JP2003131416A - Image forming apparatus and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming apparatus which demonstrates particularly excellent cleanability without impairing various characteristics such as electrostatic property and retains high image quality and high reliability. SOLUTION: The image forming apparatus has a latent image forming means to form an electrostatic latent image on the surface of a photoreceptor and a developing means to develop the electrostatic latent image with a developer to obtain a toner image, wherein the surface layer of the photoreceptor contains fluororesin particles in 0.1-40 mass% of the mass of the surface layer and the developer contains an electrostatic charge image developing toner which satisfies the following relations (1)-(3); (1) the shape factors SF1 and SF2 of the toner are 125-140 and 105-130, respectively, (2) the toner contains 8-20 mass% release agent and the exposure rate of the release agent on the surface of the toner quantified by X-ray photoelectron spectroscopy (XPS) is 11-40 at.%, and (3) the melting point of the release agent measured with a differential scanning calorimeter is 70-130 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming apparatus and an image forming method for developing an electrostatic latent image formed by an electrophotographic method or an electrostatic recording method with a developer.

[0002]

2. Description of the Related Art Conventionally, in electrophotography, an electrostatic latent image formed by charging and exposing the surface of a photoconductor is developed with colored toner to form a toner image as a visible image, and the toner image is transferred. An image is formed by transferring it to a transfer target such as paper and fixing it with a heat roll or the like. Generally, untransferred toner remains on the surface of the photoconductor after the transfer of the toner image, so that the residual toner needs to be removed by some cleaning means before the next image forming process. Further, generally, the cleaning means also removes other foreign matter attached to the surface of the photoconductor together with the residual toner.

As a cleaning means for removing the residual toner after the transfer, there are various means such as a fur brush, a magnetic brush, a rubber blade, and the like. A means for scraping off the toner by rubbing the photosensitive member is generally used because it is inexpensive and has high performance stability. Polyurethane rubber is often used for the elastic body used as the material of the cleaning blade due to its excellent wear resistance.

Further, as an electrophotographic photoconductor, organic photoconductive materials are widely used in comparison with inorganic photoconductors such as selenium-based and amorphous silicon photoconductors because of wide selection of materials and excellent environmental characteristics. Organic photoconductors using substances are predominant.

In recent years, the image quality of this type of image forming apparatus has been improved, and one direction for improving the image quality is as follows.
The size of toner is becoming smaller. By reducing the diameter, it is possible to improve the reproducibility of dots in the toner image formed on the surface of the photoconductor.

By the way, as a conventional method for producing a toner, there is a kneading and pulverizing method. If the diameter of the toner is simply reduced by this kneading and pulverization method, the yield at the time of manufacturing the toner is deteriorated, and as a result, the manufacturing cost of the toner is increased.

Further, the shape of the toner particles produced by the conventional kneading and pulverizing method is irregular, and the surface composition is not uniform. Further, the shape of the toner particles changes depending on the pulverizability of the materials used and the conditions of the pulverization process, and the surface composition is not constant. That is, although the shape and surface composition of the toner particles slightly change depending on the pulverizability of the material used and the conditions of the pulverization process, it is difficult to intentionally control the shape and surface composition of the toner particles. Further, when toner particles are manufactured using a material having particularly high pulverizability, fine powder is often generated due to mechanical force such as shearing force in the developing machine, or the shape of toner particles is changed.

Due to these influences, in the two-component developer, the finely divided toner particles adhere to the carrier to accelerate the charge deterioration of the developer, and in the one-component developer,
Toner scattering may occur due to the expansion of the particle size distribution of the toner particles, and deterioration of image quality may easily occur due to deterioration in developability due to changes in the shape of the toner particles.

If the toner particles have an irregular shape, sufficient fluidity cannot be obtained even if a fluidity aid is added.
During use, fine particles of the fluidity aid are buried in the recesses of the toner particles due to mechanical force such as shearing force, and the fluidity of the toner decreases over time, and the developability, transferability, and cleaning properties deteriorate. There is. Further, when such toner is collected by cleaning and returned to the developing machine for use, the image quality is more likely to deteriorate. It is conceivable to further increase the fluidity aid in order to prevent these phenomena, but in this case, there arises a problem that black spots occur on the photoconductor or the fluidity aid is scattered.

On the other hand, in the case of a toner in which a release agent such as wax is internally added, the release agent is often exposed on the surface of the toner particles when combined with a thermoplastic resin. Especially with a resin that is given elasticity by a high molecular weight component and is slightly crushed,
In the case of a toner combined with a brittle wax such as polyethylene, polyethylene is often exposed on the surface of toner particles. Such a toner is advantageous in releasability at the time of fixing and cleaning of the untransferred toner from the photoreceptor, but the polyethylene of the surface layer of the toner particles is detached from the surface of the toner particles due to shearing force in the developing machine, Easily transferred to developing rolls, photoreceptors, carriers, etc. These stains reduce the reliability as a developer.

Under these circumstances, in recent years, there has been an attempt to intentionally control the shape and surface composition of toner particles to solve the above problems, and particularly, research on producing toner by a wet method has been actively conducted. became. For example, Japanese Patent Laid-Open No. 63-2827
49 and JP-A-6-250439, a resin particle dispersion liquid and a colorant dispersion liquid in which a colorant is dispersed in an aqueous medium (solvent) are prepared by emulsion polymerization and the both are mixed. An emulsion polymerization agglomeration method has been proposed in which agglomerated particles corresponding to the toner particle size are heated to form agglomerated particles, and the temperature is further increased to fuse the agglomerated particles to produce a toner.

Further, in recent years, there has been an increasing demand for higher image quality, and particularly in color image formation, in order to realize a high definition image,
There is a remarkable tendency for the toner to have a smaller diameter and to have a uniform particle diameter. When an image is formed using a toner having a wide particle size distribution, the toner on the fine powder side in the particle size distribution causes problems such as contamination of developing rolls, charging rolls, charging blades, photoreceptors, carriers, etc., and toner scattering. It has been difficult to simultaneously realize image quality and high reliability. Further, a toner having a wide particle size distribution cannot obtain high reliability even in a system having a cleaning function, a toner recycling function, or the like.

On the other hand, the toner having a small particle size is liable to cause dull particularly in the transfer process, which becomes a factor to prevent the high image quality. It is considered that this is because the chemical adhesive force of the toner to the photoconductor, for example, non-electrostatic adhesive force such as van der Waals force increases. In order to improve such a problem, it is necessary to appropriately control the adhesive force between the toner and the photoconductor, for example, control of the shape and surface state.

In the conventional kneading and pulverizing method, it is very difficult to produce a toner having a small particle size and a uniform particle size as described above. In principle, a toner having a small particle size has a large shape distortion. The problems in the transfer process cannot be avoided. Therefore, among the wet methods, research on the emulsion polymerization aggregation method, which is particularly easy to produce a toner having a small diameter and a uniform particle diameter, has been actively conducted. However, in the case of toner particle production by the emulsion polymerization aggregation method, the reaction generally proceeds in the direction of making the shape of the irregular toner particles into a smooth spherical toner by heating, that is, in the direction of decreasing the surface area. , The smaller the surface area, that is, the smaller the particle size toner, the higher the sphericity, and the larger the particle size toner, the higher the irregularity. On the other hand, in order to obtain all of the transfer quality, transfer efficiency, cleaning property, toner durability, etc. of the shape of the toner particles, optimum design of the toner particle shape is required.

In particular, the cleaning property is remarkably deteriorated in a low temperature and low humidity environment. The cleaning property under low temperature and low humidity environment is improved by increasing the contact pressure of the cleaning blade to the photoconductor, but when it is used under high temperature and high humidity environment with such high contact pressure, The adhesive force with the cleaning blade may increase, the amount of deformation of the blade tip may increase, and the blade edge may be chipped or the cleaning blade may curl. When using spherical toner, it is necessary to strictly adjust the rubber physical properties of the cleaning blade and the set conditions to be installed in order to obtain good cleaning properties in any environment for a long period of time. It was extremely difficult to take.

When an organic photoconductor is used, the film strength is weaker than that of an inorganic photoconductor such as a selenium photoconductor or an amorphous silicon photoconductor. As a result, abrasion occurs in the developing unit and the cleaning unit in use over time, and there is a problem in long-term use.
In Japanese Unexamined Patent Publication No. 6-118681, an organosilicon compound having an increased surface layer hardness of the photoconductor is contained. Japanese Unexamined Patent Publication (Kokai) No. 7-311470 proposes a photoreceptor having a film strength that regulates the wear rate. However, although the abrasion resistance of the photoconductor film itself becomes small, the surface hardness of the photoconductor becomes high, so that toner components adhere to the photoconductor and image defects such as black spots and black streaks cannot be avoided.

Regarding the toner, for example, JP-A-61-27
In Japanese Patent Publication No. 9864, toner shape factor SF1 = {[(maximum length) ² / (projection area)] × (π / 4) × 100} (index indicating toner distortion) and SF2 = {[(perimeter length) ² /
(Projected area)] × (1 / 4π) × 100} (index indicating surface irregularities) is SF1 = 120 to 180, SF2 = 110
A so-called potato-shaped toner controlled within the range of 130 is proposed. However, in the case of the suspension polymerization toner as described in the above publication, although the above range can be achieved with respect to the shape, in the case of the toner using the release agent, the amount of the release agent exposed on the surface can be intentionally controlled. It is difficult, and in principle the amount of surface exposure is small. Therefore, problems such as peeling performance from the fixing device and offset at high temperature are likely to occur mainly in the fixing performance, and it is difficult to maintain an oilless high-quality image for a long period of time.

In the case of a toner containing a release agent component, a method of defining the release agent domain size and the number average molecular weight in the toner can be considered, for example, as disclosed in JP-A-7-31470. According to this method, the initial cleaning property is improved, and image defects such as black spots and black streaks are suppressed, but when toner with a smaller particle size is used, blade cleaning and toner contact to the photoconductor contact portion are prevented. Since the closest packing is likely to occur, the toner rolls at the contact portion, and there is a problem in the cleaning performance maintainability. In particular, there was a problem in a low temperature and low humidity environment. Further, when a large amount of the release agent component is exposed on the toner surface, filming occurs, and when the exposure is too small, the cleaning property is not a problem.
There is a problem that stable fixing performance cannot be secured when using an oilless fixing device.

Therefore, in an image forming apparatus using a toner close to a spherical toner, in order to prevent cleaning failure of a cleaning blade, a method of forming an image with a mixture of spherical toner and irregular toner is disclosed in, for example, Japanese Patent Application Laid-Open 60
It is proposed in Japanese Patent Laid-Open No. 131547/1994, Japanese Patent Laid-Open No. 6-148941 and the like. However, in this method, a mixture of spherical toner and irregular toner is used as the toner for the development, and therefore a denser and more uniform image and spherical toner can be obtained than when only the spherical toner is developed. There is a problem that high transfer efficiency, which is an advantage, cannot be obtained.

Further, in Japanese Unexamined Patent Publication No. 08-254873, an image forming apparatus composed of a plurality of developing machines for developing images of different colors is used and at least one developing machine accommodates irregular toner. However, there has been proposed a method in which a spherical toner is stored in another developing machine to form an image. Also in this method, the image developed by the developing machine containing the irregular toner is the advantage of the dense and uniform image and the spherical toner as compared with the case of developing by the developing machine containing only the other spherical toner. There is a problem that high transfer efficiency cannot be obtained. Further, the effect cannot be exhibited in the tandem type full-color image forming apparatus.

As another means for preventing cleaning failure of a cleaning blade in an image forming apparatus using spherical toner, a method of supplying a lubricant or the like to a photoconductor has been proposed (for example, Japanese Patent Laid-Open No. 5-188643). ). However, if the lubricant supply to the photoconductor is insufficient, cleaning failure occurs, and if excessive supply is likely to have an adverse effect due to filming on the photoconductor, it is necessary to uniformly supply the lubricant to the photoconductor for a long period of time. Very difficult to design. In recent years, the size of the apparatus has been reduced, and it is very difficult to secure a space for the lubricant supply device that supplies the lubricant directly to the surface of the photoconductor, especially in an image forming apparatus using a photoconductor having a small diameter. is there. Particularly, in the tandem type image forming apparatus, it is necessary to equip each photoconductor with a lubricant supply device, which is extremely disadvantageous in terms of cost reduction.

On the other hand, the image forming method proposed for cleaning the irregular toner in which the resin particles and the colorant particles are fused is disclosed in, for example, JP-A-2000-22178.
No. 4, Japanese Patent Laid-Open No. 2000-242004, and the like. In particular, Japanese Patent Laid-Open No. 2000-242004 specifies fluorine in the resin layer on the surface of the photoconductor. However, this is only for irregular-shaped toner, and is less effective for toner that is close to a spherical shape, and when near-spherical toner accumulates on the contact portion between the cleaner and the photosensitive member. It may cause poor cleaning. Further, when an amorphous toner containing a releasing agent component is used as the toner, the toner is liable to be destroyed, and an image defect occurs due to the adhesion of the toner component.

On the other hand, for controlling the toner particle size distribution,
In addition to the problem of the toner being destroyed by the mechanical force, if the original particle size distribution of the toner is wide, the particle size selectivity of development, the occurrence of scattering in transfer, the ease of cleaning, etc. are likely to be affected. Further, the contamination of the developing roll, the charging roll, the charging blade, etc. in the one-component development is likely to occur when the particle size distribution is wide.

From the above-mentioned principle of suppressing the shape distribution, it is necessary to control the particle size distribution on the small particle size side and the particle size distribution on the large particle size side to be narrower. Regarding the particle size distribution of toner particles, volume,
Alternatively, comparison can be performed using an index called GSD of number average. The volume average GSD (GSDv) can be used as an index showing the ratio on the large particle size side, and the number average GSD (GSDp) can be used as an index showing the ratio on the small particle size side. In particular, it is more preferable to use GSD (p-under) as an index showing the small particle size side ratio. In developing and / or transferring performance of toner, generally, the toner particles on the small particle size side have a large adhesive force as conventionally known, so that electrostatic control tends to be difficult, and when a two-component developer is used, the toner particles on the carrier are difficult to control. Easily remains in the. Repeated application of mechanical force leads to carrier contamination, resulting in accelerated carrier deterioration. Further, since the toner having a small particle size has a large adhesive force, the developing efficiency is lowered, and as a result, an image quality defect occurs. In the transfer step, it is difficult to transfer the small particle diameter component of the toner developed on the photoconductor, and as a result, the transfer efficiency is deteriorated, the amount of discharged toner is increased, and the image quality is deteriorated.

