JP2002221886A - Image forming method and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method which is capable of maintaining cleaning performance for a long period of time and forming good electrophotographic images when an organic photoreceptor having a siloxane- base resin layer as a surface layer and polymer toners are used and an image forming device. SOLUTION: This image forming method is characterized in that the the organic photoreceptor has the surface layer containing the resin formed by bonding of the silixane condensate and the organic polymer to each other and that the following equation 1 and equation 2 are satisfied when the average value of the dynamic torque value generated between the organic photoreceptor and a cleaning blade is defined as Y0 of the case a toner image is not formed on the organic photoreceptor and the average value of the dynamic torque value of the case the toner image is formed on the organic photoreceptor at 100% blackening rate as Y100: The formula 1 0.2>=Y100-Y0>=0.01 The formula 2 2.95>=Y100/Y0>=1.15 (the unit of Y100, Y0: N.m).

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 used in an electrophotographic copying machine, a printer and the like.

[0002]

2. Description of the Related Art In recent years, an organic photoconductor containing an organic photoconductive substance (hereinafter simply referred to as a photoconductor) is most widely used as an image carrier used in an electrophotographic image forming apparatus. Organic photoreceptors are advantageous over other photoreceptors in that materials that can be used for various exposure light sources from visible light to infrared light can be easily developed, materials that do not pollute the environment can be selected, and manufacturing costs are low. However, the only drawback is that the mechanical strength is weak, and the surface of the photoreceptor is deteriorated or scratched when a large number of sheets are copied or printed.

[0003] However, the organic photoreceptor has a large contact energy with a toner which visualizes an electrostatic latent image formed on the photoreceptor, and after transferring the toner image to a transfer material in a transfer step, the organic photoreceptor has a high contact energy. Various problems tend to occur in cleaning residual toner remaining on the photoconductor.

[0004] On the other hand, in the electrophotographic image forming method, digital image formation has become mainstream due to recent advances in digital technology. A digital image forming method is based on visualizing a small dot image of one pixel such as 400 dpi (the number of dots per 2.54 cm), and a high image quality technology for faithfully reproducing these small dot images is required. Has been requested.

On the other hand, with respect to the deterioration of the surface of the organic photosensitive member due to cleaning, various techniques for increasing the mechanical strength of the surface of the photosensitive member have been proposed. As a technique for improving the surface wear of an organic photoreceptor, a photoreceptor having a siloxane resin layer as a surface layer has been proposed in JP-A-10-275245. Unlike a conventional organic photoreceptor, the photoreceptor having the siloxane resin layer has a small surface abrasion due to cleaning, and therefore has a large frictional force with a cleaning blade (hereinafter, also simply referred to as a blade). Cleaning defects such as blade turn-up and toner slippage caused by vibration of the blade are likely to occur.

Another technique for improving image quality is a technique relating to a toner manufacturing technique. Until now, so-called pulverized toner obtained by mixing a binder resin and a pigment, kneading and then pulverizing and then classifying a toner powder in a classification step has been mainly used for forming an electrophotographic image. The toner obtained via the above method has a limit in making the particle size distribution of the toner particles uniform, and the particle size distribution and the shape of the toner particles are insufficiently uniform. It is difficult to achieve a sufficiently high image quality in an electrophotographic image using such a pulverized toner.

In recent years, an electrophotographic developer using a polymerized toner or an image forming method has been proposed as a means for achieving a uniform particle size distribution and shape of toner particles.
Since the polymerized toner is manufactured by uniformly dispersing the raw material monomers in an aqueous system and then polymerizing the same, a toner having a uniform particle size distribution and shape of the toner can be obtained.

Here, when the polymerized toner is used in an image forming apparatus using an organic photoreceptor, a new technical problem has arisen. That is, as described above, the polymerized toner is formed in a substantially spherical shape because the toner shape is formed during the polymerization process of the monomer. As is well known, the spherical residual toner on the organic photoreceptor easily causes cleaning failure. In particular, the surface of the organic photoreceptor is easily worn, and if toner adheres to the unevenness of the surface caused by the abrasion, a minute amount of toner that does not occur in an image is generated for a long period of time, and the toner that has slipped off is charged by the charging member ( (A charging wire or a charging roller) is contaminated, and as a result, image unevenness occurs in a halftone image or the like.

Various proposals have been made to improve the above-described cleaning defects such as turning over of the blade and slippage of the toner which occur in the image forming method using the organic photoreceptor or the polymerized toner. Above all, proposals have been made to change the shape of the polymerized toner from a spherical shape to an elliptical shape, and proposals to make the surface shape of the polymerized toner uneven have been made. However, even these proposals have not been sufficient solutions.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to maintain the cleaning performance for a long time when an organic photoreceptor having a siloxane resin layer as a surface layer and a polymerized toner are used. Another object of the present invention is to provide an image forming method and an image forming apparatus capable of forming a good electrophotographic image without image defects.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted various studies to solve the above-mentioned problems, and as a result, have found that the fluctuation of the torque generated between the organic photoreceptor having a specific surface layer and the cleaning blade can be properly adjusted. By adjusting the thickness within such a range, it is possible to secure good cleaning performance and to maintain stable vibration of the cleaning blade, and to solve the above-mentioned problems. That is, it has been found that the object of the present invention is achieved by adopting one of the following constitutions.

1. The electrostatic latent image formed on the organic photoreceptor is developed with a developer containing toner, and the toner image visualized by the development is transferred from the organic photoreceptor to a transfer material. An image forming method for removing residual toner by a cleaning device having a cleaning blade, wherein the organic photoreceptor has a surface layer containing a resin in which a siloxane condensate and an organic polymer are mutually bonded,
And when a toner image is not formed on the organic photoreceptor,
The average value of the dynamic torque generated between the organic photoconductor and the cleaning blade is Y ₀ , and the average value of the dynamic torque when a toner image is formed on the organic photoconductor at a 100% blackening ratio is Y.
An image forming method characterized by satisfying the following formulas (1) and (2) when ₁₀₀ is set.

Equation 1 0.2 ≧ Y ₁₀₀ −Y ₀ ≧ 0.01 Equation 2 2.95 ≧ Y ₁₀₀ / Y ₀ ≧ 1.15 (Unit of Y ₁₀₀ and Y ₀ : N · m) The electrostatic latent image formed on the organic photoreceptor is developed with a developer containing toner, and the toner image visualized by the development is transferred from the organic photoreceptor to a transfer material. An image forming method for removing residual toner by a cleaning device having a cleaning blade, wherein the organic photoreceptor has a surface layer containing a resin in which a siloxane condensate and an organic polymer are mutually bonded, and the organic photoreceptor When a toner image is not formed on the organic photoconductor, the average value of the dynamic torque generated between the organic photoconductor and the cleaning blade is Y ₀ , and the dynamic torque when the toner image is formed on the organic photoconductor at a 100% blackening rate is Y ₀ . when the average value of the torque value was Y _100, wherein the minimum time required for dynamic torque value to change from Y ₀ to Y _{10 0} (τ) is configured from 0.010 to 0.500 seconds Picture Image forming method.

3. The electrostatic latent image formed on the organic photoreceptor is developed with a developer containing toner, and the toner image visualized by the development is transferred from the organic photoreceptor to a transfer material. An image forming method for removing residual toner by a cleaning device having a cleaning blade, wherein the organic photoreceptor has a surface layer containing a resin in which a siloxane condensate and an organic polymer are mutually bonded,
And when a toner image is not formed on the organic photoreceptor,
The average value of the dynamic torque generated between the organic photoconductor and the cleaning blade is Y ₀ , and the average value of the dynamic torque when a toner image is formed on the organic photoconductor at a 100% blackening ratio is Y.
_The minimum time (τ) required to satisfy Expressions 1 and 2 when ₁₀₀ is set and to change the dynamic torque value from Y ₀ to Y ₁₀₀ is 0.010 to 0.500 seconds. An image forming method comprising:

4. The image forming method according to any one of claims 1 to 3, wherein the resin is formed by reacting an organic polymer having a siloxane condensate.

5. The image forming method according to any one of the above items 1 to 4, wherein the resin forms a crosslinked structure over the entire surface layer.

6. Wherein the siloxane condensate has a charge transporting group as a partial structure.
The image forming method according to any one of the above items.

[7] The image forming method according to any one of Items 1 to 6, wherein the organic polymer is a polycarbonate polymer.

8. Any one of the above 1 to 6, wherein the organic polymer is a polyarylate polymer
Item.

9. The image forming method according to any one of Items 1 to 6, wherein the organic polymer is a polyester-based polymer.

10. Wherein the siloxane condensate is formed at the main chain terminal of the organic polymer.
10. The image forming method according to any one of 9.

11. As the toner of the developer, the coefficient of variation of the shape coefficient of the toner particles is 16% or less, and the number variation coefficient of the number and particle size distribution of the toner particles is 27%.
% Or less, wherein the toner is 1% or less.
The image forming method according to claim 10.

12. (1) The toner according to (1), wherein a toner containing 65% by number or more of toner particles having a shape coefficient in a range of 1.2 to 1.6 is used as the toner of the developer.
12. The image forming method according to any one of items 11 to 11.

13. 13. The image forming method according to any one of items 1 to 12, wherein a toner containing 50% by number or more of toner particles having no corners is used as the toner of the developer.

14. The image forming method according to any one of Items 1 to 13, wherein a toner having a number average particle diameter of toner particles of 3 to 8 μm is used as the toner of the developer.

15. Assuming that the particle size of the toner particles is D (μm) as the toner of the developer, the natural logarithm lnD is plotted on the horizontal axis, and the horizontal axis is the number-based particle size distribution divided into a plurality of classes at intervals of 0.23. In the histogram shown,
The relative frequency (m ₁ ) of the toner particles contained in the mode,
The toner according to any one of 1 to 14, wherein a toner having a sum (M) of 70% or more with respect to the relative frequency (m ₂ ) of the toner particles included in the class having the highest frequency next to the mode is used. Item 2. The image forming method according to Item 1.

16. An image forming apparatus using the image forming method according to any one of 1 to 15.

The present invention will be described in more detail. FIG. 1 is a schematic configuration diagram showing the overall configuration of an image forming apparatus using the image forming method of the present invention.

The image forming apparatus shown in FIG. 1 is a digital image forming apparatus, and includes an image reading section A, an image processing section B (not shown), an image forming section C, and transfer paper transfer as transfer paper transfer means. It is composed of a section D.

An automatic document feeder for automatically feeding a document is provided above the image reading section A.
The document placed on the document 11 is separated and conveyed one by one by a document conveying roller 112, and an image is read at a reading position 113a. The document for which reading of the document has been completed is discharged onto the document discharge tray 114 by the document conveying roller 112.

On the other hand, the image of the original placed on the platen glass 113 is read in a V-shape by a reading operation at a speed v of a first mirror unit 115 comprising an illumination lamp and a first mirror constituting a scanning optical system. Reading is performed by moving the second mirror unit 116 including the second and third mirrors located in the same direction at the speed v / 2.

The read image is formed on a light receiving surface of an image sensor CCD, which is a line sensor, through a projection lens 117. The linear optical image formed on the image pickup device CCD is sequentially subjected to A / D conversion after being photoelectrically converted into an electric signal (luminance signal), and subjected to processing such as density conversion and filter processing in an image processing unit B. After that, the image data is temporarily stored in the memory.

In the image forming unit C, as an image forming unit, a drum-shaped photosensitive member (hereinafter, also referred to as a photosensitive drum) 121 serving as an image bearing member, a charger 122 serving as a charging unit, and a developing unit are provided around the drum. A developing device (hereinafter also referred to as a developing device) 123, a transfer device 124 as a transfer unit, a separator 125 as a separating unit, a cleaning device 126, and a PCL (precharge lamp) 127 are arranged in the order of operation. The photoreceptor 121 is formed by coating a photoconductive compound on a drum substrate, and is, for example, an organic photoreceptor (O
PC) is preferably used and is driven and rotated clockwise as shown.

After the rotating photosensitive member 121 is uniformly charged by the charger 122, the exposure optical system 130 performs image exposure based on the image signal called from the memory of the image processing section B. Exposure optical system 1 as writing means
Reference numeral 30 denotes a laser diode (not shown) as a light source,
An optical path is bent by a reflection mirror 132 through a rotating polygon mirror 131, an fθ lens (no sign), and a cylindrical lens (no sign) to perform main scanning. Image exposure is performed on the photoconductor 121 at the position of Ao. Then, a latent image is formed by rotation (sub-scan) of the photoconductor 121. In one example of the present embodiment, a character portion is exposed to form a latent image.

The latent image on the photosensitive member 121 is subjected to reversal development by the developing device 123, and a visible toner image is formed on the surface of the photosensitive member 121. In the transfer paper transport section D, a paper feed unit 141 (A) as a transfer paper storage unit in which transfer papers P of different sizes are stored below the image forming unit;
141 (B) and 141 (C) are provided, and a manual paper feed unit 142 for performing manual paper feed is provided on the side. Transfer paper P selected from any of them is guided by guide rollers 143. Paper is fed along the conveyance path 140,
The transfer sheet P is temporarily stopped by a pair of registration rollers 144 for correcting the inclination and deviation of the transfer sheet to be fed, and then re-feeded.
And the photosensitive member 121 is guided by the transfer entry guide plate 146.
The upper toner image is transferred to the transfer sheet P by the transfer unit 124 at the transfer position Bo, and then the charge is removed by the separator 125, the transfer sheet P is separated from the surface of the photoconductor 121, and is transferred to the fixing unit 150 by the transfer device 145. You.

The fixing device 150 has a fixing roller 151 and a pressure roller 152, and transfers the transfer paper P to the fixing roller 15.
1 and the pressure roller 152,
The toner is fused by heating and pressing. The transfer paper P on which the toner image has been fixed is discharged onto the discharge tray 164.

FIG. 2 is a configuration diagram of a cleaning device having the cleaning blade of the present invention.

In the present invention, the cleaning blade 12
Preferred values of the contact load P and the contact angle θ of the 6A photoconductor are P = 5 to 40 N / m and θ = 5 to 35 °.

The cleaning 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 cleaning blade is preferably 0.5 to 10 mm.

The contact load P is the cleaning blade 126
A is a pressure contact force P ′ when A is brought into contact with the photosensitive drum 121.
Is the normal direction vector value.

The contact angle θ is 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.

The present invention is characterized in that the relationship regarding the fluctuation of the dynamic torque value generated between the organic photoreceptor and the cleaning blade satisfies the above equations (1) and (2).

In the equations (1) and (2), Y ₀ and Y ₁₀₀ are respectively 100% of the average value of the dynamic torque value of the cleaning blade when no toner image is formed on the organic photoreceptor of the present invention.
This is an average value of dynamic torque values when a toner image is formed at a blackening ratio.

The dynamic torque value of the cleaning blade when a toner image is not formed on the organic photoreceptor of the present invention indicates a dynamic torque value when a white background image is formed on the entire surface of the photoreceptor.
In the case of digital reversal development, image areas where image exposure is not performed,
In normal development used in analog copiers and the like, it indicates a dynamic torque value when a white background image is formed.

