors have been widely used as electrophotographic photoreceptors (hereinafter also simply referred to as "photoreceptors") used in electrophotographic image forming apparatuses due to their advantages of low cost and high productivity. This is constituted by providing a photosensitive layer (organic photosensitive layer) using an organic material as a photoconductive substance (charge-generating substance or charge-transporting substance) on a support. As an organic photoreceptor, a photoreceptor having a laminated photosensitive layer is mainly used because of its advantages of high sensitivity and diversity of material design. In this, a charge generation layer containing a charge generation substance such as a photoconductive dye or a photoconductive pigment, and a charge transport layer containing a charge transport substance such as a photoconductive polymer or a photoconductive low molecular weight compound are laminated. It consists of
Electrical and/or mechanical external forces are directly applied to the surface of the photoreceptor during charging, exposure, development, transfer, and cleaning, so the photoreceptor is required to have durability against these external forces. Specifically, it is required to have durability against occurrence of scratches and wear on the surface due to these external forces, that is, scratch resistance and wear resistance.
In general, the following techniques are known for improving the scratch resistance and wear resistance of the surface of an organic photoreceptor.
A photoreceptor having a surface layer of a hardened layer using a hardening resin as a binder resin.
A photoreceptor having a surface layer of a charge-transporting cured layer formed by curing and polymerizing a monomer having a carbon-carbon double bond and a charge-transporting monomer having a carbon-carbon double bond with heat or light energy. .
A photoreceptor having a surface layer of a charge-transporting cured layer formed by curing and polymerizing a hole-transporting compound having a chain polymerizable functional group in the same molecule with electron beam energy.
Furthermore, in recent years, due to the increasing market needs for higher speed and longer life of image forming apparatuses, there is a demand for a photoreceptor having even higher scratch resistance and abrasion resistance. In order to meet this demand, a photoreceptor having an abrasion-resistant protective layer (over coat layer: OCL) on the surface of the photoreceptor has been developed, and a technique for increasing the mechanical strength of the surface layer has been established.
However, when the wear of the photoreceptor is suppressed, the surface of the photoreceptor becomes difficult to refresh, and blurring of the electrostatic latent image called "image deletion" tends to occur particularly in a high-humidity environment. The cause of image deletion is considered as follows. Discharge products such as ozone and _NOx are generated mainly by the charging means and adhere to the surface of the photoreceptor. Since the surface of the photoreceptor has a low surface friction coefficient and is hard, it is difficult to be scraped off, and discharge products adhering to the surface are difficult to remove. In addition, the discharge products attached to the surface of the photoreceptor that are difficult to remove absorb moisture in a high-humidity environment, lowering the charge retention capacity of the surface of the photoreceptor and causing blurring of the electrostatic latent image.
Therefore, especially when the hardness of the photoreceptor is high, it becomes more difficult to remove the discharge products adhering to the surface of the photoreceptor, and image smearing is more likely to occur.
As a method for preventing image defects caused by discharge products such as image smearing,
In Patent Document 1, a heater is arranged around the photoreceptor, and for the purpose of reducing power consumption, it is determined whether or not to operate the heater by detecting the load torque of the motor generated when the photoreceptor is rotationally driven. is proposed.
Patent Document 2 proposes a method of adding abrasive particles for polishing the surface of the photoreceptor to the developer in the developing means. In this method, abrasive particles are accumulated in cleaning means in contact with the photoreceptor from the developing means via the photoreceptor, and the abrasive particles rub the surface of the photoreceptor to remove discharge products. there is
Further, Japanese Patent Application Laid-Open No. 2002-200000 proposes a method of containing a metallic soap in a developer and supplying the metallic soap from a developer carrying member to the surface of a photoreceptor. In this method, zinc stearate, which is a metal soap, is supplied through a developing means to coat the surface of the photoreceptor, thereby suppressing image deletion while maintaining abrasion resistance.

Japanese Patent Application Laid-Open No. 2005-173021 JP-A-2000-47545 JP-A-2005-121833

However, arranging the heater around the photosensitive member as in Patent Document 1 leads to an increase in size and power consumption of the image forming apparatus. Furthermore, downtime such as heating control occurs, and usability is reduced.
In addition, when abrasive particles are supplied to the photoreceptor as in Patent Document 2, the surface of the photoreceptor is also polished together with the discharge products, making it impossible to maintain the high scratch resistance and high wear resistance necessary for extending the life of the photoreceptor.
In addition, as in Patent Document 3, if the surface of the photoreceptor is coated with metallic soap supplied from the developer, it is possible to achieve both abrasion resistance and suppression of image deletion. Since the metal soap applied is scraped off by the cleaning means, it is necessary to constantly supply the metal soap from the developing means. Therefore, image deletion occurs under conditions where the amount of metal soap supplied is insufficient, such as when the developing means is separated from the photoreceptor, or when the amount of metal soap in the developer is reduced in the latter half of the life of the developing device. something happened.
SUMMARY OF THE INVENTION It is an object of the present invention to provide a process cartridge capable of suppressing the occurrence of image smearing by maintaining the amount of metal soap supplied to the surface of an image carrier even in a configuration in which the durability of the image carrier is enhanced. That is.

In order to achieve the above object, the process cartridge of the present invention comprises:
A process cartridge used in an image forming apparatus,
a rotatable image carrier having a peripheral surface on which a latent image is formed;
developing means for supplying a developer to the image carrier for developing the latent image on the image carrier;
a cleaning member that contacts the peripheral surface of the image carrier to clean the peripheral surface;
The developer is
containing toner particles and a toner having a metallic soap;
The image carrier has a peripheral surface on which a plurality of grooves extending in the peripheral direction of the peripheral surface are formed so as to be aligned in the rotation axis direction. Rz) is 0 . 10 ≤ Rz ≤ 0.70 (μm), and the average interval (Sm) of the unevenness of the peripheral surface is 5 ≤ Sm ≤ 70.0 (μm) ,
The peripheral surface has a ten-point average surface roughness of the peripheral surface of the image carrier smaller than the average particle size of the metallic soap, and the metallic soap is supplied from the toner to the grooves on the surface of the image carrier. so that the average particle diameter of the metal soap is 0.15 μm or more and 2.00 μm or less
It is characterized by
In order to achieve the above object, the image forming apparatus of the present invention includes:
a device body;
a process cartridge of the present invention, which is detachable from the apparatus main body;
characterized by comprising

According to the present invention, it is possible to provide a process cartridge capable of suppressing the occurrence of image deletion with a simple configuration and control while maintaining the durability of the image carrier.

Schematic cross-sectional view of an image forming apparatus according to Embodiment 1 of the present invention 1 is a schematic cross-sectional view of a process cartridge according to Embodiment 1 of the present invention; FIG. Schematic diagram of a polishing apparatus for polishing the surface of a photoreceptor according to Embodiment 1 of the present invention. Schematic diagram of toner in Embodiment 1 of the present invention FIG. 3 is a conceptual diagram of the surface layer thickness of the surface layer containing the organosilicon compound in Embodiment 3 of the present invention. Schematic diagrams showing examples of the form of a photoreceptor according to an embodiment of the present invention. Schematic diagram showing a surface modification device in an embodiment of the present invention Schematic diagram showing the processing chamber of the surface modification apparatus used in the embodiment of the present invention Schematic diagram showing the stirring blade of the surface modification device used in the embodiment of the present invention Schematic diagram showing a rotating body of a surface modification apparatus used in an embodiment of the present invention Schematic diagram showing a rotating body of a surface modification apparatus used in an embodiment of the present invention

In the present invention, unless otherwise specified, the descriptions of "○○ or more and XX or less" and "○○ to XX", which represent numerical ranges, mean numerical ranges including the lower and upper limits that are endpoints.
Embodiments or examples of the present invention will be exemplarily described in detail below with reference to the drawings. However, the dimensions, materials, shapes, relative positions, and the like of the components described in the embodiment or example may be changed as appropriate depending on the configuration of the device to which the invention is applied and various conditions, and therefore may not be particularly specific. Unless otherwise stated, they are not intended to limit the scope of the invention only to them.

[Embodiment 1]
As a means for achieving the object of the present invention, the surface of an image carrier (photoreceptor) is roughened to form fine unevenness on the surface of the image carrier (photoreceptor), and metal soap is formed on the surface of the image carrier (photoreceptor). is stored to maintain the amount of metal soap on the surface of the image carrier (photoreceptor), thereby suppressing the occurrence of image deletion.

<Overall Schematic Configuration of Image Forming Apparatus>
An overall configuration of an electrophotographic image forming apparatus (image forming apparatus) according to an embodiment of the present invention will be described. FIG. 1 is a schematic cross-sectional view of an image forming apparatus 100 according to Embodiment 1 of the present invention. Examples of image forming apparatuses to which the present invention can be applied include copiers and printers using an electrophotographic system, and here, a case where the present invention is applied to a laser printer will be described. The image forming apparatus 100 of Embodiment 1 is a full-color laser printer that employs an in-line method and an intermediate transfer method. Image forming apparatus 100 can form a full-color image on a recording material (for example, recording paper, plastic sheet, cloth, etc.) according to image information. Image information is sent to the image forming apparatus 100 from an image reading device (not shown) connected to the image forming apparatus 100 or a host device (not shown) such as a personal computer communicably connected to the image forming apparatus 100 . is entered.

Image forming apparatus 100 includes first, second, and third image forming units for forming yellow (Y), magenta (M), cyan (C), and black (K) images, respectively, as a plurality of image forming units. , and fourth image forming units SY, SM, SC, and SK. In this embodiment, the first to fourth image forming units SY, SM, SC, and SK are arranged in a line in a direction crossing the vertical direction.
In this embodiment, the configurations and operations of the first to fourth image forming units SY, SM, SC, and SK are substantially the same except that the colors of the images to be formed are different. Therefore, hereinafter, the suffixes Y, M, C, and K given to the reference numerals to indicate that the elements are provided for one of the colors are omitted unless distinction is particularly required. explain.

In the first embodiment, the image forming apparatus 100 has four drum-type electrophotographic photosensitive members (hereinafter referred to as photosensitive members) 1 arranged side by side in a direction intersecting the vertical direction as a plurality of image carriers. A photoreceptor 1 as an image carrier that carries an electrostatic latent image (electrostatic image) is rotationally driven by driving means (not shown). A scanner unit (exposure device) 30 is arranged in the image forming apparatus 100 . The scanner unit 30 is exposure means for forming an electrostatic latent image on the photoreceptor 1 by irradiating a laser based on image information. Further, in the image forming apparatus 100 , an intermediate transfer belt 31 as an intermediate transfer member for transferring the toner images on the photoconductors 1 onto the recording material 12 is arranged so as to face the four photoconductors 1 . . An intermediate transfer belt 31 formed of an endless belt as an intermediate transfer member contacts all the photosensitive members 1 and circulates (rotates) in the direction of an arrow B (counterclockwise).

Four primary transfer rollers 32 as primary transfer means are provided side by side on the inner peripheral surface side of the intermediate transfer belt 31 so as to face each photosensitive member 1 . Then, a voltage having a polarity opposite to the normal charging polarity of the toner is applied to the primary transfer roller 32 from a primary transfer bias power supply as primary transfer bias applying means (not shown). As a result, the toner image on the photosensitive member 1 is transferred (primary transfer) onto the intermediate transfer belt 31 .

A secondary transfer roller 33 as a secondary transfer unit is arranged on the outer peripheral surface side of the intermediate transfer belt 31 . A voltage having a polarity opposite to the normal charge polarity of the toner is applied to the secondary transfer roller 33 from a secondary transfer bias power supply as secondary transfer bias applying means (not shown). As a result, the toner image on the intermediate transfer belt 31 is transferred (secondary transfer) onto the recording material 12 . For example, when forming a full-color image, the above-described processes are sequentially performed in the image forming stations SY, SM, SC, and SK, and the toner images of the respective colors are sequentially superimposed and primarily transferred onto the intermediate transfer belt 31 . After that, the recording material 12 is conveyed to the secondary transfer portion in synchronization with the movement of the intermediate transfer belt 31 . The four-color toner images on the intermediate transfer belt 31 are collectively secondary-transferred onto the recording material 12 by the action of the secondary transfer roller 33 which is in contact with the intermediate transfer belt 31 via the recording material 12 . be.

Toner remaining on the intermediate transfer belt 31 without being transferred onto the recording material 12 by the secondary transfer roller 33 is conveyed to an intermediate transfer member cleaning device 35 and removed.
The recording material 12 to which the toner image has been transferred is conveyed to the fixing device 34 . The toner image is fixed on the recording material 12 by applying heat and pressure to the recording material 12 in the fixing device 34 .

In this embodiment, the photoreceptor 1 and a charging roller 2, a developing roller 4, a cleaning blade 8, and the like, which will be described later as process means acting on the photoreceptor 1, are integrated, that is, integrally formed into a cartridge. , forming a process cartridge 7 .

<Schematic Configuration of Process Cartridge>
The overall structure of the process cartridge 7 mounted in the image forming apparatus 100 of Embodiment 1 will be described. FIG. 2 is a cross-sectional (main cross-sectional) view of the process cartridge 7 of Embodiment 1 viewed along the longitudinal direction (rotational axis direction) of the photoreceptor 1 . The process cartridge 7 is attachable to and detachable from the image forming apparatus 100 via a mounting means such as a mounting guide and a positioning member (not shown) provided in the image forming apparatus 100 . In the first embodiment, the process cartridges 7 for each color have the same shape, and the process cartridges 7 for each color have yellow (Y), magenta (M), cyan (C), and black (Y), respectively. K) toner 10 of each color is stored. In the first embodiment, the entire process cartridge 7 is detachably attached to the image forming apparatus 100. However, the present invention is not limited to such a configuration. For example, the developing device 3, which will be described later, of the process cartridge 7 may be independently (separately from the photoreceptor unit 13, which will be described later) detachable from the image forming apparatus 100. FIG.
In the first embodiment, the configuration and operation of the process cartridges 7 for each color are substantially the same except for the type (color) of the toner 10 contained therein.

The process cartridge 7 has a developing device 3 having a developing roller 4 and the like, and a photoreceptor unit 13 having the photoreceptor 1 .

The developing device 3 includes a developing roller 4, a toner supply roller 5, a toner conveying member 22, and a developing frame 18 that rotatably supports them. The development frame 18 includes a development chamber 18 a in which the development roller 4 and the toner supply roller 5 are arranged, and a toner storage chamber (developer storage chamber) 18 b that stores the toner 10 . The development chamber 18a and the toner storage chamber 18b communicate through an opening 18c.

A toner conveying member 22 for conveying the toner 10 to the developing chamber 18a is provided in the toner storage chamber 18b. there is
In the developing chamber 18a, a developing roller 4 is provided as a toner carrier (developer carrier) that contacts the photoreceptor 1 and rotates in the direction of arrow D in the figure. In the first embodiment, the developing roller 4 and the photoreceptor 1 rotate so that their surfaces move in the same direction at the facing portion (contact portion), that is, so that the directions of rotation are opposite to each other. .
A toner supply roller (hereinafter referred to as "supply roller") 5 serving as a toner supply member for supplying the toner 10 transported from the toner storage chamber 18b to the development roller 4 is arranged inside the development chamber 18a. . Further, in the developing chamber 18a, a toner amount regulating member 6 for controlling the coating amount of the toner 10 on the developing roller 4 supplied by the supply roller 5 and for imparting electric charges is arranged.