On the other hand, although the toner particles having a large particle size have a small adhesive force, they tend to cause non-uniform gap formation in the transfer process or cause scattering to the non-image area,
It is greatly involved in image quality deterioration. Further, since it also causes toner scattering during development, it also causes a decrease in reliability due to contamination inside the machine. These problems become more serious when the toner shape approaches a spherical shape in order to realize high transfer efficiency.

Further, the toner is subjected to various stresses in the electrophotographic process, but in order to maintain stable toner performance, the exposure of the release agent to the toner surface is controlled in addition to the toner shape and particle size control. There is a need. When the exposure on the surface is large, the fixing performance such as offset at high temperature is excellent, but the durability of the toner particles themselves is lowered, and there is a problem in the development and / or transfer performance.
When the exposure on the surface is small, the reliability of the fixing performance mainly deteriorates such as the problem of high temperature offset and the strength of the fixed image at low temperature.

As described above, in order to achieve high image quality with the small particle size toner, which has been actively studied in the electrophotographic process in recent years, it is important to reduce stress applied to the toner during the developing, transferring, fixing and cleaning steps. In particular, it is necessary to overcome transfer of small particle size toner containing a release agent, difficulty in cleaning, and image defects due to adhesion to the photoconductor. However, it is difficult to control not only the particle size distribution but also the above-mentioned shape distribution and the surface release agent exposure amount in the conventional kneading and pulverization type toner. It was not possible to avoid the principle aspect of increasing the number. Therefore, since the particles on the small particle size side easily enter the cleaner and the photoconductor contact portion, the stress received by them becomes particularly large. as a result,
Maintaining high image quality for a long period of time due to reduced transfer efficiency, reduced transferability (image defects such as mottle), toner filming in the cleaning process, and image defects due to toner components adhering to the surface of the photoconductor such as comet. Was difficult.

On the other hand, even if the emulsion polymerization agglomeration method which can obtain a toner having a small particle size and a spherical shape at a low cost is used, the toner having a small particle size has the principle of having a high sphericity. It has been difficult to provide an image forming apparatus and an image forming method that achieve stable cleaning performance even in an environment, suppress image defects due to toner filming for a long period of time, and do not impair developability and fixability.

[0029]

SUMMARY OF THE INVENTION An object of the present invention is to eliminate the above-mentioned problems in the prior art. That is,
An object of the present invention is to provide an image forming apparatus and an image forming method which are excellent in cleaning property without deteriorating various characteristics such as charging property, developing property and fixing property, and which maintain high image quality and high reliability for a long period of time.

[0030]

[Means for Solving the Problems] In order to solve the above problems,
As a result of earnest studies, the present inventor has found that the present invention as described below can solve the problem. That is,
The present invention <1> An image including at least a latent image forming unit that forms an electrostatic latent image on the surface of a photoconductor, and a developing unit that develops the electrostatic latent image with a developer to obtain a toner image. In the forming apparatus, the surface layer of the photoreceptor contains 0.1 to 40% by mass of fluororesin particles based on the mass of the surface layer, and the developer is the following (1) to (3). An image forming apparatus comprising an electrostatic charge image developing toner satisfying the relationship. (1) The shape factors SF1 and SF2 are respectively 125
~ 140 and 105-130. (However, SF1
= (Π / 4) × (L ² / A) × 100, SF2 = (1 /
4π) × (l ² / A) × 100, L is the maximum length, l
Is the perimeter, and A is the projected area. (2) A release agent of 8 to 20 is added to the electrostatic image developing toner.
The release rate of the release agent on the surface of the toner for developing an electrostatic charge image is 11 to 40 atm%, which is included by mass% and quantified by X-ray photoelectron spectroscopy (XPS). (3) The melting point of the release agent measured by a differential scanning calorimeter is 70 to 130 ° C.

<2> Further, there is provided a cleaning means for cleaning the electrostatic image developing toner remaining on the surface of the photoconductor after transfer with a cleaning blade, and the cleaning blade has a 300% modulus of 14000 to 29400 kpa. Tear strength is 5
The image forming apparatus according to <1>, wherein the image forming apparatus has a density of 0000 N / m or more.

<3> The cleaning blade comes into contact with the surface layer of the photoconductor at a contact pressure of 9.8 × 10 ^{−3 to} 4.9 × 1.
The contact speed is 0 ^-2 N / mm, the contact angle is 10 to 40 °, and the blade deformation amount is 0.5 to 2.0 mm. mm / sec)
And the film thickness wear amount B (μm) of the photoreceptor during running per 1 kPV cycle are 2.86 × 10 ⁻⁵ ≦ B
/A≦3.33×10 ⁻⁴ <2>
The image forming apparatus described in 1.

<4> The image forming apparatus according to any one of <1> to <3>, wherein the electrostatic image developing toner is composed of particles formed by aggregating resin fine particles in a solvent. is there.

<5> At least a latent image forming step of forming an electrostatic latent image on the surface of the photoreceptor, a developing step of developing the electrostatic latent image with a developer to obtain a toner image, and a step of applying the toner image. A transfer step of transferring to the surface of the transfer material to obtain a transfer image, a fixing step of fixing the transfer image to obtain a fixed image,
A cleaning step of removing the toner image remaining after the transfer from the surface of the photoconductor, wherein the surface layer of the photoconductor contains fluorine resin particles in an amount of 0.1 to 40 of the surface layer mass. The image forming method is characterized in that the developer contains a toner for developing an electrostatic image satisfying the following relationships (1) to (3). (1) Shape factor SF1 = 125 to 140, SF2 = 10
5-130. (However, SF1 = (π / 4) × (L ² / A) × 100,
SF2 = (1 / 4π) × (l ² / A) × 100,
L is the maximum length, l is the perimeter, and A is the projected area. (2) The exposure rate of the release agent on the surface of the toner for developing an electrostatic charge image, which contains the release agent and is quantified by X-ray photoelectron spectroscopy (XPS), is 11 to 40 atm%. (3) The melting point of the releasing agent measured by a differential scanning calorimeter is 70 to 130 ° C., and the releasing agent is contained in the toner for developing an electrostatic image in an amount of 8 to 20% by mass.

<6> In the cleaning step, cleaning treatment is performed by a cleaning blade, and the 300% modulus of the cleaning blade is 1400.
0-29400kpa, tear strength 50000N /
The image forming method according to <5>, wherein the image forming method is m or more.

<7> Contact pressure of the cleaning blade with the surface layer of the photoconductor 9.8 × 10 ^{−3 to} 4.9 × 1
The contact speed is 0 ^-2 N / mm, the contact angle is 10 to 40 °, and the blade deformation amount is 0.5 to 2.0 mm. mm / sec)
And the film thickness wear amount B (μm) of the photoreceptor during running per 1 kPV cycle are 2.86 × 10 ⁻⁵ ≦ B
/A≦3.33×10 ⁻⁴ <6>
The image forming method described in 1.

<8> The image forming method according to any one of <5> to <7>, wherein the toner for developing an electrostatic image comprises particles formed by aggregating resin fine particles in a solvent. is there.

Further, it is preferable that the image forming apparatus and the image forming method of the present invention each include any one or more of the following requirements (1) to (6).

(1) The coefficient of static friction between the cleaning blade and the surface layer of the photoconductor is 0.3 to 1.0.

(2) The thickness of the surface layer of the photoreceptor is 10 to 10.
50 μm, and the surface roughness Rz of the surface of the photoconductor is 0.
Must be 5-1 μm.

(3) The film strength of the surface layer of the photoreceptor is 20 to 30 under a load of 10 g as measured by the Vickers method.

(4) The hardness (JIS A) of at least the contact portion of the cleaning blade with the photosensitive member is 75 or more, and the tensile strength of the cleaning blade is 37240 kpa or more.

(5) The electrostatic image developing toner further satisfies the following relationships (a) to (f). (A) The average volume particle size distribution index GSDv is 1.25 or less. (However, GSDv = (D84v / D16v)
^1/2 , D84v is 8 accumulated in volume distribution of particle size
The particle size value is 4%, and D16v is the particle size value that is cumulative 16% from the small diameter side in the particle size volume distribution. (B) The average number particle size distribution index GSDp is 1.25 or less. (However, GSDp = (D84p) / D16p)
^1/2 , and D84p is the cumulative 8 in the particle size distribution.
The particle size value is 4%, and D16p is the particle size value that is cumulative 16% from the small diameter side in the number distribution of particle sizes. ) (C) Small particle size side number particle size distribution index GSDp-under
Is 1.27 or less. (However, GSDp-unde
r = (D50p / D16p), where D50p is a particle size value that is cumulative 50% in the particle size number distribution, and D1
6p is a particle size value that makes a cumulative 16% from the smaller size side. (D) The cumulative volume average particle diameter D50v is 3 to 7 μm. (E) The size of the release agent in the cross section of the toner observed from the transmission electron microscope is 150 to 1500 nm, and the release agent particles of 1000 nm or more are not exposed on the toner surface. (F) A total of 0.5 to 10 mass% of inorganic fine particles having a number average particle diameter of 5 to 30 nm and inorganic fine particles having a number average particle diameter of 30 to 100 nm are contained.

(6) The developer is a two-component developer comprising a carrier and the electrostatic charge developing toner,
The carrier is resin-coated.

As described above, the reason why the cleaning property of the spherical toner is difficult as compared with the conventional amorphous toner is as follows.
This is because spherical toner with a low rolling friction coefficient rolls between the cleaning blade and the photoconductor, and in order to improve the cleaning performance when using spherical toner, it is necessary to use it for a long period of time and in the operating environment. Regardless, it is important to stably suppress the rolling of spherical toner.
Further, in order to maintain the cleaning property while suppressing the abrasion of the surface of the photoconductor for a long period of time and improve the image defect due to the adhesion of the toner containing the release agent to the photoconductor, the friction coefficient of the photoconductor surface is suppressed and the toner is As such, it is important to suppress the shape and the exposure rate of the release agent on the surface. Therefore, in the present invention, in order to suppress the friction coefficient of the surface of the photoconductor, fluorine-based resin particles such as tetrafluoroethylene resin are added to the surface layer of 0.
Using the above-mentioned photoreceptor containing 1 to 40 wt%, shape factor SF1 = 125 to 140, SF2 = 105 to 13
The above problem was solved by using the above-mentioned electrostatic charge developing toner containing 0 to 100% by mass of the release agent.

In the present invention, the 300% modulus is 14700 kPa or more and 29400 kPa or less (150 kPa).
gf / cm ² or more and 300 kgf / cm ² or less), and using a cleaning blade made of an elastic material that has a tear strength of 50000 N / m or more, a microdeformation of the cleaning blade tip particularly when spherical toner is used Rolling in a part can be stably suppressed for a long period of time.

[0047]

BEST MODE FOR CARRYING OUT THE INVENTION <Image Forming Apparatus> The image forming apparatus of the present invention comprises at least a latent image forming means for forming an electrostatic latent image on the surface of a photoreceptor and a developer for developing the electrostatic latent image. And a developing means for obtaining a toner image by means of a cleaning blade. It is provided. Hereinafter, the image forming apparatus of the present invention will be described in detail, focusing on the photoconductor, the developer, and the cleaning blade.

(Photoreceptor) The photoreceptor used in the image forming apparatus of the present invention has an organic photosensitive layer formed on a conductive support. The organic photosensitive layer includes at least a charge generation layer formed by binding a charge generation material using a suitable resin as a binder (binder resin), and a charge transport layer in which a charge transport material is dispersed or dissolved in a binder resin. And two layers, and an undercoat layer, a protective layer, and the like are formed as necessary. Further, the surface layer of the photoconductor contains 0.1 to 40% by mass of the fluorine-based resin particles based on the mass of the surface layer. Here, the "surface layer" means a layer formed on the outermost surface of the photoreceptor, for example, when the charge transport layer is provided on the outermost surface of the photoreceptor, the charge transport layer is the surface layer. When a protective layer is further provided, the protective layer serves as a surface layer, and each contains the fluororesin particles. Hereinafter, the conductive support and each layer will be described.

Conductive support: As the conductive support,
Any conventional material may be used. For example, metals such as aluminum, nickel, chromium, and stainless steel; aluminum, titanium, nickel, chromium, stainless steel, plastic films provided with thin films of gold, vanadium, tin oxide, indium oxide, ITO, etc .; conductivity imparting Paper coated with or impregnated with an agent, a plastic film, and the like; Further, if necessary, the surface of the conductive support is
Various types of processing can be performed within a range that does not affect the image quality. For example, surface anodizing treatment, chemical treatment or coloring treatment, or irregular reflection treatment such as graining or liquid honing can be performed.

An undercoat layer may be formed on the surface of the conductive support, if desired. The undercoat layer is an acetal resin such as polyvinyl butyral, polyvinyl alcohol resin, polyamide resin, cellulose resin, gelatin, polyurethane resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate- In addition to polymer resin compounds such as maleic anhydride resin, silicone resin, phenol-formaldehyde resin and melamine resin, there are organometallic compounds containing zirconium, titanium, aluminum, manganese, silicon atoms and the like. These compounds can be used alone or as a mixture of a plurality of compounds or as a polycondensate. The thickness of the undercoat layer is preferably 0.1 to 50 μm, and 0.2 to
More preferably, it is 30 μm.

Charge generation layer: The charge generation layer is formed on the conductive support (when an undercoat layer is formed, on the undercoat layer). As the charge generating material contained in the charge generating layer, phthalocyanine pigments such as metal-free phthalocyanine, chlorogallium phthalocyanine, hydroxygallium phthalocyanine, dichlorotin phthalocyanine, and titanyl phthalocyanine can be used. A chlorogallium phthalocyanine crystal having strong diffraction peaks at (2θ ± 0.2 °) of at least 7.4 °, 16.6 °, 25.5 ° and 28.3 °, a Bragg angle (2θ ± 2) for CuKα characteristic X-ray.
0.2 °) of at least 7.7 °, 9.3 °, 16.9
CuKα, a metal-free phthalocyanine crystal having strong diffraction peaks at °, 17.5 °, 22.4 ° and 28.8 °
Bragg angle (2θ ± 0.2 °) of characteristic X-ray of at least 7.5 °, 9.9 °, 12.5 °, 16.3 °,
Hydroxygallium phthalocyanine crystals having strong diffraction peaks at 18.6 °, 25.1 ° and 28.3 °,
Bragg angle (2θ ± 0.2 for CuKα characteristic X-ray)
At least 9.6 °, 24.1 ° and 27.2
A titanyl phthalocyanine crystal having a strong diffraction peak at ° can be used.

In addition, as the charge generating material, quinone pigment, perylene pigment, indigo pigment, bisbenzimidazole pigment, anthrone pigment, quinacridone pigment and the like can be used. The above charge generating materials may be used alone or in combination of two or more.

