JP2001242756A - Image forming method and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method and an image forming device for forming a highly durable and high-definition image, and more particularly to provide an image forming method and an image forming device for forming a highly durable and high-definition image by using an electrophotographic photoreceptor having a surface layer of high hardness. SOLUTION: The image forming method is characterized in that the toner remaining on an electrophotographic photoreceptor is cleaned by making a elastic rubber blade abut in the counter direction on the electrophotographic photoreceptor and making the elastic rubber blade vibrate in the magnitude of 10-200 μm, and that the turbidity of the toner is 50 or less, and the saturated water content of the toner at 30 deg.C and 80 RH% is 0.1-2.0 mass %.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method and an image forming apparatus, and more particularly, to an image forming method and an image forming apparatus used in a copier and a printer.

[0002]

2. Description of the Related Art In recent years, organic photoconductors have been widely used as electrophotographic photoconductors. Organic photoreceptors have advantages over other photoreceptors such as easy development of materials corresponding to various exposure light sources from visible light to infrared light, selection of materials without environmental pollution, and low manufacturing cost. However, the drawback is that the mechanical strength is weak, and the surface of the photoreceptor deteriorates and scratches occur when printing a large number of sheets.

The surface of an electrophotographic photosensitive member (hereinafter, also simply referred to as a photosensitive member) is directly applied with an electric or mechanical external force by a charging device, a developing device, a transfer means, a cleaning device, etc., so that the durability thereof is low. Required.

Specifically, the photoreceptor is required to have durability against abrasion and scratches on the surface of the photoreceptor due to friction, active oxygen such as ozone generated during corona charging, and surface deterioration due to nitrogen oxides.

Heretofore, as a subject for improving the durability of an organic photoreceptor, there has been a strong demand for suppressing the abrasion of an elastic rubber blade (cleaning rubber blade) due to abrasion. As an approach therefor, techniques such as providing a high-strength protective layer on the surface of the photoreceptor have been studied. For example, JP-A-9-190004 and JP-A-1-190004
Japanese Patent Application Laid-Open No. 0-251277 describes a photoreceptor using a siloxane resin excellent in strength for a surface layer. However, a protective layer using a siloxane resin has high strength and low abrasion. However, since the siloxane resin is a relatively hydrophilic resin, it has various problems in an image forming process of repeated use.

According to the studies made by the present inventors, an unreacted hydrolyzable group or silanol group is liable to remain on the film surface of an organosilicon-based siloxane resin crosslinked film, and the adsorption of water molecules in a high humidity environment is prevented. There are sensitive issues. If there are many unreacted groups, adsorption of water molecules and discharge products generated during charging is likely to occur in a high-humidity environment, and as a result, the surface resistance will decrease, and problems such as image blurring (also called image blurring) will occur. I do.

[0007] The above phenomenon is particularly noticeable in a portion located near the band electrode when the photoconductor is stopped. For example, in a heating device installed near the photoconductor, the image flow phenomenon is sufficiently suppressed to below the band electrode. It was difficult to do. This is considered that even if the operation of the apparatus is stopped, harmful substances such as active oxygen generated during the operation stop near the band electrode and accumulate on the surface of the photoconductor whose rotation has been stopped. A conventional heating device installed near the photoreceptor, such as blowing exhaust air, cannot uniformly heat the surface of the photoreceptor, and absorbs water molecules in a high-humidity environment or at a low temperature. Is considered insufficient to prevent

The inventors of the present invention have found that the phenomenon such as the image deletion is accelerated depending on the type of toner used for image formation. That is, when a toner having a large adhesive force between the toner and the photoconductor, for example, a toner having a high water content or a toner releasing fine powder smaller than the toner is used, the toner and the free fine powder are partially cleaned on the surface of the photoconductor. The cleaning member repeatedly passes through the cleaning portion without being cleaned, and as a result, filming occurs on the surface of the photoconductor under the influence of the pressing force of the cleaning portion. Image defects such as image deletion and black spots are likely to occur in the portion where the filming has occurred. In addition, since the filming occurrence surface and the non-occurrence surface have different abrasion speeds of the photoreceptor surface against abrasion by a cleaning blade or the like,
The photosensitive member is apt to cause a film thickness deviation. Further, it has been found that the photoreceptor having the siloxane resin easily causes these image defects even if the filming occurs slightly.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide an image forming method and an image forming apparatus having high durability and high image quality. More specifically, an electrophotographic photosensitive member having a surface layer of high hardness is provided. An object of the present invention is to provide a highly durable and high quality image forming method using a body and an image forming apparatus.

[0010]

That is, it has been found that the object of the present invention can be achieved by adopting any one of the following constitutions.

1. After transferring the toner image on the electrophotographic photoreceptor to a transfer material, in an image forming method for cleaning the toner remaining on the electrophotographic photoreceptor in a cleaning step, an elastic rubber blade is used in the cleaning step,
The elastic rubber blade is brought into contact with the electrophotographic photosensitive member in the counter direction, and the elastic rubber blade is
Vibration is performed at a vibration magnitude of 0 to 200 μm to clean the toner remaining on the electrophotographic photoreceptor, the turbidity of the toner used in the image forming method is 50 or less, and the toner is used at 30 ° C. An image forming method, wherein the saturated water content in an 80 RH% environment is 0.1% or more and 2.0% by mass or less.

2. 2. The image forming method according to the above item 1, wherein the electrophotographic photosensitive member has a heating device.

3. The electrophotographic photoreceptor has at least a plurality of resin layers on a cylindrical conductive support.
3. The image forming method according to the above item 1 or 2, wherein one is a resin layer containing a siloxane-based resin having a structural unit having charge transport performance and having a crosslinked structure.

4. 4. The image forming method according to the item 3, wherein the resin layer containing the siloxane-based resin is a surface layer.

[0015] 5. A siloxane-based resin having a structural unit having the charge transport performance, and a siloxane-based resin having a cross-linked structure, a hydroxyl group, or an organosilicon compound having a hydrolyzable group,
5. The image forming method according to the above item 3 or 4, wherein the image forming method is a siloxane-based resin obtained by reacting the compound represented by the general formula (1).

6. 6. The image forming method according to the above item 5, wherein Z in the general formula (1) is an oxygen atom.

[7] The image forming method according to any one of Items 3 to 6, wherein the resin layer containing the siloxane-based resin contains an antioxidant.

[8] 8. The image forming method according to the item 7, wherein the antioxidant is a hindered phenol antioxidant or a hindered amine antioxidant.

9. The image forming method according to any one of Items 3 to 8, wherein the resin layer containing the siloxane-based resin contains organic or inorganic particles.

[10] The image forming method according to any one of Items 3 to 9, wherein the resin layer containing the siloxane-based resin contains colloidal silica.

11. The image forming method according to any one of Items 1 to 10, wherein the turbidity of the toner is 30 or less.

12. The toner has a volume average particle size of 4 to 9 μm.
12. The image forming method according to any one of items 1 to 11, wherein the number of toner particles having a m of 3.0 μm or less is 30% by number or less.

13. Assuming that the particle diameter of the toner is D (μm), the natural logarithm InD is plotted on the horizontal axis, and the horizontal axis is set to 0.1.
A histogram showing the number-based particle size distribution divided into a plurality of classes at 23 intervals, and includes the relative frequency (m ₁ ) of the toner particles included in the most frequent class and the frequent class next to the most frequent class. Wherein the sum of relative frequencies (M) with the relative frequency (m ₂ ) of the toner particles is 70% or more.
3. The image forming method according to any one of 2.

14. In an image forming apparatus for cleaning toner remaining on the electrophotographic photosensitive member by a cleaning unit after transferring the toner image on the electrophotographic photosensitive member to a transfer material, an elastic rubber blade is used for the cleaning unit. A rubber blade is brought into contact with the electrophotographic photoreceptor in a counter direction, and the elastic rubber blade is vibrated at a vibration magnitude of 10 to 200 μm to clean toner remaining on the electrophotographic photoreceptor. The turbidity of the toner used in the image forming apparatus is 50 or less, and the saturated water content of the toner in a 30 ° C., 80 RH% environment is 0.1 to 2.0% by mass. Image forming device.

[15] In an image forming apparatus for cleaning toner remaining on the electrophotographic photosensitive member by a cleaning unit after transferring the toner image on the electrophotographic photosensitive member to a transfer material, an elastic rubber blade is used for the cleaning unit, A rubber blade is brought into contact with the electrophotographic photoreceptor in a counter direction, and the elastic rubber blade is vibrated at a vibration magnitude of 10 to 200 μm to clean toner remaining on the electrophotographic photoreceptor. The turbidity of the toner used in the image forming apparatus is 50 or less, and the saturated water content of the toner in a 30 ° C., 80 RH% environment is 0.1 to 2.0 mass%;
And an image forming apparatus, wherein the electrophotographic photosensitive member has a heating device.

16. In an image forming apparatus in which a toner image on an electrophotographic photoreceptor is transferred to a transfer material and toner remaining on the electrophotographic photoreceptor is cleaned by a cleaning means, the cleaning means has a hardness at 25 ± 5 ° C. according to JISA. At least 65 on a scale, 25 ° C ± 0.2 ° C
Using an elastic rubber blade of polyurethane rubber having a rebound resilience of 20 or more and 75 or less, contacting the elastic rubber blade with the electrophotographic photosensitive member in the counter direction, and Vibration is performed at a vibration magnitude of 10 to 200 μm to clean the toner remaining on the electrophotographic photosensitive member, and the turbidity of the toner used in the image forming apparatus is 50 or less. 0.1% saturated water content in 80 RH% environment
An image forming apparatus characterized by being at least 2.0 mass%.

The present invention will be described in more detail. By adopting the configuration of the present invention described above, the present inventors provide an image forming method for cleaning toner remaining on an electrophotographic photosensitive member with an elastic rubber blade. It is possible to prevent the blade turning up without excessively increasing the frictional force generated therebetween, effectively remove the toner remaining on the electrophotographic photosensitive member, and obtain a good and stable image for a long period of time. And found that it can be obtained.

An embodiment of an image forming method and an image forming apparatus applied to the present invention will be described below.

FIG. 1 is a schematic diagram showing the overall structure of the image forming apparatus of the present invention. The image forming apparatus shown in FIG.
The image forming apparatus is a digital image forming apparatus, and includes an image reading unit A, an image processing unit B (not shown), an image forming unit C, and a transfer paper transport unit D as a transfer paper transport unit.

An automatic document feeder for automatically feeding a document is provided above the image reading section A.
The original placed on the original 1 is moved by the original transport roller 12 to the original
The sheets are separated and conveyed, and the image is read at the reading position 13a. The document for which the reading of the document has been completed is discharged onto the document discharge tray 14 by the document conveying roller 12.

On the other hand, the image of the original when placed on the platen glass 13 is read out at a speed v of a first mirror unit 15 comprising an illumination lamp and a first mirror constituting a scanning optical system, and a V-shaped image is formed. Reading is performed by moving the second mirror unit 16 including the second mirror and the third mirror located at the speed v / 2 in the same direction.

The read image is formed on a light receiving surface of an image sensor CCD as a line sensor through a projection lens 17. The line-shaped optical image formed on the image sensor CCD is sequentially photoelectrically converted into an electric signal (brightness signal), and then A
After performing / D conversion and performing processing such as density conversion and filter processing in the image processing unit B, the image data is temporarily stored in the memory.

In the image forming section C, as an image forming unit, a drum-shaped photosensitive member (hereinafter, also referred to as a photosensitive drum) 21 serving as an image carrier, a charger 22 serving as charging means, and a developing means , A transfer unit 24 as a transfer unit, a separator 25 as a separation unit, a cleaning unit 26, and a PCL (precharge lamp) 27 are arranged in the order of operation. The photoreceptor 21 is formed by applying a photoconductive compound on a drum substrate. For example, an organic photoreceptor (OPC) is preferably used, and is driven to rotate clockwise in the drawing.

After the rotating photoconductor 21 is uniformly charged by the charger 22, the exposure optical system 30 performs image exposure based on the image signal called from the memory of the image processing unit B. The exposure optical system 30 serving as a writing unit uses a laser diode (not shown) as a light emitting light source, passes through a rotating polygon mirror 31, an fθ lens (no symbol), and a cylindrical lens (no symbol) to bend an optical path by a reflection mirror 32, thereby performing main scanning. The photoreceptor 21
Is subjected to image exposure at the position Ao,
A latent image is formed by one rotation (sub-scan). In one example of the present embodiment, a character portion is exposed to form a latent image.