Independent voltages are applied to the developing roller 4, the supply roller 5, and the toner amount regulating member 6 from a high voltage power source (not shown). The toner 10 supplied to the developing roller 4 by the supply roller 5 is triboelectrically charged by rubbing between the developing roller 4 and the regulating member 6, and the layer thickness is regulated at the same time as being charged. The regulated toner 10 on the developing roller 4 is conveyed to a portion facing the photoreceptor 1 by the rotation of the developing roller 4, and the electrostatic latent image on the photoreceptor 1 is developed and visualized as a toner image.
In the first embodiment, when the electrostatic latent image on the photoreceptor 1 is developed and visualized as a toner image, the developing roller 4 is rotationally driven while being in contact with the peripheral surface of the photoreceptor 1 . That is, it is a contact development system in which the developer carrier is brought into contact with the image carrier in order to develop the latent image on the image carrier with the developer. This is to make it easier to supply the metal soap externally added to the toner onto the photoreceptor 1, which will be described later in the details of the toner.

On the other hand, the photoreceptor unit 13 has a cleaning frame 9 as a frame for supporting each member of the photoreceptor unit 13 such as the photoreceptor 1 . The photoreceptor 1 is rotatably attached to the cleaning frame 9 via a bearing (not shown). Photoreceptor 1 is rotationally driven in the direction of arrow A in the figure by receiving the driving force of a driving motor provided in the main body of image forming apparatus 100 .

In the photoreceptor unit 13, a charging roller 2 and a cleaning blade (cleaning member) 8 as a plate-shaped elastic body are arranged so as to be in contact with the peripheral surface of the photoreceptor 1. As shown in FIG. A voltage is applied to the metal core of the charging roller 2 from a high-voltage power source (not shown) to charge the surface of the photoreceptor 1 to a predetermined voltage. One end of the cleaning blade 8 is fixed to a metal plate 8a which is a plate-shaped support, and the other end which is a free end contacts the photoreceptor 1, forming a contact portion (hereinafter referred to as a "cleaning nip") with the photoreceptor 1. ) is formed.
The metal sheet 8 a is fixed to the cleaning frame 9 . One end of the metal sheet 8a is fixed to the cleaning frame 9, and the cleaning blade 8 is fixed to the other free end. The metal sheet 8a has one L-shaped bent plate portion fixed to the cleaning frame 9 with fasteners such as screws, and the other plate portion extending in a direction substantially perpendicular to the one plate portion. A cleaning blade 8 is fixed to the tip thereof (see FIG. 2). The metal plate 8a (the other plate portion) and the cleaning blade 8 integrally extend in substantially the same direction from the fixed end (one plate portion) of the metal plate 8a. The extending direction is the direction (opposite direction) to the rotation direction of the photoreceptor 1 at the portion of the peripheral surface of the photoreceptor 1 with which the tip (the other end) of the cleaning blade 8 abuts. The direction in which the metal sheet 8a and the cleaning blade 8 extend is from the bottom to the top. The rotating direction of the photoreceptor 1 is the direction in which the portion of the circumferential surface of the photoreceptor 1 with which the tip (the other end) of the cleaning blade 8 abuts moves from above to below.
Note that the attitude of the process cartridge 7 in FIG. 2 is the attitude when it is installed in the image forming apparatus main body (during use). indicates the positional relationship, direction, etc. in this posture. 2 corresponds to the vertical direction, and the horizontal direction corresponds to the horizontal direction. It should be noted that this arrangement configuration setting is based on the premise that the image forming apparatus is installed on a horizontal plane as a normal installation state.
As the cleaning blade 8 rubs against the peripheral surface of the photoreceptor 1 , the toner 10 and fine particles remaining in the transfer process are scraped off from the photoreceptor 1 . To prevent the occurrence of image problems due to The toner 10 removed from the photoreceptor 1 by the cleaning blade 8 falls and is stored in the waste toner storage chamber 9 a provided below the cleaning blade 8 in the cleaning frame 9 .

<Details of photoreceptor>
The photoreceptor (photosensitive drum) 1 in Embodiment 1 was produced by the manufacturing method described in Japanese Patent No. 4027407. As shown in FIG. FIG. 6A is a schematic cross-sectional view of the photoreceptor 1 in Embodiment 1. FIG. As shown in FIG. 6A, the photosensitive member 1 is formed on a cylindrical conductive metal support 1d, a conductive layer 1e as an undercoat layer of the support 1d, and the undercoat layer 1e. It consists of a photosensitive layer (charge generation layer 1f1, charge transport layer 1f2) 1f and a protective layer 1g formed on the photosensitive layer 1f. The surface 1a of the photoreceptor 1 (protective layer 1g) is roughened by polishing.

(support)
In Embodiment 1, the photoreceptor 1 has a support 1d. In Embodiment 1, the support 1d is preferably a conductive support having electrical conductivity. Further, the shape of the support 1d includes a cylindrical shape, a belt shape, a sheet shape, and the like. Among them, a cylindrical support is preferable. Also, the surface of the support 1d may be subjected to an electrochemical treatment such as anodization, blasting, cutting, or the like. As a material for the support 1d, metal, resin, glass, or the like is preferable.

Examples of metals include aluminum, iron, nickel, copper, gold, stainless steel, and alloys thereof. Among them, an aluminum support using aluminum is preferable.
Conductivity may be imparted to the resin or glass by treatment such as mixing or coating with a conductive material.

Further, in Embodiment 1, a conductive layer 1e may be provided on the support 1d. By providing the conductive layer 1e, it is possible to cover scratches and irregularities on the surface of the support 1d and to control reflection of light on the surface of the support 1d. The conductive layer 1e preferably contains conductive particles and a resin. Materials for the conductive particles include metal oxides, metals, and carbon black.

Metal oxides include zinc oxide, aluminum oxide, indium oxide, silicon oxide, zirconium oxide, tin oxide, titanium oxide, magnesium oxide, antimony oxide, and bismuth oxide. Metals include aluminum, nickel, iron, nichrome, copper, zinc, silver and the like. Among these, metal oxides are preferably used as the conductive particles, and titanium oxide, tin oxide, and zinc oxide are particularly preferably used.

When a metal oxide is used as the conductive particles, the surface of the metal oxide may be treated with a silane coupling agent or the like, or the metal oxide may be doped with an element such as phosphorus or aluminum or an oxide thereof.
Also, the conductive particles may have a laminated structure including core particles and a coating layer that covers the particles. Examples of core material particles include titanium oxide, barium sulfate, and zinc oxide. The coating layer includes metal oxides such as tin oxide.
When metal oxides are used as the conductive particles, the volume average particle diameter is preferably 1 nm or more and 500 nm or less, more preferably 3 nm or more and 400 nm or less.

Examples of resins include polyester resins, polycarbonate resins, polyvinyl acetal resins, acrylic resins, silicone resins, epoxy resins, melamine resins, polyurethane resins, phenol resins, and alkyd resins.

In addition, the conductive layer 1e may further contain silicone oil, resin particles, masking agents such as titanium oxide, and the like.
The average film thickness of the conductive layer 1e is preferably 1 μm or more and 50 μm or less, and particularly preferably 3 μm or more and 40 μm or less.
The conductive layer 1e can be formed by preparing a conductive layer coating liquid containing each of the above materials and a solvent, forming a coating film thereon, and drying the coating film. Solvents used in the coating liquid include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents and the like. Examples of the dispersion method for dispersing the conductive particles in the conductive layer coating liquid include methods using a paint shaker, a sand mill, a ball mill, and a liquid collision type high-speed disperser.

(Undercoat layer)
In Embodiment 1, an undercoat layer 1f is provided on the support 1d or the conductive layer 1e. By providing the undercoat layer 1f, the adhesion function between the layers is enhanced, and the charge injection blocking function can be imparted.
The undercoat layer 1f preferably contains a resin. Alternatively, the undercoat layer may be formed as a cured film by polymerizing a composition containing a monomer having a polymerizable functional group.

Resins include polyester resins, polycarbonate resins, polyvinyl acetal resins, acrylic resins, epoxy resins, melamine resins, polyurethane resins, phenol resins, polyvinyl phenol resins, alkyd resins, polyvinyl alcohol resins, polyethylene oxide resins, polypropylene oxide resins, and polyamide resins. , polyamic acid resins, polyimide resins, polyamideimide resins, cellulose resins, and the like.
Examples of the polymerizable functional group possessed by the monomer having a polymerizable functional group include an isocyanate group, a blocked isocyanate group, a methylol group, an alkylated methylol group, an epoxy group, a metal alkoxide group, a hydroxyl group, an amino group, a carboxyl group, a thiol group, Carboxylic anhydride groups, carbon-carbon double bond groups, and the like.

In addition, the undercoat layer 1f may further contain an electron transporting substance, a metal oxide, a metal, a conductive polymer, or the like for the purpose of enhancing electrical properties. Among these, electron transport substances and metal oxides are preferably used.
Examples of electron-transporting substances include quinone compounds, imide compounds, benzimidazole compounds, cyclopentadienylidene compounds, fluorenone compounds, xanthone compounds, benzophenone compounds, cyanovinyl compounds, halogenated aryl compounds, silole compounds, and boron-containing compounds. . An electron-transporting substance having a polymerizable functional group may be used as the electron-transporting substance, and an undercoat layer may be formed as a cured film by copolymerizing the electron-transporting substance with the above-mentioned monomer having a polymerizable functional group.
Metal oxides include indium tin oxide, tin oxide, indium oxide, titanium oxide, zinc oxide, aluminum oxide, and silicon dioxide. Metals include gold, silver, and aluminum.
In addition, the undercoat layer 1f may further contain an additive.

The average film thickness of the undercoat layer 1f is preferably from 0.1 μm to 50 μm, more preferably from 0.2 μm to 40 μm, and particularly preferably from 0.3 μm to 30 μm.
The undercoat layer 1f can be formed by preparing an undercoat layer coating solution containing each of the above materials and a solvent, forming a coating film, and drying and/or curing the coating film. Solvents used in the coating liquid include alcohol solvents, ketone solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents and the like.

(Charge generation layer)
The charge generation layer 1f1 preferably contains a charge generation substance and a resin. Examples of charge-generating substances include azo pigments, perylene pigments, polycyclic quinone pigments, indigo pigments, and phthalocyanine pigments. Among these, azo pigments and phthalocyanine pigments are preferred. Among the phthalocyanine pigments, oxytitanium phthalocyanine pigments, chlorogallium phthalocyanine pigments, and hydroxygallium phthalocyanine pigments are preferred.
The content of the charge-generating substance in the charge-generating layer 1f1 is preferably 40% by mass or more and 85% by mass or less, and 60% by mass or more and 80% by mass or less with respect to the total mass of the charge-generating layer 1f1. is more preferred.

Resins include polyester resins, polycarbonate resins, polyvinyl acetal resins, polyvinyl butyral resins, acrylic resins, silicone resins, epoxy resins, melamine resins, polyurethane resins, phenol resins, polyvinyl alcohol resins, cellulose resins, polystyrene resins, and polyvinyl acetate resins. , polyvinyl chloride resin, and the like. Among these, polyvinyl butyral resin is more preferable.
In addition, the charge generation layer 1f1 may further contain additives such as an antioxidant and an ultraviolet absorber. Specific examples include hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, and benzophenone compounds.

The average film thickness of the charge generation layer 1f1 is preferably 0.1 μm or more and 1 μm or less, more preferably 0.15 μm or more and 0.4 μm or less.
The charge-generating layer 1f1 can be formed by preparing a charge-generating layer coating liquid containing each of the materials and solvents described above, forming a coating film thereon, and drying the coating film. Solvents used in the coating liquid include alcohol solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, aromatic hydrocarbon solvents and the like.

(Charge transport layer)
The charge transport layer 1f2 preferably contains a charge transport material and a resin. Examples of charge-transporting substances include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from these substances. be done. Among these, triarylamine compounds and benzidine compounds are preferred.
The content of the charge transport substance in the charge transport layer 1f2 is preferably 25% by mass or more and 70% by mass or less, and is 30% by mass or more and 55% by mass or less with respect to the total mass of the charge transport layer 1f2. is more preferred.

Examples of resins include polyester resins, polycarbonate resins, acrylic resins, and polystyrene resins. Among these, polycarbonate resins and polyester resins are preferred. A polyarylate resin is particularly preferable as the polyester resin.
The content ratio (mass ratio) of the charge transport substance and the resin is preferably 4:10 to 20:10, more preferably 5:10 to 12:10.
Also, the charge transport layer 1f2 may contain additives such as antioxidants, ultraviolet absorbers, plasticizers, leveling agents, slipperiness agents, and abrasion resistance improvers. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oils, fluororesin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, boron nitride particles etc.

The average film thickness of the charge transport layer 1f2 is preferably 5 μm or more and 50 μm or less, more preferably 8 μm or more and 40 μm or less, and particularly preferably 10 μm or more and 30 μm or less. In the first embodiment, the thickness is set to 12 μm.
The charge-transporting layer 1f2 can be formed by preparing a charge-transporting-layer coating liquid containing each of the materials and solvents described above, forming a coating film thereon, and drying the coating film. Solvents used in the coating liquid include alcohol solvents, ketone solvents, ether solvents, ester solvents, and aromatic hydrocarbon solvents. Among these solvents, ether solvents and aromatic hydrocarbon solvents are preferred.

In Embodiment 1, a laminated photoreceptor having a charge generation layer 1f1 and a charge transport layer 1f2 is used, but a single layer photoreceptor containing both a charge generation material and a charge transport material may be used. good. A single-layer type photoreceptor can be formed by preparing a coating solution for a photosensitive layer containing a charge generating substance, a charge transporting substance, a resin and a solvent, forming this coating film, and drying it. The charge-generating substance, charge-transporting substance, and resin are the same as those in the laminated photoreceptor.

(protective layer)
The photoreceptor 1 in Embodiment 1 is provided with an abrasion-resistant protective layer 1g as the outermost layer in order to improve abrasion resistance. The durability can be improved by providing the protective layer 1g.
The protective layer 1g preferably contains conductive particles and/or a charge-transporting substance, and a resin.

Conductive particles include particles of metal oxides such as titanium oxide, zinc oxide, tin oxide, and indium oxide.
Charge-transporting substances include polycyclic aromatic compounds, heterocyclic compounds, hydrazone compounds, styryl compounds, enamine compounds, benzidine compounds, triarylamine compounds, and resins having groups derived from these substances. Among these, triarylamine compounds and benzidine compounds are preferred.
Examples of resins include polyester resins, acrylic resins, phenoxy resins, polycarbonate resins, polystyrene resins, phenol resins, melamine resins, and epoxy resins. Among them, polycarbonate resins, polyester resins, and acrylic resins are preferred.

Alternatively, the protective layer 1g may be formed as a cured film by polymerizing a composition containing a monomer having a polymerizable functional group. The reaction at that time includes thermal polymerization reaction, photopolymerization reaction, radiation polymerization reaction, and the like. Examples of the polymerizable functional group possessed by the monomer having a polymerizable functional group include an acrylic group and a methacrylic group. A material having charge transport ability may be used as the monomer having a polymerizable functional group.