Examples of the binder resin in the charge generation layer include the following. That is, polycarbonate resin such as bisphenol A type or bisphenol Z type, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, polystyrene resin, polyvinyl acetate resin, styrene-butadiene copolymer resin, vinylidene chloride-acrylonitrile copolymer Examples thereof include coalescing resin, vinyl chloride-vinyl acetate-maleic anhydride resin, silicone resin, phenol-formaldehyde resin, poly-N-vinylcarbazole and the like. These binder resins can be used alone or in combination of two or more. The compounding ratio (mass ratio) of the charge generating material and the binder resin is preferably in the range of 10: 1 to 1:10.

As the solvent used to disperse the charge generating material, a solvent capable of dissolving the binder resin can be appropriately selected. As a method for dispersing the charge generation material in the resin, a method such as a roll mill, a ball mill, a vibrating ball mill, an attritor, a sand mill, a colloid mill or a high pressure homogenizer can be used.

Examples of the coating method include a dip coating method, a push-up coating method, a spray coating method, a roll coater coating method, and a gravure coater coating method. The thickness of the charge generation layer is generally 0.01 to 5 μm, preferably 0.05.
It is set in the range of up to 2.0 μm.

Charge transport layer: The charge transport layer is formed on the charge generation layer. When the charge transport layer is the surface layer of the photoreceptor, the charge transport layer contains fluorine-based resin particles. The content of the fluororesin particles in the charge transport layer is essentially 0.1 to 40 mass% of the total mass of the charge transport layer, and preferably 1 to 30 mass%. Content is 1
If it is less than mass%, the modification effect due to dispersion of the fluorine-based resin particles is not sufficient, and if it exceeds 40 mass%, the light transmission property is lowered and the residual potential is increased by repeated use.

The fluorine resin particles include tetrafluoroethylene resin, trifluorochloroethylene resin, hexafluoropropylene resin, vinyl fluoride resin, vinylidene fluoride resin,
It is desirable to appropriately select one kind or two or more kinds from the difluorodichloroethylene resin and the copolymer thereof, and the tetrafluoroethylene resin and the vinylidene fluoride resin are particularly preferable. The volume average particle diameter of the primary particle diameter of the fluororesin particles is preferably 0.05 to 1 μm, and more preferably 0.1 to 0.5 μm.
If the volume average particle size is less than 0.05 μm, aggregation during dispersion tends to proceed, and if it exceeds 1 μm, image quality defects are likely to occur.

Further, the charge transport layer may contain inorganic particles. The content of the inorganic particles in the charge transport layer is appropriately 0.1 to 30% by mass, and particularly preferably 1 to 20% by mass based on the total amount of the charge transport layer. If the content is less than 1% by mass, the modifying effect due to the dispersion of the inorganic particles is not sufficient.
When it exceeds 0% by mass, the residual potential increases due to repeated use.

Examples of the inorganic particles include alumina, silica, titanium oxide, zinc oxide, cerium oxide, zinc sulfide, magnesium oxide, copper sulfate, sodium carbonate, magnesium sulfate, potassium chloride, calcium chloride, sodium chloride, nickel sulfate, and the like. Examples thereof include antimony, manganese dioxide, chromium oxide, tin oxide, zirconium oxide, barium sulfate, aluminum sulfate, silicon carbide, titanium carbide, boron carbide, tungsten carbide and zirconium carbide, and silica is preferably used. These may be used alone or in admixture of two or more if necessary. As the silica particles, those produced by a chemical flame CVD method are preferable, and as specific examples, those produced by subjecting chlorosilane gas to a gas phase reaction in a high temperature flame of an oxygen-hydrogen mixed gas or a hydrocarbon-oxygen mixed gas. Is preferred.

The inorganic particles are preferably hydrophobized with a hydrophobizing agent. As the hydrophobizing agent, for example, a siloxane compound, a silane coupling agent, a titanium coupling agent, a polymeric fatty acid or a metal salt thereof, etc. are used. Examples of the siloxane compound include dihydroxypolysiloxane and octamethylcyclotetrasiloxane. As the silane coupling agent, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β- (N -Vinylbenzylaminoethyl) γ-aminopropyltrimethoxysilane hydrochloride, hexamethyldisilazane, methyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane , Dodecyltrimethoxysilane, phenyltrimethoxysilane,
Examples thereof include o-methylphenyltrimethoxysilane and p-methylphenyltrimethoxysilane.

The number average particle diameter of the inorganic particles is preferably 0.005 to 2.0 μm,
More preferably, it is from 01 to 1.0 μm. 0.00
If it is less than 5 μm, sufficient mechanical strength of the surface of the photoreceptor cannot be obtained and aggregation during dispersion tends to proceed. If it exceeds 2 μm, the surface roughness of the photoconductor becomes large, and the cleaning blade is worn or damaged to deteriorate the cleaning characteristics, and image blurring easily occurs.

As the charge transport material, for example, 2,5-
Oxadiazole derivatives such as bis (p-diethylaminophenyl) -1,3,4-oxadiazole; 1,3
5-triphenyl-pyrazolin, 1- [pyridyl-
(2)]-3- (p-Diethylaminostyryl) -5-
Pyrazoline derivatives such as (p-diethylaminostyryl) pyrazoline; aromatic tertiary amino compounds such as triphenylamine, tri (p-methylphenyl) aminyl-4-amine, dibenzylaniline; N, N'-bis (3 -Methylphenyl) -N, N'-diphenylbenzidine and other aromatic tertiary diamino compounds; 3- (4'-dimethylaminophenyl) -5,6-di- (4'-methoxyphenyl) -1,2 , 4-Triazine and other 1,2,4-triazine derivatives; 4-diethylaminobenzaldehyde-
Hydrazone derivatives such as 1,1-diphenylhydrazone;
Quinazoline derivatives such as 2-phenyl-4-styryl-quinazoline; Benzofuran derivatives such as 6-hydroxy-2,3-di (p-methoxyphenyl) benzofuran; p-
Α-stilbene derivatives such as (2,2-diphenylvinyl) -N, N-diphenylaniline; enamine derivatives; N
-Carbazole derivatives such as ethylcarbazole; poly-
Examples thereof include hole transport materials such as N-vinylcarbazole and its derivatives. Further, quinone compounds such as chloranil and broanthraquinone; tetraanoquinodimethane compounds; fluorenone compounds such as 2,4,7-trinitrofluorenone, 2,4,5,7-tetranitro-9-fluorenone; xanthone compounds Compounds; thiophene compounds;
A polymer having a group composed of the above compound in its main chain or side chain can also be mentioned. These charge transport materials can be used alone or in combination of two or more.

Examples of the binder resin include acrylic resin, polyarylate, polyester resin, polycarbonate resin such as bisphenol A type or bisphenol Z type; polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene copolymer, polyvinyl butyral. , Polyvinyl formal, polysulfone, polyacrylamide, polyamide, chlorine rubber, and other insulating resins; polyvinyl carbazole, polyvinyl anthracene, polyvinyl pyrene, and other organic photoconductive polymers; and the like.

In the charge transport layer, the above charge transport substance and the binder resin are dissolved in a suitable solvent (when the charge transport layer serves as a surface layer, together with the above-mentioned fluorine-based resin particles and, if necessary, inorganic particles). It can be formed by applying the dried solution and drying. Examples of the solvent used for forming the charge transport layer include aromatic hydrocarbon solvents such as toluene and chlorobenzene; methanol, ethanol,
Aliphatic alcohol solvents such as n-butanol; ketone solvents such as acetone, cyclohexanone, 2-butanone; halogenated aliphatic hydrocarbon solvents such as methylene chloride, chloroform, ethylene chloride; tetrahydrofuran, dioxane, ethylene glycol, diethyl ether A cyclic or linear ether solvent such as; or a mixed solvent thereof can be used.

The compounding ratio (mass ratio) of the charge transport material and the binder resin is preferably 10: 1 to 1: 5. Fluorine-based resin particles in the charge transport layer, further as a method of dispersing the inorganic particles, roll mill, ball mill, vibrating ball mill, attritor, sand mill, high pressure homogenizer,
A method such as an ultrasonic disperser or a colloid mill can be used.

As an example of dispersion of the coating liquid for forming the charge transport layer, a binder resin dissolved in the above solvent, a fluorine-based resin in the case where the inorganic particles or the charge transport layer serve as a surface layer in a solution of the charge transport material, etc. A method of dispersing particles can be mentioned. It is also effective to add a small amount of a dispersion aid in order to improve the dispersion stability of the dispersion liquid and prevent aggregation during coating film formation. As the dispersion aid, a fluorosurfactant,
Fluorine-based polymers, silicone-based polymers, silicone oils and the like can be mentioned, but from the viewpoint of high sensitivity and reduction of residual potential during repeated use, 0.1-1.0 mass% of fluorine-based graft polymer is preferably used. It

Examples of the coating method include a dip coating method, a push-up coating method, a spray coating method, a roll coater coating method and a gravure coater coating method. The thickness of the charge transport layer is generally 5 to 60 μm, preferably 10 to 50 μm.
It is set in the range of μm. The above range is preferably selected from the viewpoints of abrasion resistance of the surface and charge retention performance. Further, the surface roughness Rz when the charge transport layer is a surface layer is measured by, for example, a surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd., JIS-94 standard) or the like, and is in the range of 0.01 to 1.0 μm (preferably, 0.
1 to 0.8 μm) is suitably selected from the viewpoint of maintaining the transfer performance, the cleaning performance, and these both at the same time.

Protective layer: The protective layer is an arbitrary layer formed on the charge transport layer, and if the fluorinated resin particles are contained in an amount of 0.1 to 40% by mass based on the mass of the surface layer, other composition. For example, a conventionally known one can be applied. The film thickness is preferably 1 to 50 μm, and the surface roughness Rz is preferably 0.01 to 1.0 μm.

The surface hardness of the photoconductor is represented by Vickers hardness. The Vickers hardness of the surface of the photoreceptor having the above-mentioned layer structure is preferably in the range of 20 to 30 under a load of 10 g, and from the viewpoint of abrasion resistance by a cleaner having high hardness and reduction of abrasion given to the cleaner. That value is selected.

For the purpose of preventing the deterioration of the photoreceptor due to ozone or oxidizing gas generated when the electrophotographic apparatus is operated, or light or heat, an antioxidant, a light stabilizer,
Additives such as heat stabilizers can be added. For example,
Examples of antioxidants include hindered phenols, hindered amines, paraphenylenediamines, arylalkanes, hydroquinones, spirochromans, spiroindanones and their derivatives, organic sulfur compounds and organic phosphorus compounds. Examples of the light stabilizer include derivatives such as benzophenone, benzazole, dithiocarbamate, and tetramethylpipene. Further, a leveling agent such as silicone oil may be added to the surface layer for the purpose of improving the smoothness of the surface.

(Developer) The toner for electrostatic charge development, which is a constituent of the developer, must satisfy the following relationships (1) to (3). That is, (1) Shape factors SF1 and SF2 are 125
~ 140 and 105-130. (However, SF1
= (Π / 4) × (L ² / A) × 100, SF2 = (1 /
4π) × (l ² / A) × 100, L is the maximum length, l
Is the perimeter, and A is the projected area. When the shape factor SF1 exceeds 140, the fluidity of the toner is lowered, and the transferability is adversely affected from the initial stage. Further, if the shape factor SF1 is less than 125, cleaning failure may occur, which causes mechanical contamination and reliability deterioration.
The shape factor SF2 corresponds to the unevenness of the toner surface. S
When F2 exceeds 130, the transferability deteriorates from the initial stage.
If the SF2 is less than 105, the transferability is good, but cleaning failure occurs especially for small particle size toner. The preferable range of the shape factors SF1 and SF2 is, respectively,
SF1 is 125-135 and SF2 is 105-125
Is.

The shape factor of toner is obtained as follows. Toner is scattered on a glass slide, the image observed with an optical microscope is taken into a Luzex image analyzer through a video camera, and the maximum length and projected area of 1000 or more toner particles are measured and substituted into the above formula, and the average value is calculated. Is the shape factor.

(2) A release agent is contained in the toner for developing an electrostatic image in an amount of 8 to 20% by mass, and X-ray photoelectron spectroscopy (XP
The exposure rate of the release agent on the surface of the toner for developing an electrostatic charge image (hereinafter, may be simply referred to as “exposure rate”) quantified by S) is 11 to 40 atm%. When the content of the release agent contained in the electrostatic image developing toner is less than 8% by mass, image defects such as black spots and black streaks due to the release agent component adhering to the photoconductor are suppressed, but the fixing performance, In particular, it causes a problem in peeling performance at high temperatures. On the other hand, when it exceeds 20% by mass, the amount of the surface-released release agent increases and image defects such as black spots and black streaks due to the adhesion of the release agent component become a problem. Further, since the ratio of the scattered light inside the image is increased, the transparency of the image on the OHP film may be lowered and the coloring property may be lowered. The preferred content is
It is 9 to 18% by mass.

If the exposure rate is less than 11 atm%, the fixing performance is not affected initially, but the long-term maintainability is difficult. Further, when the fixing device is deteriorated, the offset on the high temperature side and the strength of the fixed image on the low temperature side are adversely affected. on the other hand,
If it exceeds 40 atm%, the fixing performance will not be affected, but
Filming may occur on the carrier, the developing roll, the photoconductor, and the like. In addition, a phenomenon in which an external additive added to impart fluidity is buried in the toner easily occurs. A preferable exposure rate is 13 to 30 atm%. The exposure rate of the release agent on the surface of the toner for developing the electrostatic image is, for example, X-ray photoelectron spectrometer (XP) manufactured by JEOL Ltd.
S, JPS-9000MX)
The peaks caused by the pigment and the release agent can be separated and quantified.

(3) The melting point of the releasing agent measured by a differential scanning calorimeter is 70 to 130 ° C. If the temperature is lower than 70 ° C., offset tends to occur during fixing. Also, 130
When the temperature exceeds ℃, the fixing temperature becomes high and the smoothness of the surface of the fixed image cannot be obtained and the glossiness is impaired. A preferable melting point is 80 to
It is 120 ° C. The melting point of the release agent is ASTM D3418.
It is preferable to measure and obtain the main component maximum peak measured according to −8. For the measurement of the main component maximum peak, it is preferable to use, for example, DSC-7 manufactured by Perkin Elmer. At this time, the melting points of indium and zinc are used to correct the temperature of the detection unit of the apparatus, and the heat of fusion of indium is used to correct the amount of heat. An aluminum pan was used as a sample, and an empty pan was set as a control, and the temperature rising rate was 10 ° C / mi.
Measure with n.