The latent image on the photoconductor 21 is subjected to reversal development by the developing device 23, and a visible toner image is formed on the surface of the photoconductor 21. In the transfer paper transport section D, paper feed units 41 (A) and 41 serving as transfer paper storage means in which transfer papers P of different sizes are stored below the image forming unit.
(B) and 41 (C) are provided, and a manual paper feed unit 42 for performing manual paper feed is provided on the side, and the transfer paper P selected from any of them is supplied to a guide roller 43.
The transfer paper P is fed along the transport path 40, and the transfer paper P is temporarily stopped and then re-fed by a pair of registration rollers 44 for correcting the inclination and deviation of the fed transfer paper.
The toner image on the photoconductor 21 is transferred to the transfer paper P by the transfer device 24 at the transfer position Bo, being guided by the transport path 40, the pre-transfer roller 43a, and the transfer entry guide plate 46,
Next, the charge is removed by the separator 25, and the transfer paper P is separated from the surface of the photoconductor 21, and is conveyed to the fixing device 50 by the conveying device 45.

The fixing device 50 has a fixing roller 51 and a pressure roller 52. By passing the transfer paper P between the fixing roller 51 and the pressure roller 52, the transfer paper P is heated and pressed to remove toner. Weld. The transfer paper P on which the toner image has been fixed is discharged onto the discharge tray 64.

FIG. 2 is a front view showing the structure of the photosensitive member and its periphery in the image forming apparatus of the present invention. In FIG. 2, reference numeral 21 denotes a photoconductor, 71 denotes a heater serving as a heating element provided on an inner peripheral surface for heating the photoconductor 21, and 72 denotes a photoconductor temperature provided in contact with or near the outer periphery of the photoconductor. Is a temperature sensor as temperature detecting means for detecting the temperature.

As shown in FIG. 1, the image forming apparatus of the present invention has an environmental condition detecting means 73 for detecting the environmental condition of the environment in which the image forming apparatus is installed.
Is provided. The environmental condition detecting means 73 includes a temperature sensor 731 for detecting the temperature of the environment, and a humidity sensor 732 for detecting the humidity of the environment.

FIG. 3 is a view for explaining the mechanism of vibration of the elastic rubber blade. The elastic rubber blade 26A
In the present invention, the rebound resilience at 25 ° C. ± 0.2 ° C. is 20
It is made of polyurethane rubber of not less than 75 and is abutted on the photosensitive drum 21 in the counter direction as shown in FIG.
As the photosensitive drum rotates in the direction of the arrow, the photosensitive drum moves to a dotted line 26a in accordance with the mutual friction coefficient. However, due to the resilience of the blade, the photosensitive drum is step-slipped to a dotted line 26b, and the toner slips on the drum surface due to the step slip. Is removed and cleaned.

In the present invention, when performing the step slip, the magnitude of vibration K1 based on the measurement method described later is set to 10 to 20.
Vibration in the range of 0 μm. In the measurement method described later, the acceleration of the blade vibration is read by a piezo sensor 130 set at a position of about 3 mm from the blade tip as shown in FIG.
1 and the arithmetic processing 133 is performed to output the magnitude of blade vibration (the amplitude of the blade at the sensor set position) K μm. By comparing this data with K1 of 10 to 200 μm, it is determined whether the blade condition is appropriate or inappropriate.
Blade replacement or blade contact load P (g / cm),
The contact angle θ °, the free length 1 mm and the like are corrected so that image formation is performed under appropriate conditions.

In the present invention, if the magnitude of the vibration of the elastic rubber blade is smaller than 10 μm, the energy of the vibration becomes small, and the toner slips under the blade to cause image fogging. Is more likely to occur.

If the magnitude of the vibration is larger than 200 μm, the energy of the vibration of the blade becomes excessive, causing the blade to turn over or to bounce on the photoreceptor to generate horizontal line fog (black streaks). cause.

The measurement of the magnitude of the vibration of the elastic rubber blade is as follows. The sensor of the acceleration detector NP-3210 manufactured by Ono Sokki Co., Ltd. was attached to the center of the elastic rubber blade (3 mm from the tip), and the vibration when the photoconductor was rotated at a constant speed was read by the sensor for 10 seconds. The output data from the sensor is referred to as "ONO SO
The KKI CF6400 4-channel intelligent FF analyzer performs arithmetic processing to obtain an average value of the amplitude of the vibration, which is defined as the magnitude of the vibration of the blade.

Next, a description will be given with reference to FIG. 4 illustrating the cleaning mechanism. In the present invention, preferable values of the contact load P and the contact angle θ of the elastic rubber blade to the photoreceptor are P = 5 to 40 g / cm and θ = 5 to 35 °.

The elastic rubber blade free length L represents the length of the tip of the blade before deformation from the end of the support member 191 as shown in FIG. A preferred value of the free length is L = 6 to 15 mm. The thickness of the elastic rubber blade is preferably 0.5 to 10 mm.

The contact load P is a vector value in the normal direction of the pressing force P 'when the blade 26A is brought into contact with the photosensitive drum 21.

The contact angle θ represents the angle between the tangent line X at the contact point A of the photosensitive member and the blade before deformation (indicated by a dotted line in the drawing). 172 is a fixing screw for fixing the support member, and 193 is a load spring.

In the present invention, the vibration of the elastic rubber blade is set to 1
It has been found that by controlling and using the particles in the range of 0 to 200 μm, there is no reversal of the blade, the cleaning property is improved, and the abrasion of the photosensitive layer is reduced.

By simultaneously controlling the hardness and the rebound resilience of the physical properties of the elastic rubber blade for cleaning the resin layer of the present invention, the reversal of the blade can be suppressed more effectively. If the JISA hardness of the blade at 25 ± 5 ° C. is smaller than 65, the blade is likely to be inverted, and if it is larger than 80, the cleaning performance is reduced. When the rebound resilience exceeds 75, reversal of the blade tends to occur, and when the rebound resilience is 20 or less, the cleaning performance deteriorates. If the hardness and the rebound resilience do not satisfy the claims at the same time, the effect cannot be obtained. Further, the rebound resilience is preferably 20 or more and 40 or less. (Both the JISA hardness and the rebound resilience are measured based on the vulcanized rubber physical test method of JIS K6301. The value of the rebound resilience indicates%.) By controlling the hardness and rebound resilience of the elastic rubber blade, the blade is inverted for a long time. No stable cleaning performance can be maintained. As a result, it is possible to provide a highly durable image forming method with less wear and excellent cleaning properties. It can be suppressed effectively.

Urethane rubber, silicon rubber, fluorine rubber, chloropyrene rubber, butadiene rubber, and the like are known as materials for the elastic rubber blade used in the blade cleaning method. Of these, urethane rubber is other rubber. It is particularly preferred in that it has excellent wear characteristics as compared with For example, urethane rubber obtained by reacting and curing a polycaprolactone ester and a polyisocyanate described in JP-A-59-30574 is preferable.

Next, the structure for controlling the temperature of the photosensitive member according to the present invention will be described. FIG. 5 is a configuration diagram for temperature control according to the present invention. Temperature sensor 72 and temperature sensor 7
The temperature information detected by the environmental condition detecting means 73 including the humidity sensor 31 and the humidity sensor 732 and the environmental information including the environmental temperature and the environmental humidity are input to the control means 80, and the control means 80 determines the driving means based on the information. Energizing circuit 70
To control the temperature of the photoreceptor by controlling the heater 71.

In controlling the temperature of the photosensitive member of the present invention, a plurality of different control temperatures depending on the mode are applied.

It is preferable to apply a plurality of control temperatures according to the environmental conditions. The above-described temperature control of the photoconductor will be specifically described with reference to a temperature control flowchart.

FIG. 6 is a flowchart showing the flow of temperature control of the photosensitive member in the warm-up mode.

When it is detected by the mode management section 81 in FIG. 5 that the power is turned on (F1), a warm-up mode is selected and set to execute warm-up (F2). When the warm-up mode is set, the control unit 80 controls the temperature of the photoconductor. First, control is performed by the environmental condition detecting means 73 so as to detect the environmental temperature and humidity when the power is turned on (F
9). The detected environmental temperature information and humidity information are input to the control means 80, and based on the environmental information, the first control temperature is selected from the table of Table 1 and the second control temperature is selected from the table of Table 2. Then, the first control temperature and the second control temperature applied in the warm-up mode are set (F10). Hereinafter, in each mode, it is preferable to apply the first control temperature and the second control temperature set when the power is turned on, in order to simplify the control. The execution of the temperature control of the photoconductor is started with the set first control temperature and the second control temperature (F11). First, the heater 71 is turned on so that the photoconductor is at the second control temperature, and temperature control is performed so that the photoconductor is heated (F12). When it is detected that the temperature of the photoconductor has reached the second control temperature due to the heating (F13), the process is continued at the second control temperature for a predetermined time of 2 minutes, and the lapse of 2 minutes is detected (F14). ), The control temperature is switched to the first control temperature (F15) to lower the temperature of the photoconductor. First
It is detected that the temperature has decreased to the control temperature (F16).
Then, the warm-up of the photoconductor is completed (F17), and the temperature control of the photoconductor in the warm-up mode is ended.

The physical properties of the elastic rubber blade used for the elastic rubber blade; hardness and rebound resilience are measured as JISA hardness and rebound resilience based on the vulcanized rubber physical test method of JIS K6301.

<< Electrophotographic Photoreceptor >> The constitution of the photoreceptor preferably used in the present invention will be described below.

Conductive Support The conductive support used in the photoreceptor of the present invention may be in the form of a sheet or a cylinder. However, in order to design an image forming apparatus in a compact form, a cylindrical conductive support may be used. Supports are preferred.

The cylindrical conductive support of the present invention means a cylindrical support necessary for forming an image endlessly by rotating, and has a straightness of 0.1 mm or less and a runout of 0.1 mm or less. Conductive supports in the range are preferred. Exceeding the ranges of the roundness and the shake make it difficult to form a good image.

As the conductive material, a metal drum of aluminum, nickel, or the like, a plastic drum on which aluminum, tin oxide, indium oxide, or the like is deposited, or a paper or plastic drum coated with a conductive substance can be used. The conductive support preferably has a specific resistance of 10 ³ Ωcm or less at room temperature.

In the present invention, having at least a plurality of resin layers on the conductive support means that two or more layers in which the resin has a main function in forming the layers are on the conductive support. And, as the resin layer, an undercoat layer, a photosensitive layer, a surface layer,
Further, at least two layers out of layers such as the charge generation layer and the charge transport layer may be provided as resin layers.

Hereinafter, preferred layer constitutions of the electrophotographic photosensitive member of the present invention will be described. Undercoat Layer The undercoat layer (UCL) used in the photoreceptor of the present invention is used to improve the adhesion between the conductive support and the photosensitive layer or to prevent charge injection from the support. Is provided between the photosensitive layer, the material of the undercoat layer, polyamide resin, vinyl chloride resin, vinyl acetate resin,
Copolymer resins containing two or more of the repeating units of these resins are exemplified. Among these undercoat resins, a polyamide resin is preferable as a resin capable of reducing an increase in residual potential due to repeated use. The thickness of the undercoat layer using these resins is preferably 0.01 to 0.5 μm.

The undercoat layer most preferably used in the present invention is an undercoat layer using a curable metal resin obtained by thermosetting an organic metal compound such as a silane coupling agent or a titanium coupling agent. The thickness of the undercoat layer using a curable metal resin is preferably 0.1 to 2 μm.

Photosensitive Layer The photosensitive layer of the photoreceptor of the present invention may have a single-layer structure in which a charge generation function and a charge transport function are provided in one layer on the undercoat layer, but more preferably. It is preferable that the function of the photosensitive layer is separated into a charge generation layer (CGL) and a charge transport layer (CTL layer). By adopting a configuration in which functions are separated, an increase in residual potential due to repeated use can be controlled to be small, and other electrophotographic characteristics can be easily controlled according to the purpose. It is preferable that the photoreceptor for negative charging has a configuration in which a charge generation layer (CGL) is provided on the undercoat layer, and a charge transport layer (CTL layer) is provided thereon. In the case of a positively charged photoreceptor, the order of the layer configuration is opposite to that of the negatively charged photoreceptor. The most preferred photosensitive layer structure of the present invention is a negatively charged photosensitive member having the function-separated structure.