The average value Y ₀ of the dynamic torque value of the cleaning blade when no toner image is formed is obtained by sampling the dynamic torque value at the time of forming a white background image on the photosensitive member for 10 seconds every 1 data / 10 msec. Expressed as the simple average of

The dynamic torque value of the cleaning blade when a toner image having a blackening rate of 100% is formed on the organic photoreceptor of the present invention is defined as a blackening degree of 100% over the entire surface of the photoreceptor. A dynamic torque value when an image is output at 0.55 to 0.75 mg / cm ² .

[0047] 10 average value of dynamic torque value of the cleaning blade in the case of forming a toner image of 100% blackened ratio Y ₁₀₀ is a dynamic torque value at the time of solid black image formed on the photoreceptor for each data / 10 msec Sampling for a second, and expressing as a simple average of the total data.

The dynamic torque value acting on the cleaning blade was measured using a dynamic torque measuring device described later.

The cleaning apparatus according to the present invention is characterized in that the minimum time (τ) required to change the dynamic torque value from Y ₀ to Y ₁₀₀ is 0.010 to 0.500 seconds.

The minimum time (τ) required to change the dynamic torque value from Y ₀ to Y ₁₀₀ is the boundary area where a solid black image is continuously drawn from a white background image and the black image is shifted from the white background image to a black background image. Is the shortest time for the dynamic torque value appearing at to reach the level from Y ₀ to Y ₁₀₀ . The measurement in the shortest time is performed under the condition that each image is formed for one minute or more in order to stabilize the image forming conditions of the white background image and the solid black image.

FIG. 3 is a graph showing the measurement of dynamic torque generated by friction of the cleaning blade with the organic photoreceptor of the present invention.

The region C in FIG. 3 shows the dynamic torque waveform of the white background image portion, and the region D shows the dynamic torque waveform of the solid black image portion.
Shortest required from Y ₀ to change to Y ₁₀₀ time (tau) is in FIG. 3 e to f, ie the shortest time to migrate to the level of Y ₀ to Y _100.

Method of Measuring Dynamic Torque Value of the Present Invention The dynamic torque value of the present invention is measured by a torque measuring device (ONO SOKKI MD204R, Inc.) between the motor for driving the photosensitive drum and the drive shaft of the photosensitive drum. ) Was installed. FIG. 16 is a conceptual diagram of the torque measuring device. This torque measuring device includes a drive shaft of the photosensitive drum and its drive motor, a charger 122, an exposure optical system 130, a developing device 123, a toner supply unit 123H, and a cleaning device 126. For the torque measurement, a cleaning blade was set in the cleaning device, and a dynamic torque value was measured for each set condition. The dynamic torque value of the cleaning blade is detected by the torque measuring instrument, and the signal of the measuring instrument is taken into an arithmetic display (Ono Sokki TS3600A) and subjected to data processing by a personal computer, and the Y ₀ , Y ₁₀₀ and τ was calculated. The measurement of the dynamic torque value is performed, for example, under the condition of a peripheral speed of the photosensitive drum φ80 mm and 280 mm / sec. The sampling of dynamic torque value is 1 data / 10
msec. Also, at the start of the torque measuring device, a setting powder of a fluororesin powder was sprayed on the photosensitive member and the cleaning blade, and the photosensitive member was rotated for one minute.

The image forming method of the present invention is based on the case where the average value of the dynamic torque value of the cleaning blade when the toner image is not formed on the organic photoreceptor is Y ₀ , and the toner image is formed at 100% blackening rate. formula 1 when the average value of the dynamic torque value of the cleaning blade was Y _100, and is configured to satisfy the equation 2.

Equation 1 0.2 ≧ Y ₁₀₀ −Y ₀ ≧ 0.01 Equation 2 2.95 ≧ Y ₁₀₀ / Y ₀ ≧ 1.15 (Y ₁₀₀ , Y ₀ unit: N · m) Y ₁₀₀ and Y _If the relationship of ₀ is out of the above range, the toner easily passes through, and a white streak-like image defect or image unevenness is likely to occur in a halftone image.

The above range of Y ₁₀₀ and Y ₀ is preferably 0.1
8 ≧ Y ₁₀₀ −Y ₀ ≧ 0.02, 2.85 ≧ Y ₁₀₀ / Y ₀ ≧
1.2, particularly preferably 0.12 ≧ Y ₁₀₀ −Y ₀ ≧ 0.0
5, 2.3 ≧ Y ₁₀₀ / Y ₀ ≧ 1.3.

[0057] The image forming method of the present invention is the shortest required to change the dynamic torque value of the cleaning blade from Y ₀ to Y _{1 00} time (tau) is 0.010 to 0.500 seconds. If τ is less than 0.010, the blade bounces, instantaneous toner slip-through tends to occur, and line-shaped image defects parallel to the blade tend to occur. on the other hand,
When τ is longer than 0.500 seconds, the blade rubbing force against the photosensitive member cannot sufficiently follow the change in image density, and toner slips easily through the photosensitive member. Filming easily occurs on the top. Further, the preferable range of τ is 0.015 to 0.5.
400 seconds, a particularly preferred range is 0.05 to 0.300 seconds.

The cleaning blade used in the present invention is preferably an elastic rubber blade. The physical properties of the cleaning blade are controlled simultaneously by controlling the rubber hardness and the rebound resilience. Can be suppressed. Blade J at 25 ± 5 ° C
When the ISA hardness is less than 65, reversal of the blade is likely to occur, and when it is more than 80, the cleaning performance decreases. When the rebound resilience exceeds 80, reversal of the blade tends to occur, and when the rebound resilience is 20 or less, the cleaning performance deteriorates. More preferable rebound resilience is 20 or more and 80.
It is as follows. The Young's modulus is preferably in the range of 294 to 588 N / cm ² . (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%.) As the material of the elastic rubber blade used for the cleaning blade, urethane rubber, silicon rubber, Fluoro rubber, chloroprene rubber, butadiene rubber, and the like are known. Of these, urethane rubber is particularly preferable because of its excellent wear characteristics compared to other rubbers. For example, JP-A-59-30
Urethane rubber obtained by reacting and curing a polycaprolactone ester and a polyisocyanate described in No. 574 is preferable.

In the present invention, in the method of fixing the cleaning blade to the support member, it is preferable that the cleaning blade is substantially held on the support member on the photosensitive member contact surface side. By employing such a holding method, torque fluctuation of the cleaning blade can be stabilized. FIG. 4 is a diagram showing a method of fixing the cleaning blade to the support member. In FIG. 4, the contact method of (a) is preferable to (b).

The condition for properly pressing the cleaning blade against the surface of the photoreceptor is determined by a delicate balance of various characteristics, and is considerably narrow. It depends on the characteristics such as the thickness of the cleaning blade and the setting requires accuracy. However, the thickness of the cleaning blade cannot be always set under proper conditions because the thickness of the cleaning blade may vary at the time of manufacture. It may deviate from the proper area. In particular, when combined with an organic photosensitive layer using a high molecular weight binder resin, if it deviates from an appropriate region, image defects such as white spots or black spots due to filming and local toner adhesion are likely to occur.

Therefore, it is necessary to take measures for canceling the variation in the characteristics of the cleaning blade, etc., and the above-described setting does not affect the pressure contact force on the photosensitive member surface even if the thickness of the cleaning blade varies. The method will be effective.

In the present invention, it is preferable that the free end of the cleaning blade is pressed against the photosensitive member in a direction opposite to the rotation direction (counter direction).

The cleaning blade may be sprayed with a fluorine-based lubricant on the edge of the cleaning blade, if necessary, or the following fluorine-based polymer and fluorine-based polymer may be further applied on the tip of the cleaning blade over the entire width direction. It is preferable to apply a dispersion in which the base resin powder is dispersed in a fluorine-based solvent.

Next, the organic photoreceptor of the present invention will be described. The surface layer of the organic photoreceptor of the present invention has a surface layer containing a resin in which a siloxane condensate and an organic polymer are mutually bonded. Such a resin includes an organic polymer having a metal alkoxide group and an organosilicon compound represented by the following general formula (1):
By the reaction with the hydrolysis product of the organosilicon compound or the siloxane condensate, an organic polymer having a siloxane condensate at the terminal can be formed, and the organic polymers having the siloxane condensate react with each other. By doing so, the siloxane condensate block and the organic polymer block are mixed, and a resin having strong abrasion resistance and the like in which the entire surface layer is bonded by a crosslinked structure is formed.

Here, the surface layer does not merely function as a protective layer, but may have a function of a protective layer, a charge transport function, and the like.

Here, the reaction of the present invention means a chemical reaction such as a condensation reaction, a polycondensation reaction, or a cross-linking reaction, and as a result, a reaction that forms a chemical bond such as a covalent bond, an ionic bond, or a hydrogen bond. . The siloxane condensate refers to a resin structure in which siloxane bonds (Si-O-Si bonds) are three-dimensionally repeated.

Formula (1) R _n Si (Z) _4-n (wherein, R represents an organic group in which carbon is directly bonded to silicon in the formula, and Z represents a hydroxyl group or a hydrolyzable group. Where n is an integer of 0 to 3) Z in the general formula (1) is a hydrolyzable group, and is a methoxy group, an ethoxy group, a methylethylketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, a propoxy group, or a butoxy group. Methoxyethoxy group, halogen atom and the like. Examples of the organic group in which carbon is directly bonded to silicon represented by R include alkyl groups such as methyl, ethyl, propyl and butyl, aryl groups such as phenyl, tolyl, naphthyl and biphenyl, γ-glycidoxypropyl, β An epoxy-containing group such as-(3,4-epoxycyclohexyl) ethyl, a (meth) acryloyl group of γ-acryloxypropyl and γ-methacryloxypropyl,
hydrous groups such as γ-hydroxypropyl and 2,3-dihydroxypropyloxypropyl, vinyl groups such as vinyl and propenyl, mercapto groups such as γ-mercaptopropyl, γ-aminopropyl, N-β (aminoethyl)-
Examples include amino-containing groups such as γ-aminopropyl, halogen-containing groups such as γ-chloropropyl, 1,1,1-trifluoropropyl, nonafluorohexyl, and perfluorooctylethyl, and other nitro and cyano-substituted alkyl groups. be able to. When _n of R _n is 2 or 3, the plurality of organic groups bonded to the same silicon atom may be the same as each other;
It may be different.

When two or more organosilicon compounds represented by the above general formula (1) are used in producing the siloxane condensate component of the present invention, R of each organosilicon compound may be the same or different. You may.

Specific examples of the organosilicon compound represented by the general formula (1) include the following compounds.

That is, examples of the compound in which n is 0 include tetrachlorosilane, diethoxydichlorosilane, tetramethoxysilane, phenoxytrichlorosilane, tetraacetoxysilane, tetraethoxysilane, tetraallyloxysilane, tetrapropoxysilane, and tetraisopropoxy. Silane, tetrakis (2-methoxyethoxy) silane, tetrabutoxysilane, tetraphenoxysilane,
Examples include tetrakis (2-ethylbutoxy) silane and tetrakis (2-ethylhexyloxy) silane.

Examples of compounds wherein n is 1 include trichlorosilane, methyltrichlorosilane, vinyltrichlorosilane, ethyltrichlorosilane, allyltrichlorosilane, n-propyltrichlorosilane, n-butyltrichlorosilane, chloromethyltriethoxysilane, methyl Trimethoxysilane, mercaptomethyltrimethoxysilane, trimethoxyvinylsilane, ethyltrimethoxysilane, 3,3,4,4,5,5,6,6,6-nonafluorohexyltrichlorosilane, phenyltrichlorosilane, 3,3 , 3-trifluoropropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 2
-Aminoethylaminomethyltrimethoxysilane, benzyltrichlorosilane, methyltriacetoxysilane,
Chloromethyltriethoxysilane, ethyltriacetoxysilane, phenyltrimethoxysilane, 3-allylthiopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-bromopropyltriethoxysilane, 3-allylaminopropyltrimethoxy Silane, propyltriethoxysilane, hexyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-methacryloxypropyltrimethoxysilane, bis (ethylmethylketoxime) methoxymethylsilane,
Pentyltriethoxysilane, octyltriethoxysilane, dodecyltriethoxysilane and the like can be mentioned.

Examples of compounds wherein n is 2 include dimethyldichlorosilane, dimethoxymethylsilane, dimethoxydimethylsilane, methyl-3,3,3-trifluoropropyldichlorosilane, diethoxysilane, diethoxymethylsilane, dimethoxymethyl-silane. 3,3,3-trifluoropropylsilane, 3-chloropropyldimethoxymethylsilane, chloromethyldiethoxysilane, diethoxydimethylsilane, dimethoxy-3-mercaptopropylmethylsilane, 3,3,4,4,5,5 , 6,6,6-
Nonafluorohexylmethyldichlorosilane, methylphenyldichlorosilane, diacetoxymethylvinylsilane, diethoxymethylvinylsilane, 3-methacryloxypropylmethyldichlorosilane, 3-aminopropyldiethoxymethylsilane, 3- (2-aminoethylaminopropyl) Dimethoxymethylsilane, t-butylphenyldichlorosilane, 3-methacryloxypropyldimethoxymethylsilane, 3- (3-cyanopropylthiopropyl) dimethoxymethylsilane, 3- (2-acetoxyethylthiopropyl) dimethoxymethylsilane, dimethoxymethyl -2-piperidinoethylsilane, dibutoxydimethylsilane, 3-dimethylaminopropyldiethoxymethylsilane, diethoxymethylphenylsilane,
Diethoxy-3-glycidoxypropylmethylsilane,
3- (3-acetoxypropylthio) propyldimethoxymethylsilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxymethyloctadecylsilane and the like.

The organosilicon compound used as a raw material of the siloxane condensate component having a crosslinked structure generally has the number of hydrolyzable groups (4-
n): That is, when n is 3, the polymerization reaction of the organosilicon compound is suppressed. When n is 0, 1 or 2, a polymerization reaction easily occurs. In particular, when n is 1 or 0, the crosslinking reaction can be advanced to a high degree. Therefore, by controlling these, it is possible to control the storability of the obtained coating layer liquid and the hardness of the coating film.

In the present invention, the organic polymer having a metal alkoxide group is an organic polymer having a functional group having a metal alkoxide group at the main chain or side chain terminal of the organic polymer.
The organic polymer may be a branched polymer, but is preferably a linear polymer. The organic polymer may be a one-component polymer or a multi-component copolymer. Further, a plurality of organic polymers may be mixed and used.

Here, the organic polymer refers to a polymer whose main skeleton is composed of repeating units of an organic compound.

The organic polymer may be a vinyl-type polymer obtained by radical polymerization, but is preferably a polycondensation-type organic polymer such as polycarbonate, polyallylate and polyester.

Polycarbonate is a polymer having a carbonate structure (—OCOO—), and polyester is a polymer having an ester structure (—OCO—). Among polyesters, polyarylate having an aryl ester structure is particularly preferable. preferable.

Further, in the present invention, polycarbonates, polyarylates and polyesters represented by the following general formulas (A), (B) and (C) are preferred.