The electrostatic charge developing toner preferably has an average volume particle size distribution index GSDv of 1.25 or less (where GSDv = (D84v / D16v).
^1/2 , D84v is 8 accumulated in volume distribution of particle size
The particle size value is 4%, and D16v is the particle size value that is cumulative 16% from the small diameter side in the particle size volume distribution. ) When the average volume particle size distribution index GSDv exceeds 1.25, the sharpness and resolution of the image may decrease. In addition, the transferability may be deteriorated from the initial stage and the image quality may be deteriorated.

The small particle size side number particle size distribution index GSDp-under of the electrostatic charge developing toner is preferably 1.27 or less. (However, GSDp-under = (D
50p / D16p), D50p is a cumulative particle size value of 50% in the number distribution of particle sizes, and D16p is a cumulative particle size value of 16% from the smaller diameter side. When the average particle size distribution index GSDp-under of the small particle size exceeds 1.27, the ratio of the small particle toner becomes high, which may have an extremely large effect in terms of reliability in addition to the initial performance. is there. That is, as has been conventionally known, since the adhesion of the toner having a small particle size is large, electrostatic control tends to be difficult, and when a two-component developer is used, it is likely to remain on the carrier. Repeated application of mechanical force leads to carrier contamination, resulting in accelerated carrier deterioration. In addition, since small particle size toner has a large adhesive force,
A decrease in development efficiency also occurs, resulting in an image quality defect. In the transfer step, it is difficult to transfer the small-diameter component of the toner developed on the photosensitive member, and as a result, the transfer efficiency is deteriorated, and the amount of discharged toner and the image quality may deteriorate.

The average number particle size distribution index GSDp of the toner for developing an electrostatic image is preferably 1.25 or less.
(However, GSDp = (D84p) / D16p) ^1/2 , D84p is a cumulative particle size value of 84% in the particle size distribution, and D16p is 16% cumulative from the small diameter side in the particle size distribution. Is the particle size value. ) GSDp
When it exceeds 1.25, the ratio of the toner on the small particle size side becomes high as in the case of GSDp-under, which may have a great influence from the viewpoint of reliability as well as the initial performance.

The cumulative volume average particle diameter D50v of the electrostatic image developing toner is preferably 3 to 7 μm. D50
If v is less than 3 μm, the chargeability may be insufficient and the developability may be lowered, and if v is more than 7 μm, the resolution of the image may be lowered.

The size of the releasing agent in the cross section of the toner observed from the transmission electron microscope is 150 to 1500 n.
In the range of m, it is preferable that the release agent particles having a size of 1000 nm or more are not exposed on the toner surface. If it is less than the above range, there is no problem in the cleaning property, but fixing properties, particularly offset at high temperature, may occur. On the other hand, if it is larger than the above range, the ratio of the scattered light inside the image increases, which may lead to a decrease in transparency and a decrease in color developability of the image on the OHP film. The size of the releasing agent in the toner cross section is an average value of 100 or more toner particles observed with a transmission electron microscope (JEM1010) manufactured by JEOL Ltd. after embedding the toner particles in an epoxy resin and cutting. To calculate. The toner surface is, for example, a field emission scanning electron microscope (S-41 manufactured by Hitachi, Ltd.).
00) and the like, but when the release agent having a thickness of 1000 nm or more is exposed, it may cause adhesion of the photoconductor, which is not preferable.

The toner for electrostatic charge development has a number average particle diameter of 5 to 5.
30 nm inorganic fine particles and number average particle diameter of 30 to 100 nm
It is preferable that the total amount of the inorganic fine particles is 0.5 to 10% by mass. The inorganic fine particles are silica, hydrophobized silica, titanium oxide, alumina, calcium carbonate, magnesium carbonate, tricalcium phosphate, colloidal silica, cationic surface-treated colloidal silica,
Anion surface-treated colloidal silica or the like is used. These inorganic fine particles are previously subjected to a dispersion treatment using an ultrasonic disperser or the like in the presence of an ionic surfactant, but it is more preferable to use colloidal silica which does not require this dispersion treatment.

When the amount of the inorganic fine particles added is less than 0.5% by mass, sufficient toughness cannot be obtained when the toner is melted, and not only the releasability in oilless fixing cannot be improved, but also
The coarse dispersion of the fine particles in the toner when the toner is melted increases only the viscosity, and as a result, the spinnability is deteriorated, which may impair the oilless releasability. Also, 10
If it exceeds%, sufficient toughness can be obtained, but the fluidity when the toner is melted is significantly reduced, and the image glossiness may be impaired.

The ratio of the central particle diameter of the inorganic fine particles having a number average particle diameter of 5 to 30 nm to the inorganic fine particles having a number average particle diameter of 30 to 100 nm is preferably 0.7 to 3.
If it is less than 0.7, the toughness at the time of melting is obtained, but the viscosity at the time of fixing becomes large and the fluidity is poor, resulting in a decrease in the image glossiness. Although it can be obtained, it is difficult to obtain the toughness when the resin is melted, and the peelability may be impaired. That is,
Outside of the range, one of the particles of the inorganic fine particles is predominant, so that the effect of adding two or more kinds of the fine particles cannot be obtained, and either one of peelability at the time of fixing and image glossiness, Or you can't get both.

The toner for developing an electrostatic image as described above preferably comprises particles formed by aggregating resin particles in a solvent, and a resin particle dispersion liquid in which resin particles of 1 μm or less are dispersed, and a colorant are dispersed. The colorant dispersion liquid, the release agent dispersion liquid in which the release agent is dispersed, and the aggregating agent are mixed,
An aggregating step of preparing an agglomerated particle dispersion liquid in which agglomerated particles composed of the resin fine particles and the colorant are dispersed, and the agglomerated particle dispersion liquid, a fine particle dispersion liquid in which fine particles are dispersed is added and mixed, and the agglomerated particles are It is preferably manufactured through an adhesion step of adhering fine particles to prepare adhered particles and a fusing step of heating the resin particles to a temperature not lower than the glass transition point to fuse the adhered particles. The above steps will be described below.

Aggregating Step: The resin fine particles in the aggregating step are preferably a polymer which becomes a thermoplastic binder resin. Examples of the polymer include styrenes such as styrene, parachlorostyrene and α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate and methyl methacrylate. , Esters having a vinyl group such as ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate and 2-ethylhexyl methacrylate; vinyl nitriles such as acrylonitrile and methacrylonitrile; vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether. Vinyl vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; polyolefins such as ethylene, propylene and butadiene; polymers such as monomers and the like, or a combination of two or more thereof. It can be mentioned copolymers or vinyl resins consisting of mixtures is. Furthermore, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, non-vinyl condensation resin, or a mixture of these and the vinyl resin, or vinyl monomers in the coexistence of these resins are used. Examples thereof include a graft polymer obtained at the time of polymerization. These resins may be used alone or in combination of two or more.

Among the above resins, vinyl resins are particularly preferable. The vinyl resin is advantageous in that the resin particle dispersion can be easily prepared by emulsion polymerization or seed polymerization using an ionic surfactant or the like.

The method for preparing the dispersion liquid of the resin fine particles is not particularly limited, and a method appropriately selected according to the purpose can be adopted. For example, it can be prepared as follows.

The resin in the resin fine particles is a homopolymer or copolymer (vinyl-based resin) of vinyl-based monomers such as esters having the vinyl group, the vinyl nitriles, the vinyl ethers, and the vinyl ketones. When the vinyl monomer is subjected to emulsion polymerization or seed polymerization in an ionic surfactant, the resin particles of the vinyl monomer homopolymer or copolymer are ionic. A dispersion liquid obtained by dispersing it in a surfactant can be prepared.

When the resin in the resin fine particles is a resin other than the homopolymer or copolymer of the vinyl-based monomer, it dissolves in an oily solvent having a relatively low solubility in water. If present, the resin is dissolved in the oily solvent, the dissolved product is added to water together with the ionic surfactant and the polyelectrolyte, fine particles are dispersed by using a disperser such as a homogenizer, and then heated or reduced pressure. By doing so, it can be prepared by evaporating the oily solvent.

When the resin fine particles dispersed in the resin fine particle dispersion liquid are composite particles containing components other than the resin fine particles, the dispersion liquid in which these composite particles are dispersed is prepared as follows, for example. can do. For example,
Each component of the composite particles is dissolved and dispersed in a solvent, then dispersed in water together with a suitable dispersant as described above, and the solvent is removed by heating or depressurizing, or emulsion polymerization or seed polymerization. It can be prepared by a method of immobilizing by mechanically shearing or electrically adsorbing the latex surface prepared by.

The volume average particle diameter of the resin fine particles is preferably 1 μm or less, and more preferably 0.01 to 1 μm. If the volume average particle size of the resin fine particles exceeds 1 μm, the particle size distribution of the finally obtained toner for developing an electrostatic image may be widened or free particles may be generated, which may lead to deterioration in performance and reliability. . On the other hand, when the volume average particle diameter of the resin fine particles is 1 μm or less, not only the above-mentioned drawbacks are solved but also uneven distribution among the toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are caused. It is advantageous that it becomes small. The volume average particle diameter of the resin fine particles can be measured by using, for example, Microtrac or the like.

When the resin in the resin fine particles is a resin other than the homopolymer or copolymer of the vinyl monomer, the resin is soluble in an oily solvent having a relatively low solubility in water. In that case, the resin is dissolved in the oily solvent, the dissolved product is added to water together with the ionic surfactant and the polyelectrolyte, and fine particles are dispersed by using a disperser such as a homogenizer, followed by heating. Or it can be prepared by evaporating the oily solvent by reducing the pressure.

As the colorant contained in the colorant dispersion,
For example, carbon black, chrome yellow, Hansa yellow, benzidine yellow, slen yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red,
Permanent Red, Brilliant Carmine 3B, Brilliant Carmine 6B, DuPont Oil Red, Pyrazolone Red, Resole Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine. Various pigments such as green and malachite green oxalate; acridine, xanthene, azo, benzoquinone, azine, anthraquinone, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black , Polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole, xanthene, and various dyes; These colorants may be used alone or in combination of at least two (two or more). In the latter case, the color of the toner can be arbitrarily adjusted by changing the type and mixing ratio of the colorant (pigment). The colorant dispersion can be prepared, for example, by dispersing the colorant in an aqueous medium such as a surfactant.

The number average particle diameter of the colorant particles (pigment) is 0.8.
It is preferably not more than μm, and 0.05 to 0.5 μm
Is more preferable. When the number average particle diameter exceeds 0.8 μm, the particle size distribution of the finally obtained toner for developing an electrostatic image is widened or free particles are generated, which leads to deterioration in performance and reliability. When the number average particle diameter is smaller than 0.05 μm, not only the coloring property in the toner is deteriorated, but also the shape controllability, which is one of the features of the emulsion aggregation method, is impaired, and a toner having a shape close to a true sphere is obtained. You won't get it. Also,
The number% of particles having a particle diameter of 0.8 μm or more is preferably less than 10%, and substantially 0%. The presence of such coarse particles impairs the stability of the agglomeration process, not only releases the coarse colored particles but also broadens the particle size distribution. Particle size is 0.
The number% of particles having a size of 05 μm or less is preferably 5% or less. The presence of such fine particles impairs the shape controllability in the fusing step, and a so-called smooth particle having a shape factor SF1 of 130 or less cannot be obtained. On the other hand, when the average particle diameter, the coarse particles, and the fine particles of the colorant particles are within the above range, the above-mentioned defects are not present, uneven distribution among the toners is reduced, and the dispersion in the toner is improved, and the performance is improved. It is advantageous that the dispersion of the reliability is small. The average particle size of the colorant particles can be measured using, for example, Microtrac or the like. The amount of the colorant added is preferably set in the range of 2 to 20% by mass of the total mass of the toner particles.

For the colorant (pigment), rosin,
A surface modification treatment may be performed with a polymer or the like. The surface-modified colorant is sufficiently stabilized in the colorant dispersion, and after the colorant is dispersed in the colorant dispersion to a desired average particle size, resin particles are dispersed. This is advantageous in that the colorants do not aggregate even in the aggregating step during mixing with the liquid, and a good dispersed state can be maintained. On the other hand, the coloring agent that has been subjected to excessive surface modification treatment may be released without being aggregated with the resin particles in the aggregation step. Therefore, the surface modification treatment is performed under optimal conditions that are appropriately selected. Examples of the polymer include an acrylonitrile polymer and a methyl methacrylate polymer.

As the conditions for the surface modification, generally, a polymerization method in which a monomer is polymerized in the presence of a colorant (pigment), a colorant (pigment) is dispersed in a polymer solution to reduce the solubility of the polymer, and coloring is performed. A phase separation method or the like in which the agent (pigment) is deposited on the surface can be used.

In the release agent dispersion liquid, components (particles) such as internal additives may be dispersed in addition to the release agent. The release agent is preferably dispersed in water together with an ionic surfactant and a polymer electrolyte such as a polymer acid or polymer base. Then, the release agent dispersion liquid can be prepared by subjecting the release agent to fine particles by applying strong shearing using a homogenizer or a pressure discharge type dispersion machine while heating the release agent to a temperature higher than the melting point of the release agent. When the other internal additive is an inorganic particle or the like, it can be prepared by dispersing the inorganic particle or the like in an aqueous medium such as the surfactant.

Examples of the releasing agent include low molecular weight polyolefins such as polyethylene, polypropylene and polybutene;
Silicones having a softening point by heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; carnauba wax, rice wax, candelilla wax, wax, jojoba oil, etc. Such as plant waxes; animal waxes such as beeswax; minerals such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, petroleum waxes, and modified products thereof; . These release agents may be used alone or in combination of two or more.

The volume average particle diameter of the internal additive is preferably 1 μm or less, and more preferably 0.01 to 1 μm. If the volume average particle size exceeds 1 μm, the particle size distribution of the finally obtained toner for developing an electrostatic image may be widened or free particles may be generated, which may lead to deterioration in performance and reliability. On the other hand, when the volume average particle diameter of the resin particles is within the above range, not only the above drawbacks are eliminated, but also uneven distribution among the toners is reduced, dispersion in the toner is improved, and variations in performance and reliability are caused. Is advantageous in that The volume average particle diameter can be measured using, for example, a Microtrac or the like.

Examples of the dispersion medium for preparing the resin particle dispersion, the colorant dispersion, and the release agent dispersion include an aqueous medium. Examples of the aqueous medium include distilled water, water such as ion-exchanged water, alcohols and the like. These may be used alone or in combination of two or more.

The means for preparing the various dispersions (resin particle dispersion, colorant dispersion, release agent dispersion) is not particularly limited, but, for example, a rotary shearing homogenizer or media is used. Ball mill, sand mill,
Examples thereof include known dispersing devices such as Dynomill.