The structure of the photosensitive layer of the function-separated negatively charged photosensitive member will be described below. Charge generation layer Charge generation layer: The charge generation layer contains a charge generation material (CGM). As other substances, a binder resin and other additives may be contained as necessary.

As the charge generating material (CGM), a known charge generating material (CGM) can be used. For example, phthalocyanine pigments, azo pigments, perylene pigments, azurenium pigments, and the like can be used. Among them, CGM that can minimize the increase in residual potential due to repeated use
Has a steric and potential structure capable of forming a stable aggregation structure between a plurality of molecules, and specifically includes CGM of a phthalocyanine pigment and a perylene pigment having a specific crystal structure. For example, Bragg angle 2θ for Cu-Kα ray
CGM such as titanyl phthalocyanine having a maximum peak at 27.2 °, and benzimidazole perylene having a maximum peak at 2θ of 12.4 have almost no deterioration due to repeated use, and the residual potential increase can be reduced.

When a binder is used as the CGM dispersion medium in the charge generation layer, a known resin can be used as the binder, but the most preferable resin is a formal resin, a butyral resin, a silicon resin, a silicon-modified butyral resin, a phenoxy resin. Resins. The ratio between the binder resin and the charge generating substance is preferably from 20 to 600 parts by mass per 100 parts by mass of the binder resin.
By using these resins, the increase in residual potential due to repeated use can be minimized. The thickness of the charge generation layer is preferably from 0.01 μm to 2 μm.

Charge transport layer Charge transport layer: The charge transport layer contains a charge transport material (CTM) and a binder resin for dispersing the CTM to form a film.
As other substances, additives such as antioxidants may be contained as necessary.

As the charge transport material (CTM), a known charge transport material (CTM) can be used. For example, triphenylamine derivatives, hydrazone compounds, styryl compounds, benzidine compounds, butadiene compounds and the like can be used. These charge transport materials are usually dissolved in a suitable binder resin to form a layer. Among these, the CTM that can minimize the increase in residual potential due to repeated use has a high mobility and a characteristic in which the ionization potential difference with the CGM to be combined is 0.5 (eV) or less, and is preferably 0. .25 (eV) or less.

The ionization potential of CGM and CTM is measured with a surface analyzer AC-1 (manufactured by Riken Keiki Co., Ltd.).

Examples of the resin used for the charge transport layer (CTL layer) include polystyrene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin,
Phenolic resin, polyester resin, alkyd resin,
A polycarbonate resin, a silicon resin, a melamine resin, and a copolymer resin containing two or more of repeating units of these resins. In addition to these insulating resins, poly-
A high-molecular organic semiconductor such as N-vinylcarbazole may be used.

The most preferred binder for these CTLs is a polycarbonate resin. Polycarbonate resins are most preferred for improving the dispersibility and electrophotographic properties of CTM. The ratio of the binder resin to the charge transporting material is preferably from 10 to 200 parts by mass per 100 parts by mass of the binder resin. The thickness of the charge transport layer is preferably from 10 to 40 μm.

Surface Layer (Resin Layer Containing a Siloxane Resin Having Charge Transporting Performance) The electrophotographic photoreceptor of the present invention having a high hardness and a small increase in residual potential is a siloxane resin containing a charge transporting structural unit. A photoreceptor having a resin layer containing a surface layer as a surface layer is preferred. The siloxane-based resin layer is typically formed by applying and drying a coating composition using an organosilicon compound represented by the following general formula (2) as a raw material. These raw materials form a condensate (oligomer) of an organosilicon compound in a hydrophilic solvent by hydrolysis and a subsequent condensation reaction. By coating and drying these coating compositions, a resin layer containing a siloxane-based resin having a three-dimensional network structure can be formed.

Formula (2) (R) _n -Si- (X) _{4-n In the} formula, Si represents a silicon atom, R represents an organic group in which carbon is directly bonded to the silicon atom, and X represents a hydroxyl group. Or, represents a hydrolyzable group, and n represents an integer of 0 to 3.

In the organosilicon compound represented by the general formula (2), examples of the organic group in which carbon represented by R is directly bonded to silicon include alkyl groups such as methyl, ethyl, propyl and butyl, phenyl and tolyl. , Naphthyl, aryl groups such as biphenyl, γ-glycidoxypropyl, β-
Epoxy-containing groups such as (3,4-epoxycyclohexyl) ethyl, (meth) acryloyl groups such as γ-acryloxypropyl and γ-methacryloxypropyl, γ-hydroxypropyl and 2,3-dihydroxypropyloxypropyl Hydroxyl groups, vinyl, vinyl-containing groups such as propenyl, mercapto-containing groups such as γ-mercaptopropyl, γ-
Amino-containing groups such as aminopropyl and N-β (aminoethyl) -γ-aminopropyl; γ-chloropropyl;
Examples include a halogen-containing group such as 1,1-trifluorofluoropropyl, nonafluorohexyl, and perfluorooctylethyl, and other nitro and cyano-substituted alkyl groups. Particularly, an alkyl group such as methyl, ethyl, propyl, and butyl is preferable. Examples of the hydrolyzable group for X include an alkoxy group such as methoxy and ethoxy, a halogen group, and an acyloxy group. Particularly, an alkoxy group having 6 or less carbon atoms is preferable.

The organosilicon compounds represented by the general formula (2) may be used alone or in combination of two or more. However, it is preferable that at least one of the organosilicon compounds represented by the general formula (2) used is an organosilicon compound in which n is 0 or 1.

Further, when n is 2 or more in the specific compound of the organosilicon compound represented by the general formula (2), a plurality of Rs may be the same or different. Similarly, when n is 2 or less, a plurality of Xs may be the same or different. When two or more organosilicon compounds represented by the general formula (2) are used, R and X may be the same or different between the respective compounds.

The resin layer is preferably formed by adding colloidal silica to a composition containing the above-mentioned organosilicon compound or its hydrolytic condensate. Colloidal silica is silicon dioxide particles dispersed in a colloidal form in a dispersion medium. Colloidal silica may be added at any stage of adjusting the composition of the coating solution. Colloidal silica may be added in the form of an aqueous or alcoholic sol,
The aerosol formed in the gas phase may be directly dispersed in the coating solution of the present invention.

In addition, metal oxides such as titania and alumina may be added in the form of sol or particles.

Colloidal silica or the tetrafunctional (n = 0) or trifunctional (n = 1) organosilicon compound gives the resin layer film of the present invention elasticity and rigidity by forming a crosslinked structure. When the ratio of the bifunctional organosilicon compound (n = 2) increases, the rubber elasticity increases and the hydrophobicity increases.
The functional organosilicon compound (n = 3) does not become a polymer, but has a function of increasing hydrophobicity by reacting with unreacted residual SiOH groups.

As the surface layer of the present invention, which is required to have high hardness and high elasticity, tetrafunctional (n =
It is preferable to form a siloxane-based resin layer having elasticity and rigidity by using at least one of 0) and trifunctional (n = 1) as a raw material.

The resin layer further contains a siloxane-based resin containing a structural unit having a charge transporting property by a condensation reaction of the compound represented by the general formula (1) with the organosilicon compound or the condensate. By modifying the resin layer, an increase in the residual potential of the resin layer can be suppressed.

The compound represented by the general formula (1) is subjected to a condensation reaction with a hydroxyl group on the surface of colloidal silica,
It may be incorporated in the siloxane-based resin layer.

In the present invention, a siloxane-based ceramic resin layer formed by adding a metal hydroxide other than colloidal silica (for example, a hydrolyzate of each alkoxide of aluminum, titanium and zirconium) may be used.

In the general formula (1), B is a charge-transporting compound structure
And a monovalent or higher group. Where B is a charge transport compound
Including the compound structure means that (R) in the general formula (1)₁—ZH) group
Whether the compound structure except for has charge transport performance, or
Is (R) in the general formula (1). ₁-ZH) group by a hydrogen atom
Means that the substituted BH compound has charge transport performance
I do.

The above-mentioned charge transporting compound is a compound exhibiting the property of having electron or hole drift mobility. Another definition is Time-Of-Flight.
It can be defined as a compound capable of obtaining a detection current due to charge transport by a known method capable of detecting charge transport performance such as a method.

The total amount (H) of the organosilicon compound having a hydroxyl group or a hydrolyzable group, and the condensate formed from the organosilicon compound having a hydroxyl group or a hydrolyzable group, and the compound of the formula (1) The composition ratio in the composition (I) is preferably 100: 3 to 50: 100, more preferably 100: 10 to 50:10 by mass ratio.
It is between 0.

In the present invention, colloidal silica or other metal oxides may be added. When colloidal silica or other metal oxides (J) are added, the total amount (H) + compound (I) It is preferable to use 1 to 30 parts by mass of (J) based on 100 parts by mass of the total component.

When the total amount (H) is used within the above range, the surface layer of the photosensitive member of the present invention has high hardness and elasticity. Excess or deficiency of the colloidal silica component (J) has the same tendency as the total amount (H). on the other hand,
When the compound (I) is used in the above range, the electrophotographic characteristics such as sensitivity and residual potential characteristics are good, and the hardness of the photoconductor surface layer is high.

For forming the siloxane-based resin layer, it is preferable to use a condensation catalyst in order to accelerate the condensation reaction. The condensation catalyst used here may be a catalyst that has at least one of a catalyst that acts in contact with the condensation reaction and a catalyst that acts to shift the reaction equilibrium of the condensation reaction to the production system.

As a specific condensation catalyst, a known catalyst such as an acid, a metal oxide, a metal salt and an alkylaminosilane compound which has been conventionally used for a silicon hard coat material can be used. For example, organic carboxylic acids, nitrous acid,
Alkali metal salts of sulfurous acid, aluminate, carbonic acid and thiocyanic acid, organic amine salts (tetramethylammonium hydroxide, tetramethylammonium acetate), tin organic acid salts (stannas octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyl) Timmercaptide, dibutyltin thiocarboxylate, dibutyltin malate and the like.

In the general formula (1), as the group having a charge transporting compound structure represented by B, there are a hole transport type and an electron transport type. The hole transport type is oxazole, oxadiazole, thiazole, triazole, imidazole,
Groups containing structural units such as imidazolone, imidazoline, bisimidazolidine, styryl, hydrazone, benzidine, pyrazoline, triarylamine, oxazolone, benzothiazole, benzimidazole, quinazoline, benzofuran, acridine, phenazine and groups derived from these derivatives. Is mentioned. On the other hand, the electron transport type includes succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, melitic anhydride, tetratocyanoethylene, tetratocyanoquinodimethane, nitrobenzene, dinitrobenzene, trinitrobenzene, tetranitrobenzene, and nitrobenzene. Benzonitrile, picryl chloride,
Quinone chlorimide, chloranil, bromanyl, benzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, 4-nitrobenzophenone, 4,
4'-dinitrobenzophenone, 4-nitrobenzalmalone dinitrile, α-cyano-β- (p-cyanophenyl) -2- (p-chlorophenyl) ethylene, 2,7-
Dinitrofluorenone, 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitrofluorenone,
9-fluoronylidenedicyanomethylenemalonitrile,
Polynitro-9-fluoronylidenedicyanomethylenemalonitrile, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, perfluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitro Examples include groups containing chemical structural units such as salicylic acid, phthalic acid and melitic acid, and groups derived from derivatives thereof, but are not limited to these structures.

Examples of typical compounds represented by the general formula (1) are shown below. Examples of compounds in which Z is an oxygen atom in the general formula (1) are shown below.

[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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Next, examples of the compound in which Z is an NH group in the general formula (1) are shown below.

[0100]

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Next, examples of compounds in which Z is a mercapto group (SH) in the general formula (1) are shown below.

[0102]

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The most preferred compound represented by the following general formula (1) is a compound wherein Z is a hydroxyl group (OH) and m is 2 or more. A compound in which Z is a hydroxyl group (OH) and m is 2 or more is a resin layer having high hardness and a small increase in residual potential due to the compound reacting with the organosilicon compound and penetrating into the network structure of the siloxane-based resin. Can be formed.