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In the general formula (A), R ₁ and R ₂ are each independently a halogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a vinyl group, an allyl group, a substituted or unsubstituted group having 6 to 12 carbon atoms. An unsubstituted aryl group, a substituted or unsubstituted cycloalkyl group having 5 to 7 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryloxy group having 6 to 12 carbon atoms; b is independently 0
To Y, and Y is a single bond, -O-, -CO-,
-S -, - SO -, - SO 2 -, - CR 3 R 4 -, a substituted or unsubstituted cycloalkylidene group, a substituted having 2 to 12 carbon atoms, or unsubstituted alkylene group having 5-11 carbon atoms, A 9,9′-fluorenylidene group, a 1,8-menthanediyl group, a 2,8-menthanediyl group, a substituted or unsubstituted pyradylidene group, or a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, provided that R ₃ And R _{4 are} each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 12 carbon atoms.

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In the general formula (B), R ₁ , R ₂ and Y have the same meanings as those in the general formula (A).

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In the general formula (C), R ₅ is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkylene group having 5 to 12 carbon atoms, or a substituted or unsubstituted arylene group. And R ₆ has 1 to 10 carbon atoms.
A substituted or unsubstituted alkylene group having 5 to 12 carbon atoms
Is a substituted or unsubstituted cycloalkylene group.

Further, the molecular weight of the organic polymer having a metal alkoxide group is preferably from 1,000 to 20,000,
2,000 to 10,000 are most preferred. When the molecular weight is less than 1,000, film properties such as abrasion resistance of the surface layer after polycondensation tend to be insufficient, and when the molecular weight is more than 20,000, sufficient smoothness of the surface layer is hardly achieved.

The metal alkoxide group preferably has a metal alkoxide at the main chain terminal (either one terminal or both terminals) of the organic polymer. By using an organic polymer having a metal alkoxide at the main chain terminal, a siloxane condensate is formed at the main chain terminal, and an organic polymer having a free structure in the main chain portion is formed. Condensation forms a surface layer in which the siloxane condensate and the organic polymer of the main chain part are present as blocks, respectively, and a surface layer with small fluctuations in dynamic torque value and good cleaning properties is easily obtained. In particular, when an organic polymer having an alkoxysilyl group represented by the following general formula (D) at a main chain terminal is used, a fluctuation in dynamic torque value is small, and a surface layer having good film properties and good cleaning properties is easily obtained. However, a metal alkoxide group may be present in a side chain other than the main chain. The method of introducing a metal alkoxide group into a polymer is described in detail in JP-A-11-209596 and the like.

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In the formula, R ₁ is at least one group selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. In the case of individual, they may be the same or different. X is an alkoxy group, and when there are a plurality of alkoxy groups, they may be the same or different. a is an integer of 0 to 2.

The surface layer of the present invention has a charge transporting group as a partial structure of the resin constituting the surface layer, so that it can have electrophotographic characteristics such as sensitivity characteristics as an electrophotographic photosensitive member and charging characteristics. . In order to incorporate the charge transporting group into the resin structure, a reactive charge is required at the time of the above-mentioned polycondensation, that is, at the time of the polycondensation using the organic polymer having a metal alkoxide group and the organosilicon compound of the general formula (1). This is achieved by allowing a transport compound to be present and allowing the polycondensation reaction involving the reactive charge transport compound to proceed.

The charge transporting group of the present invention is a structural unit having the property of having electron or hole drift mobility, or a charge transporting compound residue.
It is a structural unit or a charge transporting compound residue from which a detection current due to charge transport can be obtained by a known method capable of detecting charge transport performance such as a me-Of-Flight method.

Here, the reactive charge transporting compound means the above-mentioned organosilicon compound or a charge transporting compound having a reactive group capable of chemically bonding to a polymer having a metal alkoxide group. Hereinafter, the reactive charge transporting compound will be described.

Examples of the reactive charge transporting compound include a charge transporting compound having a hydroxyl group, a mercapto group, an amino group and a silyl group.

The charge transporting compound having a hydroxyl group is represented by the following general formula (2). Formula _{(2) X- (R 7 -OH} ) m wherein, X: charge transport group, R _7: a single bond, a substituted or unsubstituted alkylene group, an arylene group, m: is an integer from 1 to 5 .

Among them, there are the following as typical ones. For example, a triarylamine-based compound has a triarylamine structure such as triphenylamine as a charge transporting group = X, and has an alkylene or arylene group extended from a carbon atom constituting X or extended from X. A compound having a hydroxyl group through the intermediate is preferably used.

Next, a synthesis example of the charge transporting compound having a hydroxyl group will be described. Synthesis of Compound B-1

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Step A In a four-headed kolben equipped with a thermometer, a cooling tube, a stirrer, and a dropping funnel, 49 g of the compound (1) and 184 phosphorus oxychloride were added.
g was added and dissolved by heating. 117 g of dimethylformamide was gradually added dropwise from the dropping funnel.
The mixture was kept at ９５95 ° C. and stirred for about 15 hours. Next, the reaction solution was gradually poured into a large excess of warm water, and then slowly cooled while stirring.

The precipitated crystals were filtered and dried, and then purified by adsorption of impurities using silica gel or the like and recrystallization with acetonitrile to obtain Compound (2). Yield 30
g. Step B 30 g of compound (2) and 100 ml of ethanol were charged into a kolben and stirred. After gradually adding 1.9 g of sodium borohydride, the solution was kept at 40 to 60 ° C. and stirred for about 2 hours. Next, the reaction solution was gradually poured into about 300 ml of water, and stirred to precipitate crystals. After filtration, the resultant was sufficiently washed with water and dried to obtain a compound (3). The yield was 30 g.

The charge transporting compound having a mercapto group is represented by the following general formula (3). X- (R ₈ -SH) _m wherein X: a charge transporting group, R ₈ : a single bond, a substituted or unsubstituted alkylene, an arylene group, and m: an integer of 1 to 5.

The charge transporting compound having an amine group is represented by the following general formula (4). X- (R ₉ -NR ₁₀ H) _m wherein X: charge transporting group, R ₉ : single bond, substituted, unsubstituted alkylene, substituted, unsubstituted arylene group, R ₁₀ : A hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, m: an integer of 1 to 5;

Among the charge transporting compounds having an amino group, in the case of a primary amine compound (—NH ₂ ), two hydrogen atoms may react with an organosilicon compound and be linked to a siloxane structure. In the case of a secondary amine compound (—NHR ₁₀ ), one hydrogen atom reacts with the organosilicon compound, and R ₁₀ may be a group that remains as a branch or a group that causes a cross-linking reaction, and includes a charge transport material. It may be a compound residue.

Further, the charge transporting compound having a silyl group is represented by the following general formula (5). Formula (5) B - in _{- (R 1 -Si (R 11} ) 3-a (R 12) a) n -type, B is a group containing a structural unit having charge transportability, R ₁₁ is a hydrogen atom , A substituted or unsubstituted alkyl group or an aryl group, R ₁₂ represents a hydrolyzable group or a hydroxyl group, and R ₁ represents a substituted or unsubstituted alkylene group. a represents an integer of 1 to 3, and n represents an integer.

Representative examples of the general formulas (2) to (5) are shown below.

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The reactive charge transporting compound of the present invention is preferably a compound having a plurality of reactive groups in the same molecule. As a result, the reactivity of the reactive charge transporting compound with the organosilicon compound is improved, and the surface layer of the present invention has good charge transporting properties.

The charge transporting group of the present invention indicates a chemical structural component corresponding to the charge transporting group X in the general formulas (2) to (5). As a specific compound structure of the charge transporting group X, for example, as a hole transporting type CTM, oxazole, oxadiazole, thiazole, triazole, imidazole, imidazolone, imidazoline, bisimidazolidin, styryl, hydrazone, benzidine, pyrazoline Having a chemical structure such as stilbene compound, amine, oxazolone, benzothiazole, benzimidazole, quinazoline, benzofuran, acridine, phenazine, aminostilbene, poly-N-vinylcarbazole, poly-1-vinylpyrene, poly-9-vinylanthracene. Groups.

On the other hand, the electron transport type CTM includes succinic anhydride, maleic anhydride, phthalic anhydride, pyromellitic anhydride, melitic anhydride, tetracyanoethylene, tetracyanoquinodimethane, nitrobenzene, dinitrobenzene, trinitrobenzene, Tetranitrobenzene, nitrobenzonitrile, picryl chloride, quinone chlorimide, chloranil, bromanyl, benzoquinone, naphthoquinone, diphenoquinone, tropoquinone, anthraquinone, 1-chloroanthraquinone, dinitroanthraquinone, 4-nitrobenzophenone, 4,4'-dinitrobenzophenone, 4-nitrobenzalmalonedinitrile, α-cyano-β- (p-cyanophenyl) -2-
(P-chlorophenyl) ethylene, 2,7-dinitrofluorene, 2,4,7-trinitrofluorenone, 2,
4,5,7-tetranitrofluorenone, 9-fluorenylidenedicyanomethylenemalononitrile, polynitro-9-fluoronylidenedicyanomethylenemalonodinitrile, picric acid, o-nitrobenzoic acid, p-nitrobenzoic acid, 3, Examples include groups having a chemical structure such as 5-dinitrobenzoic acid, pentafluorobenzoic acid, 5-nitrosalicylic acid, 3,5-dinitrosalicylic acid, phthalic acid, and melitic acid.

The molecular weight of the reactive charge transporting compound used in the present invention is preferably 700 or less and 100 or more. 70
By using a reactive charge transporting compound of 0 or less,
It is possible to form a surface layer having a small residual electric charge, good electrophotographic characteristics, and excellent cleaning properties. Further, a reactive charge transporting compound having a molecular weight of 450 or less and 100 or more is preferable.

The charge transporting group X is shown as a monovalent group in the above formula, but the reactive charge transporting compound to be reacted with the organosilicon compound and the siloxane condensate component is 2
When it has two or more reactive functional groups, it may be bonded as a divalent or higher crosslink group in the resin, or may be bonded simply as a pendant group.

The mass ratio of the charge transporting group to the total mass of the polymer main chain component and the siloxane condensate component in the surface layer of the invention is preferably from 1: 0.01 to 10:10. If the mass ratio of the charge transporting group is small, the electrophotographic characteristics (charging, sensitivity, residual potential characteristics, etc.) during repeated use are degraded, while if it is large, the film strength is reduced.

The mass ratio of the polymer main chain component, the siloxane condensate component and the charge transporting group in the surface layer of the present invention is such that the polymer main chain component is 1 and the siloxane condensate component is 0.25 to 4;
It is preferable that the charge transporting group has a mass ratio of 0.02 to 50. When the mass ratio of the siloxane condensate component is small, the film strength is reduced. On the other hand, when the mass ratio is large, the cleaning property is deteriorated and the blade is easily turned up. Further, the adhesiveness to the lower photosensitive layer is deteriorated. If the mass ratio of the charge transporting group is small, the electrophotographic characteristics (charging, sensitivity, residual potential characteristics, etc.) during repeated use are degraded, while if it is large, the film strength is reduced.

The above surface layer may contain metal oxide particles as long as the effects of the present invention are not impaired. By incorporating the metal oxide particles, the wear resistance of the surface layer of the present invention can be further improved, and the cleaning performance of the toner and the stability of the cleaning blade against turning up can be improved.

The metal oxide particles have a primary particle size of 5 nm to
Preferably it is 500 nm. These metal oxide particles are usually synthesized by a liquid phase method and can be obtained as colloid particles. Examples of metal atoms include Si, T
i, Al, Cr, Zr, Sn, Fe, Mg, Mn, N
i, Cu and the like.

The metal oxide particles preferably have a compound group reactive with the organosilicon compound on the surface of the particles. As the reactive compound group,
Examples include a hydroxyl group and an amino group. By using metal oxide particles having such a reactive group, the present invention forms a complex surface layer in which the surface of the metal oxide particles is chemically bonded to the siloxane condensate component, and is used for blade cleaning and the like. It is possible to form a surface layer having good electrophotographic properties, which is not easily worn by abrasion. The amount is preferably 0.1 to 30% by mass of the total mass of the surface layer. If the amount of these components exceeds 30% by mass, the cleaning performance deteriorates, and the image in a high humidity environment deteriorates.

The surface layer may contain organic fine particles and the like. By blending these, the surface energy of the surface layer can be reduced, and the cleaning characteristics can be improved. As organic fine particles, fluorine resin,
Silicone resins, acrylic resins, olefin resins and the like are mentioned, and particularly preferable ones are fluorine resins such as polytetrafluoroethylene and polyvinyldene fluoride and olefin resins such as polyethylene and polypropylene. Organic fine particles may be used alone or in combination of two or more.

The size of the organic fine particles may be 0.01 to 1. 1 as an average volume particle size or a maximum length of a particle projected image.
It is desirably 0 μm, preferably 0.01 to 0.3 μm. The compounding amount of the organic fine particles is 0.1% of the total mass of the surface layer.
1-30 mass% is preferable. If the amount of these components exceeds 30% by mass, the sensitivity of the photoreceptor decreases, and the residual potential of the photoreceptor increases during repeated use, causing fog.

Further, an antioxidant having a hindered phenol, hindered amine, thioether or phosphite partial structure can be added to the surface layer in the present invention.
This is effective in improving the potential stability and image quality when the environment changes.

Here, the hindered phenol means 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).

Further, examples of the hindered amine include compounds having an organic group represented by the following structural formula.

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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.

Examples of the antioxidant having a hindered phenol partial structure include, 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.

The following are examples of typical antioxidant compounds.

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Examples of commercially available antioxidants include the following compounds, for example, “Irganox 107
6, Irganox 1010, Irganox 1098, Irganox 245, Irganox 1330, Irganox 3114, Irganox 1076, 3,5-di-t-butyl- 4
-Hydroxybiphenyl "or more hindered phenols," Sanol LS2626 "," Sanol LS76 "
5 "," Sanol LS2626 "," Sanol LS77 "
0 "," Sanol LS744 "," Tinuvin 144 ",
“Tinuvin 622LD”, “Mark LA57”, “Mark LA67”, “Mark LA62”, “Mark LA6”
8 "," mark LA63 "or more hindered amine-based,
"SUMILIZER TPS", "SUMILIZER TP-D" or higher thioether, "Mark 2112", "Mark PE"
P-8 "," Mark PEP-24G "," Mark PEP "
-36 "," Mark 329K "," Mark HP-10 "
The phosphite type is mentioned above. Among these, hindered phenol and hindered amine antioxidants are particularly preferred. The addition amount of the antioxidant is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the surface layer.

Next, a method for manufacturing the surface layer will be described. In the present invention, the surface layer may be formed by any method as long as the above-mentioned surface layer is formed. Hereinafter, a typical method for producing the surface layer of the present invention will be described.

The surface layer of the present invention comprises at least one selected from the group consisting of an organosilicon compound represented by the general formula (1), a hydrolyzate of the organosilicon compound and a condensate of the organosilicon compound, and a metal alkoxide. After applying a coating solution containing an organic polymer having a group on a conductive support or the like,
It can be formed by curing.

The surface layer of the present invention can be formed by applying a coating solution containing an organic polymer having a siloxane condensate on a conductive support or the like and then curing the coating.

It is preferable that a reactive charge transporting compound is contained in the coating solution, and that the curing including the reactive charge transporting compound proceeds.

Specifically, a coating solution obtained by mixing an organic polymer having a metal alkoxy group with an organic silicon compound and a reactive charge transporting compound may be applied and cured, or an organic polymer having a metal alkoxy group may be applied. The compound and the organosilicon compound may be mixed to form a siloxane condensate at the terminal of the organic polymer in advance, and then a coating solution mixed with the organosilicon compound and the reactive charge transport compound may be applied and cured.