As the charge control agent, various charge control agents commonly used such as a quaternary ammonium salt compound, a nigrosine compound, a dye composed of a complex of aluminum, iron, chromium, or a triphenylmethane pigment can be used. However, a material that is hardly dissolved in water is preferably used from the viewpoints of controlling the ionic strength that affects the stability of aggregation and coalescence and reducing the pollution of wastewater. Further, it is preferable to add and mix a surfactant to the aqueous medium.

Examples of the above-mentioned surfactant include anionic surfactants such as sulfate ester type, sulfonate type, phosphoric acid ester type and soap type; cationic surface active agents such as amine salt type and quaternary ammonium salt type. Agents: Polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based nonionic surfactants, and the like are preferable. Among these, ionic surfactants are preferable, and anionic surfactants and cationic surfactants are more preferable. The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The surfactants may be used alone or in combination of two or more.

Specific examples of the anionic surfactants include fatty acid soaps such as potassium laurate, sodium oleate and sodium castor oil; sulfates such as octyl sulfate, lauryl sulfate, lauryl ether sulfate and nonylphenyl ether sulfate. Lauryl sulfonate, dodecyl sulfonate, dodecyl benzene sulfonate, triisopropyl naphthalene sulfonate, sodium alkyl naphthalene sulfonate such as dibutyl naphthalene sulfonate, naphthalene sulfonate formalin condensate, monooctyl sulfosuccinate, dioctyl sulfosuccinate, lauric amide sulfonate, olein Sulfonates such as acid amide sulfonates; lauryl phosphate, isopropyl phosphate Feto, phosphoric acid esters such as nonyl phenyl ether phosphate; sodium dialkyl sulfosuccinate sodium dioctyl sulfosuccinate; lauryl disodium sulfosuccinate, polyoxyethylene sulfo sulfosuccinate salts such as succinic acid lauryl disodium; and the like.

Specific examples of the cationic surfactant include laurylamine hydrochloride, stearylamine hydrochloride,
Amine salts such as oleylamine acetate, stearylamine acetate, stearylaminopropylamine acetate; lauryltrimethylammonium chloride, dilauryldimethylammonium chloride, distearylammonium chloride, distearyldimethylammonium chloride, lauryldihydroxyethylmethylammonium chloride, oleyl Quaternary ammonium salts such as bispolyoxyethylenemethylammonium chloride, lauroylaminopropyldimethylethylammonium ethosulfate, lauroylaminopropyldimethylhydroxyethylammonium perchlorate, alkylbenzenedimethylammonium chloride and alkyltrimethylammonium chloride; and the like.

Specific examples of the nonionic surfactant include alkyl ethers such as polyoxyethylene octyl ether, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; polyoxyethylene octylphenyl. Alkyl phenyl ethers such as ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene laurate, polyoxyethylene stearate,
Alkyl esters such as polyoxyethylene oleate;
Alkylamines such as polyoxyethylene lauryl amino ether, polyoxyethylene stearyl amino ether, polyoxyethylene oleyl amino ether, polyoxyethylene soybean amino ether, polyoxyethylene beef tallow amino ether; polyoxyethylene lauric acid amide, polyoxyethylene Alkyl amides such as stearic acid amide and polyoxyethylene oleic acid amide; vegetable oil ethers such as polyoxyethylene castor oil ether and polyoxyethylene rapeseed oil ether; lauric acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide Alkanolamides of polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethyl Nso sorbitan monostearate,
Sorbitan ester ethers such as polyoxyethylene sorbitan monooleate; and the like.

A dispersion in which agglomerated particles containing at least resin particles are dispersed is obtained by adding a metal salt polymer solution such as polyaluminum chloride to the resin particle dispersion or the colorant dispersion and the release agent dispersion. It is prepared by adding and mixing, and by heating in the range of room temperature to the glass transition temperature of the resin, the resin particles and the colorant are aggregated to form aggregated particles. The volume average particle diameter of the aggregated particles is 3 to 8 μ.
It is preferably in the range of m.

The resin particle dispersion, the colorant dispersion,
The content of the resin particles in the mixed liquid when the release agent dispersion is mixed is 40% by mass or less, and preferably 2 to 20% by mass. The content of the colorant may be 50% by mass or less,
It is preferably from 2 to 20% by mass. The content of the release agent may be 20% by mass or less, and 9 to 18% by mass.
Is preferred. Further, the content of the other components (internal additives) may be such that the object of the present invention is not impaired, and is generally extremely small, specifically 0.01 to 5 mass. %, 0.5-2% by mass
A degree is preferable.

Adhering step: In the adhering step, when the aggregated particle dispersion liquid is prepared, the releasing agent dispersion liquid is added and mixed to adhere the releasing agent fine particles to the aggregated particles to form particles, and then the resin-containing Is a step of adding and mixing a fine particle dispersion liquid (the resin fine particle dispersion liquid) in which the fine particles are dispersed to further adhere resin-containing fine particles to the particles to form adhered particles. It is preferable that the attaching step is performed plural times.

In the attaching step, the colorant fine particle dispersion liquid in which fine particles of the colorant are dispersed is added and mixed into the aggregated particle dispersion liquid in which the resin fine particles are aggregated to adhere the colorant fine particles to the aggregated particles. After forming the adhered particles, a step of adding and mixing a resin fine particle dispersion liquid in which resin fine particles are dispersed to further adhere the resin fine particles to the adhered particles to form the adhered particles; or a resin in the aggregated particle dispersion liquid. The resin-containing fine particles in which the fine particles are dispersed are added and mixed to adhere the resin fine particles to the agglomerated particles to form the adhered particles, and then the inorganic fine particle dispersion liquid in which the inorganic fine particles are dispersed is added and mixed to form the adhered particles. It is preferable that the step of further adhering inorganic fine particles to the step of forming adhering particles; In the attaching step, the resin fine particle dispersion is added and mixed into the aggregated particle dispersion prepared in the aggregating step, and the resin fine particles are attached to the aggregated particles to form adhered particles. Since the fine particles correspond to particles newly added to the aggregated particles, they may be referred to as “additional particles”.

The method of adding and mixing the resin fine particle dispersion is not particularly limited, and may be, for example, gradually and continuously, or may be divided into a plurality of times and stepwise. In this way, by adding and mixing the resin fine particles (additional particles), generation of minute particles can be suppressed, and the particle size distribution of the obtained electrostatic charge image developing toner can be made sharp. In addition, when the addition and mixing are carried out stepwise by dividing into a plurality of times, a layer of the resin fine particles is laminated stepwise on the surface of the agglomerated particles, and a structural change occurs from the inside to the outside of the particles of the electrostatic image developing toner. And a composition gradient can be provided, the surface hardness of the particles can be improved, the particle size distribution can be maintained and fluctuations can be suppressed during fusion in the fusion process, and stability during fusion can be improved. It is advantageous in that it is not necessary to add a surfactant or a stabilizer such as a base or an acid, and the addition amount thereof can be suppressed to the minimum limit, which enables cost reduction and quality improvement. .

When the adhesion step is carried out as described above, the agglomerated particles are used as mother particles, and a coating layer of the resin fine particles (additional particles) is formed on the surface of the mother particles. The layer of the resin fine particles (additional particles) may be one layer, or may be two or more layers, and the number of layers is generally the same as the number of times of the adhesion step.

Fusing step: In the fusing step, the mixed liquid containing the agglomerated particles (mixed liquid after the attaching step) is heat-treated at a temperature not lower than the glass transition point of the resin fine particles, generally 70 to 120 ° C. to fuse the agglomerated particles. Then, a toner particle-containing liquid (toner particle dispersion liquid) is obtained. The obtained toner particle-containing liquid is subjected to centrifugal separation or suction filtration to separate the toner particles, and washed with ion-exchanged water 1 to 3 times. Thereafter, the toner particles are separated by filtration, washed with ion-exchanged water 1 to 3 times and dried to obtain an electrostatic image developing toner.

The absolute value of the charge amount of the electrostatic image developing toner is preferably in the range of 20 to 50 μc / g, more preferably 25 to 40 μc / g. If the charge amount is less than 20 μc / g, background stains are likely to occur, and if it exceeds 50 μc / g, the image density is likely to decrease. The ratio of the charge amount in the summer and the charge amount in the winter of this toner for developing an electrostatic image is 0.7.
The range of -1.3 is more preferable. If the ratio is out of the preferred range, the toner environment dependency is strong and the charging stability is insufficient, which may be practically undesirable. The charging polarity is preferably negative.

The ratio (Mw) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography in the toner for developing an electrostatic image.
2-30 are preferable and, as for the molecular weight distribution represented by / Mn), 3-20 are more preferable. When the molecular weight distribution represented by the ratio (Mw / Mn) exceeds 30, the light transmittance and the coloring property are insufficient, and in particular, when the toner for developing an electrostatic image is developed or fixed on the film, The image projected by transmission tends to be an unclear and dark image or a projection image which is opaque and does not develop color. When it is less than 2, the viscosity of the toner at the time of high-temperature fixing is remarkably lowered, and offset easily occurs. On the other hand, the ratio (Mw / M
When the molecular weight distribution represented by n) is within the above numerical range, the light transmittance and the coloring property are sufficient, and the viscosity of the toner for developing an electrostatic charge image at the time of high-temperature fixing is prevented from decreasing, and the occurrence of offset occurs. Can be effectively suppressed.

In the toner for developing an electrostatic charge image finally obtained by heating as described above, inorganic particles or organic particles are added to the surface in a dry state by applying a shearing force to a fluidity aid. Or as a cleaning aid. Examples of the inorganic particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, tricalcium phosphate, and cerium oxide, all of which are usually used as external additives on the toner surface. Examples of the organic particles include all particles that are usually used as external additives on the toner surface, such as vinyl resins, polyester resins, and silicone resins. Examples of the cleaning aid include, for example, ethylene bisstearyl amide, fatty acid amides such as oleic amide, zinc stearate,
Examples thereof include fatty acid metal salts such as calcium stearate.

The developer used in the image forming apparatus of the present invention is not particularly limited as long as it contains the toner for developing an electrostatic image, and may have an appropriate component composition depending on the purpose. For example, the above-mentioned toner for developing an electrostatic charge image may be used alone as a one-component type electrostatic charge image developer, or may be used in combination with a carrier as a two-component type electrostatic charge image developer.

The carrier is not particularly limited,
It is possible to use a carrier known per se, for example, JP-A-62-39879 and JP-A-56-11.
Known carriers such as the resin-coated carrier described in Japanese Patent No. 461 can be used. The mixing ratio of the above-mentioned toner for developing an electrostatic image and the carrier in the electrostatic image developer is not particularly limited and can be appropriately selected depending on the purpose.

(Cleaning Blade) The cleaning blade used in the image forming apparatus of the present invention is a cleaning blade for pressing the photosensitive member to remove the residual toner, and has a 300% modulus of 14000 kPa.
~ 29400 kPa (150-300 kgf / c
m ² ), tear strength is preferably 50,000 N / m or more. In particular, it is preferable that the contact portion with the photoconductor has the above-mentioned physical properties, and specifically, it is preferable that the contacting part is made of an elastic body having the above-mentioned physical properties.

The specific method for measuring the 300% modulus is in accordance with the JIS K6301 (1988 version) vulcanized rubber physical property test method, and more detailed conditions are described in JIS K6301 (1988 version). The shaped rubber test piece was left in an environment of 23 ° C. for 1 hour or more, and pulled by a fixed jig at a constant speed,
It is preferable to apply a method of calculating a value obtained by dividing the load when the elongation amount becomes 300% of the original length by the cross-sectional area of the rubber test piece as a measured value.

If the 300% modulus is lower than 14000 kPa, stress concentration may occur at the edge tip of the cleaning blade that is slidingly deformed by the photosensitive member, resulting in edge chipping and the like, and durability may deteriorate. On the other hand, 300%
If the modulus is higher than 29400 kPa, the followability due to the deformation of the cleaning blade with respect to the surface shape of the photoconductor becomes poor, and cleaning failure due to poor contact is likely to occur. 300% modulus is 15680-2
2540 kPa (160 to 230 kgf / cm ² ) is more preferable, and 16660 to 19600 kPa.
(170 to 200 kgf / cm ² ) is more preferable.

The specific measuring method of the tear strength is based on the tear test method of JIS K6252 (2000 version) vulcanized rubber. More detailed conditions are JIS K6252 (2000 version) vulcanization. The maximum load until the test piece is torn by pulling the rubber test piece of the shape described in the rubber tear test method for 1 hour or more in an environment of 23 ° C and pulling it at a constant speed with a specified jig Is preferably measured and the tear strength Tr is calculated by the following calculation formula. (Calculation formula) Tr = F / t {Tr: Tear strength (N /
m), F: maximum load (N), t: thickness of test portion of test piece (m)}

If the tear strength is less than 50,000 N / m, chipping of edges is likely to occur and durability is deteriorated, which is not preferable. Also, tear strength is 50000N
When it is / m or more, it is possible to prevent the cleaning blade from being chipped even under high temperature and high humidity. The tear strength is more preferably 68600 N / m (70 kgf / cm) or more, and 73500 N / m (75
(kgf / cm) or more, more preferably 78
It is particularly preferably 400 N / m (80 kgf / cm) or more.

As for the hardness (JIS A scale) of the cleaning blade, it is preferable that the hardness of at least the contact portion with the photosensitive member is 75 or more,
It is more preferably 75 to 85, further preferably 77 to 80. If the hardness is less than 75, the cleaning blade becomes less elastic and the contact pressure becomes lower, and the contact area with the photoconductor increases, which causes an increase in frictional force and a decrease in slidability, resulting in durability. It is not preferable because the property tends to decrease. If the hardness exceeds 85, scratches are likely to occur on the surface of the photoreceptor, which is not preferable.

The tensile strength of the cleaning blade is 37240 kPa (380 kgf / cm ² ).
It is preferable that it is not less than 39200 kPa (400
More preferably, it is at least kgf / cm ² . When the tensile strength is less than 37240 kPa, the durability of the cleaning blade may be insufficient, which is not preferable. The specific measuring method of tensile strength is JI
SK6251 (2000 version) This is based on the tensile test method for vulcanized rubber. More detailed conditions are J
A rubber test piece having the shape described in ISK6251 (2000 version) tensile test method for vulcanized rubber is allowed to stand for 1 hour or more in an environment of 23 ° C., and pulled by a fixed jig at a constant speed to perform a test. Measure the maximum load until the piece breaks.