The protective layer 1g may contain additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a leveling agent, a lubricating agent, and an abrasion resistance improver. Specifically, hindered phenol compounds, hindered amine compounds, sulfur compounds, phosphorus compounds, benzophenone compounds, siloxane-modified resins, silicone oils, fluororesin particles, polystyrene resin particles, polyethylene resin particles, silica particles, alumina particles, boron nitride particles. etc.

The average film thickness of the protective layer 1g is preferably 0.5 μm or more and 10 μm or less, and preferably 1 μm or more and 7 μm or less.
The protective layer 1g can be formed by preparing a protective layer coating liquid containing each of the above materials and a solvent, forming a coating film, and drying and/or curing the coating film. Solvents used in the coating liquid include alcohol solvents, ketone solvents, ether solvents, sulfoxide solvents, ester solvents, and aromatic hydrocarbon solvents.
In Embodiment 1, the average film thickness of the protective layer 1g was set to 3 μm.

(roughening treatment)
The photoreceptor 1 of Embodiment 1 is subjected to surface roughening treatment to form minute irregularities on the surface in order to maintain the effect of the metal soap. According to Japanese Patent No. 4027407, a groove extending in the circumferential direction of the peripheral surface of the photosensitive member 1 and having a width of 0.5 μm or more and 40 μm or less is formed in the longitudinal direction (generatrix direction, the photoconductor 1). It is formed so that it may line up in multiple numbers in the rotating shaft direction).
FIG. 6B shows an example of the state of the grooves 1b formed on the peripheral surface 1a of the photoreceptor 1. As shown in FIG. As shown in FIG. 6(b), each groove 1b is an annular groove extending in the circumferential direction on the peripheral surface 1a of the photoreceptor 1, and arranged so as to be spaced apart from each other in the generatrix direction of the peripheral surface 1a. is formed in In other words, the peripheral surface 1a has a configuration in which flat portions 1c in which no grooves 1b are formed and grooves 1b are alternately formed in the generatrix direction. The area in which the groove 1b is formed on the peripheral surface 1a should include at least the area where the cleaning blade 8 contacts, and does not necessarily need to be formed over the entire length of the peripheral surface 1a.
In addition, as described in the above publication, the groove 1b is not limited to the structure formed so as to extend in the same direction as the circumferential direction as shown in FIG. 6(b). For example, the groove 1b may be formed at an angle of 10° with respect to the circumferential direction. Alternatively, the grooves 1b may be formed at an angle of ±30° with respect to the circumferential direction, and the grooves 1b with different angles may cross each other. In the present embodiment, the term "substantially circumferential direction" includes both a complete circumferential direction and a substantially circumferential direction. is the direction of less than

FIG. 3 is a schematic diagram of a polishing device for polishing the surface of the photoreceptor 1. As shown in FIG.
The polishing sheet 40 is wound in the direction of the arrow by a winding mechanism (not shown). Photoreceptor 1 rotates in the direction of the arrow. Backup roller 41 rotates in the direction of the arrow. As the polishing conditions, a polishing sheet manufactured by Riken Corundum Co., Ltd. (trade name: GC#3000, base layer sheet thickness: 75 μm) was used as the polishing sheet 40, and a urethane roller with a hardness of 20° (outer diameter: 50 mm) was used as the backup roller 41. Penetration amount: 2.5 mm, sheet feeding amount: 200 to 40
At 0 mm/s, the feed direction of the polishing sheet and the rotation direction of the photoreceptor were the same, and polishing was performed for 5 to 30 seconds.
The surface roughness of the photoreceptor 1 after polishing was measured under the following conditions using a surface roughness measuring instrument (trade name: SE700, SMB-9, manufactured by Kosaka Laboratory Ltd.).
Measurements were taken at positions 30, 110 and 185 mm from the upper end of the coating in the longitudinal direction of photoreceptor 1. After rotating 120° forward, measurements were also taken at positions 30, 110 and 185 mm from the upper end of the coating. Further, after rotating it forward by 120°, it was measured in the same manner. Measurement conditions were as follows: measurement length: 2.5 mm, cutoff value: 0.8 mm, feed rate: 0.1 mm/s, filter characteristics: 2CR, leveling: straight line (whole area).
Photoreceptors a to d were produced by changing the polishing time under the above roughening treatment conditions. Photoreceptor e is a photoreceptor that has not been roughened.

<Developer>
In the present invention, the developer contains toner particles and a toner having a metallic soap.
In addition, the developer of the first embodiment contains toner particles, inorganic silicon fine particles present on the surfaces of the toner particles, and toner having metallic soap.
In the present invention, the toner particles preferably contain a binder resin as a constituent component.
Examples of binder resins include polyester resins, vinyl resins, epoxy resins, and polyurethane resins.
The polyester resin may be produced using a generally known method of polycondensation of an alcohol component and an acid component.
Examples of vinyl resins include styrene and its derivatives; unsaturated monoolefins; unsaturated polyenes; α-methylene aliphatic monocarboxylic acid esters; acrylic acid esters; vinyl ketones; It may be produced by polymerizing a polymerizable monomer such as acrylic acid or methacrylic acid derivative.
The toner particles may contain a release agent. The release agent is not particularly limited as long as it can enhance the releasability, and examples thereof include the following.
Aliphatic hydrocarbon waxes such as polyolefin copolymers, polyolefin waxes, microcrystalline waxes, paraffin waxes and Fischer-Tropsch waxes.
The content of the release agent is preferably 1.0 parts by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or the polymerizable monomer forming the binder resin. It is more preferably 5.0 parts by mass or more and 25.0 parts by mass or less.
The toner can be used as either a magnetic one-component toner or a non-magnetic one-component toner, but the non-magnetic one-component toner is preferred.
When used as a non-magnetic one-component toner, coloring agents include conventionally known various dyes and pigments.
Black colorants include carbon black or those toned to black using the yellow, magenta, and cyan colorants shown below.
Examples of yellow colorants include monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.
Examples of magenta colorants include monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.
Cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like.
The content of the coloring agent is preferably 1.0 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin or the polymerizable monomer forming the binder resin.
The toner particles may contain charge control agents. A known charge control agent can be used. In particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferred. Furthermore, when the toner particles are produced by a direct polymerization method, a charge control agent which has a low polymerization inhibitory property and substantially no solubilized substances in an aqueous medium is particularly preferred.
Examples of charge control agents that control toner particles to be negatively chargeable include the following.
As organometallic compounds and chelate compounds, monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids and dicarboxylic acid metal compounds. Others include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, or esters, phenol derivatives such as bisphenol, and the like. Furthermore, urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, and calixarenes are included.
On the other hand, examples of the charge control agent for controlling the toner particles to be positively charged include the following.
nigrosine and nigrosine modifications such as fatty acid metal salts; guanidine compounds; imidazole compounds; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate; and their lake pigments; triphenylmethane dyes and their lake pigments (the lake agents include phosphotungstic acid, phosphomolybdic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; resin charge control agents.
These charge control agents may be contained alone or in combination of two or more. The amount of these charge control agents to be added is preferably 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer forming the binder resin.

<Toner details>
FIG. 4 shows a schematic diagram of the toner used in the first embodiment. In the first embodiment, the toner 45 is used in which the inorganic silicon fine particles 45b are externally added to the toner particles 45a to ensure fluidity and improve chargeability.
The toner used in the first embodiment is a non-magnetic one-component polymerized toner having a negatively charged polarity, and has a weight average particle diameter of 7.0 μm.
Furthermore, in addition to the inorganic silicon fine particles 45b, metal soap (not shown) is externally added for the purpose of suppressing image deletion. By supplying the metal soap to the photoreceptor to form a protective film, adhesion of discharge products and the like can be reduced, and image deletion on the photoreceptor 1 can be suppressed.
Examples of inorganic silicon microparticles include silica microparticles such as wet-process silica microparticles and dry-process silica microparticles, and hydrophobized silica microparticles obtained by surface-treating these silica microparticles with a silane coupling agent, a titanium coupling agent, silicone oil, or the like. is mentioned.
Dry-process silica fine particles are produced, for example, by utilizing the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.
SiCl ₄ +2H ₂ +O ₂ →SiO ₂ +4HCl
In this production process, it is also possible to obtain composite fine particles of silica and other metal oxides by using other metal halide compounds such as aluminum chloride or titanium chloride together with silicon halide compounds. contain.
The number average particle diameter (D1) of the primary particles of the inorganic silicon fine particles is preferably 5 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, and 25 nm or more, and is 500 nm or less, 400 nm or less, 300 nm or less, and 250 nm or less. , 200 nm or less. The numerical ranges can be combined arbitrarily.
The content of the inorganic silicon fine particles is preferably 0.1 parts by mass or more and 10.0 parts by mass or less, and 1.0 parts by mass or more and 5.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles. is more preferable.

A metallic soap is externally added to the toner of the present invention. By supplying metal soap to the photosensitive drum to form a protective film, adhesion of discharge products and the like can be reduced, and image deletion on the photosensitive drum 1 can be suppressed.
Metal soap is a general term for long-chain fatty acids and metal salts other than sodium and potassium. Specific examples include metal salts of fatty acids such as stearic acid, myristic acid, lauric acid, ricinoleic acid and octylic acid and metals such as lithium, magnesium, calcium, barium and zinc.
More specific examples include lead stearate, cadmium stearate, barium stearate, calcium stearate, aluminum stearate, zinc stearate, magnesium stearate, zinc laurate and zinc myristate. The types of metal soaps are not limited to these.
In an embodiment of the present invention, zinc stearate was externally added as a metallic soap.
The content of the metal soap in the toner is preferably 0.60% by mass or less, 0.50% by mass or less, 0.40% by mass or less, and 0.30% by mass or less. On the other hand, the content is preferably 0.05% by mass or more, 0.10% by mass or more, 0.15% by mass or more, and 0.20% by mass or more. The numerical ranges can be combined arbitrarily.
The larger the content, the more effective it is in suppressing image deletion, but if added excessively, the fluidity of the toner is lowered, which may affect the solid followability.
The average particle size of the metal soap is preferably 0.15 μm or more and 2.00 μm or less.
If the particle size is smaller than 0.15 μm, it becomes difficult for the toner to be supplied to the grooves on the surface of the photoreceptor. On the other hand, if the particle size is larger than 2.00 μm, it is likely to separate from the toner, and is left behind in the developing container without being able to pass through the toner regulating member in the developing device, making it difficult to supply to the surface of the photoreceptor.
The average particle size of metal soap was measured by the following method.
10 mL of ethanol was added to 0.5 g of metal soap, and ultrasonically dispersed for 5 minutes using an ultrasonic disperser manufactured by Nippon Seiki Co., Ltd. Next, the obtained metallic soap dispersion was measured by Nikkiso Co., Ltd. Microtrac Laser Diffraction/Scattering Particle Size Distribution Analyzer (SPA type) in which ethanol was circulated as a measurement solvent, and the DV value was 0.6 to 0.6. Add to 0.8. Then, the particle size distribution in this state was measured, and the median diameter was defined as the average particle diameter.
The metal soap having the above average particle size may be produced, for example, by using a double decomposition method in which an aqueous solution of a fatty acid salt and an aqueous solution or dispersion of an inorganic metal salt are reacted.
In an embodiment of the present invention, zinc stearate with an average particle size of 0.60 μm was used. The average particle size of zinc stearate is preferably 0.15 to 2.00 μm.
The metal soap is attached to the toner particles by being charged to have a polarity opposite to that of the toner, and is supplied onto the photosensitive drum during non-image formation.

A known means can be used as a method for producing toner particles, and a kneading pulverization method or a wet production method can be used. A wet production method can be preferably used from the viewpoint of uniformity of particle size and shape controllability. Furthermore, the wet production method includes a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, an emulsion aggregation method, and the like.
Here, the suspension polymerization method will be explained. In the suspension polymerization method, first, a polymerizable monomer for forming a binder resin and, if necessary, other additives such as a colorant are dispersed using a dispersing machine such as a ball mill or an ultrasonic dispersing machine. is uniformly dissolved or dispersed to prepare a polymerizable monomer composition (preparation step of polymerizable monomer composition). At this time, if necessary, a polyfunctional monomer, a chain transfer agent, a wax as a release agent, a charge control agent, a plasticizer, and the like can be appropriately added.

Next, the polymerizable monomer composition is put into an aqueous medium prepared in advance, and droplets of the polymerizable monomer composition are formed by a stirrer or a disperser having a high shear force. (granulation step).

It is preferable that the aqueous medium in the granulation step contains a dispersion stabilizer in order to control the particle size of the toner particles, sharpen the particle size distribution, and suppress coalescence of the toner particles in the production process.
Dispersion stabilizers are generally classified broadly into macromolecules that generate repulsive force due to steric hindrance and poorly water-soluble inorganic compounds that stabilize dispersion by electrostatic repulsive force. Fine particles of poorly water-soluble inorganic compounds are preferably used because they are dissolved by acid or alkali and can be dissolved and easily removed by washing with acid or alkali after polymerization.

After the granulation step or while performing the granulation step, the temperature is preferably set to 50° C. or higher and 90° C. or lower to polymerize the polymerizable monomer contained in the polymerizable monomer composition to obtain a toner. A particle dispersion is obtained (polymerization step).

In the polymerization step, it is preferable to perform a stirring operation so that the temperature distribution in the container becomes uniform. When the polymerization initiator is added, it can be added at any timing and required time. Further, in order to obtain a desired molecular weight distribution, the temperature may be raised in the second half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers, by-products, etc. from the system, the second half of the reaction or the end of the reaction may be heated. Afterwards, a portion of the aqueous medium may be distilled off by a distillation operation. The distillation operation can be performed under normal pressure or reduced pressure.

As for the particle size of the toner particles, the weight average particle size (D4) is preferably 3.0 μm or more and 10.0 μm or less from the viewpoint of obtaining high-definition and high-resolution images. The weight average particle diameter (D4) of toner will be described later. The toner particle dispersion thus obtained is sent to a filtration step for solid-liquid separation of the toner particles and the aqueous medium.

Solid-liquid separation for obtaining toner particles from the obtained toner particle dispersion can be carried out by a general filtration method. It is preferable to carry out further washing, such as by spraying. After sufficient washing is performed, solid-liquid separation is performed again to obtain a toner cake. Thereafter, it is dried by a known drying means, and if necessary, is classified to separate a particle group having a particle size other than the predetermined one to obtain toner particles. The separated particle groups having non-predetermined particle sizes may be reused to improve the final yield.

(Method for Measuring Weight Average Particle Diameter D4 of Toner Particles)
The weight average particle size (D4) of the toner particles was calculated as follows. As a measurement device, a precision particle size distribution measurement device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electric resistance method equipped with a 100 μm aperture tube was used. The attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) was used for setting the measurement conditions and analyzing the measurement data. The measurement was performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, "ISOTONII" (manufactured by Beckman Coulter, Inc.), which is prepared by dissolving special grade sodium chloride in ion-exchanged water so that the concentration becomes about 1% by mass, was used.