Here, the above-mentioned curing refers to an organic polymer having a metal alkoxy group at the terminal of the main chain, or an organic polymer having a metal alkoxy group at the terminal of the main chain and an organic silicon compound, a reactive charge transporting compound or the like. Means that the coating solution is gelled and dried to form a resin layer.

By the curing, the polycondensation of the organic polymer or siloxane progresses and becomes three-dimensional, and the siloxane condensate, the organic polymer, and the reactive charge transporting compound are converted via the metal alkoxy group or the reactive group. It chemically bonds, thereby forming a surface layer having good abrasion resistance, adhesion to the photosensitive layer and cleaning properties.

In any of the above production methods, the mass ratio of the organic silicon compound, the siloxane condensate or the organic polymer having a metal alkoxy group, and the reactive charge transporting compound in the coating liquid, which are the raw materials, is determined in the surface layer obtained. The mass ratio of the organic polymer component, the siloxane condensate component, and the charge transporting structural component may be within the above-mentioned range. For example, the compound of the general formula (1) was used as the organosilicon compound. In this case, the mass ratio of the organosilicon compound, the organic polymer having a metal alkoxy group, and the reactive charge transporting compound is 1
A mass ratio of from 00:25 to 400: 1 to 1000 is preferred.

In order to accelerate the reaction of the organosilicon compound, the organic polymer having a metal alkoxy group, and the reactive charge transporting compound, it is preferable to add a metal chelate compound in the coating solution or during the process of forming the coating solution. . Here, the metal chelate compound is a chelate compound of a metal selected from the group of zirconium, titanium and aluminum (hereinafter, referred to as metal chelate compound (III)). The metal chelate compound (III) promotes the hydrolysis and / or partial condensation reaction between the organosilicon compound and the organic polymer having a metal alkoxy group, and the reactive charge transporting compound, and forms a three-component co-condensate. It is thought to act to promote formation.

Examples of such a metal chelate compound (III) include compounds represented by the general formulas (6), (7) and (8), or partial hydrolysates of these compounds.

Formula (6) Zr (OR_Five)_p(R₆COCHCOR₇)_4-p General formula (7) Ti (OR_Five)_q(R₆COCHCOR₇)_4-q General formula (8) Al (OR_Five)_r(R₆COCHCOR₇)_3-r R in general formulas (6), (7) and (8)_FiveAnd R
₆Are each independently a monovalent hydrocarbon having 1 to 6 carbon atoms
Groups, specifically, ethyl group, n-propyl group, i-pro
Pill group, n-butyl group, sec-butyl group, t-butyl
Group, n-pentyl group, n-hexyl group, cyclohexyl
Group, phenyl group, etc.,₇Is R_FiveAnd R ₆the same as
In addition to the monovalent hydrocarbon group having 1 to 6 carbon atoms,
16 alkoxy groups, specifically, a methoxy group, an ethoxy group
Si group, n-propoxy group, i-propoxy group, n-buto
Xyl group, sec-butoxy group, t-butoxy group, lauri
A ruoxy group, a stearyloxy group and the like. Also, p
And q are integers of 0 to 3, and r is an integer of 0 to 2.

Specific examples of such metal chelate compound (III) include zirconium tri-n-butoxyethylacetoacetate, zirconium di-n-butoxybis (ethylacetoacetate), and zirconium n-butoxytris (ethyl). Acetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium,
Zirconium chelate compounds such as tetrakis (acetylacetoacetate) zirconium and tetrakis (ethylacetoacetate) zirconium; di-i-propoxybis (ethylacetoacetate) titanium, di-
titanium chelate compounds such as i-propoxybis (acetylacetate) titanium and di-i-propoxybis (acetylacetone) titanium; aluminum di-i-propoxyethylacetoacetate, aluminum di-i-propoxyacetylacetonate, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (ethylacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetate Aluminum chelate compounds such as natobis (ethylacetoacetate) aluminum and the like. Of these compounds, tri-n-butoxyethylacetoacetate zirconium, di-i-propoxybis (acetylacetonato) titanium, di-i
-Aluminum propoxy-ethyl acetoacetate,
Tris (ethyl acetoacetate) aluminum is preferred. These metal chelate compounds (III) can be used alone or in combination of two or more.

The addition amount of the metal chelate compound (III)
All of the coating solution solids (the coating solution solids are the components remaining after drying the coating solution) such as an organic silicon compound, an organic polymer having a siloxane condensate or a metal alkoxy group, and a reactive charge transporting compound. The compounding amount to the mass is 0.01
-20% by mass, preferably 0.5-20% by mass. If the amount of the metal chelate compound (III) is too small, the three-dimensional surface layer resin may not be achieved, while if it is too large, the pot life of the coating liquid is deteriorated.

The curing conditions after applying the coating solution for the surface layer depend on the reactivity of the organic polymer or organosilicon compound having a metal alkoxy group to be used.
It is preferable to carry out drying at 0 ° C. for 30 minutes to 6 hours.

In order to accelerate these curing reactions, it is preferable that an organic solvent is present. As the organic solvent usable here, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are preferable. The amount of the organic solvent used is not limited to the amount of the organosilicon compound, but is adjusted according to the purpose of use.

As the solvent for accelerating the curing reaction, a solvent capable of uniformly dissolving an organic silicon compound, an organic polymer having a metal alkoxy group, and a charge transporting compound having a reactive group is preferably used. As these solvents, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are used, and particularly preferred are the solvents exemplified below.

Examples of alcohol solvents include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, t-butyl alcohol, n-hexyl alcohol, n-octyl alcohol, ethylene glycol, diethylene glycol, Examples include triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol mono n-butyl ether, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl acetate.

As the ketone solvent, ketone solvents such as ethyl methyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, acetone and cyclohexanone are preferably used.

Hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and n-hexane; carbon tetrachloride, chloroform, dichloromethane, chloroethane,
Dichloroethane, chlorobenzene, dichlorobenzene,
Halogenated hydrocarbon solvents such as trichlorobenzene; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, diethyl ether and dibutyl ether; ethyl acetate, n-propyl acetate and n-acetic acid
Ester solvents such as -butyl and propylene carbonate, and the like, but are not limited thereto.

These organic solvents can be used alone or in combination of two or more. The method for adding the organic solvent is not particularly limited, and may be added at the time of preparing the surface layer coating solution of the present invention and / or at an appropriate stage after the preparation.

A curing accelerator can be further added to the surface layer coating solution, if necessary.

As the curing accelerator, naphthenic acid, octylic acid
Alkaline such as luic acid, nitrous acid, sulfurous acid, aluminate, and carbonic acid
Li metal salts; such as sodium hydroxide and potassium hydroxide
Lucari compound: alkyl titanic acid, phosphoric acid, p-toluene
Acidic compounds such as enesulfonic acid and phthalic acid; ethylene
Diamine, hexanediamine, diethylenetriamine,
Triethylenetetramine, tetraethylenepentamine,
Piperidine, piperazine, metaphenylenediamine, d
Hardness of tanolamine, triethylamine, epoxy resin
Various modified amines used as an agent, γ-aminopro
Piltriethoxysilane, γ- (2-aminoethyl)-
Aminopropyltrimethoxysilane, γ- (2-amino
Ethyl) -aminopropylmethyldimethoxysilane, γ
-Amines such as anilinopropyltrimethoxysilane
Compound, (C_FourH₉)_TwoSn (OCOC₁₁H_{twenty three})_Two, (C_Four
H₉)_TwoSn (OCOCH = CHCOOCH_Three)_Two, (C_Four
H₉)_TwoSn (OCOCH = CHCOOC_FourH₉)_Two, (C₈
H₁₇)_TwoSn (OCOC₁₁H _{twenty three})_Two, (C₈H₁₇)_TwoSn
(OCOCH = CHCOOCH_Three)_Two, (C₈H₁₇)_TwoSn
(OCOCH = CHCOOC_FourH₉)_Two, (C₈H₁₇)_TwoS
n (OCOCH = CHCOOC₈H₁₇)_Two, Sn (OCO
CC₈H₁₇)_TwoCarboxylic acid type organotin compounds such as
(C_FourH₉)_TwoSn (SCH_TwoCOO)_Two, (C_FourH₉)_TwoSn
(SCH_TwoCOOC₈H₁₇)_Two, (C₈H₁₇)_TwoSn (SC
H_TwoCOO)_Two, (C₈H₁₇)_TwoSn (SCH _TwoCH_TwoCO
O)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOCH_TwoCH_TwoO
COCH_TwoS)_Two, (C₈H₁₇)_TwoSn (SCH_TwoCOOC
H_TwoCH_TwoCH_TwoCH_TwoOCOCH_TwoS)_Two, (C₈H₁₇)_TwoS
n (SCH_TwoCOOC₈H₁₇)_Two, (C₈H₁₇)_TwoSn (S
CH_TwoCOOC₁₂H_{twenty five})_Two,

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Mercaptide-type organotin compounds such as

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A sulfide type organotin compound such as (C
_{4 H 9) 2 SnO, (} C 8 H 17) 2 SnO, (C 4 H 9) 2 Sn
Organic tin compounds such as reaction products of organic tin oxides such as O, (C ₈ H ₁₇ ) ₂ SnO and ester compounds such as ethyl silicate, ethyl silicate 40, dimethyl maleate, diethyl maleate and dioctyl phthalate. used.

The amount of the curing accelerator added in the coating solution is 0.1 to 20 parts by mass based on 100 parts by mass of the solid content of the coating solution (the solid content means a component remaining after drying in the components of the coating solution).
It is parts by mass, preferably 0.5 to 100 parts by mass. If these amounts are too small, the strength of the film may be reduced, while if too large, the pot life of the coating liquid deteriorates.

The surface layer of the present invention can be prepared by adding the above-mentioned metal oxide particles, organic fine particles, and antioxidants to the coating solution as required.

Next, the structure of the photoreceptor of the present invention other than the surface layer will be described. The photoreceptor having a surface layer according to the present invention can be applied to an inorganic photoreceptor using selenium, amorphous silicon, or the like. However, for the purpose of the present invention, an organic electrophotographic photoreceptor (also referred to as an organic photoreceptor) is used. It is preferred to apply a surface layer. In the present invention, the organic photoreceptor means an electrophotographic photoreceptor constituted by providing an organic compound with one of a charge generation function and a charge transport function indispensable for the configuration of the electrophotographic photoreceptor, It includes all known organic electrophotographic photosensitive members such as a photosensitive member composed of a known organic charge generating substance or organic charge transporting substance, and a photosensitive member composed of a polymer complex having a charge generating function and a charge transporting function.

The layer constitution of the organic photoreceptor is not particularly limited, but may be a charge generation layer, a charge transport layer, or a charge generation / charge transport layer (a layer having the functions of charge generation and charge transport in the same layer).
It is preferable to adopt a configuration in which a photosensitive layer such as that described above and the surface layer of the present invention are coated thereon.

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

The cylindrical conductive support means a cylindrical support necessary for forming an image endlessly by rotating, and has a straightness of 0.1 mm or less and a run-out of 0.1 mm.
Conductive supports in the following ranges 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 / 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.

The conductive support used in the present invention may have a surface on which a sealed alumite film is formed. The alumite treatment is usually performed in an acidic bath such as chromic acid, sulfuric acid, oxalic acid, phosphoric acid, boric acid, and sulfamic acid, but anodizing treatment in sulfuric acid gives the most preferable result. In the case of the anodic oxidation treatment in sulfuric acid, the sulfuric acid concentration is preferably 100 to 200 g / L, the aluminum ion concentration is 1 to 10 g / L, the liquid temperature is about 20 ° C., and the applied voltage is preferably about 20 V. It is not limited. The average thickness of the anodic oxide coating is usually 2
0 μm or less, particularly preferably 10 μm or less.

Intermediate Layer In the present invention, an intermediate layer having a barrier function may be provided between the conductive support and the photosensitive layer.

In the present invention, in order to improve the adhesion between the conductive support and the photosensitive layer or to prevent charge injection from the support, an intermediate layer (below the support) is provided between the support and the photosensitive layer. (Including a subbing layer). Examples of the material for the intermediate layer include polyamide resins, vinyl chloride resins, vinyl acetate resins, and copolymer resins containing two or more of the repeating units of these resins. Among these undercoating 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 intermediate layer using these resins is 0.01 to 0.5 μm.
Is preferred.

The intermediate layer most preferably used in the present invention is an intermediate layer using a curable metal resin obtained by thermosetting an organic metal compound such as a silane coupling agent and a titanium coupling agent. The thickness of the intermediate 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-layered structure in which a charge generation function and a charge transport function are provided in one layer on the intermediate layer. It is preferable to adopt a configuration in which the functions of the layers are separated into a charge generation layer (CGL) and a charge transport layer (CTL). 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. In the photoreceptor for negative charging, a charge generation layer (C
GL) and a charge transport layer (CTL) 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 substance (CGM), a known charge generating substance (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 among 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 a dispersion medium for CGM in the charge generation layer, a known resin can be used as the binder, but the most preferred resin is a formal resin, a butyral resin, a silicone resin, a silicone-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) include polystyrene, acrylic resin, methacrylic resin, vinyl chloride resin, vinyl acetate resin, polyvinyl butyral resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, and alkyd. Resins, polycarbonate resins, silicone resins, melamine resins, and copolymer resins containing two or more of the 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.

Protective Layer By providing the surface layer of the present invention as a protective layer on the surface of the photoreceptor, a photoreceptor having the most preferred layer constitution of the present invention can be obtained.

Examples of solvents or dispersion media used for forming layers such as the intermediate layer and the photosensitive layer include n-butylamine, diethylamine, ethylenediamine, isopropanolamine, triethanolamine, triethylenediamine, N, N-
Dimethylformamide, acetone, methyl ethyl ketone, methyl isopropyl ketone, cyclohexanone, benzene, toluene, xylene, chloroform, dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,1,2-trichloroethane, 1,1,1-
Examples include trichloroethane, trichloroethylene, tetrachloroethane, tetrahydrofuran, dioxolan, dioxane, methanol, ethanol, butanol, isopropanol, ethyl acetate, butyl acetate, dimethyl sulfoxide, methyl cellosolve and the like. The present invention is not limited to these, but dichloromethane, 1,2
-Dichloroethane, methyl ethyl ketone and the like are preferably used. In addition, these solvents can be used alone or as a mixed solvent of two or more kinds.

The coating method for producing the electrophotographic photosensitive member of the present invention includes dip coating, spray coating,
A coating method such as a circular amount control type coating is used, but the coating process on the upper layer side of the photosensitive layer is performed by spray coating or a circular amount control type in order to minimize dissolution of the lower layer film and to achieve a uniform coating process. A typical example is a circular slide hopper type. It is preferable to use a coating method such as coating. It is most preferable that the surface layer of the present invention employs the above-mentioned circular amount control type coating processing method. The circular amount control type coating is described in detail in, for example, JP-A-58-189061.

Next, the toner used in the present invention will be described. The toner of the present invention is preferably a polymerized toner having a relatively uniform particle size distribution and shape of individual toner particles. Here, the polymerization toner is the generation of the resin for the toner binder and the toner shape is the polymerization of the raw material monomer of the binder resin,
And a toner formed by a subsequent chemical treatment. More specifically, it means a toner obtained through a polymerization reaction such as suspension polymerization or emulsion polymerization and, if necessary, a subsequent step of fusing particles together.