The cleaning blade is generally formed into a shape that can be used as a cleaning blade for a photosensitive member in an electrophotographic apparatus. For example, there is no particular limitation on the overall shape as long as it has a so-called blade shape such that the edge portion of the cleaning blade comes into contact with the surface of the photoconductor, and the thickness is generally 1.5 to
It is selected from the range of 2.5 mm, preferably 1.8-2.
It is selected from between 2 mm. The free length of the cleaning blade (the length between the position where the cleaning blade is fixed in the apparatus and the position of the edge portion that abuts on the photosensitive member) is generally selected from 5 to 15 mm, preferably 7 mm. It is selected from the range of up to 12 mm. The width may be appropriately set according to the axial length of the photoconductor (specifically, the axial length of the portion of the photoconductor where the latent image is formed).

The material of the cleaning blade is not particularly limited as long as it is an elastic body satisfying the above physical properties, and various elastic bodies can be used. As a specific elastic body, an elastic body such as polyurethane, silicone rubber, nitrile rubber, or chloroprene rubber can be used.

Examples of the polyurethane elastic body include polyurethane generally synthesized through an addition reaction of an isocyanate with a polyol and various hydrogen-containing compounds.
As the polyol (component), a polyether-based polyol such as polypropylene glycol or polytetramethylene glycol; a polyester-based polyol such as an adipate-based polyol, a polycaprolactam-based polyol or a polycarbonate-based polyol; or the like can be used.
As the isocyanate (component), an aromatic polyisocyanate such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate, toluidine diisocyanate; hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate Aliphatic polyisocyanates such as; and the like can be used.

A urethane prepolymer was prepared from any one of the above polyols and any one of the above isocyanates, a curing agent was added to the urethane prepolymer, the mixture was poured into a predetermined mold, crosslinked and cured, and then aged at room temperature. Can be manufactured. As the curing agent, dihydric alcohols such as 1,4-butanediol and trihydric or higher polyhydric alcohols such as trimethylolpropane and pentaerythritol are usually used in combination.

An example of the image forming apparatus of the present invention is shown in FIG.
In FIG. 1, 101 is a photoconductor drum containing fluorine-based resin particles in the above-mentioned surface layer, 102 is a transfer belt as an intermediate transfer member, and the transfer belt 102 is belt rollers 121, 123 and 124, and a backup. It is arranged so as to be stretched by a roller 122 and contact the surface of the photosensitive drum 101.

Around the photosensitive drum 101, developing devices 105, 106, 107 corresponding to the colors BK (black), Y (yellow), M (magenta), and C (cyan),
108 is provided, and the conductive roller 1 is provided at a position facing the photosensitive drum 101 with the transfer belt 102 interposed therebetween.
25 are provided. Further, the cleaning means 20 including the above-mentioned cleaning blade 10 is provided above the conductive roller 125.

Around the transfer belt 102, a bias roller 103 serving as a transfer electrode, an electrode roller 126, and a peeling claw 1 are provided.
13, belt cleaner 109, feed roller 143
Is provided. The bias roller 103 includes a cleaning blade 131, and the transfer belt 102
It is arranged at a position facing the backup roller 122 with the sheet sandwiched therebetween. The electrode roller 126 is provided around the backup roller 122 and inside the transfer belt 102.
Is provided.

A peeling claw 113 is arranged between the backup roller 122 and the belt roller 124. A belt cleaner 109 is arranged at a position facing the belt roller 124 with the transfer belt 102 interposed therebetween.

In the vicinity of the bias roller 103, there are arranged a feed roller 143, a tray 104 for supplying a sheet 141 ′ from a sheet bundle 141 made of a transfer target sheet, and a pickup roller 142.

The image forming method of the present invention will be described by taking the image forming apparatus shown in FIG. 1 as an example. Arrow A on the photoconductor drum 101
With rotation in the direction, the surface thereof is uniformly charged by a charging device (not shown). Image writing means (not shown) such as a laser writing device on the surface of the charged photosensitive drum 101
This forms an electrostatic latent image of the first color. This electrostatic latent image is developed by any one of the developing devices to form a toner image T. For example, if the electrostatic latent image written on the photoconductor drum 101 corresponds to black image information, this electrostatic latent image is developed by the developing device 105 containing black (BK) toner, A black toner image T is formed on the surface of the photosensitive drum 101.

In the case of forming a monochromatic image, the toner image T moves to the primary transfer portion where the conductive roller 125 is arranged by the rotation of the photosensitive drum 101, and the toner image T has the opposite polarity to the toner image T. By applying an electric field, the toner image T is electrostatically primarily transferred onto the surface of the transfer belt 102. Unfixed toner image T that has been primarily transferred
Is moved by the transfer belt 102 that orbits in the B direction,
The toner image T is secondarily transferred onto the sheet 141 ′ sent from the tray 104 by the pickup roller and the feed roller 143 between the backup roller 122 and the bias roller 103 that applies a transfer voltage having a polarity opposite to the charging polarity of the toner. It After that, the toner image T is secondarily transferred onto the paper 141 ′ and fixed by a fixing device (not shown) to form an image.

On the other hand, when forming a full-color image in which a plurality of colors are superimposed, the steps of forming the toner image T on the surface of the photosensitive drum 101 and the primary transfer of the toner image T are repeated by the number of colors. The final color toner image T
The peeling claw 113 and the belt cleaner 109 are separated from the transfer belt 102 until the primary transfer is performed on the transfer belt 102.

For example, in the case of forming a full-color image in which toner images T of four colors are superposed, the photosensitive drum 101
Toner images T of black, yellow, magenta, and cyan are formed on the surface every one rotation, and these toner images T are sequentially primary-transferred onto the transfer belt 102.

Further, the transfer belt 102 circulates in the B direction at the same cycle as the photoconductor drum 101 while holding the black toner image T that has been primarily transferred first, and the surface of the transfer belt 102 is rotated once. Each time, the yellow, magenta, and cyan toner images T are transferred so as to be superimposed on the black toner image T. In this way, toner images of four colors are sequentially formed and superposed on the transfer belt 102, and a full-color image is formed on the surface of the transfer belt 102 before the transfer onto the paper 141 ′. After that, the paper 141 '
Then, the full-color image is secondarily transferred and fixed by a fixing device (not shown) to form a full-color image.

By the way, the toner remaining on the photosensitive drum 101 after the transfer is removed by the cleaning blade 10 of the cleaning means 20 while revolving in the direction of arrow A.

FIG. 2 shows a state in which the cleaning blade is pressed against the surface of the photoconductor. In FIG. 2, 2 is a cleaning blade (similar to reference numeral 10 in FIG. 1),
Reference numeral 1 denotes a photoconductor that rotates in the direction of arrow A. The cleaning blade 2 is pressed against the surface of the photoconductor 1 by the holding member 3, for example. Here, the pressing linear pressure (contact pressure) of the cleaning blade to the photoconductor is 9.8 × 10 ^{−3 to} 4.9 × 10 ⁻² N / mm (1.0
˜5.0 gf / mm), and more preferably 3.9 × 10 ^{−2 to} 4.9 × 10 ⁻² N / mm (4.0 to 4.0 gf / mm).
It can also be used with a high pressing linear pressure of 5.0 gf / mm). The cleaning linear pressure is 9.
When it is smaller than 8 × 10 ⁻³ N / mm (1.0 gf / mm), cleaning unevenness may occur, and
When it is larger than 9 × 10 ^-2 N / mm (5.0 gf / mm), the surface of the photoconductor may be damaged or the abrasion amount may increase, which is not preferable.

Amount of biting of the cleaning blade (amount of deformation of the cleaning blade by being pressed against the surface of the photosensitive member, more specifically, d in FIG. 2, which should be bite when the cleaning blade is not deformed). As depth) 0.5-2.0m
The thickness is preferably m, and more preferably 0.8 to 1.6 mm. Further, the contact angle of the cleaning blade with the photoconductor (the angle formed by the tangent line of the photoconductor surface and the cleaning blade) is preferably 10 to 40 °, and more preferably 15 to 35 °. . If it is smaller than the above-mentioned angle range, the surface of the photosensitive member may be bumped, resulting in poor cleaning. If it is larger than the above range, the problem of blade flipping may occur.

In addition, the amount B (μm) of abrasion of the photoconductor during the 1 kPV cycle running and the photoconductor (in the case of FIG. 1,
The relationship between the peripheral speed A (mm / sec) of the photosensitive drum 101 is preferably in the range of 2.86 × 10 ⁻⁵ ≦ B / A ≦ 3.33 × 10 ⁻⁴ . If it is less than the above range, although the surface layer of the photoconductor is certainly high, filming of the toner component may occur in combination with a cleaning blade having high hardness and modulus.
On the other hand, if it exceeds the above range, the surface strength is low, and the electrical characteristics may be deteriorated due to abrasion.

The coefficient of static friction between the cleaning blade and the photoconductor may be, for example, a surface tester manufactured by HEIDON, whether the photoconductor is a sheet, a plate, an endless belt, or a drum. Can be measured at. The static friction coefficient is preferably in the range of 0.3 to 1.0. If the coefficient of static friction is less than the above range, the frictional resistance on the surface of the photoconductor is reduced and the adhesive force between the toner and the photoconductor is also reduced, so that the toner slip on the photoconductor is reduced. It becomes better and the cleaning property becomes better.
However, since the amount of the dispersant added to the coating film in order to reduce the friction coefficient is large, there is a case in which repetitive stability is concerned such as an increase in residual potential of the photoconductor. Further, if it exceeds the above range, slippage of the photoreceptor surface becomes worse,
The contact state of the cleaning blade is not stable, the contact pressure increases, and the toner slips worse. Further, since the adhesive force between the toner and the photoconductor is also increased, the toner slippage may be deteriorated and a problem may occur in the cleaning maintainability. In addition, the problem of cleaner wear may occur.

(Image Forming Method) The image forming method of the present invention comprises at least a latent image forming step of forming an electrostatic latent image on the surface of a photosensitive member, and developing the electrostatic latent image with a developer to form a toner image. A developing step for obtaining the toner image, a transferring step for transferring the toner image onto the surface of a transfer material to obtain a transferred image, a fixing step for fixing the transferred image to obtain a fixed image, and a toner image remaining after the transfer for the photoreceptor. A cleaning step of removing from the surface, wherein the surface layer of the photoconductor has a fluorine-based resin particle in an amount of 0.1 to 0.1% by mass of the surface layer.
The content of the developer is 40% by mass, and the developer has the following (1) to
It is characterized in that it contains an electrostatic charge image developing toner satisfying the relationship of (3). (1) Shape factor SF1 = 125 to 140, SF2 = 10
5-130. (However, SF1 = (π / 4) × (L ² /
A) × 100, SF2 = (1 / 4π) × (l ² / A) ×
100, L is the maximum length, l is the perimeter, and A is the projected area. (2) The exposure rate of the release agent on the surface of the toner for developing an electrostatic charge image, which contains the release agent and is quantified by X-ray photoelectron spectroscopy (XPS), is 11 to 40 atm%. (3) The melting point of the releasing agent measured by a differential scanning calorimeter is 70 to 130 ° C., and the releasing agent is contained in the toner for developing an electrostatic image in an amount of 8 to 20% by mass. The image forming method of the present invention is preferably carried out by using the above-described image forming apparatus of the present invention.

In the image forming method of the present invention, it is preferable that the image forming method further includes a recycling step. The recycling step is a step of transferring the electrostatic charge image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling step can be carried out using an image forming apparatus such as a toner recycling system type copier or facsimile machine. Further, the present invention can be applied to a recycling system in which the cleaning step is omitted and the toner is collected simultaneously with the development.

[0147]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

—Preparation of Resin Fine Particle Dispersion— Styrene (manufactured by Wako Pure Chemical Industries) ... 320 parts by mass, n-butyl acrylate (manufactured by Wako Pure Chemical Industries) ... 80 parts by mass, β-carboxyethyl acrylate (manufactured by Rhodia Nikka) ): 9 parts by mass, 1'10 decanediol diacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.): 1.5 parts by mass, dodecanethiol (manufactured by Wako Pure Chemical Industries): 2.7 parts by mass, mixing the above Dissolve this, dissolve in 550 g of ion-exchanged water containing 4 g of anionic surfactant Dowfax (manufactured by Rhodia), further disperse and emulsify in a flask, and slowly stir and mix for 10 minutes, while stirring and mixing ammonium persulfate 6 g. 50 g of ion-exchanged water in which was dissolved was added.
Next, the system was thoroughly replaced with nitrogen, and then the system was heated to 70 ° C. in an oil bath while stirring the flask, and emulsion polymerization was continued for 5 hours. Thus, an anionic resin particle dispersion liquid having a volume average particle diameter of 210 nm, a solid content of 43%, a glass transition point of 51.0 ° C. and Mw of 30,000 was prepared.

—Preparation of Colorant Particle Dispersion Liquid (1) — Phthalocyanine pigment (PVFASTBLUE manufactured by Dainichiseika Co., Ltd.) ... 90 g, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) ... 10 g, ion-exchanged water ... 240 g, the above components were mixed and dispersed for 10 minutes using a homogenizer (Ultra Turrax 750 manufactured by IKA), and then a circulating ultrasonic disperser (RUS-600T manufactured by Nippon Seiki Seisakusho).
CVP) to prepare a colorant particle dispersion (1).
The number average particle diameter of the colorant in the colorant dispersion liquid (1) is 15
At 0 nm, the number of particles having a particle size of 0.03 μm or less was 4.0% by number, and the number of particles having a particle size of 0.5 μm or more was 0.5% by number.

-Preparation of Colorant Particle Dispersion Liquid (2) -Carbon Black (R330, manufactured by CABOT) ... 90 g, anionic surfactant (Neogen SC, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) ... 10 g, Deionized water: 240 g, and the above components were mixed to prepare a colorant particle dispersion (2) under the same conditions as the colorant dispersion (1). Colorant dispersion (2)
The number average particle diameter of the colorant in Example was 155 nm, the number of particles having a particle diameter of 0.03 μm or less was 5.0% by number, and the number of particles having a particle diameter of 0.5 μm or more was 0.5% by number.

—Preparation of Colorant Particle Dispersion Liquid (3) — C.I. I Pigment Red 122 (manufactured by Dainichi Kasei Co., Ltd., ECR-185) ... 90 g, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) ... 10 g, ion-exchanged water ... 240 g The above was mixed to prepare a colorant particle dispersion (3) under the same conditions as the colorant dispersion (1). Colorant dispersion (3)
The number average particle size of the colorant in Example was 165 nm, the number of particles having a particle size of 0.03 μm or less was 6.0% by number, and the number of particles having a particle size of 0.5 μm or more was 0.5% by number.