Before conducting the measurement and analysis, the dedicated software was set as follows.
On the "Change standard measurement method (SOMME)" screen of the dedicated software, set the total count number of control mode to 50000 particles, set the number of measurements to 1, and set the Kd value to "standard particle 10.0 μm" (Beckman Coulter Co.) was used to set the values obtained. The threshold and noise level were automatically set by pressing the "threshold/noise level measurement button". Also, the current was set to 1600 μA, the gain was set to 2, the electrolyte was set to ISOTON II, and a check was put in the “flash of aperture tube after measurement”.

On the "pulse-to-particle size conversion setting" screen of the dedicated software, the bin interval was set to logarithmic particle size, the particle size bin was set to 256 particle size bins, and the particle size range was set to 2 μm to 60 μm.
A specific measuring method is as follows.
(1) About 200 mL of the electrolytic aqueous solution was placed in a 250 mL round-bottomed glass beaker exclusively for Multisizer 3, set on a sample stand, and stirred with a stirrer rod counterclockwise at 24 rpm. Then, using the dedicated software's "Flush Aperture Tube" function, dirt and air bubbles inside the aperture tube were removed.
(2) About 30 mL of the electrolytic aqueous solution was placed in a 100 mL flat-bottom glass beaker. As a dispersant, "Contaminon N" (a 10% by mass aqueous solution of a neutral detergent for cleaning precision measuring instruments at pH 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersant. ) was diluted with ion-exchanged water to about 3 times the mass, and about 0.3 ml of the diluted solution was added.
(3) An ultrasonic disperser "Ultrasonic Dispersion System Tetra 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W and containing two oscillators with an oscillation frequency of 50 kHz with a phase shift of 180 degrees was prepared. About 3.3 L of ion-exchanged water was placed in the water tank of the ultrasonic disperser, and about 2 mL of Contaminon N was added to this water tank. (4) The beaker of (2) was set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser was operated. Then, the height position of the beaker was adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker was maximized.
(5) While the electrolytic aqueous solution in the beaker of (4) was irradiated with ultrasonic waves, about 10 mg of toner particles were added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment was continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water in the water tank was appropriately adjusted to 10°C or higher and 40°C or lower.
(6) The electrolytic aqueous solution of (5) above, in which toner particles are dispersed, is dropped into the round-bottomed beaker of (1) above set in the sample stand, and adjusted so that the measured concentration is about 5%. bottom. The measurement was continued until the number of measured particles reached 50,000.
(7) The measurement data was analyzed with the dedicated software attached to the apparatus, and the weight average particle size (D4) was calculated. Incidentally, the weight average particle diameter (D4) is the "average diameter" on the "analysis/volume statistical value (arithmetic mean)" screen when graph/vol% is set in the dedicated software.

<Example>
Hereinafter, "parts" of each material are all based on mass unless otherwise specified.
In Embodiment 1, toner a to which inorganic silicon fine particles and metal soap are externally added is produced by using the above toner production method.
Table 2 shows the external addition conditions for toner a. The details of the speed and time, which are external addition conditions, are as described in JP-A-2016-38591.
Moreover, the metal soap externally added together with the inorganic silicon fine particles is zinc stearate.
A manufacturing method of toner a to be used is shown.
(Preparation step of aqueous medium 1)
To 1000.0 parts of ion-exchanged water in a reaction vessel, 14.0 parts of sodium phosphate (12 hydrate, manufactured by Rasa Kogyo Co., Ltd.) was added, and the mixture was kept at 65° C. for 1.0 hour while purging with nitrogen.
T. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12000 rpm, a calcium chloride aqueous solution obtained by dissolving 9.2 parts of calcium chloride (dihydrate) in 10.0 parts of ion-exchanged water is mixed together. to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 10% by mass hydrochloric acid was added to the aqueous medium to adjust the pH to 5.0, and an aqueous medium 1 was obtained.
(Preparation step of polymerizable monomer composition)
・Styrene: 60.0 parts ・C.I. I. Pigment Blue 15:3: 6.5 parts The above material was put into an attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.), and zirconia particles with a diameter of 1.7 mm were dispersed at 220 rpm for 5.0 hours to obtain a pigment. A dispersion was prepared. The following materials were added to the pigment dispersion.
・Styrene: 20.0 parts ・n-Butyl acrylate: 20.0 parts ・Crosslinking agent (divinylbenzene): 0.3 parts ・Saturated polyester resin: 5.0 parts (propylene oxide-modified bisphenol A (2 mol adduct) and terephthalic acid (molar ratio 10:12), glass transition temperature Tg = 68 ° C., weight average molecular weight Mw = 10000, molecular weight distribution Mw / Mn = 5.12)
Fischer-Tropsch wax (melting point 78°C): 7.0 parts K. A homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used to uniformly dissolve and disperse at 500 rpm to prepare a polymerizable monomer composition.
(Granulation step) The temperature of the water-based medium 1 was set to 70°C, T.I. K. While maintaining the rotation speed of the homomixer at 12000 rpm, the polymerizable monomer composition was charged into the aqueous medium 1, and 9.0 parts of t-butyl peroxypivalate as a polymerization initiator was added. The mixture was granulated for 10 minutes while maintaining 12000 rpm with the stirring device.
(Polymerization process)
After the granulation step, the agitator was changed to a propeller agitating blade, and while stirring at 150 rpm, the mixture was maintained at 70°C and polymerized for 5.0 hours. gone. The temperature of the resulting slurry was cooled to obtain a slurry of toner particles.
(Washing and drying process)
Hydrochloric acid was added to the slurry of the toner particles to adjust the pH to 1.5 or less, and the mixture was allowed to stand with stirring for 1 hour, followed by solid-liquid separation using a pressure filter to obtain a toner cake. This was reslurried with ion-exchanged water to form a dispersion again, and then subjected to solid-liquid separation with the aforementioned filter. After reslurry and solid-liquid separation were repeated until the electrical conductivity of the filtrate became 5.0 μS/cm or less, solid-liquid separation was finally performed to obtain a toner cake.
The resulting toner cake was dried with a flash jet dryer (manufactured by Seishin Enterprises), and a multi-division classifier utilizing the Coanda effect was used to cut fine and coarse particles to obtain toner particles a. The drying conditions were a blowing temperature of 90.degree. C., a dryer outlet temperature of 40.degree.

(Preparation of inorganic silicon fine particles)
590.0 g of methanol, 42.0 g of water, and 48.0 g of 28 mass % aqueous ammonia were added and mixed in a 3-liter glass reactor equipped with a stirrer, a dropping funnel and a thermometer. The resulting solution was adjusted to 35° C., and while stirring, 1100.0 g (7.23 mol) of tetramethoxysilane and 395.0 g of 5.5% by mass ammonia water were simultaneously added. Tetramethoxysilane was added dropwise over 6 hours, and aqueous ammonia was added dropwise over 5 hours. After the dropwise addition was completed, stirring was continued for 0.5 hour for hydrolysis to obtain a methanol-water dispersion of hydrophilic spherical sol-gel silica fine particles. Then, an ester adapter and a cooling tube were attached to the glass reactor, and the dispersion was thoroughly dried at 80° C. under reduced pressure. The obtained silica particles were heated at 400° C. for 10 minutes in a constant temperature bath.
The obtained silica fine particles were pulverized by a pulverizer (manufactured by Hosokawa Micron Corporation).
After that, 500 g of fine silica particles were charged into a polytetrafluoroethylene inner cylindrical stainless steel autoclave having an inner volume of 1000 ml. After replacing the inside of the autoclave with nitrogen gas, while rotating the stirring blade attached to the autoclave at 400 rpm, 0.5 g of HMDS (hexamethyldisilazane) and 0.1 g of water were atomized with a two-fluid nozzle. It was sprayed evenly on the silica fine particles. After stirring for 30 minutes, the autoclave was closed and heated at 220° C. for 2 hours. Subsequently, while the system was heated, the system was decompressed to perform a deammonification treatment to obtain fine silica particles (inorganic silicon fine particles, the number average particle size of the primary particles being 80 nm).

(External Addition of Inorganic Silicon Fine Particles and Metal Soap)
Toner a was obtained by externally adding the silica fine particles and metal soap to toner particles a according to the method described in the example of JP-A-2016-38591.
That is, the silica fine particles (so that the content in the toner satisfies the conditions in the table) and zinc stearate (so that the content in the toner is 0.20% by mass) are added to the toner particles a. , using the apparatus a (surface modification apparatus) 101 shown in FIGS. Thereafter, coarse particles were removed using a 200-mesh sieve to obtain Toner a.
As shown in FIG. 7, the toner processing apparatus 101 includes a processing chamber (processing tank) 110, a stirring blade 120 as a stirring means, a rotating body 130, a driving motor 150, and a control section 160. As shown in FIG. The processing chamber 110 is for accommodating a processed object containing toner particles and external additives. The stirring blade 120 is rotatably provided at the bottom of the processing chamber 110 below the rotor 130 in the processing chamber. Rotating body 130 is rotatably provided above stirring blade 120 . FIG. 8 shows a schematic diagram of the processing chamber 110 . For convenience of explanation, FIG. 8 shows a state in which the inner peripheral surface (inner wall) 110a of the processing chamber 110 is partially cut. The processing chamber 110 is a cylindrical container with a substantially flat bottom, and is equipped with a drive shaft 111 for attaching the stirring blade 120 and the rotating body 130 substantially at the center of the bottom. 9(a) and 9(b) show schematic diagrams of a stirring blade 120 as a swirling means (FIG. 9(a) shows a top view and FIG. 9(b) shows a side view). The stirring blade 120 is configured to be able to stir up the object to be processed, including the toner particles and the external additive, within the processing chamber 110 by rotating. The stirring blade 120 has a blade portion 121 extending outward (radially outward (outer diameter direction), outer diameter side) from the center of rotation, and the tip of the blade portion 121 soars the material to be processed. It has a raised shape. The stirring blade 120 is fixed to the drive shaft 111 at the bottom of the processing chamber 110 and rotates clockwise (in the direction of arrow R) when viewed from above (in the state shown in FIG. 9A). Due to the rotation of the stirring blade 120, the object to be processed rises while rotating in the same direction as the stirring blade 120 within the processing chamber 110, and eventually descends due to gravity. In this manner, the objects to be processed are uniformly mixed. Schematic diagrams of the rotor 130 are shown in FIGS. FIG. 10(a) is a top view of the rotor 130, and FIG. 10(b) is a side view. 11(a) is a top view showing the rotating body 130 installed in the processing chamber 110, FIG. 11(b) is a perspective view showing a main part of the rotating body 130, and FIG. 11(c) is FIG. 10(b). 1 is a diagram showing a cross section AA of FIG. Rotating body 130 is located above stirring blade 120 in processing chamber 110, is fixed to same drive shaft 111 as stirring blade 120, and rotates in the same direction as stirring blade 120 (arrow R direction). The rotating body 130 is composed of a rotating body main body 131 and a processing section 132 having a processing surface 133 that collides with an object to be processed by rotation of the rotating body 130 to process the object. Treated surface 1
33 extends in the outer diameter direction from the outer peripheral surface 131a of the rotor body 131, and a region of the processing surface 133 farther from the rotor body 131 is rotated than a region closer to the rotor body 131 than that region. It is formed so as to be positioned downstream of the body 130 in the direction of rotation. That is, in FIG. 11A , the processing surface 133 is arranged to be inclined in the direction of rotation R of the rotor 130 with respect to the radial direction of the rotor 130 . Due to the rotation of the rotating body 130, the object to be treated collides with the treatment surface 133, thereby performing crushing processing of external additive agglomerates.

In Embodiment 1, the surface of the photoreceptor is roughened to form fine unevenness on the surface of the photoreceptor, and the metal soap externally added to the toner particles is supplied to the unevenness to fix the surface of the photoreceptor. It is characterized in that the amount of metal soap is maintained to suppress the occurrence of image deletion.
The surface of the photoreceptor is roughened, and the peripheral surface of the image carrier has a ten-point average surface roughness (Rz) of 0<Rz≦0.70 (μm) (preferably 0.10≦Rz≦ 0.50 (μm)), and the average interval (Sm) of the irregularities on the peripheral surface is 0<Sm≦70 (μm) (preferably 5≦Sm≦70 (μm)). By setting the amount in the above range, it is possible to provide a structure in which the metal soap can be stably maintained on the surface of the image carrier (photoreceptor), and as a result, image deletion can be suppressed over a long period of time.

The 10-point average surface roughness (Rz) of the peripheral surface of the image carrier and the average spacing (Sm) of the unevenness were determined based on the JIS standard (JIS B 0601) using a surface roughness measuring instrument manufactured by Kosaka Laboratory Co., Ltd. Using a Surfcorder Model SE3500, measurements were made under the following conditions.
Detector: R2 μm
0.7mN diamond stylus Filter: 2CR
Cutoff value: 0.8mm
Measurement length: 2.5mm
Feeding speed: 0.1mm
In the present invention, 3 points in the meridian direction of the photoreceptor and 4 points in the circumferential direction at each point, totaling 12 points, were used as measurement points.

On the other hand, as shown in FIG. 6B, the average spacing (Sm) of the irregularities on the peripheral surface of the image carrier means that in the generatrix direction (longitudinal direction) of the plurality of grooves 1b arranged in the generatrix direction of the peripheral surface 1a. It can be defined as the spacing, or the spacing in the generatrix direction (longitudinal direction) of the flat portion 1c.

As Examples 1 and 3 of the present invention and Comparative Examples 1 and 2, combinations of toner a and photosensitive members having different surface roughness as shown in Table 3 were prepared.

(experiment)
In order to confirm the occurrence of image deletion in Examples 1 to 3 and Comparative Examples 1 and 2, 10,000 sheets of paper were continuously fed per day at a printing rate of 1%, and then left in the machine for one day. compared.
The image deletion test was evaluated by printing a halftone image on one sheet. Evaluation is as follows.
〇: Not generated (no white spots due to latent image dullness or outline blurring at image borders in the entire image)
×: Occurred (overall or part of the image due to latent image dullness and outline blurring at image boundaries)
Paper threading and testing were performed in an environment of 32° C. and 80% RH. The total number of sheets passed was up to 50,000 sheets.
Also, the photosensitive member surface speed was 296 mm/s, the developing roller surface speed was 425 mm/s, the photosensitive member surface potential was −500 V, the voltage applied to the developing roller was −350 V, the voltage of the supply roller was −450 V, and the voltage of the regulating member was −450 V.
Table 4 shows the experimental results.

As shown in Table 4, in Examples 1 to 3, image deletion was good throughout the experiment. On the other hand, in Comparative Example 2 using a photoreceptor that has not been subjected to roughening treatment, image deletion occurs after 40,000 sheets, although the image quality is good up to 30,000 sheets. This is because the metal soap fills the grooves formed on the surface of the photoreceptor by the roughening treatment, so that the metal soap remains on the surface of the photoreceptor without being removed by the cleaning blade, resulting in the effect of suppressing image deletion. can be considered to be maintained.

On the other hand, in the photoreceptor without surface roughening treatment of Comparative Example 2, Sm, which represents the average spacing of unevenness on the peripheral surface of the photoreceptor, is large, and the end face of the cleaning blade follows the entire surface of the photoreceptor surface in the longitudinal direction without gaps. Since the deposited metal soap is removed, the effect of suppressing image deletion by the metal soap is not exhibited.

Further, in Comparative Example 1, although the photoreceptor was roughened, image deletion occurred after 40,000 sheets, as in Comparative Example 2 without roughening. Since the photoreceptor d of Comparative Example 2 had deep grooves, a large amount of metal soap was required to completely fill the grooves, and the effect was not sufficiently exhibited.

In general, when the abrasion of the photoreceptor is suppressed, the surface of the photoreceptor becomes difficult to refresh, and image defects such as image smearing are likely to occur in a high-humidity environment.
A toner in which a metallic soap is externally added to toner particles is effective for image smearing, but the metallic soap is scraped off the photoreceptor by a cleaning blade, and the effect is difficult to maintain.
In the structure of Embodiment 1, the surface of the photoreceptor is roughened, and the range of ten-point average surface roughness (Rz) of the peripheral surface of the image carrier is 0<Rz≦0.70 (μm). and the range of the average interval (Sm) of the irregularities on the peripheral surface is 0<Sm≦70.0 (μm). By controlling each parameter within the above range, it is possible to stably maintain the metal soap on the surface of the photoreceptor, thereby suppressing image deletion over a long period of time.

[Embodiment 2]
In Embodiment 1 of the present invention, the case of using a toner to which inorganic silicon fine particles are externally added as shown in FIG. 4 has been described.
The inventors conducted experiments by changing the state of the surface layer of the toner, and found that the toner in which fine particles containing an organosilicon polymer are present on the surface of the toner particles has a favorable effect.
This is because, as in Embodiment 1, in the toner in which the inorganic silicon fine particles are present on the surface of the toner particles, the inorganic silicon fine particles easily scrape the surface of the photoreceptor, and deep scratches (grooves) are locally generated on the surface of the photoreceptor. Sometimes.
As a result, the metal soap is insufficiently supplied to the deep scratches, resulting in image deletion.
On the other hand, in the case of a toner in which fine particles containing an organic silicon polymer are present on the surface of the toner particles instead of the inorganic silicon fine particles, the surface free energy is smaller than that of the inorganic silicon fine particles and the frictional property is low. It can be considered that deep scratches are less likely to occur on the body surface.
In Embodiment 2 of the present invention, by using a toner in which fine particles containing an organosilicon polymer are present on the surface of the toner particles, the durability of the photoreceptor can be maintained even in a configuration with a longer life, and a simple process can be performed. The configuration is characterized in that the configuration suppresses the occurrence of image smearing. It should be noted that the description of the portions of the second embodiment that overlap with those of the first embodiment will be omitted.

<Toner in Which Fine Particles Containing Organosilicon Polymer are Present on the Surface of Toner Particles>
In Embodiment 2, the developer contains toner particles, fine particles containing an organosilicon polymer present on the surface of the toner particles and having a structure represented by the following formula (1), and a toner containing a metallic soap. do.
R—SiO _3/2 (1)
The R represents a hydrocarbon group having 1 to 6 carbon atoms. R is preferably an aliphatic hydrocarbon group having 1 or more and 5 or less carbon atoms or a phenyl group, and more preferably an aliphatic hydrocarbon group having 1 or more and 3 or less carbon atoms. Preferred examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group, and a vinyl group.
Moreover, the adhesion rate of the fine particles is preferably 30% or more and 90% or less.

(Fine particles containing organosilicon polymer)
The microparticles containing an organosilicon polymer are preferably microparticles containing polyalkylsilsesquioxane obtained by dehydration condensation of alkyltrialkoxysilane, and more preferably polyalkylsilsesquioxane microparticles. .
The polyalkylsilsesquioxane has an R—SiO _3/2 structure (R represents a hydrocarbon group having 1 to 6 carbon atoms) obtained by hydrolyzing a trifunctional silane. ) is a network polymer.
Examples of the alkyltrialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, n-propyltriethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, isobutyltrialkoxysilane. Ethoxysilane, n-hexylmethoxysilane, n-hexyltriethoxysilane, and the like can be used. These may be used individually by 1 type, and may use 2 or more types together.

(Method for producing microparticles containing organosilicon polymer)
A 2000 mL flask was charged with 200.0 g of water and 0.1 g of acetic acid as a catalyst, and stirred at 30°C. 100.0 g of methyltrimethoxysilane was added thereto and stirred for 2 hours. This is referred to as process A.
150 g of water, 200.0 g of methanol and 5 g of sodium hydroxide were put into a 500 mL flask and stirred at 30° C. for 5 minutes to prepare an alkaline aqueous catalyst. This alkaline aqueous catalyst was put into the 2000 mL flask of step A above. It was then stirred for 10 minutes. This is referred to as process B.
2500 g of water was put into a 5000 mL flask, and the whole amount of the aqueous solution obtained in step B was put into the flask while stirring at 35°C. After that, stirring was continued for 8 hours to obtain a dispersion containing polymethylsilsesquioxane fine particles. This is referred to as process C.
The dispersion liquid obtained in Step C was suction filtered to form a cake of polymethylsilsesquioxane microparticles. Furthermore, methanol washing was performed twice. Then, it was dried under reduced pressure at 40° C. for 24 hours to obtain white fine particles. After that, the particle size was adjusted by sieving the white fine particles with an air classifier. Polymethylsilsesquioxane fine particles (A) were thus obtained. The polymethylsilsesquioxane fine particles (A) had a number average particle diameter of 102 nm.

(Method for measuring number average particle diameter of microparticles containing organosilicon polymer)
The number-average particle diameter of the fine particles was measured from an image of the fine particles magnified 100,000 times using a field emission scanning electron microscope (FE-SEM) "S-4800, Hitachi High-Technologies".
First, fine particles were suspended in methanol to a concentration of about 0.5% by mass, and dispersed for 1 minute with a homogenizer (output 20 W) to prepare a liquid. After that, it was dropped onto a pedestal for observation and air-dried. This was subjected to platinum vapor deposition for 30 seconds, and an enlarged image of 100,000 times was obtained using the above FE-SEM. Next, the obtained images were printed, and at that time, a plurality of images that could measure 100 or more were output. 100 pieces were randomly selected from these prints, and the major axis was measured with a vernier caliper. The arithmetic average value of the 100 long diameters was taken as the number average particle diameter (unit: nm).

(Toner production example)
In a 20 L reaction vessel, 400 parts by mass of ion-exchanged water and 450 parts by mass of 0.1M Na _{PO aqueous} solution were added, heated to 60°C, and then mixed with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). , and stirred at 6,000 rpm. 68 parts of a 1.0 M-CaCl ₂ aqueous solution was added to this to obtain an aqueous medium containing a calcium phosphate salt.

on the other hand,
・Styrene 75 parts ・n-Butyl acrylate 25 parts ・C.I. I. Pigment Blue 15:3 5 parts Polyester resin 5 parts (weight average molecular weight = 12500, acid value = 5.5 mgKOH/g)
- Aluminum compound of dialkylsalicylic acid 1 part - Hydrocarbon wax 3 parts (endothermic peak = 80°C, half width = 8, weight average molecular weight = 750)
Ester wax 9 parts (endothermic peak = 67°C, half width = 4, weight average molecular weight = 690)
・Divinylbenzene 0.05 parts

The above formulation was put into a 5 L container and heated to 60° C., and uniformly dissolved and dispersed at 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 3.5 parts of a polymerization initiator, 2,2'-azobis(2,4-dimethylvaleronitrile), was dissolved in this to prepare a polymerizable monomer composition. The polymerizable monomer composition is added to the aqueous medium, and stirred at 10,000 rpm with a TK homomixer at 70° C. under _N2 atmosphere to granulate droplets of the polymerizable monomer composition. bottom.
After that, while stirring with a paddle stirring blade, when the polymerization conversion rate of the polymerizable vinyl monomer reaches 90%, a 0.1 mol/liter sodium hydroxide aqueous solution is added to adjust the pH of the aqueous dispersion medium to 8. was prepared to
Further, the temperature was raised to 80° C. at a rate of temperature rise of 40° C./hr, and reaction was carried out for 4 hours.
After completion of the polymerization reaction, residual monomers were distilled off under reduced pressure. After cooling, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 3 hours to dissolve the calcium phosphate.
After filtering and washing with water, the particles were dried at 40° C. for 48 hours, and fine particles and coarse particles were removed by air classification to obtain toner particles b. The weight average particle size (D4) of the toner particles b was 7.0 μm.
To 100 parts of the toner particles, 2.0 parts of polymethylsilsesquioxane fine particles (A) and zinc stearate (so that the content in the toner is 0.20% by mass) are externally added by a method described later. Thus, toner b of the present embodiment was obtained.

(Method for Measuring Weight Average Particle Diameter D4 of Toner Particles)
The weight average particle size (D4) of the toner particles was calculated as follows. As a measurement device, a precision particle size distribution measurement device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube was used. The attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) was used for setting the measurement conditions and analyzing the measurement data. The measurement was performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, "ISOTON II" (manufactured by Beckman Coulter, Inc.), which is prepared by dissolving special grade sodium chloride in ion-exchanged water so as to have a concentration of about 1% by mass, was used.

Before conducting the measurement and analysis, the dedicated software was set as follows.
On the "Change standard measurement method (SOMME)" screen of the dedicated software, set the total count number of control mode to 50000 particles, set the number of measurements to 1, and set the Kd value to "standard particle 10.0 μm" (Beckman Coulter Co.) was used to set the values obtained. The threshold and noise level were automatically set by pressing the "threshold/noise level measurement button". Also, the current was set to 1600 μA, the gain was set to 2, the electrolyte was set to ISOTON II, and a check was put in the “flash of aperture tube after measurement”.

On the "pulse-to-particle size conversion setting" screen of the dedicated software, the bin interval was set to logarithmic particle size, the particle size bin was set to 256 particle size bins, and the particle size range was set to 2 μm to 60 μm.
A specific measuring method is as follows.
(1) About 200 mL of the electrolytic aqueous solution was placed in a 250 mL round-bottomed glass beaker exclusively for Multisizer 3, set on a sample stand, and stirred with a stirrer rod counterclockwise at 24 rpm. Then, using the dedicated software's "Flush Aperture Tube" function, dirt and air bubbles inside the aperture tube were removed.
(2) About 30 mL of the electrolytic aqueous solution was placed in a 100 mL flat-bottom glass beaker. As a dispersant, "Contaminon N" (a 10% by mass aqueous solution of a neutral detergent for cleaning precision measuring instruments at pH 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersant. ) was diluted with ion-exchanged water to about 3 times the mass, and about 0.3 ml of the diluted solution was added.
(3) An ultrasonic disperser "Ultrasonic Dispersion System Tetra 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W and containing two oscillators with an oscillation frequency of 50 kHz with a phase shift of 180 degrees was prepared. About 3.3 L of ion-exchanged water was placed in the water tank of the ultrasonic disperser, and about 2 mL of Contaminon N was added to this water tank. (4) The beaker of (2) was set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser was operated. Then, the height position of the beaker was adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker was maximized.
(5) While the electrolytic aqueous solution in the beaker of (4) was irradiated with ultrasonic waves, about 10 mg of toner particles were added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment was continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water in the water tank was appropriately adjusted to 10°C or higher and 40°C or lower.
(6) The electrolytic aqueous solution of (5) above, in which toner particles are dispersed, is dropped into the round-bottomed beaker of (1) above set in the sample stand, and adjusted so that the measured concentration is about 5%. bottom. The measurement was continued until the number of measured particles reached 50,000.
(7) The measurement data was analyzed with the dedicated software attached to the apparatus, and the weight average particle size (D4) was calculated. Incidentally, the weight average particle diameter (D4) is the "average diameter" on the "analysis/volume statistical value (arithmetic mean)" screen when graph/vol% is set in the dedicated software.

(Method for measuring adhesion rate of fine particles to surface of toner particles)
A method for measuring the fixation rate (%) of the polymethylsilsesquioxane fine particles (A) is shown below.

160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a concentrated sucrose solution. 31 g of the sucrose concentrate and Contaminon N (a pH 7 neutral detergent for cleaning precision measuring instruments consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) were placed in a centrifugation tube (capacity: 50 mL). 6 mL of a mass % aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion. 1.0 g of toner is added to this dispersion, and clumps of toner are loosened with a spatula or the like.

The centrifuge tube is shaken on a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution is transferred to a swivel rotor glass tube (capacity 50 mL) and separated in a centrifuge (manufactured by H-9R Kokusan Co., Ltd.) at 3500 rpm for 30 minutes. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the separated toner on the uppermost layer is collected with a spatula or the like. After the collected aqueous solution containing the toner is filtered with a vacuum filter, it is dried with a dryer for 1 hour or more. The dried product is pulverized with a spatula, and the amount of silicon is measured with fluorescent X-rays. The rate (%) of fine particles adhering to the surface of the toner particles is calculated from the element amount ratio of the measurement object between the toner after washing and the toner before washing.

Fluorescent X-ray measurement of each element conforms to JIS K 0119-1969, but specifically as follows.
As a measurement device, a wavelength dispersive X-ray fluorescence spectrometer "Axios" (manufactured by PANalytical) and attached dedicated software "SuperQver.4.0F" (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data. Use Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 10 mm, and the measurement time is 10 seconds. When measuring light elements, a proportional counter (PC) is used, and when measuring heavy elements, a scintillation counter (SC) is used.

As a measurement sample, about 1 g of washed toner or unwashed toner was placed in a special aluminum ring with a diameter of 10 mm for press, and was flattened. (manufacturer), pressurized at 20 MPa for 60 seconds, and pellets molded to a thickness of about 2 mm are used.

Measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and the concentration is calculated from the count rate (unit: cps), which is the number of X-ray photons per unit time.

As a method for quantifying the amount of silicon in the toner, for example, silica (SiO ₂ ) fine powder is added to 0.5 parts by mass per 100 parts by mass of toner particles, and thoroughly mixed using a coffee mill. do. Similarly, 2.0 parts by mass and 5.0 parts by mass of fine silica powder are mixed with the toner particles, respectively, and these are used as samples for the calibration curve.
For each sample, a pellet of the sample for the calibration curve was prepared as described above using a tablet press, and when PET was used as the analyzing crystal, the diffraction angle (2θ) was observed at 109.08°. The Si-Kα ray count rate (unit: cps) is measured. At this time, the acceleration voltage and current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A linear function calibration curve is obtained with the obtained X-ray count rate on the vertical axis and the amount of SiO ₂ added in each calibration curve sample on the horizontal axis.

Next, the toner to be analyzed is made into pellets as described above using a tablet press, and the Si--Kα ray count rate is measured. Then, the content of silicon in the toner is obtained from the above calibration curve. The ratio of the amount of silicon in the toner after washing to the amount of silicon in the toner before washing calculated by the above method is obtained and defined as the fixation rate (%).

(External attachment method)
The toner of Embodiment 2 was obtained by externally adding polymethylsilsesquioxane fine particles (A) and metal soap to toner particles b according to the method described in the example of JP-A-2016-38591.
That is, 2.00 parts by mass of polymethylsilsesquioxane fine particles (A) and zinc stearate (so that the content in the toner is 0.20% by mass) are added to 100 parts by mass of toner particles b. , using the apparatus a (surface modification apparatus) 101 shown in FIGS. Thereafter, coarse particles were removed using a 200-mesh sieve to obtain toner b.

As shown in FIG. 7, the toner processing apparatus 101 includes a processing chamber (processing tank) 110, a stirring blade 120 as a stirring means, a rotating body 130, a driving motor 150, and a control section 160. As shown in FIG. The processing chamber 110 is for accommodating a processed object containing toner particles and external additives. The stirring blade 120 is rotatably provided at the bottom of the processing chamber 110 below the rotor 130 in the processing chamber. Rotating body 130 is rotatably provided above stirring blade 120 . FIG. 8 shows a schematic diagram of the processing chamber 110 . For convenience of explanation, FIG. 8 shows a state in which the inner peripheral surface (inner wall) 110a of the processing chamber 110 is partially cut. The processing chamber 110 is a cylindrical container with a substantially flat bottom, and is equipped with a drive shaft 111 for attaching the stirring blade 120 and the rotating body 130 substantially at the center of the bottom. 9(a) and 9(b) show schematic diagrams of a stirring blade 120 as a swirling means (FIG. 9(a) shows a top view and FIG. 9(b) shows a side view). The stirring blade 120 is configured to be able to stir up the object to be processed, including the toner particles and the external additive, within the processing chamber 110 by rotating. The stirring blade 120 has a blade portion 121 extending outward (radially outward (outer diameter direction), outer diameter side) from the center of rotation, and the tip of the blade portion 121 soars the material to be processed. It has a raised shape. The stirring blade 120 is fixed to the drive shaft 111 at the bottom of the processing chamber 110 and rotates clockwise (in the direction of arrow R) when viewed from above (in the state shown in FIG. 9A). Due to the rotation of the stirring blade 120, the object to be processed rises while rotating in the same direction as the stirring blade 120 within the processing chamber 110, and eventually descends due to gravity. In this manner, the objects to be processed are uniformly mixed. Schematic diagrams of the rotor 130 are shown in FIGS. FIG. 10(a) is a top view of the rotor 130, and FIG. 10(b) is a side view. 11(a) is a top view showing the rotating body 130 installed in the processing chamber 110, FIG. 11(b) is a perspective view showing a main part of the rotating body 130, and FIG. 11(c) is FIG. 11(b). 1 is a diagram showing a cross section AA of FIG. Rotating body 130 is located above stirring blade 120 in processing chamber 110, is fixed to same drive shaft 111 as stirring blade 120, and rotates in the same direction as stirring blade 120 (arrow R direction). The rotating body 130 is composed of a rotating body main body 131 and a processing section 132 having a processing surface 133 that collides with an object to be processed by rotation of the rotating body 130 to process the object. The processing surface 133 extends in the outer diameter direction from the outer peripheral surface 131a of the rotor main body 131, and the region of the processing surface 133 farther from the rotor main body 131 is closer to the rotor main body 131 than the region of the processing surface 133. , are positioned on the downstream side of the rotating body 130 in the direction of rotation. That is, in FIG. 11A , the processing surface 133 is arranged to be inclined in the direction of rotation R of the rotor 130 with respect to the radial direction of the rotor 130 . Due to the rotation of the rotating body 130, the object to be treated collides with the treatment surface 133, thereby performing crushing processing of external additive aggregates.

The content of the polymethylsilsesquioxane fine particles in the toner is preferably 0.01 parts by mass or more and 3.00 parts by mass or less with respect to 100.00 parts by mass of the toner particles.
The adherence ratio of the fine particles to the surface of the toner particles obtained by this method can be adjusted by changing the peripheral speed of the blade tip and the time during the two-stage treatment.
In the present invention, the fixation rate is preferably 30% or more and 90% or less. If the fixation rate is less than 30%, the chances of contact between toner particles increase, which may change the toner adhesion force and change the chargeability. Moreover, it is difficult to obtain a fixation rate higher than 90% by the above external addition method.

In Embodiment 2, by using a toner to which organosilicon polymer fine particles are externally added, the uneven shape of the roughened surface of the photoreceptor can be adjusted to the range of the ten-point average surface roughness (Rz) of the peripheral surface. is 0<Rz≦0.7 (μm), and the range of the average interval (Sm) of the unevenness of the peripheral surface can be maintained at 0<Sm≦70 (μm). As a result, it is possible to maintain the image deletion suppressing effect of the metal soap. It is also a preferred embodiment that the toner does not use inorganic silicon fine particles as an external additive.

<Example>
In Embodiment 2, a toner b to which organosilicon polymer fine particles and a metal soap are externally added is produced by using the above toner production method.
Table 5 shows external additive conditions for toner b. The metal soap externally adds zinc stearate as in the first embodiment.

Combinations of toners and photosensitive members as shown in Table 6 were prepared.

(experiment)
In order to confirm the occurrence of image smearing in Examples 1, 4, and Comparative Example 3, 10,000 sheets of paper were continuously fed per day at a printing rate of 1%, then left in the machine for a day, and the presence or absence of image smearing after standing was compared. bottom.
The image deletion test was evaluated by printing one halftone image. Evaluation is as follows.
〇: Not generated (no white spots due to latent image dullness or outline blurring at image borders in the entire image)
×: Occurs (overall or part of the image due to latent image dullness and outline blurring at image boundaries)
Paper threading and testing were performed in an environment of 32° C. and 80% RH. The total number of sheets passed was up to 70,000 sheets.
Also, the photosensitive member surface speed was 296 mm/s, the developing roller surface speed was 425 mm/s, the photosensitive member surface potential was −500 V, the voltage applied to the developing roller was −350 V, the voltage of the supply roller was −450 V, and the voltage of the regulating member was −450 V.
Table 7 shows the experimental results.

As shown in Table 7, image bleeding in Example 4 using toner b having fine particles containing an organosilicon polymer was good throughout the experiment. On the other hand, in Example 1 using the toner a to which the inorganic silicon fine particles were externally added, although the image quality was good up to 50,000 sheets, image deletion occurred after 60,000 sheets. When the surface of the photoreceptor is compared, the photoreceptor of Example 1 when the image deletion occurs has deep scratches like the photoreceptor d used in Comparative Example 3. was changing from This is because the inorganic silicon fine particles externally added to the toner scraped the surface of the photoreceptor in contact with the photoreceptor, such as the developing section and the cleaning section, forming local deep scratches (grooves). guessed. If the grooves are formed deep, a large amount of metal soap is required until the grooves are completely filled, which may reduce the effect of suppressing image deletion.
On the other hand, in Example 4 using toner b having fine particles containing an organosilicon polymer, the initial roughened shape was maintained throughout the experiment. Fine particles containing an organosilicon polymer have a smaller surface free energy and a lower frictional property than inorganic silicon fine particles, so it is believed that deep scratches are less likely to occur on the surface of the photoreceptor.

In Comparative Example 3, since the photosensitive member d in which deep grooves were formed from the beginning was used, even if the fine particles externally added to the toner b were fine particles containing an organosilicon polymer, 40,000 sheets were required. Image blur has occurred.

In the configuration of the second embodiment, the ten-point average surface roughness (Rz) of the peripheral surface of the image carrier is reduced to 0<Rz≦0 by using the toner b having fine particles containing an organosilicon polymer. .70 (μm), and the range of the average interval (Sm) of the irregularities on the peripheral surface can be maintained within the range of 0<Sm≦70.0 (μm). As a result, the metal soap can be stably maintained on the surface of the photoreceptor drum, and the durability of the photoreceptor can be maintained even in a longer-life configuration, and the occurrence of image smearing can be suppressed with a simple configuration. It has become possible.

[Embodiment 3]
In Embodiment 1 of the present invention, the case of using a toner to which inorganic silicon fine particles are externally added as shown in FIG. 4 has been described.
Further, in the second embodiment, the case of using the toner having the fine particles containing the organosilicon polymer on the surface of the toner particles has been described.
Next, Embodiment 3 will be described.
Embodiment 3 relates to a toner in which the developer contains toner particles, an organosilicon polymer having a structure represented by the following formula (1) covering the surfaces of the toner particles, and a metal soap.
R—SiO _3/2 (1)
(The above R represents a hydrocarbon group having 1 to 6 carbon atoms.)
This toner is characterized in that the organosilicon polymer is less likely to come off from the toner than in the case of using the toner of Embodiment 2, so that only metallic soap can be efficiently supplied to the grooves of the photoreceptor.
In the following description, descriptions of the same parts as those of the above-described embodiment are omitted.

<Toner>
In Embodiment 3, a toner containing toner particles and an organosilicon polymer having a structure represented by formula (1) covering the surfaces of the toner particles is used.

When the surface of the toner particles is coated with the organosilicon polymer having the structure represented by formula (1), the toner particles have a surface layer which is the outermost layer. That is, the toner particles have a surface layer containing an organosilicon polymer having a structure represented by formula (1).
The surface layer is very hard compared to conventional toner particles. Therefore, from the viewpoint of fixability, it is also preferable to provide a portion where the surface layer is not formed on a part of the surface of the toner particles.

However, the ratio of the number of splitting axes in which the thickness of the surface layer containing the organosilicon polymer is 2.5 nm or less (hereinafter also referred to as the ratio of the thickness of the surface layer of 2.5 nm or less) is 20.0% or less. is preferred. This condition approximates that at least 80.0% or more of the surface of the toner particles is composed of a surface layer containing an organosilicon polymer of 2.5 nm or more. That is, when this condition is satisfied, the surface layer containing the organosilicon polymer sufficiently covers the surface of the toner particles. More preferably, it is 10.0% or less. The measurement can be defined by cross-sectional observation using a transmission electron microscope (TEM), the details of which will be described later.

(Organosilicon polymer having a structure represented by formula (1))
The toner has toner particles and an organosilicon polymer having a structure represented by formula (1) covering the surfaces of the toner particles.
R—SiO _3/2 (1)
(R represents a hydrocarbon group having 1 to 6 carbon atoms.)

In the organosilicon polymer having the structure represented by formula (1), one of the four valences of Si atoms is bonded to R and the remaining three are bonded to O atoms. The O atom forms a state in which both of its two valences are bonded to Si, that is, a siloxane bond (Si--O--Si).
Considering Si atoms and O atoms as an organosilicon polymer, it is expressed as —SiO _3/2 because it has two Si atoms and three O atoms.

Furthermore, in the chart obtained by ²⁹ Si-NMR measurement of the tetrahydrofuran (THF)-insoluble portion of the toner particles, the ratio of the peak area attributed to the structure of formula (1) to the total peak area of the organosilicon polymer was 20%. It is preferable that it is above. Although the detailed measurement method will be described later, this approximates that the organosilicon polymer contained in the toner particles has a partial structure represented by R—SiO _3/2 at 20% or more. .

As described above, the —SiO _3/2 structure means that three of the four valences of Si atoms are bonded to oxygen atoms, and these oxygen atoms are bonded to other Si atoms. If one of the oxygens is a silanol group, the structure of the organosilicon polymer is represented by R--SiO _2/2 --OH. Furthermore, if two oxygens are silanol groups, the structure will be R--SiO _1/2 (--OH) ₂ . Comparing these structures, more oxygen atoms forming a bridge structure with Si atoms is closer to the silica structure represented by SiO ₂ . Therefore, the more the —SiO _3/2 skeleton is, the lower the surface free energy of the toner particle surface can be, resulting in excellent environmental stability and member contamination resistance.

In addition, due to the durability due to the structure represented by formula (1) and the hydrophobicity and chargeability of R in formula (1), a low molecular weight (Mw of 1000 or less) resin that is present inside the surface layer and is easy to seep out. , and low glass transition temperature (Tg is 40° C. or lower) resin bleeding is suppressed. Bleeding of the release agent can also be suppressed in some cases.

The ratio of the peak area of the structure represented by formula (1) depends on the type and amount of the organosilicon compound used to form the organosilicon polymer, and the reaction temperature of hydrolysis, addition polymerization, and condensation polymerization during the formation of the organosilicon polymer. , reaction time, reaction solvent and pH.

In the structure represented by formula (1), R is a hydrocarbon group having 1 to 6 carbon atoms. This tends to stabilize the charge amount. An aliphatic hydrocarbon group having 1 to 6 carbon atoms or a phenyl group, which is particularly excellent in environmental stability, is preferable.

In the embodiment of the present invention, R is more preferably an aliphatic hydrocarbon group having 1 or more and 3 or less carbon atoms in order to further improve chargeability and antifogging. If the chargeability is good, the transferability is good and the amount of residual toner after transfer is small, so that the contamination of the drum, the charging member and the transfer member is improved.
Preferred examples of the aliphatic hydrocarbon group having 1 to 3 carbon atoms include a methyl group, an ethyl group, a propyl group and a vinyl group. From the viewpoint of environmental stability and storage stability, R is more preferably a methyl group.

A sol-gel method is preferable as an example of the production of the organosilicon polymer. The sol-gel method is a method of hydrolyzing and condensation-polymerizing a liquid raw material as a starting raw material to form a sol state and then gelling, and is used in a method of synthesizing glasses, ceramics, organic-inorganic hybrids, and nanocomposites. By using this production method, functional materials in various shapes such as surface layers, fibers, bulk bodies, and fine particles can be produced from the liquid phase at low temperatures.

Specifically, the organosilicon polymer present on the surface layer of the toner particles is preferably produced by hydrolysis and polycondensation of a silicon compound represented by alkoxysilane.
By providing the surface layer containing the organosilicon polymer on the toner particles, it is possible to obtain a toner with improved environmental stability, less deterioration in toner performance during long-term use, and excellent storage stability. .

Furthermore, the sol-gel method starts from a liquid and forms a material by gelling the liquid, so various microstructures and shapes can be produced. In particular, when the toner particles are produced in an aqueous medium, the particles are easily precipitated on the surface of the toner particles due to the hydrophilicity of the hydrophilic group such as the silanol group of the organosilicon compound. The fine structure and shape can be adjusted by the reaction temperature, reaction time, reaction solvent, pH, the type and amount of the organometallic compound, and the like.

The organosilicon polymer is preferably a polycondensation product of an organosilicon compound having a structure represented by the following formula (Z).

（式（Ｚ）中、Ｒ_１は、炭素数１以上６以下の炭化水素基を表し、Ｒ_２、Ｒ_３及びＲ_４は、それぞれ独立して、ハロゲン原子、ヒドロキシ基、アセトキシ基、又は、アルコキシ基を表す。）

(In formula (Z), R ₁ represents a hydrocarbon group having 1 to 6 carbon atoms; R ₂ , R ₃ and R ₄ each independently represent a halogen atom, a hydroxy group, an acetoxy group, or represents an alkoxy group.)

Hydrophobicity can be improved by the hydrocarbon group (preferably alkyl group) of R ₁ , and toner particles with excellent environmental stability can be obtained. An aryl group, such as a phenyl group, which is an aromatic hydrocarbon group can also be used as the hydrocarbon group. When the hydrophobicity of R ₁ is large, the charge amount tends to increase in various environments. Therefore, in view of environmental stability, R ₁ is preferably an aliphatic hydrocarbon group having 1 or more and 3 or less carbon atoms. It is preferably a methyl group, more preferably a methyl group.

R ₂ , R ₃ and R ₄ are each independently a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group (hereinafter also referred to as a reactive group). These reactive groups form a crosslinked structure through hydrolysis, addition polymerization, and condensation polymerization, and a toner excellent in member contamination resistance and development durability can be obtained. From the viewpoint of moderate hydrolyzability at room temperature and deposition and coating properties on the surface of toner particles, an alkoxy group having 1 to 3 carbon atoms is preferable, and a methoxy group or an ethoxy group is more preferable. preferable. Also, the hydrolysis, addition polymerization and condensation polymerization of R ₂ , R ₃ and R ₄ can be controlled by reaction temperature, reaction time, reaction solvent and pH.

In order to obtain the organosilicon polymer used in the embodiment of the present invention, three reactive groups (R ₂ , R ₃ and R ₄ ) in one molecule excluding R ₁ in the formula (Z) shown above Organosilicon compounds (hereinafter also referred to as trifunctional silanes) may be used singly or in combination.

Examples of the above formula (Z) include the following.
Methyltrimethoxysilane, Methyltriethoxysilane, Methyldiethoxymethoxysilane, Methylethoxydimethoxysilane, Methyltrichlorosilane, Methylmethoxydichlorosilane, Methylethoxydichlorosilane, Methyldimethoxychlorosilane, Methylmethoxyethoxychlorosilane, Methyldiethoxychlorosilane, Methyl triacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxysilane trifunctional methylsilanes such as hydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane;
ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltri Trifunctional such as methoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane sex silane.
Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, phenyltrihydroxysilane.

Moreover, an organosilicon polymer obtained by using the following together with an organosilicon compound having a structure represented by formula (Z) may be used to the extent that the effects of the present invention are not impaired. An organosilicon compound with four reactive groups in one molecule (tetrafunctional silane), an organosilicon compound with two reactive groups in one molecule (bifunctional silane), or an organosilicon compound with one reactive group ( monofunctional silane). Examples include the following.

dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriemethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-(2-amino ethyl)aminopropyltriethoxysilane, vinyltriisocyanatesilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinylethoxydihydroxysilane, vinyldimethoxyhydroxysilane, vinylethoxymethoxyhydroxysilane, Trifunctional vinylsilanes, such as vinyldiethoxyhydroxysilane.

Furthermore, the content of the organosilicon polymer in the toner particles is preferably 0.5% by mass or more and 10.5% by mass or less.
When the content of the organosilicon polymer is 0.5% by mass or more, the surface free energy of the surface layer can be further reduced, the fluidity can be improved, and the member contamination and fogging can be suppressed. . Charge-up can be made difficult to occur because it is 10.5% by mass or less. The content of the organosilicon polymer is controlled by the type and amount of the organosilicon compound used to form the organosilicon polymer, the method of producing toner particles during the formation of the organosilicon polymer, reaction temperature, reaction time, reaction solvent and pH. can be done.

It is preferable that the surface layer and the toner particles are in contact with each other without gaps. As a result, the occurrence of bleeding due to the resin component, release agent, etc. inside the toner particles is suppressed from the surface layer of the toner particles, and a toner excellent in storage stability, environmental stability and development durability can be obtained. In addition to the organosilicon polymer described above, the surface layer may contain resins such as styrene-acrylic copolymer resins, polyester resins and urethane resins, and various additives.

The suspension polymerization method described above will be described in more detail.
As the polymerizable monomer, the following vinyl-based polymerizable monomers can be preferably exemplified.
Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- styrene derivatives such as n-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene; methyl acrylate; , ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n - acrylic polymerizable monomers such as nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate , n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate , diethyl phosphate ethyl methacrylate, methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl esters such as vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone.

As the dispersion stabilizer for the sparingly water-soluble inorganic compound, one containing any one of magnesium, calcium, barium, zinc, aluminum and phosphorus is preferably used. More preferably, one of magnesium, calcium, aluminum and phosphorus is desired. Specifically, the following are mentioned.
Magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, hydroxyapatide.
Organic compounds such as polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salts of carboxymethyl cellulose, and starch may be used in combination with the dispersion stabilizer. It is preferable to use 0.01 parts by mass or more and 2.00 parts by mass or less of these dispersion stabilizers with respect to 100 parts by mass of the polymerizable monomer.
Furthermore, in order to make these dispersion stabilizers finer, 0.001 parts by mass or more and 0.1 parts by mass or less of a surfactant may be used together with 100 parts by mass of the polymerizable monomer. Specifically, commercially available nonionic, anionic, and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate and calcium oleate are preferably used.

An oil-soluble initiator is generally used as the polymerization initiator used in the suspension polymerization method. For example:
2,2'-azobisisobutyronitrile, 2,2'-azobis-2,4-dimethylvaleronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4 - azo compounds such as methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropyl peroxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, tert- Butyl peroxy-2-ethylhexanoate, benzoyl peroxide, tert-butyl peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl hydroperoxide, di-tert-butylperoxide peroxide initiators such as oxide, tert-butyl peroxypivalate and cumene hydroperoxide;
If necessary, a water-soluble initiator may be used in combination with the polymerization initiator, and examples thereof include the following. ammonium persulfate, potassium persulfate, 2,2'-azobis(N,N'-dimeleneisobutyroamidine) hydrochloride, 2,2'-azobis(2-aminodinopropane) hydrochloride, azobis(isobutylamidine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

These polymerization initiators can be used singly or in combination, and in order to control the degree of polymerization of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor, etc. can be further added and used.

Here, in the case of forming the surface layer having the organosilicon polymer, in the case of forming the toner particles in the aqueous medium, the hydrolyzate of the organosilicon compound is added as described above while performing the polymerization process in the aqueous medium. can be added to form the surface layer. The surface layer may be formed by adding a hydrolyzate of an organosilicon compound to the polymerized toner particle dispersion as the core particle dispersion. In the case of a kneading pulverization method other than an aqueous medium, the obtained toner particles are dispersed in an aqueous medium and used as a core particle dispersion, and the hydrolyzate of the organosilicon compound is added as described above to form the surface layer. can be formed.

(Method for preparing THF-insoluble portion of toner particles for NMR measurement)
The tetrahydrofuran (THF)-insoluble portion of the toner particles was prepared as follows.
10.0 g of toner particles are weighed, placed in a thimble (No. 86R manufactured by Toyo Roshi Kaisha Ltd.), and placed in a Soxhlet extractor. Extraction was performed using 200 mL of THF as a solvent for 20 hours, and the filtered matter in the thimble was vacuum-dried at 40° C. for several hours.

When the surface of the toner particles is treated with an external additive or the like, the external additive is removed by the following method to obtain toner particles.
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a concentrated sucrose solution. 31 g of the sucrose concentrate and Contaminon N (a pH 7 neutral detergent for cleaning precision measuring instruments consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) are placed in a centrifugation tube (capacity 50 mL). 6 mL of a mass % aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion. 1.0 g of toner is added to this dispersion, and clumps of toner are loosened with a spatula or the like.
The centrifuge tube is shaken on a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution is transferred to a swing rotor glass tube (capacity 50 mL) and separated in a centrifuge (manufactured by H-9R Kokusan Co., Ltd.) at 3500 rpm for 30 minutes. This operation separates the toner particles from the detached external additive. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the separated toner on the uppermost layer is collected with a spatula or the like. After filtering the collected toner with a vacuum filter, it is dried with a dryer for 1 hour or more to obtain toner particles. This operation is carried out multiple times to ensure the required amount.

(Confirmation method of the structure represented by formula (1))
The following method is used to confirm the structure represented by formula (1) in the organosilicon polymer contained in the toner particles.
The hydrocarbon group represented by R in formula (1) was confirmed by 13C-NMR.

<< ¹³ C-NMR (solid) measurement conditions >>
Device: JNM-ECX500II manufactured by JEOLRESONANCE
Sample tube: 3.2 mmφ
Sample: 150 mg of tetrahydrofuran-insoluble matter of toner particles for NMR measurement
Measurement temperature: Room temperature Pulse mode: CP/MAS
Measurement nuclear frequency: 123.25 MHz ( ¹³ C)
Reference substance: adamantane (external standard: 29.5 ppm)
Sample rotation speed: 20 kHz
Contact time: 2ms
Delay time: 2s
Accumulated times: 1024 times

In this method, a methyl group (Si—CH ₃ ), an ethyl group (Si—C ₂ H ₅ ), a propyl group (Si—C ₃ H ₇ ), a butyl group (Si—C ₄ H ₉ ), pentyl group (Si—C ₅ H ₁₁ ), hexyl group (Si—C ₆ H ₁₃ ) or phenyl group (Si—C ₆ H ₅ —), etc. The hydrocarbon group represented by R was confirmed.

<<Method for calculating the ratio of the peak area attributed to the structure of formula (1) in the organosilicon polymer contained in the toner particles>>
²⁹ Si-NMR (solid) measurement of the THF-insoluble portion of the toner particles is performed under the following measurement conditions.

<< ²⁹ Si-NMR (solid) measurement conditions >>
Device: JNM-ECX500II manufactured by JEOLRESONANCE
Sample tube: 3.2 mmφ
Sample: 150 mg of tetrahydrofuran-insoluble matter of toner particles for NMR measurement
Measurement temperature: Room temperature Pulse mode: CP/MAS
Measured nuclear frequency: 97.38 MHz ( ²⁹ Si)
Reference substance: DSS (external standard: 1.534 ppm)
Sample rotation speed: 10 kHz
Contact time: 10ms
Delay time: 2s
Accumulated times: 2000 to 8000 times

After the above measurement, a plurality of silane components having different substituents and bonding groups in the tetrahydrofuran-insoluble portion of the toner particles were peak-separated into the following X1 structure, X2 structure, X3 structure, and X4 structure by curve fitting. Calculate area.
X1 structure: (Ri) (Rj) (Rk) SiO _1/2 (2)
X2 structure: (Rg)(Rh)Si(O _1/2 ) ₂ (3)
X3 structure: RmSi(O _1/2 ) ₃ (4)
X4 structure: Si(O _1/2 ) ₄ (5)

(Ri, Rj, Rk, Rg, Rh, and Rm in formulas (2), (3), and (4) are bonded to silicon, organic groups such as hydrocarbon groups having 1 to 6 carbon atoms, halogen atoms , indicates a hydroxy group, an acetoxy group, or an alkoxy group.)
In the embodiment of the present invention, in the chart obtained by ²⁹ Si-NMR measurement of the THF-insoluble portion of the toner particles, the ratio of the peak area attributed to the structure of formula (1) to the total peak area of the organosilicon polymer It is preferable that the ratio is 20% or more.
When the structure represented by the above formula (1) needs to be confirmed in more detail, it may be identified by the measurement results of ¹ H-NMR together with the measurement results of ¹³ C-NMR and ²⁹ Si-NMR.

(Method for measuring the proportion of surface layers containing an organosilicon polymer having a thickness of 2.5 nm or less, measured by cross-sectional observation of toner particles using a transmission electron microscope (TEM))
In the embodiment of the present invention, cross-sectional observation of toner particles is performed by the following method.
As a specific method for observing the cross section of the toner particles, the toner particles are sufficiently dispersed in a room-temperature-curable epoxy resin, and then cured in an atmosphere of 40° C. for 2 days. A flaky sample is cut from the obtained cured product using a microtome equipped with diamond teeth. This sample is magnified by a magnification of 10,000 to 100,000 times with a transmission electron microscope (JEM-2800 manufactured by JEOL) (TEM) to observe the cross section of the toner particles.
This can be confirmed by utilizing the difference in atomic weight between the binder resin and the surface layer material, and by utilizing the fact that the greater the atomic weight, the brighter the contrast. Ruthenium tetroxide staining and osmium tetroxide staining are used to provide contrast between materials.
The particles used for the measurement are those whose circle-equivalent diameter Dtem is obtained from the cross section of the toner particles obtained from the TEM micrograph, and whose value is within ±10% of the weight-average particle diameter D4 of the toner particles. and
As described above, using JEM-2800 manufactured by JEOL, a dark field image of the cross section of the toner particles is obtained at an accelerating voltage of 200 kV. Next, using an EELS detector GIFQuantam manufactured by Gatan, a mapping image is acquired by the Three Window method to confirm the surface layer.
Next, for one toner particle whose circle-equivalent diameter Dtem is within ±10% of the weight-average particle diameter D4 of the toner particle, the long axis L of the toner particle cross section and an axis perpendicular to the center of the long axis L The cross section of the toner particles is evenly divided into 16 with the intersection point of L90 as the center (see FIG. 5). Next, let An (n=1 to 32) be the division axis extending from the center to the surface layer of the toner particle, RAn be the length of the division axis, and FRAn be the thickness of the surface layer.
Then, the ratio of the number of dividing axes having a surface layer containing the organosilicon polymer having a thickness of 2.5 nm or less among the 32 dividing axes is obtained. For averaging, 10 toner particles are measured and the average per toner particle is calculated.

(Circle equivalent diameter (Dtem) obtained from a cross section of toner particles obtained from a transmission electron microscope (TEM) photograph)
The circle equivalent diameter (Dtem) obtained from the cross section of the toner particles obtained from the TEM photograph is obtained by the following method. First, for one toner particle, the equivalent circle diameter Dtem obtained from the cross section of the toner particle obtained from the TEM photograph is obtained according to the following formula.
[Circle equivalent diameter (Dtem) obtained from the cross section of toner particles obtained from a TEM photograph]=(RA1+RA2+RA3+RA4+RA5+RA6+RA7+RA8+RA9+RA10+RA11+RA12+RA13+RA14+RA15+RA16+RA17+RA18+RA19+RA20+RA21+RA22+RA23+RA24+RA25+RA23+RA26+RA23+RA26+RA23+RA26+RA27/RA27)
Equivalent circle diameters of 10 toner particles are obtained, and the average value per particle is calculated as the equivalent circle diameter (Dtem) obtained from the cross section of the toner particles.

(Proportion of surface layer containing organosilicon polymer having a thickness of 2.5 nm or less)
[Percentage of surface layer containing organosilicon polymer having thickness (FRAn) of 2.5 nm or less]=[{Number of splitting axes having surface layer containing organosilicon polymer having thickness (FRAn) of 2.5 nm or less] }/32]×100
This calculation is performed for 10 toner particles, and the average value of the ratio of the 10 toner particles having a surface layer thickness (FRAn) of 2.5 nm or less is obtained.
. A ratio of 5 nm or less was used.

<Method for measuring fixation rate of organosilicon polymer>
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a concentrated sucrose solution. 31 g of the concentrated sucrose solution and Contaminon N (a pH 7 neutral detergent for cleaning precision measuring instruments consisting of a nonionic surfactant, an anionic surfactant, and an organic builder) were placed in a centrifugation tube (capacity: 50 ml). 6 mL of a mass % aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) is added to prepare a dispersion. 1.0 g of toner is added to this dispersion, and clumps of toner are loosened with a spatula or the like.
The centrifuge tube is shaken on a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, the solution is replaced in a swing rotor glass tube (capacity 50 mL) and separated in a centrifuge (H-9R manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 minutes. It is visually confirmed that the toner and the aqueous solution are sufficiently separated, and the separated toner on the uppermost layer is collected with a spatula or the like. After the collected aqueous solution containing the toner is filtered with a vacuum filter, it is dried with a dryer for 1 hour or longer. The dried product is pulverized with a spatula, and the amount of silicon is measured with fluorescent X-rays. The fixation rate (%) is calculated from the ratio of the amount of the element to be measured between the toner after washing and the toner before washing.

Fluorescent X-ray measurement of each element conforms to JIS K 0119-1969, but is specifically as follows.
As a measurement device, a wavelength dispersive X-ray fluorescence spectrometer "Axios" (manufactured by PANalytical) and attached dedicated software "SuperQ ver.4.0F" (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data ) is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 10 mm, and the measurement time is 10 seconds. A proportional counter (PC) is used to measure light elements, and a scintillation counter (SC) is used to measure heavy elements.
As a measurement sample, about 1 g of the toner after washing with water and the initial toner was placed in a dedicated press aluminum ring with a diameter of 10 mm, and the toner was flattened. ), pressurized at 20 MPa for 60 seconds, and used pellets molded to a thickness of about 2 mm.
Measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and the concentration is calculated from the count rate (unit: cps), which is the number of X-ray photons per unit time.
As a method for quantifying the amount of silicon in the toner, for example, silica (SiO ₂ ) fine powder is added to 100 parts by mass of toner particles so as to be 0.5 parts by mass, and the mixture is sufficiently mixed using a coffee mill. do. Similarly, 2.0 parts by mass and 5.0 parts by mass of fine silica powder are mixed with the toner particles, respectively, and these are used as samples for the calibration curve.
For each sample, a pellet of the sample for the calibration curve was prepared as described above using a tablet press, and when PET was used as the analyzing crystal, the diffraction angle (2θ) was observed at 109.08°. The count rate (unit: cps) of Si-Kα ray is measured. At this time, the acceleration voltage and current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A linear function calibration curve is obtained with the obtained X-ray count rate on the vertical axis and the amount of SiO ₂ added in each calibration curve sample on the horizontal axis.
Next, the toner to be analyzed is made into pellets as described above using a tablet press, and the Si--Kα ray count rate of the pellets is measured. Then, the content of the organosilicon polymer in the toner is determined from the above calibration curve. The ratio of the elemental amount of the toner after washing to the elemental amount of the toner before washing calculated by the above method was obtained and defined as the fixation rate (%).

<Toner production example>
The third embodiment will be specifically described below, but the present invention is not limited to these examples. All "parts" of each material in Examples and Comparative Examples are based on mass unless otherwise specified.

(Preparation step of aqueous medium 1)
To 1000.0 parts of ion-exchanged water in a reaction vessel, 14.0 parts of sodium phosphate (12 hydrate, manufactured by Rasa Kogyo Co., Ltd.) was added, and the mixture was kept at 65° C. for 1.0 hour while purging with nitrogen.
T. K. Using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12000 rpm, a calcium chloride aqueous solution in which 9.2 parts of calcium chloride (dihydrate) is dissolved in 10.0 parts of ion-exchanged water is mixed together. to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 10% by mass hydrochloric acid was added to the aqueous medium to adjust the pH to 5.0, and an aqueous medium 1 was obtained.

(Hydrolysis step of organosilicon compound for surface layer)
60.0 parts of ion-exchanged water was weighed into a reactor equipped with a stirrer and a thermometer, and the pH was adjusted to 3.0 using 10% by mass hydrochloric acid. This was heated with stirring to bring the temperature to 70°C. Thereafter, 40.0 parts of methyltriethoxysilane, which is an organosilicon compound for the surface layer, was added and hydrolyzed by stirring for 2 hours or more. The end point of the hydrolysis was visually confirmed by confirming that the oil and water did not separate and became one layer, and then cooled to obtain a hydrolyzate of the organosilicon compound for the surface layer.

(Preparation step of polymerizable monomer composition)
- Styrene 60.0 parts - C.I. I. Pigment Blue 15:3 6.5 parts The material was put into an attritor (manufactured by Mitsui Miike Kakoki Co., Ltd.), and further dispersed using zirconia particles with a diameter of 1.7 mm at 220 rpm for 5.0 hours to disperse the pigment. A liquid was prepared. The following materials were added to the pigment dispersion.
・Styrene 20.0 parts ・n-butyl acrylate 20.0 parts ・Crosslinking agent (divinylbenzene) 0.3 parts ・Saturated polyester resin 5.0 parts (propylene oxide-modified bisphenol A (2 mol adduct) and terephthalic acid (molar ratio 10:12), glass transition temperature Tg = 68 ° C., weight average molecular weight Mw = 10000, molecular weight distribution Mw / Mn = 5.12)
- 7.0 parts of Fischer-Tropsch wax (melting point 78°C). K. A homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used to uniformly dissolve and disperse at 500 rpm to prepare a polymerizable monomer composition.

(Granulation process)
The temperature of the aqueous medium 1 is set to 70°C, T.I. K. While maintaining the rotation speed of the homomixer at 12000 rpm, the polymerizable monomer composition was charged into the aqueous medium 1, and 9.0 parts of t-butyl peroxypivalate as a polymerization initiator was added. The mixture was granulated for 10 minutes while maintaining 12000 rpm with the stirring device.

(Polymerization process)
After the granulation step, the agitator was changed to a propeller agitating blade, and while stirring at 150 rpm, the mixture was maintained at 70°C and polymerized for 5.0 hours. core particles were obtained. When the temperature of the slurry was cooled to 55° C. and the pH was measured, it was pH=5.0. While stirring was continued at 55° C., 20.0 parts of the hydrolyzate of the organosilicon compound for the surface layer was added to start forming the surface layer of the toner. After holding for 30 minutes as it is, the slurry was adjusted to pH=9.0 for completion of condensation using an aqueous sodium hydroxide solution and held for an additional 300 minutes to form a surface layer.

(Washing and drying process)
After completion of the polymerization step, the slurry of toner particles is cooled, hydrochloric acid is added to the slurry of toner particles to adjust the pH to 1.5 or less, and the mixture is left with stirring for 1 hour and then solid-liquid separated by a pressure filter to obtain toner particles. got cake. This was reslurried with ion-exchanged water to form a dispersion again, and then subjected to solid-liquid separation with the aforementioned filter. After reslurry and solid-liquid separation were repeated until the electrical conductivity of the filtrate became 5.0 μS/cm or less, solid-liquid separation was finally performed to obtain a toner particle cake.
The resulting toner particle cake was dried with a flash jet dryer (manufactured by Seishin Enterprise Co., Ltd.), and a multi-division classifier utilizing the Coanda effect was used to cut fine and coarse particles to obtain toner particles. The conditions for drying were blowing temperature of 90° C., outlet temperature of the dryer of 40° C., and supply speed of the toner particle cake was adjusted so that the outlet temperature would not deviate from 40° C. depending on the moisture content of the toner particle cake.

Silicon mapping is performed in the cross-sectional TEM observation of the toner particles, and the presence of silicon atoms in the surface layer and the ratio of the number of dividing axes having a thickness of 2.5 nm or less in the surface layer of the toner particles containing the organosilicon polymer is 20. 0% or less. In any of the toners of the following examples, the surface layer containing the organosilicon polymer was found to have silicon atoms in the surface layer by the same silicon mapping, and the ratio of the number of dividing axes having a thickness of 2.5 nm or less in the surface layer was 20. 0% or less. In this example, the obtained toner particles were used as the toner c as they were without externally adding at least inorganic silicon fine particles.

The fixation rate of the organosilicon polymer having the structure represented by the formula (1) covering the surfaces of the toner particles is preferably 30% or more and 100% or less. Further, in the example toner used in the present embodiment, the fixation rate of the organosilicon polymer having the structure represented by the formula (1), which coats the surface of the toner particles, was set to 30% or more. This is because the area of the surface layer where the organosilicon polymer does not exist increases, and the adhesion force between toner particles increases, resulting in a change in chargeability.

In Embodiment 3, a toner in which the surfaces of the toner particles are coated with an organic silicon polymer is used instead of externally adding inorganic silicon fine particles or fine particles containing an organic silicon polymer. The organosilicon polymer is less likely to come off from the toner (higher fixation rate) than in the case of using a toner to which inorganic silicon fine particles or fine particles containing an organosilicon polymer are externally added. Therefore, only the metal soap can be efficiently supplied to the grooves of the photoreceptor, and the effect of suppressing image deletion by the metal soap can be maintained.

<Example>
In Embodiment 3, toners c to e were prepared by using the above toner manufacturing method so that the fixation ratio of the organosilicon polymer was different.
The fixation rate varies depending on the toner production conditions. In this embodiment, toners with different fixation rates were produced by changing the conditions for adding the hydrolyzate in the polymerization step and the holding time after the addition. The slurry was adjusted with hydrochloric acid and an aqueous solution of sodium hydroxide. Table 8 shows the conditions for producing toners with different fixing rates.
Toners c to e produced by the above method were treated with zinc stearate as metal soap in the same manner as in Embodiment 1 so that the content in the toner was 0.20 mass %.

Combinations of toners and photosensitive members as shown in Table 9 were prepared.

(experiment)
In order to confirm the occurrence of smeared images in Examples 1 and 4 to 7, 10,000 sheets of paper were continuously fed per day at a printing rate of 1%, and then left in the machine for one day to compare the presence or absence of smeared images after standing.
The image deletion test was evaluated by printing a halftone image on one sheet. Evaluation is as follows.
〇: Not generated (no white spots due to latent image dullness or outline blurring at image borders in the entire image)
×: Occurred (overall or part of the image due to latent image dullness and outline blurring at image boundaries)
Paper threading and testing were performed in an environment of 32° C. and 80% RH. The total number of sheets passed was up to 100,000 sheets.
Also, the photosensitive member surface speed was 296 mm/s, the developing roller surface speed was 425 mm/s, the photosensitive member surface potential was −500 V, the voltage applied to the developing roller was −350 V, the voltage of the supply roller was −450 V, and the voltage of the regulating member was −450 V.
Experimental results are shown in Table 10.

As shown in Table 10, in Examples 5 to 7 using the toner in which the surface of the toner particles was coated with the organosilicon polymer, the image flow was good throughout the experiment. On the other hand, in Example 1 using the toner having inorganic silicon fine particles on the surface of the toner particles, although the image quality was good up to 50,000 sheets, image deletion occurred after 60,000 sheets. Further, in Example 4 using the toner having fine particles containing an organosilicon polymer on the surface of the toner particles, although the image quality was good up to 80,000 sheets, image deletion occurred after 90,000 sheets.
This can be considered as follows. If the fixing rate of the inorganic silicon fine particles and the fixing rate of the organic silicon polymer are low, they are easily released from the toner. Since the free inorganic silicon fine particles and the free organic silicon polymer are also supplied to the grooves on the surface of the photoreceptor in the same way as the metal soap, the inorganic silicon fine particles and the organic silicon polymer are not supplied to the grooves even though it is originally desired to supply the metal soap to the grooves. fills the gap. It is thought that the amount of metal soap supplied to the grooves is reduced when the inorganic silicon fine particles and the organic silicon polymer enter the grooves of the photoreceptor, and the effect of the metal soap in suppressing image deletion is reduced.

In order to maintain the effect of suppressing image deletion by the metallic soap, it is preferable that the fixation rate is 90% or more, 95% or more, or 97% or more as in Examples 5-7.
However, when inorganic silicon fine particles or fine particles containing an organic silicon polymer are present on the toner surface, it is difficult to obtain a fixation rate higher than 90% by the above-described method. On the other hand, a toner in which the surfaces of the toner particles are coated with an organosilicon polymer can achieve this fixing rate. It is also a preferred embodiment that the toner does not use inorganic silicon fine particles as an external additive.

1: Photoreceptor 2: Charging roller 3: Developing device 18a: Developing chamber 18b: Toner storage chamber 4: Developing roller 5: Supply roller 6: Toner amount regulating member 7: Process cartridge 8: Cleaning blade 9a: Waste toner storage chamber 10: Toner 12: Recording material 13: Photoreceptor unit 30: Scanner unit 31: Intermediate transfer belt 32: Primary transfer roller 33: Secondary transfer roller 34 : Fixing device 35: Cleaning device for intermediate transfer body 40: Polishing sheet 41: Backup roller 45: Inorganic particle externally added toner 45a: Toner particles 45b: Inorganic silicon fine particles 100: Image forming apparatus 101: Toner processing device (surface modification device), 110: processing chamber (processing tank), 110a: inner peripheral surface (inner wall), 111: drive shaft, 120: stirring blade, 121: blade portion, 130: rotating body, 131: Body of rotation 131a: Outer peripheral surface 132: Processing part 133: Processing surface 133a: First portion closest to the body of rotation 133b: The length from the center of the drive shaft is 80% of the radius of the inner peripheral surface (0.8L), 150: drive motor, 160: control unit, R: direction of rotation, θ: size of angle downstream of direction of rotation R, a: body of rotator A line connecting the nearest first portion and the second portion located at a position where the length from the drive shaft is 80% of the radius of the inner peripheral surface, b: a line of a circle centered on the drive shaft and passing through the second portion tangent at the second part

Claims (9)

A process cartridge used in an image forming apparatus,
a rotatable image carrier having a peripheral surface on which a latent image is formed;
developing means for supplying a developer to the image carrier for developing the latent image on the image carrier;
a cleaning member that contacts the peripheral surface of the image carrier to clean the peripheral surface;
The developer is
containing toner particles and a toner having a metallic soap;
The image carrier has a peripheral surface on which a plurality of grooves extending in the peripheral direction of the peripheral surface are formed so as to be aligned in the rotation axis direction. Rz) is 0 . 10 ≤ Rz ≤ 0.70 (μm), and the average interval (Sm) of the unevenness of the peripheral surface is 5 ≤ Sm ≤ 70.0 (μm) ,
The peripheral surface has a ten-point average surface roughness of the peripheral surface of the image carrier smaller than the average particle size of the metallic soap, and the metallic soap is supplied from the toner to the grooves on the surface of the image carrier. , wherein the metal soap has an average particle size of 0.15 μm or more and 2.00 μm or less . 2. A process cartridge according to claim 1, wherein said toner has inorganic silicon fine particles present on the surface of said toner particles. 3. A process cartridge according to claim 1 , wherein said metallic soap contains at least one metal selected from the group consisting of zinc, calcium and magnesium. 4. The process cartridge according to claim 1 , wherein said metal soap is zinc stearate, calcium stearate or magnesium stearate. 5. The process cartridge according to any one of claims 1 to 4 , wherein said developing means is contact developing means for performing development by bringing a developer bearing member carrying said developer into contact with said image bearing member. . A process cartridge according to any one of claims 1 to 5 , wherein said image carrier has a protective layer as an outermost layer. a frame that rotatably supports the image carrier and to which the cleaning member is fixed;
The cleaning member has a plate-like elastic body and a plate-like support supporting the plate-like elastic body,
one end of the plate-shaped elastic body is fixed to the plate-shaped support, and the other end, which is a free end, is in contact with the peripheral surface;
One end of the plate-like support is fixed to the frame, and the plate-like elastic body is fixed to the other free end,
A direction extending from the one end of the plate-like support to the other end of the plate-like elastic body is opposite to a rotating direction of the image carrier at a portion where the other end contacts the peripheral surface. The process cartridge according to any one of claims 1 to 6 , characterized in that: 8. The image carrier according to any one of claims 1 to 7 , wherein, in a posture during use, the image carrier rotates so that the peripheral surface moves downward at a portion with which the cleaning member abuts. 1. The process cartridge according to 1. a device body;
a process cartridge according to any one of claims 1 to 8 , which is detachable from the apparatus main body;
An image forming apparatus comprising:

Images