As the polymerized toner used in the image forming method of the present invention, a toner having a specific shape is preferable. Hereinafter, the polymerized toner preferably used in the present invention will be described.

As the preferred polymerized toner applicable to the present invention, toner particles having a shape factor in the range of 1.2 to 1.6 are 65% by number or more, and the variation coefficient of the shape factor is 1
By using a toner that is 6% or less. It has been found that such a polymerized toner can stabilize the torque fluctuation of the cleaning blade and exhibits excellent cleaning performance.

The difference in the stability of the torque fluctuation of the cleaning blade due to the toner also depends on the particle size of the toner particles. The smaller the particle size, the higher the adhesion to the image bearing member, and thus the torque is excessive. And the probability of toner passing through the cleaning blade is high.
However, when the toner particle diameter is large, such a slip-through is reduced, but there is a problem that image quality such as resolution is deteriorated.

As a result of examination from the above viewpoints, the use of a toner having a coefficient of variation of the shape factor of the toner of 16% or less and a number variation coefficient of 27% or less in the number particle size distribution of the toner is as follows. It has been found that it is excellent in cleaning properties and fine line reproducibility and can form high-quality image for a long period of time.

Also, by controlling the number of toner particles having no corners to 50% by number or more and controlling the number variation coefficient in the number and particle size distribution to 27% or less, excellent cleaning performance and fine line reproducibility and high quality image quality can be obtained for a long time. Can be formed.

The shape factor of the toner of the present invention is represented by the following equation, and indicates the degree of roundness of toner particles.

Shape coefficient = ((maximum diameter / 2) ² × π) / projected area Here, the maximum diameter is defined as the parallel line when the projected image of the toner particles on the plane is sandwiched between two parallel lines. Means the width of the particle at which the distance between the particles becomes maximum. The projection area refers to the area of the projected image of the toner particles on the plane.

In the present invention, the shape factor can be determined by taking a photograph in which the toner particles are magnified 2000 times with a scanning electron microscope, and referring to the photograph based on this photograph.
The measurement was performed by analyzing a photographic image using "IMAGE ANALYZER" (manufactured by JEOL Ltd.). In this case, the shape factor of the present invention was measured by using the above formula using 100 toner particles.

The polymerized toner according to the present invention is preferably such that the number of toner particles having a shape factor in the range of 1.2 to 1.6 is at least 65% by number, more preferably 7%.
0% by number or more.

When the toner particles having the shape factor in the range of 1.2 to 1.6 are 65% by number or more, the triboelectric charging property in the developer conveying member and the like becomes more uniform, and the excessively charged toner Is not accumulated, and the toner is more easily exchanged than the surface of the developer conveying member. Therefore, problems such as a development ghost are less likely to occur. Further, the toner particles are less likely to be crushed, so that the contamination of the charging member is reduced, and the charging property of the toner is stabilized.

The method for controlling the shape factor is not particularly limited. For example, a method of spraying toner particles in a hot air flow, a method of repeatedly applying mechanical energy by an impact force in a gas phase, or a method of adding a toner particle in a solvent that does not dissolve a toner to give a swirling flow, etc. Thus, there is a method in which a toner having a shape factor of 1.2 to 1.6 is prepared, and is added to a normal toner so as to fall within the range of the present invention. Also, controlling the overall shape at the stage of adjusting the so-called polymerization toner,
There is a method in which a toner whose shape factor is adjusted to 1.0 to 1.6 or 1.2 to 1.6 is similarly added to a normal toner to adjust the shape.

The coefficient of variation of the shape factor of the polymerized toner preferably used in the present invention is calculated from the following equation.

Coefficient of variation = [S / K] × 100 (%) [where S represents the standard deviation of the shape coefficient of 100 toner particles, and K represents the average value of the shape coefficient. The variation coefficient of the shape factor is 16% or less, preferably 14% or less. When the variation coefficient of the shape factor is 16% or less, the gap of the transferred toner layer is reduced, the fixing property is improved, and the offset is less likely to occur. Further, the charge amount distribution becomes sharp, and the image quality is improved.

In order to uniformly control the shape factor of the toner and the variation coefficient of the shape factor without extremely varying lots, the resin particles (polymer particles) are formed in a process of polymerization, fusion, and shape control. An appropriate process end time may be determined while monitoring the characteristics of certain toner particles (colored particles).

Monitoring means that a measuring device is incorporated in-line and process conditions are controlled based on the measurement result. That is, for example, in the case of a polymerization toner formed by incorporating measurement of shape and the like inline and assembling or fusing resin particles in an aqueous medium, the shape and particle size are sequentially measured in a process such as fusing. Is measured, and the reaction is stopped when the desired shape is obtained.

Although the monitoring method is not particularly limited, a flow type particle image analyzer FPIA-
2000 (manufactured by Toa Medical Electronics Co., Ltd.) can be used. This apparatus is suitable because the shape can be monitored by performing image processing in real time while passing the sample liquid. That is, a pump or the like is used from the reaction field to constantly monitor and measure the shape and the like, and stop the reaction when the desired shape and the like are obtained.

The number particle size distribution and the number variation coefficient of the toner of the present invention are measured by Coulter Counter TA-II or Coulter Multisizer (manufactured by Coulter Co., Ltd.). In the present invention, a Coulter Multisizer was used, connected to an interface (manufactured by Nikkaki) for outputting a particle size distribution and a personal computer. The aperture used in the Coulter Multisizer is 100 μm and the aperture is 2 μm.
The volume and number of the above toners were measured to calculate the particle size distribution and the average particle size. The number particle size distribution represents the relative frequency of the toner particles with respect to the particle size, and the number average particle size represents the median size in the number particle size distribution.

The number variation coefficient in the number particle size distribution of the toner is calculated from the following equation. Number variation coefficient = [S / Dn] × 100 (%) [where S represents a standard deviation in the number particle size distribution, and D
n indicates a number average particle size (μm). The number variation coefficient of the toner of the present invention is 27% or less, and preferably 25% or less. When the number variation coefficient is 27% or less, the gap of the transferred toner layer is reduced, the fixing property is improved, and the offset is less likely to occur. Further, the charge amount distribution is sharpened, the transfer efficiency is increased, and the image quality is improved.

The method for controlling the number variation coefficient of the present invention is not particularly limited. For example, a method of classifying toner particles by wind force can be used, but classification in a liquid is effective for further reducing the number variation coefficient. As a method of classifying in a liquid, there is a method of separating and collecting toner particles according to a sedimentation speed difference caused by a difference in toner particle diameter by controlling a rotation speed by using a centrifugal separator.

In particular, when a toner is produced by a suspension polymerization method, a classification operation is indispensable in order to reduce the number variation coefficient in the number particle size distribution to 27% or less. In the suspension polymerization method,
Before polymerization, it is necessary to disperse the polymerizable monomer in an aqueous medium into oil droplets of a desired size as a toner. That is, mechanical shearing by a homomixer, a homogenizer, or the like is repeated on a large oil droplet of the polymerizable monomer to reduce the oil droplet to a size of about a toner particle. In the method by a gentle shear, the number and particle size distribution of the obtained oil droplets becomes broad, and therefore,
The particle size distribution of the toner obtained by polymerizing this becomes wide. For this reason, a classification operation is required.

The non-corner toner particles of the present invention refer to toner particles having substantially no projections on which electric charges are concentrated or projections which are easily worn out by stress. Assuming that the major axis of the toner particle T is L, when the inside of the circle C having a radius (L / 10) is rolled while being in contact with the peripheral line of the toner particle T at one point on the inside, The case where the circle C does not substantially protrude outside the toner T is referred to as “toner particles without corners”. “Cases that do not substantially protrude” refer to cases where there are no more than one protrusion having a protruding circle. Further, “the major axis of the toner particles” refers to the width of the particle at which the interval between the parallel lines is the largest when the projected image of the toner particles on the plane is sandwiched between two parallel lines. FIGS. 15B and 15C show projected images of toner particles having corners, respectively.

The measurement of the toner having no corner was performed as follows. First, a photograph in which toner particles are enlarged by a scanning electron microscope is taken, and further enlarged to obtain a photographic image of 15,000 times. Next, the presence or absence of the corners is measured for this photographic image. This measurement was performed for 100 toner particles.

In the toner of the present invention, the proportion of toner particles having no corners is at least 50% by number, preferably at least 70% by number. When the ratio of the toner particles having no corners is 50% by number or more, generation of fine particles is less likely to occur due to stress with the developer conveying member and the like.
It is possible to prevent the presence of toner that is excessively adherent to the surface of the developer transport member, to suppress contamination of the developer transport member, and to sharpen the charge amount. In addition, the amount of toner particles that are easily worn or broken and the number of toner particles having a portion where charges are concentrated are reduced, the charge amount distribution becomes sharp, the chargeability is stabilized, and good image quality can be formed over a long period of time.

The method for obtaining toner having no corners is not particularly limited. For example, as described above, as a method of controlling the shape coefficient, a method of spraying toner particles into a hot air flow, a method of repeatedly applying mechanical energy by an impact force in a gas phase, or a method of dissolving a toner It can be obtained by adding to a solvent that does not contain and giving a swirling flow.

In the polymerization toner formed by associating or fusing the resin particles, the surface of the fused particles has many irregularities at the stage of stopping the fusion, and the surface is not smooth. By setting conditions such as the temperature, the number of rotations of the stirring blade, and the stirring time, toner having no corners can be obtained. These conditions vary depending on the physical properties of the resin particles. For example, by setting the rotation speed higher than the glass transition temperature of the resin particles, the surface becomes smooth and a toner having no corners can be formed.

The toner of the present invention preferably has a number average particle diameter of 3 to 8 μm. When toner particles are formed by a polymerization method, the particle diameter can be controlled by the concentration of the coagulant, the amount of the organic solvent added, the fusing time, and the composition of the polymer itself.

When the number average particle diameter is 3 to 8 μm, the presence of toner having excessive adhesion to the developer conveying member or toner having low adhesion can be reduced in the fixing step, and the developing property is improved. In addition to being able to stabilize for a long period of time, the transfer efficiency is increased, the image quality of halftone is improved, and the image quality of fine lines and dots is improved.

In the polymerized toner preferably used in the present invention, when the particle size of the toner particles is D (μm), the natural logarithm InD is plotted on the horizontal axis, and the horizontal axis is divided into a plurality of classes at intervals of 0.23. in histogram showing the particle size distribution of number criteria, the relative frequency of the toner particles contained in the modal class (m _1), the relative frequency of the toner particles contained in the following frequent the rank of the modal class (m ₂ ) And (M) is 7
The toner is preferably 0% or more.

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 above-mentioned histogram showing the number-based particle size distribution is obtained by plotting a natural logarithm InD (D: particle size of individual toner particles) at 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.

Among the methods for controlling the shape factor of the toner, a polymerization toner is preferred because it is simple as a production method and has excellent surface uniformity as compared with a pulverized toner.

The toner of the present invention is prepared by a suspension polymerization method or emulsion polymerization of a monomer in a liquid to which an emulsion of necessary additives is added.
It can be produced by a method of producing fine polymer particles, and then adding an organic solvent, a coagulant and the like to associate. A method of preparing by mixing and associating with a dispersion liquid such as a release agent or a colorant necessary for the composition of the toner at the time of association, or dispersing a toner component such as a release agent or a colorant in a monomer. And then emulsion polymerization. Here, the association means that a plurality of resin particles and colorant particles are fused.

The aqueous medium in the present invention means a medium containing at least 50% by mass of water.

That is, various constituent materials such as a colorant and, if necessary, a release agent, a charge control agent, and a polymerization initiator are added to the polymerizable monomer, and a homogenizer, a sand mill, a sand grinder, an ultrasonic dispersion Various constituent materials are dissolved or dispersed in the polymerizable monomer by a machine or the like. The polymerizable monomer in which these various constituent materials are dissolved or dispersed is dispersed in an aqueous medium containing a dispersion stabilizer into oil droplets of a desired size as a toner using a homomixer, a homogenizer, or the like. Thereafter, the stirring mechanism is moved to a reaction device, which is a stirring blade described later, and heated to cause the polymerization reaction to proceed. After completion of the reaction, the toner of the present invention is prepared by removing the dispersion stabilizer, filtering, washing and drying.

Further, as a method of producing the toner of the present invention, a method of preparing by associating or fusing resin particles in an aqueous medium can also be mentioned. This method is not particularly limited.
No. 5,252, JP-A-6-329947, and JP-A-9-15904. That is, a method of associating a plurality of fine particles composed of a resin and a colorant with resin particles and dispersed particles of a constituent material such as a colorant or the like, particularly after dispersing these using an emulsifier in water, the critical aggregation concentration At the same time as adding the above flocculant and salting out, the formed polymer itself is heated and fused at a temperature equal to or higher than the glass transition temperature to gradually form a fused particle, thereby gradually growing the particle size. At this point, a large amount of water was added to stop the growth of the particle size, and the surface of the particle was smoothened while heating and stirring to control the shape. The toner of the invention can be formed. Here, an organic solvent infinitely soluble in water may be added together with the coagulant.

As the polymerizable monomer constituting the resin, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-chlorostyrene, 3,4- Dichlorostyrene,
p-phenylstyrene, p-ethylstyrene, 2,4-
Dimethylstyrene, p-tert-butylstyrene, p
-N-hexylstyrene, pn-octylstyrene,
pn-nonylstyrene, pn-decylstyrene, p
Styrene or a styrene derivative such as -n-dodecylstyrene, methyl methacrylate, ethyl methacrylate,
N-butyl methacrylate, isopropyl methacrylate,
Methacrylate derivatives such as isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, and dimethylaminoethyl methacrylate. , Methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate,
Acrylic ester derivatives such as n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, phenyl acrylate, etc .; olefins such as ethylene, propylene, isobutylene, vinyl chloride, vinylidene chloride, vinyl bromide , Vinyl fluoride, halogenated vinyls such as vinylidene fluoride, vinyl esters such as vinyl propionate, vinyl acetate, vinyl benzoate, vinyl ethers such as vinyl methyl ether and vinyl ethyl ether, vinyl methyl ketone, vinyl ethyl ketone , Vinyl ketones such as vinylhexyl ketone, N-vinyl compounds such as N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone, vinyl compounds such as vinylnaphthalene and vinylpyridine, acrylonitrile, Acrylonitrile, there are acrylic acid or methacrylic acid derivatives such as acrylamide. These vinyl monomers can be used alone or in combination.

Further, it is more preferable to use a polymerizable monomer constituting the resin in combination with one having an ionic dissociation group. For example, those having a substituent such as a carboxyl group, a sulfonic acid group, and a phosphate group as a constituent group of the monomer, specifically, acrylic acid, methacrylic acid,
Maleic acid, itaconic acid, cinnamic acid, fumaric acid, monoalkyl maleate, monoalkyl itaconate, styrenesulfonic acid, allylsulfosuccinic acid, 2-acrylamido-2-methylpropanesulfonic acid, acid phosphooxyethyl Methacrylate,
3-chloro-2-acid phosphooxypropyl methacrylate and the like.

Further, divinylbenzene, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate,
Polyfunctional vinyls such as neopentyl glycol diacrylate can be used to form a crosslinked resin.