—Preparation of Colorant Particle Dispersion Liquid (4) — C.I. I Pigment Red 185 (manufactured by Clariant) ... 90 g, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) ... 10 g, ion-exchanged water ... 240 g, mixing the above and coloring A colorant particle dispersion (4) was prepared under the same conditions as the agent dispersion (1). Colorant dispersion (4)
The number average particle diameter of the coloring agent in 170 was 170 nm, the number of particles having a particle diameter of 0.03 μm or less was 7% by number, and the number of particles having a particle diameter of 0.5 μm or more was 0.5% by number.

—Preparation of Colorant Particle Dispersion Liquid (5) — C.I. I Pigment Yellow 74 (manufactured by Clariant) ... 90 g, anionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: Neogen SC) ... 10 g, ion-exchanged water ... 240 g, the above are mixed to give a colorant. A colorant particle dispersion liquid (5) was prepared under the same conditions as the dispersion liquid (1). Colorant dispersion (5)
The number average particle diameter of the colorant in Example 1 was 175 nm, the number of particles having a particle diameter of 0.03 μm or less was 6% by number, and the number of particles having a particle diameter of 0.5 μm or more was 0.3% by number.

—Preparation of Release Agent Dispersion Liquid (1) — Polyethylene Wax as Release Agent (Toyo Petrolite PW725, melting point 103 ° C.) ... 90 g Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.) Manufactured: Neogen SC) ... 10 g Ion-exchanged water ... 240 g The above materials are mixed and dispersed for 10 minutes using a homogenizer (Ultra Turrax 750 manufactured by IKA Co., Ltd.), followed by dispersion treatment with a pressure discharge homogenizer. Number average particle size 200
A release agent dispersion liquid (1) having a thickness of nm was prepared.

—Preparation of Toner Particles 1— (Aggregating Step) Ion-exchanged water: 500 g, resin particle dispersion liquid: 250 g, colorant dispersion liquid (1) ... 36 g, release agent dispersion liquid (1 ) ... 56 g, inorganic fine particle dispersion liquid (Snowtex OL, manufactured by Nissan Chemical Co., Ltd.). ． ． 10 g, inorganic fine particle dispersion (Nissan Chemical Co., Snowtex OS). ． ． 10 g, a coagulant [polyaluminum chloride manufactured by Asada Chemical Co., Ltd.]. ． ． ． 0.5 g of the above mixed components in a round stainless steel flask, homogenizer (Ultra Turrax T50, manufactured by IKA)
And mixed and dispersed. The mixing was performed by dividing the resin particle dispersion liquid, the colorant dispersion liquid, and the release agent dispersion liquid into three parts, and stepwise. After that, the flask was gently heated to 40 ° C. with stirring in an oil bath for heating and held for 60 minutes.
Heated to ° C. After holding at 50 ° C. for 60 minutes, the particle size was measured with a Coulter counter (Multisizer 2 manufactured by Coulter), and it was confirmed that aggregated particles of 4.5 μm were generated. The temperature of the heating oil bath was further raised and maintained at 52 ° C. for 1 hour. When the particle size (volume average particle size, the same applies hereinafter) was measured, it was confirmed that aggregated particles of 5.0 μm were generated.

(Adhesion Step) 60 g of the resin particle dispersion liquid was gently added to the dispersion liquid containing the aggregated particles prepared above, and the temperature of the heating oil bath was further raised to 54 ° C.
Held for 1 hour. The particle size of the obtained adhered particles was measured and found to be 5.8 μm.

(Fusing Step) Next, a 1 mol / liter sodium hydroxide aqueous solution was added to adjust the pH to 6.0, the stainless steel flask was sealed, and a magnetic seal was used to continue stirring 85. The mixture was gently heated to ℃ and held for 60 minutes. After that, heat to 96 ° C., 1 mol
/ Liter of nitric acid aqueous solution until pH 5.0,
Hold for 5 hours. Then, after cooling, filtering, washing with ion-exchanged water 5 times, and drying with a vacuum dryer, toner particles were prepared.

-Preparation of Toner Particles 2- (Aggregating Step) The same as the aggregating step of Toner Particles 1 except that 36 g of the colorant dispersion liquid (2) was used as the mixed component instead of the colorant dispersion liquid (1). After mixing and dispersing the mixed components in a round stainless steel flask with a homogenizer (Ultra Turrax T50, manufactured by IKA), gently heat the flask to 40 ° C. for 60 minutes while stirring the flask with a heating oil bath. Held Then, it heated up to 50 degreeC. After holding at 50 ° C. for 60 minutes, the particle size was measured with a Coulter counter (Multisizer 2 manufactured by Coulter), and it was confirmed that aggregated particles of 4.8 μm were generated. Further raise the temperature of the heating oil bath to 52
Hold at 1 ° C for 1 hour. The particle size is 5.0μ
It was confirmed that aggregated particles of m were generated.

(Adhesion Step) 60 g of the resin particle dispersion liquid was slowly added to the dispersion liquid containing the aggregate particles, and the temperature of the heating oil bath was further raised and kept at 54 ° C. for 1 hour. The particle size of the obtained adhered particles was measured and found to be 5.2 μm.

(Fusing Step) A 1 mol / liter sodium hydroxide aqueous solution was added thereto until the pH reached 6.0, the stainless steel flask was closed, and a magnetic seal was used to continue stirring at 85 ° C. The mixture was gently heated to 60 ° C., then heated to 96 ° C., a 1 mol / liter nitric acid aqueous solution was added until pH 5.0, and the mixture was maintained for 5 hours. Then, cool and filter, and add 5 with deionized water.
After washing twice, toner particles 2 were prepared by drying using a vacuum dryer.

-Preparation of Toner Particles 3- (Aggregating Step) 18 g of the colorant dispersion liquid (3) and the colorant dispersion liquid (4) 1 were used instead of the colorant dispersion liquid (1) as a mixed component.
Homogenizer (Ultra Turrax T50, manufactured by IKA Co.) in a round stainless steel flask in the same manner as in the aggregation step of toner particles 1 except that the amount was 8 g.
After being mixed and dispersed in, the flask was gently heated to 40 ° C. with stirring in an oil bath for heating and held for 60 minutes. Then, it heated up to 50 degreeC. After holding at 50 ° C. for 60 minutes, the particle size was measured with a Coulter counter (Multisizer 2 manufactured by Coulter), and it was confirmed that aggregated particles of 4.7 μm were generated. The temperature of the heating oil bath was further raised and maintained at 52 ° C. for 1 hour. When the particle size was measured, it was confirmed that aggregated particles of 4.9 μm were generated.

(Adhering Step) 60 g of the resin particle dispersion liquid was gently added to the dispersion liquid containing the aggregate particles, and the temperature of the heating oil bath was further raised and kept at 54 ° C. for 1 hour. The particle size of the obtained adhered particles was measured and found to be 5.1 μm.

(Fusing step) After adding a 1 mol / liter sodium hydroxide aqueous solution until the pH reached 6.0, the stainless steel flask was closed and gently stirred to 85 ° C. while continuing stirring with a magnetic seal. Heat 60
After holding for 1 minute, the mixture was heated to 96 ° C., and a 1 mol / liter nitric acid aqueous solution was added until the pH reached 5.0, and then the mixture was held for 5 hours. Then, after cooling, filtering, washing with ion-exchanged water 5 times, and drying with a vacuum dryer, toner particles 3 were prepared.

-Preparation of Toner Particles 4- (Aggregating Step) The same as the aggregating step of the toner particles 1, except that 36 g of the colorant dispersion liquid (5) was used as the mixed component instead of the colorant dispersion liquid (1). After mixing and dispersing the mixed components in a round stainless steel flask with a homogenizer (Ultra Turrax T50, manufactured by IKA), the flask was gently heated to 40 ° C. for 60 minutes while stirring the flask in a heating oil bath. Held Then, it heated up to 50 degreeC. After holding at 50 ° C. for 60 minutes, the particle size was measured with a Coulter counter (Multisizer 2 manufactured by Coulter), and it was confirmed that aggregated particles of 4.9 μm were generated. Further raise the temperature of the heating oil bath to 52
Hold at 1 ° C for 1 hour. The particle size is 5.1μ
It was confirmed that aggregated particles of m were generated.

(Adhesion Step) 60 g of the resin particle dispersion liquid was slowly added to the dispersion liquid containing the aggregated particles, and the temperature of the heating oil bath was further raised and kept at 54 ° C. for 1 hour. The particle size of the obtained adhered particles was measured and found to be 5.3 μm.

(Fusing step) After adding a 1 mol / liter sodium hydroxide aqueous solution until the pH reached 6.0,
The stainless steel flask was sealed, gently heated to 85 ° C. with stirring using a magnetic seal and held for 60 minutes, and then 1 mol / liter nitric acid aqueous solution was added until the pH reached 5.0, and 96 ° C. And kept for 5 hours. Then, after cooling, filtering, washing with ion-exchanged water 5 times, and drying with a vacuum dryer, toner particles 5 were prepared.

-Preparation of Toner Particles 5- (Aggregating Step) Each mixing component is treated in the same manner as in the aggregating step of Toner Particles 1 except that the amount of the release agent dispersion liquid (1) added as a mixing component is 135 g. In a round stainless steel flask, homogenizer (Ultra Turrax T50, IK
After mixing and dispersing with a heating oil bath, the flask was gently heated to 40 ° C. with stirring in an oil bath for heating and held for 60 minutes. Then, it heated up to 50 degreeC. After holding at 50 ° C for 60 minutes, the particle size was measured with a Coulter counter (Multisizer 2 manufactured by Coulter) to be 4.8μ.
It was confirmed that aggregated particles of m were generated. The temperature of the heating oil bath was further raised and maintained at 52 ° C. for 1 hour. When the particle size was measured, it was confirmed that aggregated particles of 5.0 μm were generated.

(Adhering Step) 60 g of the resin particle dispersion liquid (1) was slowly added to the dispersion liquid containing the aggregated particles, and the temperature of the heating oil bath was further raised and kept at 54 ° C. for 1 hour. The particle size of the obtained adhered particles was measured and found to be 5.2 μm.

(Fusing Step) After adding a 1 mol / liter sodium hydroxide aqueous solution until the pH reached 6.0, the stainless steel flask was closed, and magnetic stirring was continued until the temperature reached 85 ° C. Heat gently and hold for 60 minutes, then heat to 96 ° C and pour the aqueous nitric acid solution.
After H was added to 4.8, it was held for 5 hours. Then, after cooling, filtering, and washing with ion-exchanged water 5 times,
The toner particles 5 are dried by using a vacuum dryer.
Was produced.

-Preparation of Toner Particles 6- (Aggregating Step) The same mixed components as the toner particles 1 are used, and the mixed components are mixed and dispersed in a round stainless steel flask with a homogenizer (Ultra Turrax T50, manufactured by IKA). After that, the flask was gently heated to 40 ° C. with stirring in an oil bath for heating and held for 60 minutes. Then, it heated up to 50 degreeC. After holding at 50 ° C. for 60 minutes, the particle size was measured with a Coulter counter (Multisizer 2 manufactured by Coulter), and it was confirmed that aggregated particles of 4.9 μm were generated. The temperature of the heating oil bath was further raised and maintained at 52 ° C. for 1 hour. When the particle size was measured, it was confirmed that aggregated particles of 5.1 μm were generated.

(Adhering Step) 60 g of the resin particle dispersion liquid was slowly added to the dispersion liquid containing the aggregated particles, and the temperature of the heating oil bath was further raised and kept at 54 ° C. for 1 hour. The particle size of the obtained adhered particles was measured and found to be 5.3 μm.

(Fusing step) After adding a 1 mol / liter sodium hydroxide aqueous solution so as to have a pH of 6.0, the stainless steel flask was sealed and gently stirred to 85 ° C. while continuing stirring with a magnetic seal. Heat to 60
After holding for 1 minute, the mixture was heated to 96 ° C., a 1 mol / liter nitric acid aqueous solution was added until the pH became 5.5, and the mixture was kept for 10 hours. Then, after cooling, filtering, washing with ion-exchanged water 5 times, and drying with a vacuum dryer, toner particles 6 were prepared.

Preparation of Toner Particle A (Shape SF1 = 14)
0 or more, SF2 = 130 or more)-(Aggregating step) As a mixed component similar to the toner particles 1, the mixed component was mixed and dispersed in a round stainless steel flask with a homogenizer (Ultra Turrax T50, manufactured by IKA). Then, the flask was heated to 52 ° C. with stirring in a heating oil bath. After holding at 52 ° C for 60 minutes,
When the particle size was measured with a Coulter counter (Multisizer 2 manufactured by Coulter, Inc.), it was confirmed that aggregated particles of 4.7 μm were generated. The temperature of the heating oil bath was further raised and the temperature was kept at 54 ° C. for 1 hour. When the particle size was measured, it was confirmed that aggregated particles of 4.9 μm were generated.

(Adhering Step) 60 g of the resin particle dispersion liquid was slowly added to the dispersion liquid containing the aggregate particles, and the temperature of the heating oil bath was further raised and kept at 55 ° C. for 1 hour. The particle size of the obtained adhered particles was measured and found to be 5.1 μm.

(Fusing step) After adding a 1 mol / liter sodium hydroxide aqueous solution so as to have a pH of 7.0,
Close the flask made of stainless steel and heat it up to 96 ° C while continuing stirring with a magnetic seal, without adjusting the pH.
Held for hours. After that, cool and filter, and add 5 with deionized water.
After washing twice, toner particles A were prepared by drying using a vacuum dryer.

-Preparation of toner particles B (shape SF1 = 12
(Less than 5, SF2 = less than 105)-(Aggregating step) As a mixed component similar to the toner particles 1, the mixed component was mixed and dispersed in a round stainless steel flask with a homogenizer (Ultra Turrax T50, manufactured by IKA). Then, the flask was heated to 52 ° C. with stirring in a heating oil bath. After holding at 52 ° C for 60 minutes,
When the particle size was measured with a Coulter counter (Multisizer 2 manufactured by Coulter, Inc.), it was confirmed that aggregated particles of 4.7 μm were generated. The temperature of the heating oil bath was further raised and the temperature was kept at 54 ° C. for 1 hour. When the particle size was measured, it was confirmed that aggregated particles of 4.9 μm were generated.

(Adhering Step) 60 g of the resin particle dispersion liquid was slowly added to the dispersion liquid containing the aggregated particles, and the temperature of the heating oil bath was further raised and kept at 55 ° C. for 1 hour. The particle size of the obtained adhered particles was measured and found to be 5.1 μm.

(Fusing step) After adding a 1 mol / liter sodium hydroxide aqueous solution until the pH reached 5.0, the stainless steel flask was closed, and heated to 96 ° C. while continuing stirring with a magnetic seal, and heated to 1 mol / liter. L nitric acid was added until the pH reached 4.0 and kept for 5 hours.
Then, after cooling, filtering, washing with ion-exchanged water 5 times, and drying with a vacuum dryer, toner particles B were prepared.

-Preparation of Toner Particles C (Example of Large Amount of Surface Wax (Amount of Release Agent))-(Aggregating Step) Toner particles except that the addition amount of the release agent dispersion liquid (1) as a mixed component was 146 g. In the same manner as in the agglomeration step of No. 1, homogenizer (Ultra Turrax T50, IK
After mixing and dispersing (by A company), the flask was heated to 52 ° C. while stirring in a heating oil bath. After holding at 52 ° C for 60 minutes, the particle size was measured with a Coulter counter (Multisizer 2 manufactured by Coulter Co., Ltd.) to be 4.6μ.
It was confirmed that aggregated particles of m were generated. The temperature of the heating oil bath was further raised and the temperature was kept at 54 ° C. for 1 hour. When the particle size was measured, it was confirmed that aggregated particles of 4.8 μm were generated.

(Adhering Step) 60 g of the resin particle dispersion liquid was gently added to the dispersion liquid containing the aggregate particles, and the temperature of the heating oil bath was further raised and kept at 55 ° C. for 1 hour. The particle size of the obtained adhered particles was measured and found to be 5.0 μm.

(Fusing Step) After adding a 1 mol / liter sodium hydroxide aqueous solution here, the stainless steel flask was closed and heated to 97 ° C. while continuing stirring using a magnetic seal, and kept for 15 hours. Thereafter, the toner particles C were cooled, filtered, washed with ion-exchanged water 5 times, and then dried using a vacuum dryer to prepare toner particles C.

-Evaluation of Characteristics of Toner for Developing Electrostatic Image-For toner particles 1 to 6 and A to C after drying, GS
D value (GSDv, GSDp, GSDp-under),
The shape factor (SF1, SF2), release agent exposure rate, and release agent size were evaluated. The results are shown in Table 1 below. In addition, the said evaluation was performed as follows.

GSDv (volume particle size distribution index: square root of D84 / D16 in volume particle size distribution), GSDp (number particle size distribution index: square root of D84 / D16 in number particle size distribution), GSDp-under (particle size distribution index below number: number) D50 / D16) in the particle size distribution was evaluated using Multisizer II manufactured by Coulter, Inc., respectively. Shape factor SF1 (measured value by image analysis method (maximum length squared / projected area) × (π / 4) × 100) and shape coefficient SF2 (measured value by image analysis method (perimeter squared / projected area)) × (1 / 4π) × 100) is the Luzex II manufactured by Nireco Co., Ltd.
It was evaluated using I. The surface wax exposure rate (release agent exposure rate) was measured quantitatively by C1S peak separation by X-ray photoelectron spectroscopy (XPS: JPS-9000MX manufactured by JEOL Ltd.). The size of the release agent according to the cross section of the toner is determined by a transmission electron microscope (TEM: J manufactured by JEOL Ltd.).
It was measured by EM1010 by observing a cross section of 50 or more toner particles under a condition of 5000 times.

[0184]

[Table 1]

-Production of electrostatic image developer- To 50 g of the produced electrostatic image developing toner (toner particles), 0.65 g of hydrophobic silica (TS720: manufactured by Cabot) was added and blended in a sample mill. , 45
μm sieve was performed. Further, this blended product had a toner concentration of 5 with respect to a ferrite carrier having a volume average particle diameter of 50 μm coated with 1% of methacrylate (manufactured by Soken Kagaku).
%, And the mixture was stirred and mixed with a V-type blender for 20 minutes and sieved at 177 μm to prepare an electrostatic image developer.

-Production of Cleaning Blade 1- Using polytetramethylene glycol as the polyol and tolylene diisocyanate as the isocyanate, urethane prepolymers were prepared from them,
Further, a curing agent (1,4 butanediol and trimethylolpropane) was added, and the mixture was poured into a mold, crosslinked and cured, and then aged at room temperature to give a 400 mm thickness of 400 mm.
A mm × 25 mm cleaning blade was prepared. The prepared cleaning blade has a 300% modulus of 1
9200 kPa, tear strength, tensile strength,
JIS-A hardness is 85300 N / m and 40, respectively.
It was 200 Pa and 78.

—Preparation of Cleaning Blade 2— Polytetramethylene glycol was used as a polyol, and polymethylene polyphenyl polyisocyanate was used as an isocyanate to prepare urethane prepolymers from these, and a curing agent (1,4 butane). Diol), poured into the mold, cross-linked and cured, and then aged at room temperature to obtain a thickness of 2.05 mm and 400 m.
A m × 25 mm cleaning blade was prepared. The prepared cleaning blade has a 300% modulus of 14
820 kPa, tear strength, tensile strength, J
IS-A hardness is 78400 N / m and 387, respectively.
It was 20 Pa and 75.

—Preparation of Organic Photoreceptor— (Preparation of Photoreceptor 1) 4 parts by mass of polyvinyl butyral resin (S-REC BM-S, manufactured by Sekisui Chemical Co., Ltd.) was dissolved.
-To 170 parts by mass of butyl alcohol, 3 parts of an organic zirconium compound (acetylacetone zirconium butyrate)
0 parts by mass and 3 parts by mass of an organic silane compound (γ-aminopropyltrimethoxysilane) were added, mixed and stirred to prepare a coating liquid for forming an undercoat layer. This coating solution was dip-coated on an aluminum support having a diameter of 84 mm which was roughened by honing treatment, air-dried at room temperature for 5 minutes, and then the support was heated to 50 ° C. for 10 minutes, ℃, 8
Put in a thermo-hygrostat at 5% RH (dew point 47 ° C) for 20
Moisture hardening promotion treatment was performed for a minute.

Then, the mixture was placed in a hot air drier at 170 ° C. for 1 hour.
It was dried for 0 minutes. As a charge generating material, gallium phthalocyanine chloride was used, and a mixture of 15 parts by mass thereof, 10 parts by mass of vinyl chloride-vinyl acetate copolymer resin (VMCH, manufactured by Nippon Union Carbide Co.) and 300 parts by mass of n-butyl alcohol was used. It was dispersed in a sand mill for 4 hours. The obtained dispersion liquid was applied onto the undercoat layer by dip coating and dried to form a charge generation layer having a film thickness of 0.2 μm.

Next, as a cleaning step for the fluorine-based resin particles, 4
Tetrahydrofuran 6 in 20 parts by mass of fluorinated ethylene resin particles (trade name: Lubron L2, manufactured by Daikin Industries, Ltd.)
00 parts by mass was added and mixed, and the mixture was stirred for 24 hours using a mechanical stirrer. After stirring, suction filtration was performed, and the cake of tetrafluoroethylene resin particles obtained was dried under reduced pressure.

Next, 40 parts of N, N'-bis (3-methylphenyl) -N, N'-diphenylbenzidine and bisphenol Z polycarbonate resin (molecular weight 40,00) were used.
0) 60 parts by mass was sufficiently dissolved and mixed in 280 parts by mass of tetrohydrofuran and 120 parts by mass of toluene, and then 10 parts by mass of tetrafluoroethylene resin particles and hydrophobic silica ( Product name: R97
4, 5 parts by mass of Nippon Aerosil Co., Ltd. was added and further mixed, and then dispersed by a sand grinder using glass beads to prepare a tetrafluoroethylene resin particle dispersion liquid. The prepared tetrafluoroethylene resin particle dispersion liquid was applied onto the charge generation layer by dip coating, and dried to form a charge transport layer having a film thickness of 26 μm, and a photoconductor 1 was produced.

(Photoreceptors 2 and 3) By changing the addition amount of tetrafluoroethylene resin particles and the molecular weight of the binder resin in the charge transport layer as shown in Table 2 below, the hardness, surface roughness and static friction coefficient can be changed. Photosensitive members 2 and 3 were manufactured by changing the surface condition. Table 2 shows the surface conditions of the photoconductors 1 to 3.

[0193]

[Table 2]

(Examples 1 to 5 and Comparative Examples 1 to 3) -Running test and image quality evaluation-Using Docucolor 1250 manufactured by Fuji Xerox,
As shown in Table 3 below, the cleaning blades 1 and 2, the photoconductors 1 to 5, the toner particles 1 to 6 and A to D are combined to obtain high temperature and high humidity (28 ° C., 85% RH) and low temperature and low humidity ( In a full color mode at 10 ° C. and 15% RH), a running test of 100,000 sheets at an image density of 5% was carried out to evaluate the image quality at high temperature and high humidity and low temperature and low humidity. Moreover, the presence or absence of defects such as abnormal noise and contamination inside the machine after the running test was also confirmed. From the results of Table 3, Examples 1-5
Then, no particular problems occurred.

[0195]

[Table 3]

[0196]

According to the present invention, various conventional problems can be solved. That is, it is possible to provide an image forming apparatus and an image forming method, which are particularly excellent in cleaning property without deteriorating various characteristics such as charging property, developing property and fixing property, and which maintain high image quality and high reliability for a long period of time.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram showing a specific example of an image forming apparatus of the present invention.

FIG. 2 shows a state in which the cleaning blade is pressed against the surface of the photoconductor.

[Explanation of symbols]

10 ... Cleaning blade 20 ... Cleaning means 101 ... Photosensitive drum 102 ... Transfer belt 103 ... Bias roller 104 ... Tray 105, 106, 107, 108 ... Developing device 109 ... Belt cleaner 113 ... Peeling claw 122 ... Backup roller 121, 123, 124 ... Belt rollers, 125 ... Conductive roller 141 '... Paper 143 ... Feed roller T: Toner image

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasuo Kakukura             Fuji Zero, 1600 Takematsu, Minamiashigara City, Kanagawa Prefecture             X Co., Ltd. (72) Inventor Masaaki Suwabe             Fuji Zero, 1600 Takematsu, Minamiashigara City, Kanagawa Prefecture             X Co., Ltd. (72) Inventor, Kamata             Fuji Zero, 1600 Takematsu, Minamiashigara City, Kanagawa Prefecture             X Co., Ltd. F-term (reference) 2H005 AA06 AA15 CA14 DA07 EA03                       EA07 EA10                 2H068 AA06 BB31 FC15                 2H134 GA01 GB02 HD04 HD06 HD11                       HD19 KG07 KG08 KH01 KH15

Claims (7)

[Claims] 1. An image forming apparatus comprising at least a latent image forming means for forming an electrostatic latent image on the surface of a photoreceptor and a developing means for developing the electrostatic latent image with a developer to obtain a toner image. The surface layer of the photoconductor contains 0.1 to 40% by mass of fluorine-based resin particles based on the mass of the surface layer, and the developer has the following relationships (1) to (3). An image forming apparatus comprising a toner for developing an electrostatic image to be filled. (1) The shape factors SF1 and SF2 are respectively 125
~ 140 and 105-130. (However, SF1
= (Π / 4) × (L ² / A) × 100, SF2 = (1 /
4π) × (l ² / A) × 100, L is the maximum length, l
Is the perimeter, and A is the projected area. (2) A release agent of 8 to 20 is added to the electrostatic image developing toner.
The release rate of the release agent on the surface of the toner for developing an electrostatic charge image is 11 to 40 atm%, which is included by mass% and quantified by X-ray photoelectron spectroscopy (XPS). (3) The melting point of the release agent measured by a differential scanning calorimeter is 70 to 130 ° C. 2. A cleaning unit is provided for cleaning the electrostatic charge image developing toner remaining on the surface of the photoconductor after transfer with a cleaning blade, and the cleaning blade has a 300% modulus of 1400 to 29400 kpa and a tearing property. Strength is 500
The image forming apparatus according to claim 1, wherein the image forming apparatus has a speed of 00 N / m or more. 3. The contact pressure of the cleaning blade with the surface layer of the photoreceptor is 9.8 × 10 ^{−3 to} 4.9 × 10 ⁻² N.
/ Mm, contact angle 10-40 °, blade deformation amount 0.5
Abutting in the range of up to 2.0 mm, the peripheral speed A (mm
/ Sec) and the film thickness wear amount B (μm) of the photoconductor during running per 1 kPV cycle are 2.86 ×.
The image forming apparatus according to claim 2, wherein 10 ⁻⁵ ≦ B / A ≦ 3.33 × 10 ⁻⁴ . 4. The image forming apparatus according to claim 1, wherein the toner for developing an electrostatic image comprises particles formed by aggregating resin fine particles in a solvent. 5. A latent image forming step of forming an electrostatic latent image on a surface of a photoconductor, a developing step of developing the electrostatic latent image with a developer to obtain a toner image, and the toner image being transferred. An image having a transfer step of transferring to a material surface to obtain a transferred image, a fixing step of fixing the transferred image to obtain a fixed image, and a cleaning step of removing the toner image remaining after the transfer from the photoreceptor surface. In the forming method, the surface layer of the photoconductor contains 0.1 to 40% by mass of fluorine-based resin particles based on the mass of the surface layer, and the developer is one of the following (1) to (3). An image forming method comprising: a toner for developing an electrostatic charge image satisfying the relationship. (1) Shape factor SF1 = 125 to 140, SF2 = 10
5-130. (However, SF1 = (π / 4) × (L ² / A) × 100,
SF2 = (1 / 4π) × (l ² / A) × 100,
L is the maximum length, l is the perimeter, and A is the projected area. (2) The exposure rate of the release agent on the surface of the toner for developing an electrostatic charge image, which contains the release agent and is quantified by X-ray photoelectron spectroscopy (XPS), is 11 to 40 atm%. (3) The melting point of the releasing agent measured by a differential scanning calorimeter is 70 to 130 ° C., and the releasing agent is contained in the toner for developing an electrostatic image in an amount of 8 to 20% by mass. 6. The cleaning process is performed by a cleaning blade in the cleaning step, and the 300% modulus of the cleaning blade is 14000-2.
The image forming method according to claim 5, wherein the tear strength is 9400 kpa and the tear strength is 50,000 N / m or more. 7. The contact pressure of the cleaning blade with the surface layer of the photoreceptor is 9.8 × 10 ^{−3 to} 4.9 × 10 ⁻² N.
/ Mm, contact angle 10-40 °, blade deformation amount 0.5
Abutting in the range of up to 2.0 mm, the peripheral speed A (mm
/ Sec) and the film thickness wear amount B (μm) of the photoconductor during running per 1 kPV cycle are 2.86 ×.
The image forming method according to claim 6, wherein 10 ⁻⁵ ≦ B / A ≦ 3.33 × 10 ⁻⁴ .