Although the most preferred layer configuration of the photoreceptor of the present invention has been described above, other layer configurations of the photoreceptor may be used in the present invention. For example, if a resin layer containing a siloxane-based resin containing a structural unit having a charge transporting property is applied to the charge transporting layer, the above-described surface layer of the photoconductor layer can be removed. Further, when a resin layer containing a siloxane-based resin containing a structural unit having a charge transporting property is applied to a photosensitive layer having a single-layer structure, an undercoat layer and a photosensitive layer having a single-layer structure are formed on a cylindrical conductive support. The electrophotographic photoreceptor of the present invention can be formed from two resin layers.

The surface layer of the electrophotographic photosensitive member of the present invention preferably has a contact angle with water of 90 ° or more. By setting the contact angle with water to 90 ° or more, filming of paper powder and toner fine powder can be further reduced.

As a method for setting the contact angle of water to the siloxane-based resin layer having the charge transporting property of 90 ° or more, it is effective to increase the hydrophobicity of the siloxane resin layer. As a method for this, a method of introducing an F atom-containing group into the siloxane resin, a method of introducing a dimethylsiloxane skeleton, a method of introducing an aromatic group, or a method of adding resin particles or an organic polymer having water repellency such as PTFE. And the like.

Next, as the organic particles and the inorganic particles which can be used together with the above-mentioned colloidal silica in the resin layer of the present invention or can be used in place of the colloidal silica, the following can be mentioned.

<Organic Particles> Examples of the organic particles include silicone resin, polytetrafluoroethylene, polyvinylidene fluoride, poly (trifluorochloroethylene), polyvinyl fluoride, and polytetrafluoroethylene-perfluoroalkylvinyl ether copolymer. , Polytetrafluoroethylene-
Hexafluoropropylene copolymer, polyethylene-trifluoroethylene copolymer, polytetrafluoroethylene-propylene hexafluoride-perfluoroalkylvinyl ether copolymer, polyethylene, polyvinyl chloride, metal stearate, polymethyl Examples thereof include methacrylate and melamine. The volume average particle diameter is preferably 0.05 to 10 μm, and more preferably 0.1 to 5 μm. The amount of the organic particles contained in the resin layer of the present invention is preferably 0.1 to 100% by mass, more preferably 1 to 50% by mass, based on the binder resin of the resin layer. %, Sufficient printing durability and lubricity cannot be imparted to the photosensitive layer, which tends to cause poor cleaning during image formation, and does not improve the adhesion to the lower layer. If it exceeds 100% by mass, the photosensitivity of the photoreceptor decreases, and fogging is likely to occur.

<Inorganic Particles> As the inorganic particles, metal oxides such as magnesium oxide, calcium oxide, titanium oxide, zirconium oxide, tin oxide, aluminum oxide, silicon oxide (silica), indium oxide,
Examples include beryllium oxide, lead oxide, and bismuth oxide. Examples of the nitride include boron nitride, aluminum nitride, and silicon nitride. Examples of the carbide include silicon carbide and boron carbide. it can. The above-mentioned inorganic particles may be preferably subjected to a hydrophobizing treatment using a hydrophobizing agent such as a titanium coupling agent, a silane coupling agent, an aluminum coupling agent, or a high-molecular fatty acid.

The above-mentioned inorganic particles preferably have a volume average particle diameter of 0.05 to 10 μm, more preferably 0.1 to 10 μm.
５5 μm. The amount of the inorganic particles contained in the photoconductor surface layer is preferably 0.1 to 100% by mass, more preferably 1 to 50% by mass, based on the binder resin of the surface layer.
When the amount is less than 0.1%, sufficient printing durability, mechanical strength, or adhesiveness to the lower layer cannot be imparted to the surface layer of the photoreceptor. When the content exceeds 100% by mass, the surface roughness of the photoreceptor surface layer becomes large, and the cleaning member is damaged, resulting in poor cleaning.

The volume average particle size of the organic particles and the inorganic particles was measured by a laser diffraction / scattering type particle size distribution analyzer “L”.
A-700 "(manufactured by Horiba, Ltd.).

Further, by adding an antioxidant to the surface layer of the siloxane-based resin, it is possible to effectively prevent an increase in residual potential and image blur.

The antioxidant is a typical antioxidant which reacts with an autoxidizing substance present in the electrophotographic photosensitive member or on the surface of the photosensitive member under conditions of light, heat, discharge and the like. It is a substance having the property of preventing or suppressing the action. Specifically, the following compounds may be mentioned.

(1) Radical chain inhibitor • Phenolic antioxidant (hindered phenol) • Amine antioxidant (hindered amine, diallyldiamine, diallylamine) • Hydroquinone antioxidant (2) Peroxidation Decomposition agent ・ Sulfur antioxidant (thioethers) ・ Phosphoric antioxidant (phosphites) Among the above antioxidants, the radical chain inhibitor of (1) is preferable, and particularly, hindered phenol or Hindered amine antioxidants are preferred. Further, two or more kinds may be used in combination, for example, a combination of the hindered phenol antioxidant (1) and the thioether antioxidant (2) may be used. Further, a molecule containing the above structural unit, for example, a hindered phenol structural unit and a hindered amine structural unit in a molecule may be used.

Among the above antioxidants, hindered phenol-based and hindered amine-based antioxidants are particularly effective in preventing fogging and image blurring at high temperature and high humidity.

The content of the hindered phenol or hindered amine antioxidant in the resin layer is 0.01 to 2
0% by mass is preferred. When the content is less than 0.01% by mass, there is no effect on fogging and image blur at high temperature and high humidity, and when the content is more than 20% by mass, the charge transport ability in the resin layer is reduced, and the residual potential tends to increase, In addition, a decrease in film strength occurs.

The antioxidant may be incorporated in the lower charge generation layer, charge transport layer, intermediate layer and the like, if necessary. The amount of the antioxidant added to these layers is preferably 0.01 to 20% by mass with respect to each layer.

Here, hindered phenol refers to compounds having a branched alkyl group at an ortho position to the hydroxyl group of the phenol compound and derivatives thereof (however, the hydroxyl group may be modified to alkoxy).

A hindered amine compound is a compound having a bulky organic group near an N atom. As the bulky organic group, there is a branched alkyl group, and for example, a t-butyl group is preferable. For example, compounds having an organic group represented by the following structural formula are preferable.

[0120]

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R ₁₃ in the formula is a hydrogen atom or a monovalent organic group,
R ₁₄ , R ₁₅ , R ₁₆ and R _{17 each} represent an alkyl group, and R ₁₈ represents a hydrogen atom, a hydroxyl group or a monovalent organic group.

As the antioxidant having a hindered phenol partial structure, for example, JP-A-1-118137 (P.
7 to P14), but the present invention is not limited thereto.

Examples of the antioxidant having a hindered amine partial structure include, for example, JP-A-1-118138 (P7-
The compounds described in P9) may also be mentioned, but the present invention is not limited thereto.

Examples of the organic phosphorus compound include, for example, the following compounds represented by the general formula RO-P (OR) -OR. Here, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group or aryl group.

As the organic sulfur compound, for example, there are the following compounds represented by the general formula RSR. Here, R represents a hydrogen atom, a substituted or unsubstituted alkyl group, alkenyl group or aryl group.

The following are examples of typical antioxidant compounds.

[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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The following compounds are commercially available antioxidants, such as “Irganox 1076” and “Irganox 1” as hindered phenol compounds.
010 "," Ilganox 1098 "," Ilganox 245 "," Ilganox 1330 "," Ilganox 3114 "," Ilganox 1076 ",
"3,5-di-t-butyl-4-hydroxybiphenyl" and "Sanol LS262
6, "Sanol LS765", "Sanol LS77"
0 "," Sanol LS744 "," Tinuvin 144 ",
“Tinuvin 622LD”, “Mark LA57”, “Mark LA67”, “Mark LA62”, “Mark LA6”
8 "and" Mark LA63 ", and as thioethers," Sumilyzer-TPS "and" Sumilyzer TP-
D ", and as a phosphite system," Mark 211 "
2, "Mark PEP-8", "Mark PEP-24"
G "," Mark PEP-36 "," Mark 329K ",
"Mark HP-10".

In order to form the layer containing the siloxane-based resin of the present invention, the siloxane-based resin composition is usually dissolved in a solvent and applied. Methanol as a solvent,
Alcohols such as ethanol, propanol, butanol, methyl cellosolve and ethyl cellosolve and derivatives thereof; ketones such as methyl ethyl ketone and acetone; esters such as ethyl acetate and butyl acetate are used.

The siloxane-based resin layer of the present invention is preferably dried by heating. The heating promotes the crosslinking / curing reaction of the siloxane-based resin layer. The cross-linking and curing conditions vary depending on the type of solvent used and the presence or absence of a catalyst.
Heating in the range of 0 to 160 ° C for 10 minutes to 5 hours is preferable, and more preferably in the range of 90 to 120 ° C for 30 minutes to 2 hours.
Time heating is preferred.

Solvents used for dispersing and dissolving the charge generating substance and the charge transporting substance include hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and 1,2-dichloroethane; methyl ethyl ketone and cyclohexanone. Ketones; esters such as ethyl acetate and butyl acetate; alcohols such as methanol, ethanol, methyl cellosolve and ethyl cellosolve and derivatives thereof; tetrahydrofuran, 1,4-dioxane and 1,3
Ethers such as dioxolane; amines such as pyridine and diethylamine; amides such as N, N-dimethylformamide; other fatty acids and phenols; one or two of sulfur and phosphorus compounds such as carbon disulfide and triethyl phosphate; More than one species can be used.

As a coating method for producing the electrophotographic photosensitive member having the surface layer, a dip coating, a spray coating, a circular amount control type coating and the like of a coating solution can be used. In particular, in the coating process on the surface layer side of the photosensitive layer, spray coating or circular amount control type coating (a typical example is a circular slide hopper) is used to dissolve the lower layer film as much as possible and to achieve uniform coating process. Is preferred. The spray coating is described in JP-A-3-90250 and JP-A-3-269238, and the details of the circular amount control type coating are described in JP-A-58-189061.

Next, each means used in the image forming apparatus used in the image forming apparatus of the present invention will be described with reference to examples. (However, the image forming apparatus does not need to include all of these units, and may be appropriately composed of some of these units depending on the intended image forming apparatus.) Exposure for erasing the charge remaining on the photoreceptor): Light irradiation by an LED or the like is used as the pre-charging exposure means. Exposure before charging can suppress an increase in the residual potential due to a delay in the response of the photoreceptor and the occurrence of memory due to the exposure pattern. However, in the image forming apparatus of the present invention, the pre-charging exposure unit is not always necessary.

Charging means: The charging means described above is used. Image exposure means: As an exposure light source, any of white light, LED, and LD can be suitably used. In the case of a digital image, the image exposure light source is preferably an LED or LD.

Developing means: One-component and two-component developers can be used for the developing means, and both magnetic and non-magnetic toners can be suitably used. Further, contact development in which the photoconductor and the developer are in contact with each other or non-contact development in the opposite direction may be used.

Transfer means: As the transfer means, any of corona transfer, roller transfer and a transfer method using an intermediate transfer member is suitably used.

Cleaning means: The cleaning means of the present invention is based on the premise that the above-mentioned cleaning means using an elastic rubber blade is used, but a fur brush or a cleaning roller is used as an auxiliary member of the elastic rubber blade. Is also good.

When the image forming method of the present invention is used as a facsimile printer, the image exposing device 53 performs exposure for printing the received data.

The electrophotographic photoreceptor of the present invention can be applied to general electrophotographic devices such as copiers, laser printers, LED printers, and liquid crystal shutter printers. It can be widely applied to devices such as light printing, plate making, and facsimile.

Next, the toner and developer used in the present invention will be described. << Toner Used in the Present Invention >> Hereinafter, the present invention will be described in detail.

In the present invention, the turbidity of the toner is defined as follows and can be measured.

Turbidity; defined as HAZE value = diffusion component / total transmission component. Toner turbidity measurement method: 5.0 g of toner was added to surfactant 1
The mixture is dispersed in 50 ml of an aqueous solution containing 50 ml, and separated using a centrifuge (2000 rpm: 10 minutes). Since the toner component precipitates, a supernatant liquid, which is a free component, is collected. Using a COH-300A manufactured by Nippon Denshoku Co., Ltd., the ratio of the diffusion component of the total transmission component to the incident light is calculated, and the HAZE value is defined as the turbidity of the toner.

When the turbidity of the toner is larger than 50, the released components of the fine particles are large, so that the released fine particles re-aggregate in the developing device, become nuclei at the time of transfer, and cause transfer omission. Further, since a large amount of the liberated components adhere to the surface of the photoreceptor, filming is likely to occur, resulting in poor cleaning.

The method for controlling the turbidity of the toner within the range of 50 or less, more preferably 30 or less according to the above definition and measurement method includes selecting the type of the fine particle external additive adhering to the surface of the toner and selecting the type of the fine particle external additive. (Hereinafter simply referred to as fine particles)
It is important to control the degree of sticking to the toner surface.

The fine particles preferably used in the present invention have a number average particle diameter of 0.05 to 0.5 μm.

When the particle diameter of the fine particles is smaller than 0.05 μm, the transferability is lowered because the physical adhesion between the toner and the photoreceptor is not reduced. As a result, the image density is lowered.

When the particle size is larger than 0.5 μm, the fine particles once adhered are easily separated and released by the stress such as stirring in the developing device, and the released amount is accumulated in the developing device. Re-aggregate in the nucleus and become a nucleus at the time of transfer, causing transfer omission. Further, since a large amount of released components adhere to the surface of the photoconductor, filming on the surface of the photoconductor is likely to occur.

The amount of the fine particles added to the toner is from 0.05 to 5.0 parts by mass of the colored particles (toner before the addition of the fine particles) (hereinafter, unless otherwise specified, “parts” means “parts by mass”). ) Is preferred, and 1.0 to 4.0 parts is particularly preferred.

If the amount is less than 0.05 part, the effect of reducing the physical adhesive force cannot be obtained, so that the transferability tends to decrease.
If the amount is more than 5.0 parts, there is an excessive amount of fine particles on the toner surface. Therefore, the released matter is accumulated in the developing device, re-agglomerated in the developing device, and becomes a nucleus. When this is mixed into the developed toner image, transfer omission is likely to occur at the time of transfer. Further, since a large amount of the released components adhere to the surface of the photoconductor, toner filming on the surface of the photoconductor is likely to occur.

The method for controlling the state of adhesion of the fine particles to the colored particles is not limited, and any generally used external addition device for fine particles or a device for fixing or fixing to the toner surface can be used.

Specific examples of the immobilization device include a Henschel mixer, a Lödige mixer, and TURBO SPHE.
An RE mixer or the like can be used. Among them, the Henschel mixer can be suitably used in view of the fact that the mixing and fixing of the external additives can be performed by the same apparatus, and that the stirring and mixing are easy and the external heating is easy.

As a mixing method at the time of the above-mentioned fixing treatment, it is desirable to carry out the treatment at a peripheral speed of the tip of the stirring blade of 5 to 50 m / s. Preferably, the treatment is performed at 10 to 40 m / s. In addition, it is preferable that the external additive is uniformly adhered to the surface of the resin particles by performing pre-mixing. As a method of controlling the temperature, it is preferable to adjust the temperature to a necessary temperature using warm water or the like from the outside.

The method of measuring the temperature is to measure the temperature of the portion where the toner flows while the toner is being stirred and mixed. Further, it is preferable that cold water is circulated after the fixing treatment to perform the cooling and crushing steps.

As a method for controlling the degree of immobilization of the fine particles on the surface of the colored particles, the colored particles and the fine particles are stirred and mixed under a temperature condition of Tg−20 ≦ (stirring / mixing temperature) ≦ Tg + 20 to reduce the mechanical impact force. By adjusting the time during the application, the fine particle external additive can be uniformly attached to the surface of the colored particles.

[0159] The Tg referred to here means the glass transition temperature of the toner or the binder resin constituting the toner. The glass transition temperature was measured using a DSC7 differential scanning calorimeter (manufactured by PerkinElmer). Measurement method is 10 ° C
/ Min at 0 ° C to 200 ° C, then 10 ° C
After cooling from 200 ° C. to 0 ° C. at / min to eliminate the previous history, the temperature was raised from 0 ° C. to 200 ° C. at 10 ° C./min, and the endothermic peak temperature of the second heat was determined and defined as Tg. When there were a plurality of endothermic peaks, the temperature of the main endothermic peak was defined as Tg.

The Tg of the toner or the binder resin constituting the toner is preferably from 40 to 70 ° C. 40
If the temperature is lower than ℃, the storage stability of the toner is poor and the toner is aggregated. If it is higher than 70 ° C., it is not preferable from the viewpoint of fixing property and productivity.

The toner of the present invention preferably has a saturated water content in an environment of 30 ° C. and 80 RH% within a range of 0.1 to 2.0% by mass. The water content of the toner can be sufficiently dried at the same time as the fixation of the fine particles by heating the toner near the Tg in the step of fixing the fine particle external additive. 30 ° C, 80
In order to reduce the hygroscopicity of the toner under high-temperature and high-humidity conditions such as RH% environment, saturation is achieved by using a surface-treated external additive having low hygroscopicity or resin fine particles. It is effective to control the amount of water. The saturated water content in an environment of 30 ° C. and 80 RH% is set to 0.1.
To reduce the amount to less than 1% by mass, the cost for that purpose becomes too high. On the other hand, if it exceeds 2.0% by mass, the storage stability of the toner is poor and the toner is aggregated.

The water content is measured by the Karl Fischer method. In the present invention, the water content was measured using a Hiranuma automatic trace moisture analyzer AQS-724. The measurement conditions in the present invention were a vaporization temperature of 110 ° C. and a vaporization time of 25 seconds.

From the viewpoint of imparting fluidity, fine particles may be further externally added after controlling the adhesion of the fine particles, but it is necessary that the turbidity of the toner falls within the range of the present invention.

The method for measuring the number average particle diameter of the fine particles was observed using a transmission electron microscope and displayed using the values measured by image analysis.

The composition of the fine particles is not particularly limited, and any fine particles can be used.

For example, as the inorganic fine particles, various inorganic oxides, nitrides, borides and the like are preferably used. For example, silica, alumina, titania, zirconia, barium titanate, aluminum titanate, strontium titanate, magnesium titanate, zinc oxide, chromium oxide, cerium oxide, antimony oxide, tungsten oxide, tin oxide, tellurium oxide, manganese oxide, Examples include boron oxide, silicon carbide, boron carbide, titanium carbide, silicon nitride, titanium nitride, boron nitride, and the like.

Furthermore, the above-mentioned inorganic fine particles may be subjected to a hydrophobic treatment. When performing the hydrophobizing treatment, it is preferable to perform hydrophobizing treatment with a so-called coupling agent such as various titanium coupling agents and silane coupling agents, and aluminum stearate, zinc stearate,
Those subjected to a hydrophobic treatment with a metal salt of a higher fatty acid such as calcium stearate are also preferably used.

In the case of using fine resin particles, the composition is not particularly limited. Generally, fine particles of vinyl-based organic fine particles, melamine / formaldehyde condensate, polyester, polycarbonate, polyamide, polyurethane and the like are preferable. The reason for this is that it can be easily produced by a production method such as an emulsion polymerization method or a suspension polymerization method.

<< Structure and Production Method of Toner >> The toner of the present invention contains at least a resin and a colorant.
If necessary, a releasing agent or a charge control agent, which is a fixing property improving agent, can be contained. Further, an external additive composed of inorganic fine particles or organic fine particles may be added to colored particles composed of a resin and a colorant.

Examples of the monomer used for producing the toner of the present invention include styrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-phenylstyrene, p-ethylstyrene,
2,4-dimethylstyrene, pt-butylstyrene,
styrene or styrene derivatives such as pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, methyl methacrylate, ethyl methacrylate, N-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, methacrylic acid Methacrylate derivatives such as dimethylaminoethyl acrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-acrylate
-Butyl, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate,
Α-methylene fatty acid monocarboxylic acid esters such as acrylate derivatives such as phenyl acrylate, olefins such as ethylene and propylene / isobutylene, vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride;
Halogen vinyls such as vinylidene fluoride, vinyl esters such as vinyl propionate, vinyl acetate and vinyl benzoate, vinyl ethers such as vinyl methyl ether and vinyl ethyl ether, vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone, etc. Vinyl ketones, N-vinyl carbazole, N-vinyl indole,
There are N-vinyl compounds such as N-vinylpyrrolidone, vinyl compounds such as vinylnaphthalene and vinylpyridine, and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide. These vinyl monomers can be used alone or in combination.

These monomers can be made into resins by using a radical polymerization initiator. In this case, an oil-soluble polymerization initiator can be used in the suspension polymerization method or the solution polymerization method.
As this oil-soluble polymerization initiator, azoisobutyronitrile, lauryl peroxide, benzoyl peroxide and the like can be used. When an emulsion polymerization method is used, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, and hydrogen peroxide.

Various colorants are used in the toner of the present invention. As the colorants, carbon black, magnetic substances, dyes, pigments and the like can be arbitrarily used. As the carbon black, channel black, furnace black and the like can be used. Black, acetylene black, thermal black, lamp black and the like are used. As the magnetic material, ferromagnetic metals such as iron, nickel and cobalt, alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys which do not contain ferromagnetic metals but show ferromagnetism by heat treatment, For example, an alloy of a type called a Heusler alloy such as manganese-copper-aluminum, manganese-copper-tin, chromium dioxide, or the like can be used. As the dye, C.I. I. Solvent Red 1, 49, 52, 5
8, 63, 111, 122, C.I. I. Solvent Yellow 19, 44, 77, 79, 81, 8
2, 93, 98, 103, 104, 112,
162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95, etc., and mixtures thereof can also be used. Examples of the pigment include C.I. I. Pigment Red 5, 48: 1, 53:
1, 57: 1, 122, 139, 144, 1
49, 166, 177, 178, 222, C.I.
I. Pigment Orange 31, 43 and C.I. I. Pigment Yellow 14, 17, 93, 94, 13
8, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 3, 60 and the like, and mixtures thereof can also be used. The number average primary particle size varies depending on the type, but is preferably about 10 to 200 nm.

Further, low molecular weight polypropylene (number average molecular weight = 1500 to 9000) or low molecular weight polyethylene as a fixing property improving agent may be added. Further, an azo-based metal complex, a quaternary ammonium salt, or the like may be used as a charge control agent.

The particle size of the toner itself of the present invention is arbitrary, but a small particle size tends to exhibit the effects of the present invention, and a volume average particle size of 2 to 15 μm is preferable, and particularly 5 to 9 μm.
m is preferred.

Further, while satisfying the above volume average particle size,
It is desirable to classify the toner particle size distribution to a specific particle size distribution. As the particle size distribution, 16.0 μm or more is used.
0 volume% or less and 5.0 μm or less are 16.0 number% or less. If it is more than 16.0 μm and more than 2.0% by volume, the sharpness of the image quality will be poor. If the value of 5.0 μm or less is 16.0% by number or more, the amount of untransferred toner increases, resulting in a decrease in transfer rate.

A Coulter Counter TA-II type (manufactured by Coulter, Inc.) was used as an apparatus for measuring the particle size of the toner. An interface (manufactured by Nikkaki) for outputting the number distribution and volume distribution and a PC9801 personal computer (NEC) were used.
And a 1% NaCl aqueous solution is prepared using primary grade sodium chloride. As a measuring method, a surfactant, preferably an alkylbenzenesulfonate, is dispersed as a dispersion in 100 to 150 ml of the electrolytic aqueous solution in 0.1 to 0.1 ml.
Add 5 ml, and then add 2-20 mg of the measurement sample. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the particle size distribution was measured with the Coulter Counter TA-II using an aperture of 100 μm as the aperture. Measurement range is 1.26-5
It was set to 0.8 μm, and cut off without calculating a detection value of 2.00 μm or less, and the above value was obtained.

The toner of the present invention may be used as a one-component magnetic toner containing a magnetic material, for example, when used as a two-component developer by mixing with a so-called carrier, or when a non-magnetic toner is used alone. Any of them can be suitably used, but in the present invention, it is preferable to use as a two-component developer used by mixing with a carrier.

As the carrier constituting the two-component developer, either an uncoated carrier composed of only magnetic material particles such as iron or ferrite, or a resin-coated carrier in which the surface of the magnetic material particles is coated with a resin or the like can be used. Is also good. The average particle size of this carrier is 30 to 150 μm in volume average particle size.
m is preferred. The resin for coating is not particularly limited, and examples thereof include a styrene-acrylic resin.