[0222] These polymerizable monomers can be polymerized using a radical polymerization initiator. In this case, an oil-soluble polymerization initiator can be used in the suspension polymerization method. As the oil-soluble polymerization initiator, 2,2'-azobis- (2,4
-Dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvalero Azo or diazo polymerization initiators such as nitrile and azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide , Dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis-
Examples include peroxide-based polymerization initiators such as (4,4-t-butylperoxycyclohexyl) propane and tris- (t-butylperoxy) triazine, and polymer initiators having a peroxide in a side chain. .

When the 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.

Examples of the dispersion stabilizer include tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, and calcium sulfate. , Barium sulfate,
Bentonite, silica, alumina and the like can be mentioned. Further, a surfactant generally used as a surfactant such as polyvinyl alcohol, gelatin, methyl cellulose, sodium dodecylbenzenesulfonate, ethylene oxide adduct, and higher alcohol sodium sulfate can be used as a dispersion stabilizer.

As the excellent resin in the present invention, those having a glass transition point of 20 to 90 ° C. and a softening point of 8 to 90 ° C. are preferable.
The thing of 0-220 ° C is preferred. The glass transition point is measured by a differential calorimetric analysis method, and the softening point can be measured by a Koka flow tester. Furthermore, these resins have a number average molecular weight (Mn) of 10 as measured by gel permeation chromatography.
00 to 100000, weight average molecular weight (Mw) 200
Those having 0 to 1,000,000 are preferred. Further, as a molecular weight distribution, Mw / Mn is 1.5 to 100, particularly 1.8.
-70 are preferred.

The coagulant to be used is not particularly limited, but those selected from metal salts are preferably used. Specifically, as a monovalent metal, for example, a salt of an alkali metal such as sodium, potassium, and lithium, and as a divalent metal, for example, a salt of an alkaline earth metal such as calcium and magnesium, or a divalent metal such as manganese or copper Salt,
Examples include salts of trivalent metals such as iron and aluminum, and specific salts include sodium chloride, potassium chloride, lithium chloride, calcium chloride, zinc chloride, copper sulfate, magnesium sulfate, and manganese sulfate. Can be.
These may be used in combination.

It is preferable that these coagulants are added at a concentration higher than the critical coagulation concentration. The critical aggregation concentration is an index relating to the stability of the aqueous dispersion, and indicates the concentration at which aggregation occurs when a coagulant is added. This critical aggregation concentration is
It varies greatly depending on the emulsified component and the dispersant itself. For example, Seizo Okamura et al.
7, 601 (1960), edited by The Society of Polymer Science and the like, and a detailed critical aggregation concentration can be determined. As another method, a desired salt is added to the target particle dispersion at a different concentration, the 、 (zeta) potential of the dispersion is measured, and the salt concentration at which this value changes is defined as the critical aggregation concentration. You can also ask.

The addition amount of the coagulant of the present invention may be not less than the critical coagulation concentration, but is preferably 1.2 to the critical coagulation concentration.
It is better to add it at least twice, more preferably at least 1.5 times.

The infinitely soluble solvent means a solvent which is infinitely soluble in water, and in the present invention, a solvent which does not dissolve the formed resin is selected.
Specifically, methanol, ethanol, propanol,
Examples thereof include alcohols such as isopropanol, t-butanol, methoxyethanol and butoxyethanol, nitriles such as acetonitrile, and ethers such as dioxane. Particularly, ethanol, propanol and isopropanol are preferred.

The amount of the solvent to be dissolved infinitely is 1 to 100% by volume based on the polymer-containing dispersion to which the flocculant has been added.
Is preferred.

In order to make the shape uniform, it is preferable to prepare a colored particle, and after the filtration, a slurry containing 10% by mass or more of water based on the particle is fluidized and dried. Those having a polar group in the polymer are preferred. It is considered that the reason for this is that the existing water exerts an effect of slightly swelling the polymer in which the polar group is present, so that it is particularly easy to make the shape uniform.

The toner of the present invention contains at least a resin and a colorant, but may contain a releasing agent or a charge control agent as a fixability improving agent, if necessary. Further, an external additive composed of inorganic fine particles, organic fine particles, and the like may be added to the toner particles containing the resin and the colorant as main components.

As the coloring agent used in the toner of the present invention, any of carbon black, magnetic substance, dye, pigment and the like can be used arbitrarily. As the carbon black, channel black, furnace black, acetylene black,
Thermal black, lamp black and the like are used. Ferromagnetic metals such as iron, nickel, and cobalt as magnetic materials,
Alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys that do not contain ferromagnetic metals but show ferromagnetism by heat treatment, such as manganese-copper-
An alloy of a type called a Heusler alloy such as aluminum, manganese-copper-tin, chromium dioxide, or the like can be used.

As the dye, C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 1
22, C.I. I. Solvent Yellow 19, 44, 7
7, 79, 81, 82, 93, 98, 10
3, 104, 112, 162, C.I. I. Solvent Blue 25, 36, 60, 70, 93, 9
5 and the like, and a mixture thereof can also be used. Examples of the pigment include C.I. I. Pigment Red 5,
48: 1, 53: 1, 57: 1, 122, 1
39, 144, 149, 166, 177, 1
78, 222, C.I. I. Pigment Orange 31, 43 and C.I. I. Pigment Yellow 14, 17, 17
3, 94, 138, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15: 3, can be used by the same 60 or the like, can be also used a mixture thereof. The number average primary particle size varies depending on the type, but generally ranges from 10 to
About 200 nm is preferable.

As a method of adding a coloring agent, a method of adding polymer particles prepared by an emulsion polymerization method at the stage of aggregating by adding an aggregating agent to color the polymer, or a stage of polymerizing a monomer. And a method of adding a colorant, polymerizing, and forming colored particles can be used. When the colorant is added at the stage of preparing the polymer, it is preferable to use the colorant after treating the surface with a coupling agent or the like so as not to inhibit the radical polymerizability.

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.

Similarly, various known charge control agents are also available.
What can be dispersed in water can also be used. Specifically, nigrosine dyes, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines,
Quaternary ammonium salt compounds, azo-based metal complexes, salicylic acid metal salts or metal complexes thereof.

The particles of the charge controlling agent and the fixability improving agent have a number average primary particle diameter of 10 to 50 in a dispersed state.
Preferably, the thickness is about 0 nm.

In a suspension polymerization toner in which a toner component such as a colorant is dispersed or dissolved in a so-called polymerizable monomer is suspended in an aqueous medium and then polymerized to obtain a toner, a polymerization reaction is performed. By controlling the flow of the medium in the reaction vessel, the shape of the toner particles can be controlled. That is, when a large number of toner particles having a shape factor of 1.2 or more are formed, the flow of the medium in the reaction vessel is made turbulent, and the polymerization proceeds to be present in the aqueous medium in a suspended state. When the oil droplets are gradually polymerized, the oil droplets become soft particles, and when the oil droplets collide, the coalescence of the particles is promoted, and particles with an irregular shape are obtained. . When spherical toner particles having a shape factor smaller than 1.2 are to be formed, spherical particles can be obtained by using a medium flow in the reaction vessel as a laminar flow to avoid collision of the particles. By this method, the distribution of the toner shape can be controlled within the range of the present invention. Hereinafter, the reaction apparatus preferably used in the present invention will be described.

FIG. 5 is an explanatory view showing a reaction apparatus (stirring apparatus) in which a generally used stirring blade has a single-stage structure. Reference numeral 2 denotes a stirring tank, 3 denotes a rotating shaft, 4 denotes a stirring blade, 9 denotes a stirring blade. Is a turbulence forming member.

In the suspension polymerization method, by using a specific stirring blade, a turbulent flow can be formed, and the shape can be easily controlled. Although the reason for this is not clear, when the configuration of the stirring blade 4 as shown in FIG.
Only the flow that moves along the wall from the lower part to the upper part.
Therefore, conventionally, a turbulent flow is generally formed by arranging a turbulent flow forming member 9 such as a wall surface of the stirring tank 2 to increase the efficiency of stirring. However, in such a device configuration, although a turbulent flow is partially formed, the turbulent flow acts in a direction in which the flow of the fluid stagnates, and as a result, the slip with respect to the particles is reduced. Can't control.

A reactor having a stirring blade which can be preferably used in the suspension polymerization method will be described with reference to the drawings.

FIGS. 6 and 7 are a perspective view and a sectional view, respectively, showing an example of such a reactor. FIG.
In the reaction apparatus shown in FIG. 7, a rotary shaft 3 is suspended from a central portion of a vertical cylindrical stirring tank 2 having a heat exchange jacket 1 mounted on an outer peripheral portion thereof. Are provided with a lower stirring blade 40 disposed close to the bottom surface of the, and a stirring blade 50 disposed further above. The upper stirring blade 50 is disposed at an intersection angle α that precedes the rotation direction with respect to the lower stirring blade 40. When producing the toner of the present invention, the intersection angle α is preferably less than 90 degrees (°). The lower limit of the intersection angle α is not particularly limited, but is preferably about 5 ° or more, and more preferably 10 ° or more.
When a three-stage stirring blade is provided, it is preferable that the intersection angle between adjacent stirring blades is less than 90 degrees.

With such a configuration, the medium is first stirred by the stirring blades 50 provided in the upper stage, and a downward flow is formed. Next, the flow formed by the upper stirring blade 50 is further accelerated downward by the stirring blades 40 disposed in the lower stage, and a downward flow is separately formed by the stirring blades 50 themselves. It is presumed that it accelerates and proceeds. As a result, it is presumed that a basin having a large shear stress formed as a turbulent flow is formed, so that the shape of the obtained toner particles can be controlled.

In FIGS. 6 and 7, arrows indicate the direction of rotation, 7 is the upper material inlet, 8 is the lower material inlet, 9
Is a turbulent flow forming member for effective stirring.

The shape of the stirring blade is not particularly limited, but may be a square plate, a notch in a part of the blade, and one or more middle holes, so-called slits, in the center. Things and the like can be used. These specific examples are described in FIG. The stirring blade 5a shown in FIG. 14 (a) has no bore, and the stirring blade 5a shown in FIG.
b has a large middle hole 6b at the center, the stirring blade 5c shown in FIG. 5C has a horizontally long middle hole 6c (slit), and the stirring blade 5d shown in FIG. Hole 6d
(Slits). Further, in the case where a three-stage stirring blade is provided, even if the middle hole formed in the upper stirring blade and the middle hole formed in the lower stirring blade are different, they are the same. There may be.

FIGS. 8 to 12 are perspective views showing specific examples of a reactor having a stirring blade which can be preferably used. In FIGS. 8 to 12, reference numeral 1 denotes a heat exchange jacket, 2 is a stirring tank, 3 is a rotating shaft, 7 is an upper material inlet, 8 is a lower material inlet, and 9 is a turbulence forming member.

In the reaction apparatus shown in FIG.
Is formed with a bent portion 411, and the stirring blade 51 is formed with a fin (projection) 511.

In the case where the stirring blade has a bent portion, the bending angle is preferably 5 to 45 °.

The stirring blade 42 constituting the reaction apparatus shown in FIG.
, A slit 421 is formed, and a bent portion 422 and a fin 423 are formed.

Incidentally, the stirring blade 52 constituting the reaction apparatus is used.
Has the same shape as the stirring blade 50 constituting the reactor shown in FIG.

The stirring blade 4 constituting the reaction apparatus shown in FIG.
3, a bent portion 431 and a fin 432 are formed.

Incidentally, the stirring blade 53 constituting the reaction apparatus is used.
Has the same shape as the stirring blade 50 constituting the reaction apparatus shown in FIG.

The stirring blade 4 constituting the reaction apparatus shown in FIG.
4, a bent portion 441 and a fin 442 are formed.

Further, a stirring blade 54 constituting the reaction apparatus is used.
Has a central hole 541 formed at the center.

The reactor shown in FIG.
(Lower stage), a stirring blade 55 (middle stage), and a stirring blade having a three-stage configuration including a stirring blade 65 are provided.

The stirring blade having the structure having the bent portion and the projections (fins) on the upper side or the lower side effectively generates a turbulent flow.

The gap between the upper and lower stirring blades having the above configuration is not particularly limited, but it is preferable that at least a gap is provided between the stirring blades. Although the reason is not clear, it is considered that the flow of the medium is formed through the gap, so that the stirring efficiency is improved. However, the gap has a width of 0.5 to 50%, preferably 1 to 30% with respect to the liquid level in the stationary state.

Further, the size of the stirring blade is not particularly limited, but the sum of the heights of all the stirring blades is 50% to 100%, preferably 60% to 100% of the liquid level in the stationary state. 95
%.

FIG. 13 shows an example of a reaction apparatus used for forming a laminar flow in the suspension polymerization method. This reactor is characterized in that a turbulence forming member (an obstacle such as a baffle plate) is not provided.

The stirring blades 46 and 56 constituting the reaction apparatus shown in FIG. 13 have the same shape and crossing angle α as the stirring blades 40 and 50 constituting the reaction apparatus shown in FIG. 6, respectively. are doing. In FIG. 13,
1 is a jacket for heat exchange, 2 is a stirring tank, 3 is a rotating shaft,
7 is an upper material inlet, and 8 is a lower material inlet.

The reaction apparatus used for forming a laminar flow is not limited to the one shown in FIG.

The shape of the stirring blade constituting the reactor is not particularly limited as long as it does not form a turbulent flow, but is preferably formed by a continuous surface such as a square plate. It may have a curved surface.

On the other hand, in the case of a polymerization toner in which resin particles are associated or fused in an aqueous medium, the flow and temperature distribution of the medium in the reaction vessel at the fusion stage are controlled to further improve the shape after fusion. By controlling the heating temperature, the number of rotations for stirring, and the time in the control step, the shape distribution and shape of the entire toner can be arbitrarily changed.

That is, in a polymerization method toner in which resin particles are associated or fused, the flow in the reaction device is set to be a laminar flow.
By controlling the temperature, number of revolutions, and time in the fusion step and the shape control step using a stirring blade and a stirring tank that can make the internal temperature distribution uniform, the desired shape factor and uniform A toner having a shape distribution can be formed. The reason for this is that when fusion is performed in a place where a laminar flow is formed, strong stress is not applied to the particles that are undergoing aggregation and fusion (association or aggregated particles) and the flow is accelerated in a laminar flow. It is presumed that as a result of the uniform temperature distribution in the stirring tank, the shape distribution of the fused particles becomes uniform. Furthermore, heating in the subsequent shape control step,
The fused particles gradually become spherical by stirring, and the shape of the toner particles can be arbitrarily controlled.

As a stirring blade and a stirring tank used for producing a polymerization toner for associating or fusing resin particles, the same stirring blades and stirring tanks as those for forming a laminar flow in the above-mentioned suspension polymerization method can be used. For example, the one shown in FIG. 13 can be used. It is characterized in that an obstacle such as a baffle plate that forms a turbulent flow is not provided in the stirring tank. Regarding the configuration of the stirring blade, similarly to the stirring blade used in the above-mentioned suspension polymerization method, the upper stirring blade is disposed with the intersection angle α preceding the lower stirring blade in the rotation direction. In addition, a multi-stage configuration is preferable.

The shape of the stirring blade may be the same as that in the case of forming a laminar flow in the above-mentioned suspension polymerization method, and is not particularly limited as long as it does not form a turbulent flow. ) Are preferably formed by continuous surfaces, such as those having a square plate shape shown in (1), and may have a curved surface.

Further, in the toner of the present invention, more effects can be exhibited by adding and using fine particles such as inorganic fine particles and organic fine particles as external additives. It is presumed that the reason is that the embedding and desorption of the external additive can be effectively suppressed, and the effect is remarkable.

As the inorganic fine particles, it is preferable to use inorganic oxide particles such as silica, titania, and alumina. Further, it is preferable that these inorganic fine particles have been subjected to a hydrophobic treatment with a silane coupling agent, a titanium coupling agent, or the like. preferable. The degree of the hydrophobic treatment is not particularly limited, but a methanol wettability of 40 to 95 is preferable. Methanol wettability is to evaluate the wettability to methanol. In this method, inorganic fine particles to be measured are added to 50 ml of distilled water placed in a beaker having a capacity of 200 ml.
Weigh 2 g and add. Methanol is slowly dropped from a burette whose tip is immersed in the liquid until the whole of the inorganic fine particles becomes wet while being slowly stirred. When the amount of methanol required to completely wet the inorganic fine particles is a (ml), the degree of hydrophobicity is calculated by the following equation.

Degree of hydrophobicity = (a / (a + 50)) × 100 The amount of the external additive to be added is 0.1 to 5.
0 mass%, preferably 0.5 to 4.0 mass%. Various external additives may be used in combination.

A fatty acid metal salt may be added as an external additive to the toner used in the present invention. Fatty acids and metal salts thereof include undecylic acid, lauric acid, tridecylic acid, dodecylic acid, myristic acid, palmitic acid, pentadecylic acid, stearic acid, heptadecylic acid, arachiic acid, montanic acid, oleic acid, linoleic acid, arachidonic acid, etc. And metal salts thereof include salts with metals such as zinc, iron, magnesium, aluminum, calcium, sodium, and lithium. In the present invention, zinc stearate is particularly preferred.

To prepare a two-component developer, it is prepared by mixing a toner and a carrier. The toner concentration in the developer is 2 to 10% by mass.

The developing method according to the present invention is not particularly limited. Even in the contact development method in which development is performed in a state where the photoconductor surface and the developer layer are in contact with each other in the development area, the photoconductor and the developer layer are kept in a non-contact state in the development area, and an alternating electric field, etc. A non-contact developing method may be used in which the toner is caused to fly in the gap between the photosensitive member surface and the developer layer by the action of the toner to develop the toner.

[0274]

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”.

The following photoreceptors were prepared as the photoreceptors used in the evaluation of the examples. Production of Photoconductor P1 Photoconductor P1 was produced as follows. <Undercoat layer> Titanium chelate compound (TC-750 manufactured by Matsumoto Pharmaceutical Co., Ltd.) 30 g Silane coupling agent (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) 17 g 2-propanol 150 ml Using the above coating solution, a cylindrical conductive support having a diameter of 100 mm. It was applied to a thickness of 0.5 μm on the top. <Charge Generation Layer> Y-type titanyl phthalocyanine (a titanyl phthalocyanine having a maximum peak at 27.2 degrees at a Bragg angle 2θ (± 0.2) in Cu-Kα characteristic X-ray diffraction spectrum measurement) 60 g silicone-modified butyral resin (X (-40-1211M: manufactured by Shin-Etsu Chemical Co., Ltd.) 700 g 2-butanone 2000 ml was mixed and dispersed using a sand mill for 10 hours to prepare a charge generation layer coating solution. This coating solution was applied on the undercoat layer by a dip coating method to form a 0.2 μm-thick charge generation layer. <Charge Transport Layer> Charge transport substance (N- (4-methylphenyl) -N- {4- (β-phenylstyryl) phenyl} -p-toluidine) 225 g Polycarbonate (viscosity average molecular weight 30,000) 300 g Antioxidant (Exemplified Compound 1-3) 6 g of dichloromethane and 2,000 ml of dichloromethane 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 as shown in Table 1.

<Surface Layer> Main chain terminal silyl-modified polycarbonate A 30 g Methyl trimethoxysilane 70 g Reactive charge transporting compound (Exemplary compound B-1) 40 g Antioxidant (Exemplary compound 2-1) 2 g 2-propanol 200 g 2 -Butanone 100 g 3% acetic acid 10 g Aluminum chelate A (W) (Kawaken Chemical Co., Ltd.) 10 g was mixed to prepare a coating solution for the surface layer. This coating liquid was applied on the charge transport layer by a circular amount-regulating coating apparatus, and was cured by heating at 110 ° C. for 90 minutes to obtain a dry film thickness of 3.0 μm.
m was formed on the surface of the photosensitive member P1 (the surface layer of the present invention).

Synthesis Example 1 (Silyl-modified polycarbonate A at the main chain end) Commercially available bisphenol A-type polycarbonate "E.20"
00F "(manufactured by Mitsubishi Gas Chemical Company) 40.32 g (2 mmo
l) and 2.28 g (10 mmol) of bisphenol A
And 0.21 g (1.0 mmol) of zinc acetate
It was suspended in 200 ml of 2,4-trichlorobenzene and stirred at 180 ° C. for 3 hours. After cooling, the mixture was poured into a large excess of methanol, and the precipitate was separated by filtration to obtain 32.5 g of a polycarbonate diol represented by the following (diol-1) (number average molecular weight: 4200). The obtained polycarbonate diol (3.0 g) was dissolved in 30 g of toluene, 0.6 g of 3-isocyanatopropyltriethoxysilane (IPTES) was added to the solution, and the mixture was refluxed for 8 hours. The reaction solution was added dropwise to 500 ml of methanol to precipitate a reaction product. The precipitate was separated by filtration, washed with methanol, and dried under reduced pressure to obtain a main chain terminal silyl-modified polycarbonate A (yield 90.2%).

[0278]

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Preparation of Photoconductor P2 Photoconductor P2 was the same except that main chain terminal silyl-modified polycarbonate A in the surface layer was replaced with main chain terminal silyl-modified polyarylate B.
In the same manner as in Example 1, a photoconductor P2 was produced.

Synthesis Example 2 (Silyl-modified polyarylate B at the main chain terminal) Commercially available polyarylate U-100 (manufactured by Unitika) 50
g, bisphenol A 3.42 g (15 mmol)
And 0.21 g (1.0 mmol) of zinc acetate
It was suspended in 200 ml of 2,4-trichlorobenzene and stirred at 180 ° C. for 3 hours. After cooling, the mixture was poured into a large excess of methanol, and the precipitate was separated by filtration to obtain 32.5 g of a polyarylate diol (number-average molecular weight: 4400) represented by the following formula (diol-2). The obtained polyarylate diol (3.0 g) was dissolved in 30 g of toluene, 0.6 g of 3-isocyanatopropyltriethoxysilane (IPTES) was added to the solution, and the mixture was refluxed for 8 hours. The reaction solution was added dropwise to 500 ml of methanol to precipitate a reaction product. The precipitate was separated by filtration, washed with methanol, and dried under reduced pressure to obtain a main chain terminal silyl-modified polyarylate B (yield 85.2%).

[0281]

Embedded image

Preparation of Photoconductor P3 Photoconductor P1 was the same as the photoconductor P1 except that main chain terminal silyl-modified polycarbonate A in the surface layer was replaced with main chain terminal silyl-modified polyester C.
In the same manner as in the above, a photoreceptor P3 was produced.

Synthesis Example 3 (Main Chain Terminal Silyl-Modified Polyester C) Commercially available hydroxyl-terminated polyester “Elitel UE-33”
00 "(manufactured by Unitika Ltd., number average molecular weight 3200: (diol-3) below) (3.0 g) was dissolved in 30 g of toluene, and 0.5 g of 3-isocyanatopropyltriethoxysilane (IPTES) was added to the solution. And refluxed for 8 hours. The reaction solution was added dropwise to 500 ml of methanol to precipitate a reaction product. The precipitate was separated by filtration, washed with methanol, and dried under reduced pressure to obtain a main chain terminal silyl-modified polyester C (yield: 88.7%).

[0284]

Embedded image

Preparation of Photoconductor P4 Photoconductor P4 was prepared in the same manner as photoconductor P1, except that the surface layer was removed and the dry thickness of the charge transport layer was 21 μm.

Preparation of Photoconductor P5 Photoconductor P1 was prepared similarly to the charge transport layer. <Surface layer> Methyltrimethoxysilane 150 g Dimethyldimethoxysilane 30 g Reactive charge transporting compound (Exemplary compound B-1) 15 g Antioxidant (Exemplary compound 2-1) 0.75 g 2-propanol 75 g 3% Acetic acid 5 g Then, a coating solution for the resin layer was prepared. A 2 μm-thick resin layer was formed on the charge transport layer by using a circular amount-regulating coating device on the charge transport layer, and was heated and cured at 120 ° C. for 1 hour to form a siloxane resin layer. Produced.

In the following, a toner used for evaluation in Examples was prepared. 10. Preparation of Toners T1 and T2 (Example of Emulsion Polymerization Method) 0.90 kg of sodium n-dodecyl sulfate and pure water
Add 0 l and stir to dissolve. To this solution, add Regal 330
1.20 kg of R (carbon black manufactured by Cabot Corporation) was gradually added, and the mixture was stirred well for 1 hour, and then continuously dispersed for 20 hours using a sand grinder (medium type disperser). This is referred to as “colorant dispersion liquid 1”. Further, a solution composed of 0.055 kg of sodium dodecylbenzenesulfonate and 4.0 l of ion-exchanged water is referred to as “anionic surfactant solution A”.

Nonylphenol polyethylene oxide 10 mol adduct 0.014 kg and ion exchanged water 4.0 l
Is referred to as “nonionic surfactant solution B”.
223.8 g of potassium persulfate was added to 12.0 l of ion-exchanged water.
Is referred to as "initiator solution C".

A 100-liter GL (glass-lined) reactor equipped with a temperature sensor, a cooling pipe, and a nitrogen introducing device was charged with W.
3.41 kg of AX emulsion (polypropylene emulsion having a number average molecular weight of 3000: number average primary particle diameter = 120 nm / solid concentration = 29.9%), the whole amount of “anionic surfactant solution A” and “nonionic surfactant solution B” Add the whole amount and start stirring. Next, ion-exchanged water 4
Add 4.0 l.

Heating was started, and when the liquid temperature reached 75 ° C., the entire amount of “initiator solution C” was added dropwise. Then, while controlling the liquid temperature to 75 ° C. ± 1 ° C., the styrene 1
2.1 kg, 2.88 kg of n-butyl acrylate, 1.04 kg of methacrylic acid, and t-dodecyl mercaptan 54
8 g are added dropwise. After the completion of the dropwise addition, the temperature of the solution was raised to 80 ° C. ± 1 ° C., and the mixture was heated and stirred for 6 hours. Next, the liquid temperature was cooled to 40 ° C. or less, stirring was stopped, and the mixture was filtered with a pole filter to obtain “latex-A”.

The glass transition temperature of the resin particles in latex-A is 57 ° C., the softening point is 121 ° C., and the molecular weight distribution is as follows: weight average molecular weight = 12.7 million, weight average particle size is 12
It was 0 nm.

A solution obtained by dissolving 0.055 kg of sodium dodecylbenzenesulfonate in 4.0 l of ion-exchanged pure water is referred to as “anionic surfactant solution D”. Also,
A solution obtained by dissolving 0.014 kg of nonylphenol polyethylene oxide 10 mol adduct in 4.0 l of ion-exchanged water is referred to as “nonionic surfactant solution E”.

Potassium persulfate (manufactured by Kanto Chemical Co.) 200.
A solution obtained by dissolving 7 g in 12.0 l of ion-exchanged water is referred to as "initiator solution F".

A WAX emulsion (polypropylene emulsion having a number average molecular weight of 3000: number average primary particle diameter: 120 nm / solids concentration: 29.9) was placed in a 100-liter GL reactor equipped with a temperature sensor, a cooling tube, a nitrogen introducing device, and a comb baffle. %), 3.41 kg, the whole amount of “anionic surfactant solution D” and the whole amount of “nonionic surfactant solution E” are added, and stirring is started. Next, 44.0 liters of ion-exchanged water
Input. Heating is started, and when the liquid temperature reaches 70 ° C., “Initiator solution F” is added. Then, a solution prepared by previously mixing 11.0 kg of styrene, 4.00 kg of n-butyl acrylate, 1.04 kg of methacrylic acid, and 9.02 g of t-dodecylmercaptan is added dropwise. After completion of the dropwise addition, the mixture was heated and stirred for 6 hours while controlling the liquid temperature at 72 ° C. ± 2 ° C. Further, the liquid temperature was raised to 80 ° C. ± 2 ° C., and the mixture was heated and stirred for 12 hours. The liquid temperature is cooled to 40 ° C. or less, and the stirring is stopped. The solution was filtered through a Pall filter, and the filtrate was designated as "latex-B".

The glass transition temperature of the resin particles in Latex-B was 58 ° C., the softening point was 132 ° C., and the molecular weight distribution was weight average molecular weight = 245,000 and weight average particle diameter was 11
It was 0 nm.

Sodium chloride 5.36k as salting-out agent
g in 20.0 l of ion-exchanged water is referred to as "sodium chloride solution G".

A solution obtained by dissolving 1.00 g of a fluorinated nonionic surfactant in 1.00 l of ion-exchanged water is referred to as "nonionic surfactant solution H".

100 l of S with temperature sensor, cooling tube, nitrogen introduction device, particle size and shape monitoring device
The latex-A prepared above was placed in a US reactor (reactor having the structure shown in FIG. 8, intersection angle α was 20 °).
0 kg, 5.2 kg of latex-B, 0.4 kg of colorant dispersion 1 and 20.0 kg of ion-exchanged water are added and stirred. Then, the mixture was heated to 40 ° C., and 6.00 kg of sodium chloride solution G, isopropanol (manufactured by Kanto Chemical Co., Ltd.),
The nonionic surfactant solution H is added in this order. Then, after leaving it to stand for 10 minutes, the temperature was raised and the liquid temperature 85
The temperature was raised to 60 ° C. in 60 minutes, and heated and stirred at 85 ± 2 ° C. for 0.5 to 3 hours to grow the particle size while salting out / fusing. Next, 2.1 l of pure water is added to stop the particle size growth.

The salting out prepared above was placed in a 5-liter reaction vessel equipped with a temperature sensor, a cooling pipe, and a device for monitoring particle size and shape (reactor having the structure shown in FIG. 8, crossing angle α was 20 °). / Put 5.0 kg of the fused particle dispersion,
The shape was controlled by heating and stirring at a liquid temperature of 85 ° C. ± 2 ° C. for 0.5 to 15 hours. Thereafter, the mixture is cooled to 40 ° C. or less and the stirring is stopped. Next, classification is performed in the liquid by a centrifugal sedimentation method using a centrifugal separator, and the liquid is filtered through a sieve having openings of 45 μm, and the filtrate is used as an associated liquid. Then, using Nutsche,
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 non-spherical particles were dried at a suction temperature of 60 ° C. using a flash jet drier, and then dried at a temperature of 60 ° C. using a fluidized bed drier. To 100 parts by mass of the obtained colored particles, 1 part by mass of silica fine particles and 0.1 part by mass of zinc stearate were externally added and mixed with a Henschel mixer to obtain a toner by an emulsion polymerization association method as shown in the following table. In the monitoring of the salting-out / fusion step and the shape control step, the number of rotations of the stirring and the heating time are controlled to control the variation coefficient of the shape and the shape coefficient. Was adjusted to obtain toner T1 and toner T2 shown in Table 1.