<Diameter of Toner Particles> The toner of the present invention preferably has a number average particle diameter of 3 to 8 μm. In the case where toner particles are formed by a polymerization method, the particle size is determined by the concentration of the coagulant, the amount of the organic solvent added, or the fusing time, and the composition of the polymer itself, in the toner manufacturing method described in detail below. Can be controlled by

When the number average particle diameter is 3 to 8 μm, the amount of toner particles having a large adhesive force which causes filming by adhering to the photoreceptor is reduced, and the transfer efficiency is increased to improve the halftone image quality. The image quality of fine lines, dots, and the like is improved.

When the particle size of the toner particles is D (μm), the natural logarithm lnD
Is plotted on the horizontal axis, and in the histogram showing the number-based particle size distribution in which the horizontal axis is divided into a plurality of classes at intervals of 0.23, the relative frequency (m ₁ ) of the toner particles included in the most frequent class
It is preferable that the toner has a sum (M) of 70% or more of the relative frequency (m ₂ ) of the toner particles included in the class having the second highest frequency after the mode.

When the sum (M) of the relative frequency (m ₁ ) and the relative frequency (m ₂ ) is 70% or more, the dispersion of the particle size distribution of the toner particles is narrowed. By using this, the occurrence of selective development can be reliably suppressed.

In the present invention, the histogram showing the number-based particle size distribution is obtained by plotting a natural logarithm lnD (D: particle size of individual toner particles) in a plurality of classes (0 to 0) at intervals of 0.23.
0.23: 0.23 to 0.46: 0.46 to 0.69:
0.69 to 0.92: 0.92 to 1.15: 1.15
1.38: 1.38 to 1.61: 1.61 to 1.84:
1.84 to 2.07: 2.07 to 2.30: 2.30 to
2.53: 2.53 to 2.76...) Is a histogram showing the number-based particle size distribution, which is a particle size data of a sample measured by a Coulter Multisizer according to the following conditions. Is transferred to a computer via an I / O unit, and the computer creates the program using a particle size distribution analysis program.

[Measurement Conditions] (1) Aperture: 100 μm (2) Sample preparation method: electrolytic solution [ISOTON R-1
1 (manufactured by Coulter Scientific Japan)
An appropriate amount of a surfactant (neutral detergent) is added to 50 to 100 ml, and the mixture is stirred, and 10 to 20 mg of a measurement sample is added thereto. This system is prepared by subjecting it to a dispersion treatment with an ultrasonic disperser for 1 minute.

In the case of the pulverized toner, the shape factor is 1.2 to
The ratio of the 1.6 toner particles is about 60% by number. The variation coefficient of the shape factor is about 20%. In addition, the number variation coefficient in the number particle size distribution is about 30% when the classification operation after the pulverization is performed once, and the classification operation needs to be further repeated to reduce the number variation coefficient to 27% or less. There is.

In the case of the toner obtained by the suspension polymerization method, the toner is conventionally polymerized in a laminar flow, so that substantially spherical toner particles are obtained. For example, in the case of the toner described in JP-A-56-130762, The ratio of the toner particles having a coefficient of 1.2 to 1.6 is about 20% by number, and the variation coefficient of the shape coefficient is also about 18%. Further, as described above as a method for controlling the number variation coefficient in the number particle size distribution, mechanical shearing is repeated for a large oil droplet of a polymerizable monomer to reduce the oil droplet to a size of about a toner particle. Therefore, the distribution of oil droplet diameters is widened, and the particle size distribution of the obtained toner is wide, and the number variation coefficient is as large as about 32%. Therefore, a classification operation is required to reduce the number variation coefficient. .

Polymerized toners formed by associating or fusing resin particles are described, for example, in JP-A-63-163.
In the toner described in JP-A-186253, the ratio of the toner particles having a shape coefficient of 1.2 to 1.6 is 60% by number.
And the variation coefficient of the shape factor is about 18%. Further, the particle size distribution of the toner is wide and the number variation coefficient is 30%, and a classification operation is required to reduce the number variation coefficient.

The particle diameter of the toner used in the present invention is preferably 3 to 8 μm in terms of volume average particle diameter. The volume average particle size and the particle size distribution of the toner are as follows: Coulter Counter TA-II,
It can be measured using a Coulter Multisizer, SLAD1100 (Shimadzu Corporation laser diffraction particle size analyzer) or the like. Aperture diameter = 100 for Coulter Counter TA-II and Coulter Multisizer
It is obtained by measuring the particle size distribution in the range of 2.0 to 40 μm using a μm aperture.

Further, the toner preferably has 30% by volume or less of particles having a volume average particle diameter of less than 3.0 μm. The method for producing the toner is not particularly limited. In the pulverization classification method, pulverization may be performed while suppressing excessive pulverization during pulverization. Further, a method of repeatedly classifying may be employed. Further, as a method for producing a so-called polymerization toner, a method for producing a toner by a suspension polymerization method or a fusion method is also preferable.

Incidentally, the polymerization method can also be achieved by removing fine particles by centrifugation or the like in a dispersion of resin particles, if necessary.

In any case, a pulverized toner or a polymerized toner satisfying the above requirements of the present invention,
The object of the present invention can be achieved.

<Developer> The toner used in the present invention is:
Although it may be used as a one-component developer or a two-component developer,
Preferably as a two-component developer.

When the toner is used as a one-component developer, there is a method in which the toner is used as it is as a non-magnetic one-component developer. However, usually, magnetic particles having a particle size of about 0.1 to 5 μm are contained in toner particles. Used as a developer. As a method of containing the same, it is common to make the non-spherical particles contain the same as the coloring agent.

Further, it can be used as a two-component developer by mixing with a carrier. In this case, as the magnetic particles of the carrier, conventionally known materials such as metals such as iron, ferrite and magnetite, and alloys of these metals with metals such as aluminum and lead are used. Particularly, ferrite particles are preferable. The magnetic particles have a volume average particle size of 15
-100 μm, more preferably 25-60 μm.

The volume average particle size of the carrier is typically measured by a laser diffraction type particle size distribution analyzer “HELOS” equipped with a wet disperser (SYMPATIC (SYMPIC)
(ATEC)).

The carrier is preferably a carrier in which magnetic particles are further coated with a resin, or a so-called resin-dispersed carrier in which magnetic particles are dispersed in a resin. The resin composition for coating is not particularly limited, but, for example, an olefin resin, a styrene resin, a styrene-acrylic resin, a silicone resin, an ester resin, or a fluorine-containing polymer resin is used. The resin for forming the resin dispersion type carrier is not particularly limited, and known resins can be used.For example, styrene acrylic resin, polyester resin, fluorine resin, phenol resin, and the like can be used. it can.

[0197]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but embodiments of the present invention are not limited thereto. In the description, “parts” means “parts by mass”.

A photoreceptor was prepared as described below. Preparation of photoreceptor 1 The following intermediate layer coating solution was prepared, applied to a cleaned 60 mmφ cylindrical aluminum substrate by a dip coating method, and dried to a film thickness of 0.3 μm. Was formed.

<Intermediate Layer (UCL) Coating Solution> Polyamide resin (Amilan CM-8000: manufactured by Toray Industries, Ltd.) 60 g Methanol 1600 ml The following coating solutions were mixed and dispersed for 10 hours using a sand mill to prepare a charge generating layer coating solution. did. This coating solution was applied by a dip coating method to form a charge generation layer having a dry film thickness of 0.2 μm on the intermediate layer.

<Charge Generating Layer (CGL) Coating Solution> Y-type titanyl phthalocyanine (the maximum peak angle of X-ray diffraction by Cu-Kα characteristic X-ray is 27.3 at 2θ) 60 g Silicone resin solution (KR5240, 15% xylene- Butanol solution: Shin-Etsu Chemical Co., Ltd.) 700 g 2-butanone 2000 ml The following coating solutions were mixed and dissolved to prepare a charge transport layer coating solution. This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a thickness of 20 μm.

<Charge Transport Layer (CTL) Coating Solution> Charge transport substance (4-methoxy-4 '-(4-methyl-α-phenylstyryl) triphenylamine) 200 g Bisphenol Z-type polycarbonate (Iupilon Z300: Mitsubishi Gas Chemical) 300 g 1,2-dichloroethane 2000 ml The following coating solutions were mixed and dissolved to prepare a surface layer coating composition.

<Surface Layer (OCL) Coating Solution> Molecular sieve 4A (Wako Pure Chemical Industries, Ltd.) was added to 10 parts by mass of a polysiloxane resin formed from 80 mol% of methyl siloxane units and 20 mol% of methyl-phenyl siloxane units.
It was left to stand for a dehydration treatment. This resin was dissolved in 10 parts by mass of toluene, and 5 parts by mass of methyltrimethoxysilane and 0.2 parts by mass of dibutyltin acetate were added thereto to form a uniform solution. 6 parts by mass of dihydroxymethyltriphenylamine (exemplary compound B-1) and 0.3 parts by mass of hindered amine (exemplary compound 2-1) were added thereto and mixed, and this solution was applied as a surface layer having a dry film thickness of 2 μm. And 12
The resultant was cured by heating at 0 ° C. for 1 hour, thereby producing a photoreceptor 1.

Preparation of Photoconductor 2 Photoconductor 2 was prepared in the same manner as photoconductor 1, except that the following intermediate layer was used.

<Intermediate layer (UCL) coating liquid> Zirconium chelate compound ZC-540 (Matsumoto Pharmaceutical Co., Ltd.) 200 g Silane coupling agent KBM-903 (Shin-Etsu Chemical Co., Ltd.) 100 g Methanol 700 ml Ethanol 300 ml Dip coating of the above materials Then, the resultant was dried at 150 ° C. for 30 minutes to form an intermediate layer having a dry film thickness of 1.0 μm.

Preparation of Photoreceptor 3 The following dispersion was prepared and coated on a 60 mmφ cylindrical aluminum substrate obtained by drawing, and the dried film thickness was 1
A 5 μm conductive layer was formed.

<Conductive Layer (PCL) Coating Solution> Phenol resin 160 g Conductive titanium oxide 200 g Methyl cellosolve 100 ml The following intermediate layer coating solution was prepared. This coating solution was applied on the conductive layer by a dip coating method to form an intermediate layer having a dry film thickness of 0.2 μm. <Intermediate layer (UCL) coating solution> Polyamide resin (Amilan CM-8000: manufactured by Toray Industries, Ltd.) 60 g Methanol 1600 ml 1-butanol 400 ml The following coating solutions were mixed and dispersed using a sand mill for 10 hours. Prepared. This coating solution was applied onto the intermediate layer by a dip coating method to form a charge generation layer having a dry film thickness of 0.2 μm.

<Charge Generating Layer (CGL) Coating Solution> Y-type titanyl phthalocyanine 60 g Silicone resin solution (KR5240, 15% xylene-butanol solution: manufactured by Shin-Etsu Chemical Co., Ltd.) 700 g 2-butanone 2000 ml The following coating solutions were mixed and dissolved. Thus, a charge transport layer coating solution was prepared. This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a dry film thickness of 20 μm.

<Charge Transport Layer (CTL) Coating Solution> Charge transport substance (4-methoxy-4 ′-(4-methyl-α-phenylstyryl) triphenylamine) 200 g Bisphenol Z-type polycarbonate (Iupilon Z300: Mitsubishi Gas Chemical) 300g 1,2-dichloroethane 2000ml <Coating solution for surface layer (OCL)> 10 mass parts of polysiloxane resin formed from 80 mol% of methylsiloxane unit and 20 mol% of methyl-phenylsiloxane unit on the CTL. 4A was added, and the mixture was allowed to stand for 15 hours for dehydration treatment. This resin was dissolved in 10 parts by mass of toluene, and 5 parts by mass of methyltrimethoxysilane and 0.2 parts by mass of dibutyltin acetate were added thereto to form a uniform solution.

To this were added 6 parts by mass of dihydroxymethyltriphenylamine (Exemplified Compound B-1) and 0.3 parts by mass of hindered phenol (Exemplified Compound 1-3), and the mixture was mixed. It was applied as a surface layer, and was heated and cured at 120 ° C. for 1 hour to produce a photoreceptor 3.

Preparation of Photoreceptor 4 In the preparation of Photoreceptor 1, on the photoreceptor coated up to CTL, 1 mol% of a silanol group-containing methyl formed from 80 mol% of methylsiloxane units and 20 mol% of dimethylsiloxane units. Molecular sieve 4A was added to a mixed solution of 10 parts by mass of a polysiloxane resin and 10 parts by mass of toluene, and the mixture was allowed to stand for 15 hours to be dehydrated. 5 parts by mass of methyltrimethoxysilane and 0.1 part of dibutyltin acetate were added thereto.
2 parts by mass were added to make a uniform solution. To 100 parts by mass of this composition, 200 parts by mass of toluene, 40 parts by mass of 4- [N, N-bis (3,4-dimethylphenyl) amino]-[2- (triethoxysilyl) ethyl] benzene and hindered amine (exemplary compound) 2-10) 0.3 parts by mass were added and mixed, and this solution was applied as a surface layer having a dry film thickness of 2 μm, and was heated and cured at 140 ° C. for 4 hours.
Was prepared.

Preparation of Photoreceptor 5 In the preparation of Photoreceptor 1, dihydroxymethyltriphenylamine (Exemplified Compound B-1) in OCL was replaced with anodized aluminum in the OCL, and hydrazone-type Exemplified Compound B- A photoreceptor 5 was prepared in exactly the same manner except that the photoreceptor was replaced with 14.

Production of Photoconductor 6 In the production of Photoconductor 1,
Photoconductor 6 was prepared in exactly the same manner except that 5 parts by mass of colloidal silica was added to the surface layer.

Preparation of Photoreceptor 7 In the preparation of Photoreceptor 1, coating was performed in the same manner up to the charge generation layer.

<Charge Transporting Layer CTL> Charge transporting substance (Exemplified Compound B-1) 200 g Methyltrimethoxysilane 300 g Hindered phenol compound (Exemplified Compound 1-7) 1 g Colloidal silica (30% methanol solution) 8 g 1-butanol 50 g 50 g of 1% acetic acid, 2 g of aluminum tetraacetyl acetate, and 10 g of fluororesin particles (average particle size: 1 μm) were mixed and dissolved to prepare a charge transport layer coating solution. This coating solution is applied on the charge generation layer by a dip coating method.
The resultant was cured by heating at 10 ° C. for 2 hours to form a charge transport layer having a dry film thickness of 12 μm.

Preparation of Photoreceptor 8 In the preparation of Photoreceptor 1, up to the charge transport layer was formed in the same manner. Further, the following coating solution was mixed and dissolved thereon to prepare a surface layer coating composition.

<Surface Layer (OCL) Coating Solution> Charge Transport Material (Exemplary Compound B-1) 200 g Methyltrimethoxysilane 300 g Hindered Phenol Compound (Exemplary Compound 1-8) 1 g Colloidal Silica (30% methanol solution) 8 g Ethanol / T-butanol (1/1 mass ratio) 50 g 1% acetic acid 50 g aluminum tetraacetyl acetate 2 g Silicone oil KF-54 (methylphenyl silicone oil: Shin-Etsu Chemical Co., Ltd.) 1 g is mixed, dissolved and dried to a dry film thickness of 2 μm. Was applied as a surface layer, and was cured by heating at 110 ° C. for 1 hour to produce a photoreceptor 8.

Next, an image evaluation toner of the present invention was prepared as follows. * Preparation of Toner 1 100 parts of styrene-acryl resin having a mass ratio of styrene: butyl acrylate: butyl methacrylate = 75: 20: 5, 10 parts of carbon black, and 4 parts of low molecular weight polypropylene (number average molecular weight = 3500) are melted. ,
After kneading, the mixture was finely pulverized using a mechanical pulverizer and classified by an air classifier to obtain colored particles having a volume average particle size of 4.2 μm. Hydrophobic silica (degree of hydrophobicity = 75 / number average primary particle diameter = 12 nm) was added to the colored particles by 1.2.
Mass% and 0.6% by mass of 0.05 μm titanium oxide, and the peripheral speed of a Henschel mixer was set to 40 m / s, 52 ° C.
For 10 minutes to obtain a toner. This is referred to as “toner 1”.

* Preparation of Toner 2 Styrene: butyl acrylate: butyl methacrylate: acrylic acid = 100 parts of styrene-acryl resin having a mass ratio of 75: 18: 5: 2, carbon black 1
0 parts, low molecular weight polypropylene (number average molecular weight = 350
0) 4 parts were melted and kneaded, finely pulverized using a mechanical pulverizer, and classified by an air classifier to obtain colored particles having a volume average particle size of 6.2 μm. Hydrophobic silica (degree of hydrophobicity = 75 / number average primary particle diameter = 1)
2 nm) and 0.8% by mass of 0.2 μm melamine formaldehyde resin particles, and mixed at a peripheral speed of 40 m / s of a Henschel mixer at 46 ° C. for 10 minutes to obtain a toner. This is referred to as “toner 2”.

* Preparation of Toner 3 Styrene: butyl acrylate: methacrylic acid = 70:
Styrene-acrylic resin 1 having a mass ratio of 20:10
After melting and kneading 00 parts, 10 parts of carbon black, and 4 parts of low molecular weight polypropylene (number average molecular weight = 3500), pulverize using a mechanical pulverizer, classify with an air classifier, and volume average. Colored particles having a particle size of 5.0 μm were obtained. 1.0% by mass of hydrophobic silica (hydrophobicity = 75 / number average primary particle size = 13 nm) and 0.6% by mass of 0.5 μm titanium oxide were added to the colored particles, and the mixture was treated with a Henschel mixer. The toner was mixed at a peripheral speed of 30 m / s at 35 ° C. for 10 minutes to obtain a toner. This is referred to as “toner 3”.

* Preparation of Toner 4 Sodium n-dodecyl sulfate = 0.90 kg and pure water 1
Add 0.0L and dissolve with stirring. To this solution, with stirring, Regal 330R (carbon black manufactured by Cabot Corporation)
20 kg was gradually added, and then the mixture was continuously dispersed for 20 hours using a sand grinder (medium type disperser). After dispersion, ELS-8 electrophoretic light scattering photometer manufactured by Otsuka Electronics Co., Ltd.
As a result of measuring the particle size of the dispersion liquid using No. 00, the weight average particle size was 122 nm. The solid content concentration of the dispersion was 16.6% by mass as measured by a mass method based on standing drying. This dispersion is referred to as “colorant dispersion 1”.

[0221] 0.055 kg of sodium dodecylbenzenesulfonate is mixed with 4.0 L of ion-exchanged water and dissolved by stirring at room temperature. This is designated as an anionic surfactant solution A.

Nonylphenyl alkyl ether 0.01
4 kg is mixed with 4.0 L of ion-exchanged water and dissolved by stirring at room temperature. This is designated as nonionic surfactant solution A.

223.8 g of potassium persulfate is mixed with 12.0 L of ion-exchanged water, and stirred and dissolved at room temperature. This is called initiator solution A.

A 100 L reactor equipped with a temperature sensor, a cooling pipe, and a nitrogen introducing device had a number average molecular weight (Mn) of 35.
Then, 3.41 kg of the polypropylene emulsion of No. 00, anionic surfactant solution A and nonionic surfactant solution A are added, and stirring is started. Then, ion-exchanged water 44.0
Add L.

The heating is started, and when the liquid temperature reaches 75 ° C., the entire amount of the initiator solution A is added. Then, while controlling the liquid temperature to 75 ° C. ± 1 ° C., 12.1 kg of styrene
And 2.88 kg of n-butyl acrylate, 1.04 kg of methacrylic acid and 548 g of t-dodecylmercaptan.

Further, the liquid temperature was raised to 80 ° C. ± 1 ° C.
Heating and stirring were performed for 6 hours. The liquid temperature is cooled to 40 ° C. or less, and the stirring is stopped. The mixture was filtered with a pole filter to obtain latex A1.

The resin particles in the latex A1 had a glass transition temperature of 57 ° C., a softening point of 121 ° C., a molecular weight distribution of weight average molecular weight = 12.7 million, and a weight average particle size of 12 ° C.
It was 0 nm.

202.0 g of potassium persulfate is mixed with 12.0 L of ion-exchanged water, and dissolved by stirring at room temperature. This is designated as initiator solution B.

The nonionic surfactant solution A is placed in a 100 L reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a comb baffle, and stirring is started. Next, 44.0 L of ion-exchanged water is charged.

[0230] Heating is started, and when the liquid temperature reaches 70 ° C, an initiator solution B is added. At this time, styrene 1
1.0 kg, 4.00 kg of n-butyl acrylate, 1.04 kg of methacrylic acid, and t-dodecyl mercaptan 9.
And a solution obtained by previously mixing 02 g with the mixture.

Thereafter, the liquid temperature was controlled at 72 ° C. ± 2 ° C., and the mixture was heated and stirred for 6 hours. Further, the liquid temperature is set to 80 ° C.
The temperature was raised to ± 2 ° C., and the mixture was heated and stirred for 12 hours.

The temperature of the solution is cooled to 40 ° C. or less, and the stirring is stopped. The solution was filtered through a pole filter, and the filtrate was used as latex B1.

The resin particles in the latex B1 have a glass transition temperature of 58 ° C., a softening point of 132 ° C., and a molecular weight distribution of weight average molecular weight = 245,000 and weight average particle size of 115,000.
It was 0 nm.

Sodium chloride as salting-out agent = 5.36
kg and 20.0 L of ion-exchanged water are added and stirred and dissolved.
This is designated as sodium chloride solution A.

A 100-L SUS reaction vessel equipped with a temperature sensor, a cooling pipe, a nitrogen introducing device, and a comb-shaped baffle (the stirring blade was an anchor blade) was charged with the latex A1 = 2 prepared above.
0.0 kg, latex B1 = 5.2 kg, colorant dispersion 1 = 0.4 kg, and ion-exchanged water 20.0 kg are stirred. Then, the mixture is heated to 35 ° C., and sodium chloride solution A is added. Thereafter, after standing for 5 minutes, heating is started and the temperature is increased to 85 ° C. in 5 minutes (heating rate =
10 ° C / min). The mixture is heated and stirred at a liquid temperature of 85 ° C. ± 2 ° C. for 6 hours to cause salting out / fusion. Thereafter, the mixture is cooled to 30 ° C. or lower and the stirring is stopped. The solution is filtered through a sieve having an opening of 45 μm, and this filtrate is used as an association liquid. Then use a centrifuge,
Non-spherical particles in the form of a wet cake were collected by filtration from the associated liquid. Thereafter, the substrate was washed with ion-exchanged water.

The wet cake-like colored particles having been washed as described above were dried with warm air at 40 ° C. to obtain colored particles.
The volume average particle size of the colored particles was 4.3 μm. Further, the colored particles are added to hydrophobic silica (hydrophobicity = 65,
1.0% by mass of a number average primary particle size = 12 nm) and 1.0% by mass of 0.1 μm styrene-methyl methacrylate particles, and the peripheral speed of a Henschel mixer was 2%.
The mixture was mixed at 0 m / s and 30 ° C. for 10 minutes to obtain “Toner 4.”

* Preparation of Toner 5 Colored particles whose particle diameters were changed by changing the fusion conditions of toner 4 were prepared, and hydrophobic silica (hydrophobicity =
65, a number average primary particle size = 12 nm) and 1.6% by mass of 1.6 μm titanium oxide, and mixed at a peripheral speed of 5 m / s of a Henschel mixer at 24 ° C. for 10 minutes. "Toner 5" was obtained.

The characteristics of each of the toners were evaluated, and the measurement results are shown in Table 1.

[0239]

[Table 1]

Measurement method of volume average particle diameter of toner: Measured by Coulter Multisizer. Measuring method of sum of relative frequency of number distribution of toner particles: Particle size data of each toner measured by a Coulter Multisizer is transferred to a computer via an I / O unit, and the computer calculates relative frequency m ₁ and m ₂ . The sum M was determined.

Preparation of Developer A ferrite carrier coated with a silicone resin and having a volume average particle diameter of 45 μm was mixed with each of the above toners, namely, toners 1 to 5, and a developer having a toner concentration of 6% was adjusted. Used for evaluation. These five types of developers are referred to as developer 1 to developer 5, respectively, corresponding to the toner.

The volume average particle size of the carrier is typically measured by a laser diffraction type particle size distribution analyzer “HELOS” equipped with a wet disperser (SYMPATIC (SYMPIC)
(ATEC)). Examples and Comparative Examples (total of 12 examples) <Evaluation> The photoconductors were evaluated under the environmental conditions shown in Table 2 below.
In the case where the control is performed so as to maintain the predetermined temperature described in 1 above, and in the case where this control cannot be performed without a heating device, the type of the developer (the type of the toner) and the rubber blade characteristics of the cleaning unit are changed, and the elastic rubber blade is changed. A combination of the example and the comparative example in which the magnitude of the vibration was changed was prepared as shown in Table 3, and the combination was mounted on an evaluation machine in which the exposure amount was optimized using the image forming apparatus shown in FIG. The charging potential was set to -750 V, 5000 sheets of continuous copying were performed at a speed of 20 sheets / minute of A4 paper, and a total of 100,000 sheets were copied by repeating pause for 2 hours, and the following evaluation was performed.

Evaluation Process Conditions The process conditions at the time of the image evaluation were set as follows.

Charging Conditions Charger: Scorotron charger, initial charging potential was -750
V Development condition DC bias; -500 V Dsd (distance between photoreceptor and developing sleeve); 600 µm Developer layer regulation; Magnetic H-Cut method Developer layer thickness: 700 µm Developing sleeve diameter; 40 mm Transfer conditions Transfer pole; Corona transfer method ( Transfer dummy current value: 45μ
A) Cleaning conditions Cleaning blade; urethane elastic rubber blade shown in Table 3 Free length of blade; 9 mm Contact angle to photoreceptor (counter direction); 20 ° Contact load; 5 to 25 (g / cm)

[0245]

[Table 2]

[0246]

[Table 3]

(1) Image Evaluation Copy image evaluation is performed on a character image with a blackening ratio of 7%. At the start, and until the end of 100,000 copies for every 5,000 copies, a halftone, solid white image, or solid black image is obtained. Was evaluated. The image density and fog were measured using a densitometer “RD-918” (manufactured by Macbeth) for a solid white image and a solid black image at the end of 100,000. It was measured at a relative concentration of zero. The presence or absence of image blur was visually evaluated.

A. Image density ・ ・ ・: 1.4 or more / Good ・ ・ ・: 1.0 or more to less than 1.4 / No problem in practical use ×: Less than 1.0 / Problem in practical use b. Fog ・ ・ ・: Less than 0.001 / Good ・ ・ ・: 0.001 or more to less than 0.003 / No practical problem x: 0.003 or more / Practical problem c. Image blurring (evaluation of image blurring in image of character portion) ◎ ・ ・ ・ 5 or less out of 100,000 sheets / good ○ ・ ・ ・ 6 to 10 out of 100,000 sheets / No problem in practical use ×: occurrence of 11 or more sheets out of 100,000 sheets / problem in practical use d. Fine Line Reproducibility The line width of a line image corresponding to a 2-dot line image signal was measured by a print evaluation system “RT2000” (manufactured by Yarman Corporation).

A: The line width (L) of the first formed image
1) and the line width of the formed image at the end of 100,000 (L10
) Is 200 μm or less, and the change in line width (L1−L100,000) is 10 μm or less / good × ... Other than the above / practical problem e. Evaluation of Image Defects The evaluation of black spots was performed using the image analyzer "Omnicon 3000".
The size and the number of black spots were measured using a "type" (manufactured by Shimadzu Corporation), and the number of black spots having a size of 0.1 mm or more in A4 paper was determined. In addition, large defects such as streak-like image defects (black streaks and white streaks) caused by filming and transfer defects were visually judged. The criteria for determining black spots and streak-like image defects are as follows.

Black spots and streak-like image defects (evaluated by halftone, solid white image, and solid black image) ・ ・ ・: 1 or less / one A4 sheet, no streak defect / good 3 pieces / one A4 sheet, no streak defects / no problem in practical use × 4 or more / one A4 sheet, or one streak image defect
More than / practical problem f. Photoreceptor thickness loss difference: After copying 100,000 sheets, the photoreceptor thickness wear was measured.

| Photoreceptor film thickness after completion of 100,000 copies-Photoreceptor film thickness at start | = Abrasion amount Δd (μm) g. Uneven wear (μm) Absolute value of the difference in film thickness at 3 cm from the center and the end of the black photosensitive drum | Thickness of the photosensitive member at the end of 100,000-3 cm from the end at the end of 100,000 The film thickness at the point | = Δd (μm) Photoreceptor film thickness measuring method The film thickness of the photosensitive layer is measured at random at 10 places of uniform film thickness, and the average value is defined as the film thickness of the photosensitive layer. The film thickness measuring device is an eddy current type film thickness measuring device EDDY560C (HELMUT
FISCHER GMBTE CO).

H. Blade Turning During the evaluation of 100,000 copy images, the presence or absence of blade turning was evaluated.

It was determined that some elastic rubber blades were replaced due to blade turning. The results of the image evaluation are shown in Table 4 below.

[0254]

[Table 4]

In the combinations of Examples 1 to 11 in which the magnitude of vibration (10 to 200 μm) of the elastic rubber blade and the turbidity and water content of the toner were controlled to specific ranges, the image evaluation was all good. In contrast, in Comparative Examples 1 and 2 in which the magnitude of the vibration was 8 μm, and in Comparative Examples 2 and 3 in which the magnitude of the vibration was 8 μm, an image defect was generated because the vibration energy of the elastic rubber blade did not sufficiently act as a toner cleaning force. ing.

[0256]

According to the image forming method and the image forming apparatus of the present invention, in which a specific cleaning condition and a toner whose turbidity and water content are controlled in specific ranges are used, even when a large number of copies are evaluated, there is no image defect. It is clear from the above embodiment that a clear image can be obtained.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram illustrating an overall configuration of an image forming apparatus of the present invention.

FIG. 2 is a front view showing a configuration of a photosensitive member and its periphery in the image forming apparatus of the present invention.

FIG. 3 is a diagram illustrating a mechanism of vibration of an elastic rubber blade.

FIG. 4 is a diagram illustrating a cleaning mechanism.

FIG. 5 is a configuration diagram for temperature control.

FIG. 6 is a flowchart of temperature control of a photoconductor in a warm-up mode.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 21 Photoconductor 22 Charger 23 Developing device 24 Transfer device 25 Separator 26 Cleaning means 26A Elastic rubber blade 27 PCL (precharge lamp) 30 Exposure optical system 70 Current supply circuit 71 Heater 72 Temperature sensor 73 Environmental condition detecting means 731 Temperature sensor 732 humidity sensor 80 control means 81 mode management unit

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 5/07 103 G03G 5/147 502 5/147 502 503 503 503 504 504 9/08 9/08 21/00 318 F-term (reference) 2H005 AA08 AB10 DA07 EA05 EA10 2H034 AA06 BF02 BF03 BF07 2H068 AA03 AA04 AA54 BB33 BB41 CA06 FC15 4J002 CP091 EJ016 EJ026 EJ036 EJ046 EU076 FD076 4

Claims (16)

[Claims] In an image forming method for cleaning a toner image remaining on an electrophotographic photosensitive member after transferring a toner image on the electrophotographic photosensitive member to a transfer material, an elastic rubber blade is used in the cleaning step. Use
The elastic rubber blade is brought into contact with the electrophotographic photosensitive member in the counter direction, and the elastic rubber blade is
Vibration is performed at a vibration magnitude of 0 to 200 μm to clean the toner remaining on the electrophotographic photoreceptor, the turbidity of the toner used in the image forming method is 50 or less, and the toner is used at 30 ° C. An image forming method, wherein the saturated water content in an 80 RH% environment is 0.1% or more and 2.0% by mass or less. 2. The image forming method according to claim 1, wherein the electrophotographic photosensitive member has a heating device. 3. The electrophotographic photoreceptor has at least a plurality of resin layers on a cylindrical conductive support, and one of the resin layers has a structural unit having charge transport performance and has a crosslinked structure. The image forming method according to claim 1, wherein the resin layer is a resin layer containing a siloxane-based resin. 4. The image forming method according to claim 3, wherein the resin layer containing the siloxane-based resin is a surface layer. 5. It has a structural unit having the charge transporting performance.
And a siloxane-based resin having a cross-linked structure is a hydroxyl group,
Or an organosilicon compound having a hydrolyzable group, and
Obtained by reacting with the compound represented by the general formula (1)
4. A siloxane-based resin,
5. The image forming method according to item 4. General formula (1) B- (R₁-ZH)_m [In the formula, B is a monovalent compound containing a structural unit having a charge transporting property.
Or a polyvalent group; ₁Is a single bond or divalent alkyl
Z represents an oxygen atom, a sulfur atom or NH,
m represents an integer of 1 to 4. ] 6. The image forming method according to claim 5, wherein Z in the general formula (1) is an oxygen atom. 7. The image forming method according to claim 3, wherein the resin layer containing the siloxane-based resin contains an antioxidant. 8. The image forming method according to claim 7, wherein the antioxidant is a hindered phenol antioxidant or a hindered amine antioxidant. 9. The image forming method according to claim 3, wherein the resin layer containing the siloxane-based resin contains organic or inorganic particles. 10. The image forming method according to claim 3, wherein the resin layer containing the siloxane-based resin contains colloidal silica. 11. The image forming method according to claim 1, wherein the turbidity of the toner is 30 or less. 12. The toner according to claim 1, wherein the toner has a volume average particle diameter of 4 to 9 μm.
The image forming method according to claim 1, wherein the number of toner particles having a m of 3.0 μm or less is 30% by number or less. 13. When the particle diameter of the toner is D (μm), the natural logarithm InD is plotted on the horizontal axis, and the horizontal axis is 0.2.
A histogram showing the number-based particle size distribution divided into a plurality of classes at three intervals, the relative frequency (m ₁ ) of the toner particles included in the most frequent class, and the relative frequency (m ₁ ) included in the next frequent class after the most frequent class The sum of the relative frequency (M) with the relative frequency (m ₂ ) of the toner particles is 70% or more.
13. The image forming method according to any one of the above items 12. 14. An image forming apparatus in which a toner image on an electrophotographic photosensitive member is transferred to a transfer material and a toner remaining on the electrophotographic photosensitive member is cleaned by a cleaning means. Use
The elastic rubber blade is brought into contact with the electrophotographic photosensitive member in the counter direction, and the elastic rubber blade is
Vibration is performed at a vibration magnitude of 0 to 200 μm to clean the toner remaining on the electrophotographic photosensitive member, and the turbidity of the toner used in the image forming apparatus is 50 or less, and the toner has a temperature of 30 ° C. An image forming apparatus, wherein the saturated water content in an 80% RH environment is 0.1% or more and 2.0% by mass or less. 15. An image forming apparatus in which a toner image on an electrophotographic photosensitive member is transferred to a transfer material and a toner remaining on the electrophotographic photosensitive member is cleaned by a cleaning means, wherein an elastic rubber blade is provided on the cleaning means. Use
The elastic rubber blade is brought into contact with the electrophotographic photosensitive member in the counter direction, and the elastic rubber blade is
Vibration is performed at a vibration magnitude of 0 to 200 μm to clean the toner remaining on the electrophotographic photosensitive member, and the turbidity of the toner used in the image forming apparatus is 50 or less, and the toner has a temperature of 30 ° C. An image forming apparatus, wherein the saturated water content in an 80 RH% environment is 0.1% or more and 2.0% by mass or less, and the electrophotographic photosensitive member has a heating device. 16. An image forming apparatus in which a toner image on an electrophotographic photosensitive member is transferred to a transfer material and a toner remaining on the electrophotographic photosensitive member is cleaned by a cleaning device. Hardness in J
An elastic rubber blade of polyurethane rubber having an ISA scale of 65 or more and a rebound resilience at 25 ° C. ± 0.2 ° C. of 20 or more and 75 or less is used, and the elastic rubber blade is attached to the electrophotographic photosensitive member. And makes the elastic rubber blade vibrate at a vibration magnitude of 10 to 200 μm to clean the toner remaining on the electrophotographic photoreceptor and to remove the toner used in the image forming apparatus. An image forming apparatus having a turbidity of 50 or less and a saturated water content of the toner in an environment of 30 ° C. and 80 RH% of 0.1 to 2.0 mass%.