Preparation of Toner T3 (Example of Suspension Polymerization Method) Styrene = 165 g, n-butyl acrylate = 35
g, carbon black = 10 g, metal di-t-butylsalicylate = 2 g, styrene-methacrylic acid copolymer = 8 g, paraffin wax (mp = 70 ° C.) = 20
g was heated to 60 ° C., and was uniformly dissolved and dispersed at 12,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
To this, 2,2'-azobis (2,4-
(Valeronitrile) = 10 g was added and dissolved to prepare a polymerizable monomer composition. Then, 710 g of ion-exchanged water
Was added with 450 g of a 0.1 M aqueous sodium phosphate solution, and TK was added.
While stirring with a homomixer at 13000 rpm, 1.
68 g of 0M calcium chloride was gradually added to prepare a suspension in which tricalcium phosphate was dispersed. The polymerizable monomer composition was added to this suspension, and the mixture was added to a TK homomixer.
The mixture was stirred at 0000 rpm for 20 minutes to granulate the polymerizable monomer composition. Then, using a reactor (crossing angle α is 45 °) having a stirring blade configuration as shown in FIG.
The reaction was performed at 〜95 ° C. for 5 to 15 hours. Tricalcium phosphate is dissolved and removed with hydrochloric acid, and then, using a centrifuge,
Classification was performed in the liquid by centrifugal sedimentation, followed by filtration, washing and drying. In 100 parts by mass of the obtained colored particles,
1 part by mass of silica fine particles and 0.1 part by mass of zinc stearate were externally added and mixed with a Henschel mixer to obtain a toner by a suspension polymerization method.

By monitoring during the polymerization and controlling the liquid temperature, the number of rotations of the stirring, and the heating time, the variation coefficient of the shape and the shape coefficient are controlled. By adjusting the coefficient, a toner T3 shown in Table 1 below was obtained.

[0303]

[Table 1]

Preparation of Developer Preparation of Developer 1 To 100 parts of the toner T1, 0.4 parts of hydrophobic silica particles (R805: manufactured by Nippon Aerosil Co., Ltd.) having an average particle diameter of 12 nm as external additives, and titania particles ( T805: manufactured by Nippon Aerosil Co., Ltd.) and mixed with a Henschel mixer at room temperature at a peripheral speed of the stirring blade of 40 (m / sec) for 10 minutes to obtain a negatively chargeable toner. The fixation ratio of this toner was 45%.

A ferrite carrier coated with a silicone resin and having a volume average particle diameter of 60 μm was mixed with the above toner to prepare a developer 1 having a toner concentration of 5%.

Preparation of Developers 2 and 3 Developer 2 was prepared in the same manner as in preparation of developer 1 except that toner T2 was used instead of toner T1.
A developer 3 was prepared in the same manner except that the toner T3 was used instead of the toner T1.

The following rubber elastic cleaning blade was prepared as a cleaning blade of a cleaning device used for evaluation of the examples.

Cleaning blade B1: hardness: 70 °, rebound resilience: 31 Cleaning blade B2: hardness: 65 °, rebound resilience: 54 Cleaning blade B3: hardness: 75 °, rebound resilience: 76 The above hardness and rebound resilience are temperature. It is a measured value under the condition of 25 ° C.

Evaluation of Dynamic Torque and Cleanability

[0310]

[Table 2]

[0311] As shown in Table 2, the combination of the photoreceptor, the developer, the members of the cleaning blade, and the conditions of this section are set, and a digital copying machine manufactured by Konica Corporation basically has the image forming process shown in FIG. Konica 7050
(Corona charging, laser exposure, reversal development, electrostatic transfer, nail separation, cleaning process). The evaluation was 1 for each of a character image, a halftone image, a solid white image, and a solid black image with a pixel ratio of 7%.
Using an original image divided into ４ equal parts, continuous copying of 1 million A4 sheets was performed in a normal temperature and normal humidity environment (24 ° C., 60% RH). However, before starting the above evaluation, in order to make the photoconductor and the cleaning blade conform, the setting powder was sprayed on the photoconductor and the cleaning blade, and the photoconductor was rotated for 1 minute. The average of the dynamic torque value and the measurement of τ were measured using the above-described torque measuring device. Other evaluation conditions are described below. Table 3 shows the evaluation results.

Other Evaluation Conditions The other evaluation conditions using the digital copying machine Konica 7050 were set as follows.

Charging Conditions Charger: Scorotron charger, initial charging potential was -750
V Exposure conditions Exposure amount is set to an exposure amount that makes the exposed portion potential −50 V. Development conditions DC bias; −550 V Dsd; 550 μm Developer layer regulation; edge cut method Developer layer thickness; 700 μm Development sleeve diameter; 40 mm Charging method, transfer dummy current value: 45 μA Cleaning conditions The types of the cleaning blade and the setting conditions are described in Table 2.

Evaluation Items and Evaluation Criteria Halftone Image A halftone image having an image density of 0.4 was prepared, and the presence or absence of unevenness in the circumferential direction of the photoreceptor was visually determined.

The presence or absence of a white streak-like image defect in a solid black image due to a chipped blade was visually determined.

FIG. 17 is a schematic diagram for explaining a method of measuring the cleaning blade edge wear amount. As shown in FIG. 17, the cleaning blade edge abrasion amount is measured from an image obtained by enlarging the edge portion using an optical or laser microscope.

In FIG. 17, reference numeral 121 denotes a photosensitive drum;
A indicates the cleaning blade, 191 indicates the blade supporting member, and 126B indicates the edge wear amount of the cleaning blade.

Amount of Depletion of Photosensitive Layer Thickness The thickness of the photosensitive layer is measured at random at 10 locations of uniform thickness, and the average value is defined as the thickness of the photosensitive layer. The film thickness measuring device is an eddy current type film thickness measuring device EDDY560C (HELMUT
FISCER GMBTE CO), and the difference between the thicknesses of the photosensitive layers before and after the actual printing test is defined as the thickness loss.

Comprehensive evaluation A: Very little wear of the photoreceptor and blade and good cleaning performance up to 1,000,000 copies.

：: The wear of the photosensitive member and the blade was small, and the cleaning property was good up to 500,000 copies.

X: Not practical in a copier or the like in which the cleaning property is insufficient or the photoreceptor and the blade are greatly worn and high durability is required.

The evaluation results are shown in Table 3.

[0323]

[Table 3]

[0324] As is apparent from Table 3, the organic photosensitive member having a surface layer of the present invention of formula _{1 (Y 10 0 -Y 0)} , equation 2 Y
_When the values of ₁₀₀ / Y ₀ and τ are combined with the cleaning device having the numerical values in the present invention, the cleaning property of the toner is good, and there is no generation of halftone spots and white stripes due to chipping of the blade. , The blade wear amount and the photoreceptor wear amount are small, but when the photoreceptor does not have a surface layer, (Y ₁₀₀ −Y ₀ ) of Expression 1, Y ₁₀₀ / Y _{0 of} Expression 2, and τ
At least one of the values is likely to fall outside the present invention. That is, in Comparative Examples 1, 2, and 3 in which τ exceeded 0.5 seconds, the amount of wear of the photoconductor was large, halftone spots were generated, and
In the case of Comparative Examples 4 and 5 where τ is too small or too large even if there is a surface layer, halftone spots are generated. Also, Y
_In Comparative Examples 6 and 7 in which the ratio of ₁₀₀ / Y ₀ greatly exceeded 2.95, white streaks were remarkably generated due to chipping of the blade.

[0325]

As is clear from the above examples, the residual toner on the organic photoreceptor having the surface layer of the present invention is the average value of the dynamic torque value generated between the organic photoreceptor and the cleaning blade: toner When the average value of the dynamic torque value of the cleaning blade when no image is formed is Y ₀ , and the average value of the dynamic torque value of the cleaning blade when a toner image is formed at a 100% blackening ratio is Y ₁₀₀ , the above equation is used. 1, and the minimum time (τ) required to change the dynamic torque value of the cleaning blade from Y ₀ to Y ₁₀₀ is 0.010 to 0.5.
By setting the time to 00 seconds, it is possible to provide a high-quality, high-durability image forming method and an image forming apparatus with less image defects and with less wear of the blade and the photoconductor.

[Brief description of the drawings]

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

FIG. 2 is a configuration diagram of a cleaning device having the cleaning blade of the present invention.

FIG. 3 is a measurement graph of dynamic torque generated by friction of a cleaning blade with an organic photoreceptor.

FIG. 4 is a diagram illustrating a method of fixing a cleaning blade to a support member.

FIG. 5 is an explanatory diagram showing a reaction device having a single-stage stirring blade.

FIG. 6 is a perspective view showing an example of a reaction apparatus having a stirring blade which can be preferably used.

FIG. 7 is a sectional view of the reaction apparatus shown in FIG.

FIG. 8 is a perspective view showing a specific example of a reaction apparatus having a stirring blade which can be preferably used.

FIG. 9 is a perspective view showing a specific example of a reactor having a stirring blade which can be preferably used.

FIG. 10 is a perspective view showing a specific example of a reactor having a stirring blade which can be preferably used.

FIG. 11 is a perspective view showing a specific example of a reactor having a stirring blade which can be preferably used.

FIG. 12 is a perspective view showing a specific example of a reactor having a stirring blade which can be preferably used.

FIG. 13 is a perspective view showing an example of a reaction apparatus used for forming a laminar flow.

FIG. 14 is a schematic view showing a specific example of the shape of a stirring blade.

15A is an explanatory diagram showing a projected image of a toner particle having no corner, and FIGS. 15B and 15C are explanatory diagrams showing a projected image of a toner particle having a corner. FIG.

FIG. 16 is a conceptual diagram of a torque measuring device.

FIG. 17 is a schematic diagram for explaining a method of measuring a cleaning blade edge wear amount.

[Explanation of symbols]

 121 Photoconductor 122 Charger 123 Developing Device 123H Toner Replenishment Unit 124 Transfer Device 125 Separator 126 Cleaning Device 126A Cleaning Blade 127 PCL (Precharge Lamp) 130 Exposure Optical System

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H005 AA15 EA05 EA10 2H034 AA06 BF03 BF05 BF06 BF07 2H068 AA03 BB20 BB23 BB25 BB33 BB44 BB49 BB57 FA03

Claims (16)

[Claims] An electrostatic latent image formed on an organic photoreceptor is developed with a developer containing a toner, and a toner image visualized by the development is transferred from the organic photoreceptor to a transfer material. An image forming method for removing a toner remaining on an organic photoconductor by a cleaning device having a cleaning blade, wherein the organic photoconductor has a surface layer containing a resin in which a siloxane condensate and an organic polymer are mutually bonded,
And when a toner image is not formed on the organic photoreceptor,
The average value of the dynamic torque generated between the organic photoconductor and the cleaning blade is Y ₀ , and the average value of the dynamic torque when a toner image is formed on the organic photoconductor at a 100% blackening ratio is Y.
An image forming method characterized by satisfying the following formulas (1) and (2) when ₁₀₀ is set. Formula 1 0.2 ≧ Y ₁₀₀ −Y ₀ ≧ 0.01 Formula 2 2.95 ≧ Y ₁₀₀ / Y ₀ ≧ 1.15 (Unit of Y ₁₀₀ and Y ₀ : N · m) 2. An electrostatic latent image formed on an organic photoreceptor is developed with a developer containing toner, and a toner image visualized by the development is transferred from the organic photoreceptor to a transfer material. An image forming method for removing a toner remaining on an organic photoconductor by a cleaning device having a cleaning blade, wherein the organic photoconductor has a surface layer containing a resin in which a siloxane condensate and an organic polymer are mutually bonded,
And when a toner image is not formed on the organic photoreceptor,
The average value of the dynamic torque generated between the organic photoconductor and the cleaning blade is Y ₀ , and the average value of the dynamic torque when a toner image is formed on the organic photoconductor at a 100% blackening ratio is Y.
Is taken as _100, the shortest time required for dynamic torque value to change from Y ₀ to Y ₁₀₀ (tau) is 0.010 to 0.500
An image forming method, wherein the image is formed in seconds. 3. An electrostatic latent image formed on the organic photoreceptor is developed with a developer containing toner, and a toner image visualized by the development is transferred from the organic photoreceptor to a transfer material. An image forming method for removing a toner remaining on an organic photoconductor by a cleaning device having a cleaning blade, wherein the organic photoconductor has a surface layer containing a resin in which a siloxane condensate and an organic polymer are mutually bonded,
And when a toner image is not formed on the organic photoreceptor,
The average value of the dynamic torque generated between the organic photoconductor and the cleaning blade is Y ₀ , and the average value of the dynamic torque when a toner image is formed on the organic photoconductor at a 100% blackening ratio is Y.
_The minimum time (τ) required to satisfy Expressions 1 and 2 when ₁₀₀ is set and to change the dynamic torque value from Y ₀ to Y ₁₀₀ is 0.010 to 0.500 seconds. An image forming method comprising: 4. The image forming method according to claim 1, wherein the resin is formed by reacting an organic polymer having a siloxane condensate. 5. The image forming method according to claim 1, wherein the resin forms a crosslinked structure over the entire surface layer. 6. The siloxane condensate has a charge transporting group as a partial structure.
The image forming method according to any one of the above items. 7. The image forming method according to claim 1, wherein the organic polymer is a polycarbonate polymer. 8. The method according to claim 1, wherein the organic polymer is a polyarylate polymer.
Item. 9. The image forming method according to claim 1, wherein the organic polymer is a polyester polymer. 10. The method according to claim 1, wherein the siloxane condensate is formed at a main chain terminal of the organic polymer.
10. The image forming method according to any one of 9. 11. The toner of the developer, wherein the coefficient of variation of the shape factor of the toner particles is 16% or less, and the number variation coefficient of the toner particles in the number particle size distribution is 27%.
The following toner is used:
The image forming method according to claim 10. 12. The toner of the developer contains 65% by number of toner particles having a shape coefficient in a range of 1.2 to 1.6.
2. The toner according to claim 1, wherein a toner containing the above is used.
12. The image forming method according to any one of items 11 to 11. 13. The image forming method according to claim 1, wherein a toner containing 50% by number or more of toner particles having no corners is used as the toner of the developer. 14. The image forming method according to claim 1, wherein a toner having a number average particle diameter of 3 to 8 μm is used as the toner of the developer. 15. When the particle size of toner particles is D (μm) as the toner of the developer, the natural logarithm InD is plotted on the horizontal axis, and the horizontal axis is divided into a plurality of classes at intervals of 0.23. In the histogram showing the reference particle size distribution, the relative frequency (m ₁ ) of the toner particles included in the most frequent class, and the relative frequency (m ₂ ) of the toner particles included in the class having the second highest frequency after the most frequent class are described. The image forming method according to claim 1, wherein a toner having a sum (M) of 70% or more is used. 16. An image forming apparatus using the image forming method according to claim 1. Description: