JP2002311782A - Image forming method and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method and an image forming device, by which excellent cleaning performance is held over a long term, an image defect is prevented from occurring and an excellent electrophotographic image is formed even in the case of using an organic photoreceptor. SOLUTION: In this image forming method, the surface of a cleaning blade on an opposite side to the surface abutting on the organic photoreceptor comes into contact with an elastic member, and the free length (a) of the cleaning blade and the free length (b) of the elastic member satisfy relation shown by expression 1, then toner used for developer is constituted by adding particulates obtained by sticking inorganic particulates to the surfaces of resin particles to coloring particles. The expression 1 is 0.1<b/a<=0.9.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method and an image forming apparatus used in an electrophotographic copying machine, a printer and the like.

[0002]

2. Description of the Related Art In recent years, an organic photoconductor containing an organic photoconductive substance (hereinafter simply referred to as a photoconductor) is most widely used as an image carrier used in an electrophotographic image forming apparatus. Organic photoreceptors are advantageous over other photoreceptors in that materials that can be used for various exposure light sources from visible light to infrared light can be easily developed, materials that do not pollute the environment can be selected, and manufacturing costs are low. It is.

However, the image forming method using an organic photoreceptor has various problems associated with the organic photoreceptor.

For example, during repeated formation of a large number of images, defective cleaning becomes apparent, and filming (film formation by paper dust or toner) occurs due to deposition of paper dust or toner on an organic photoreceptor. Further, the transfer performance is reduced, and image unevenness or the like is generated.

Further, when a cleaning blade is used as a cleaning device, the contact friction between the organic photoreceptor and the cleaning blade often becomes unstable, and blade deterioration such as turning over of the blade and squealing of the blade is likely to occur.

On the other hand, in the electrophotographic image forming method, digital image formation has become mainstream due to the recent development of digital technology. A digital image forming method is based on visualizing small dot images of one pixel such as 400 dpi (1 inch = the number of dots per 2.54 cm), and a high resolution that faithfully reproduces these small dot images. Image quality technology is required.

One of such high image quality technologies is a technology relating to a toner manufacturing technology. That is, an electrophotographic developer using a polymerized toner or an image forming method has been proposed as a means for achieving a uniform particle size distribution and shape of toner particles. Since the polymerized toner produces a toner by uniformly dispersing the raw material monomers in an aqueous system and then polymerizing the toner, a toner having a uniform toner particle size distribution and shape can be obtained. Easy to reproduce.

However, when the above-mentioned polymerized toner is employed in an image forming apparatus using an organic photoreceptor, a new technical problem has arisen. That is, as described above, the polymerized toner is formed in a substantially spherical shape because the toner shape is formed during the polymerization process of the monomer. As is well known, spherical residual toner tends to cause poor cleaning and subsequent filming.
It lowers transfer performance and causes image unevenness and the like.

It is known to add a fluidizing agent such as hydrophobic silica to the toner in order to prevent the above-mentioned filming of the organic photoreceptor. However, since these fluidizing agents have a small primary particle size, they are easily buried in the toner surface, and their effects do not last long.

On the other hand, if an external additive having a large abrasive particle size is added to prevent filming, the surface of the organic photoreceptor becomes large due to friction with a cleaning blade and the like, and scratches are easily formed. However, there has been a problem that the durability of the photosensitive member is reduced. Therefore, there has been a need for a technical development of a stable cleaning method and a method of using an external additive in which these problems are solved and the surface wear of the organic photoreceptor is small and scratches and the like are hardly caused.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems, to maintain good cleaning performance over a long period of time even when an organic photoreceptor is used, and to eliminate image defects.
An object of the present invention is to provide an image forming method and an image forming apparatus capable of forming a good electrophotographic image.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted various studies to solve the above-mentioned problems, and as a result, have found that a toner using an external additive of fine particles having inorganic fine particles fixed on the surface of resin particles and an external additive are used. By using a cleaning method that effectively controls the polishing property of the agent, it has been found that the filming can be effectively removed without substantially damaging the surface of the organic photoreceptor.

That is, the object of the present invention is attained by adopting one of the following constitutions. 1. The electrostatic latent image formed on the organic photoconductor is developed with a developer containing a toner, and the toner image visualized by the development is transferred from the organic photoconductor to a transfer material. In the image forming method having a cleaning blade for removing the toner remaining on the organic blade, the cleaning blade is in contact with the elastic member on the surface opposite to the surface in contact with the organic photoreceptor, and the free length a of the cleaning blade and the elastic member The image forming method according to claim 1, wherein the free length b satisfies the relationship of Formula 1, and the toner used in the developer is a toner obtained by adding fine particles obtained by fixing inorganic fine particles on the surface of resin particles to colored particles. .

Equation 1 0.1 <b / a ≦ 0.9 2. The electrostatic latent image formed on the organic photoconductor is developed with a developer containing a toner, and the toner image visualized by the development is transferred from the organic photoconductor to a transfer material. An image forming method having a cleaning blade for removing the toner remaining on the elastic member, the cleaning blade being in contact with the elastic member on the surface opposite to the surface in contact with the organic photoreceptor, and having a thickness t ₁ of the cleaning blade and an elastic member. Wherein the thickness t ₂ of the image satisfies the relationship of Expression 2, and the toner used for the developer is a toner obtained by adding fine particles obtained by fixing inorganic fine particles on the surface of resin particles to colored particles. Forming method.

Equation 2 1/30 <t ₂ / t ₁ <2 3. 3. The image forming method according to the above 1 or 2, wherein the number average particle diameter of the fine particles having inorganic fine particles fixed on the surface of the resin particles is 100 nm to 2000 nm.

4. When the amount of the fine particles added is 0.
The image forming method according to any one of the above items 1 to 3, wherein the content is 1 to 3.0% by mass.

5. The toner according to any one of the above items 1 to 4, wherein the toner further comprises a fluidizing agent having a number average primary particle diameter of 5 to 49 nm in an amount of 0.1 to 3.0% by mass. Image forming method.

6. An image forming apparatus using the image forming method according to any one of the above items 1 to 5.

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

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

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

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

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

In the image forming section C, a drum-shaped photosensitive member (hereinafter, also referred to as a photosensitive drum) 121 serving as an image bearing member, a charger 122 serving as a charging unit, and a developing unit Developing device 123, a transfer device 124 as a transfer unit, a separator 125 as a separation unit,
A cleaning device 126 and a PCL (precharge lamp) 127 are arranged in the order of operation. Photoconductor 12
Numeral 1 is a photoconductive compound formed on a drum substrate by coating. For example, an organic photoreceptor (OPC) is preferably used, and is driven and rotated clockwise in the drawing.

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

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

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

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

In the cleaning device, a cleaning blade 126A and an elastic member 126B are mounted on a support member (generally a metal plate) 191. A rubber elastic body is used as a material for the cleaning blade and the elastic member, and urethane rubber, silicon rubber, fluorine rubber, chloroprene rubber, butadiene rubber, and the like are known as the material. It is particularly preferable in that it has excellent wear characteristics as compared with rubber. For example, urethane rubber obtained by reacting and curing a polycaprolactone ester and a polyisocyanate described in JP-A-59-30574 is preferable.

In the present invention, when the elastic member 126B and the cleaning blade 126A are fixed to the support member 191, the elastic member is arranged and supported such that the cleaning blade is brought into close contact with the photosensitive member on the surface opposite to the contact surface. Attach it to the member and hold it. At this time, a portion where the cleaning blade and the elastic member are in contact has a mechanism capable of reliably transmitting and absorbing the vibration generated by the blade to the elastic member. By employing such a holding method, the vibration of the cleaning blade can be effectively absorbed by the elastic member, and the vibration of the blade can be stabilized.

The conditions for properly pressing the cleaning blade against the surface of the photoreceptor are determined by a delicate balance of various characteristics, and are considerably narrow. It depends on the characteristics such as the thickness of the cleaning blade and the setting requires accuracy. However, the thickness of the cleaning blade cannot be always set under appropriate conditions because the thickness of the cleaning blade may vary at the time of manufacture. It may deviate from the proper area. In particular, when combined with an organic photosensitive layer using a high molecular weight binder resin, if it is out of an appropriate region, it causes blade turning or toner slip through.

Therefore, the present invention is required to be effective in canceling the variation in the characteristics of the cleaning blade and the like. Even if the thickness of the cleaning blade varies, the vibration of the blade can be effectively reduced by the elastic member. By the absorption, the setting condition of the cleaning blade on the photoreceptor surface can be stably maintained in an appropriate region.

In the present invention, it is preferable that the tip of the cleaning blade which is in pressure contact with the surface of the photoreceptor is pressed in a state in which a load is applied in a direction opposite to the rotation direction of the photoreceptor (counter direction). As shown in FIG. 2, it is preferable that the distal end portion of the cleaning blade forms a pressing surface when pressed against the photosensitive member.

The positional relationship between the cleaning blade and the elastic member according to the present invention is such that a step is provided between both ends as shown in FIG. Further, the free length of the elastic member is shorter than the free length of the cleaning blade. With this configuration, the elasticity of the cleaning blade absorbs the vibration of the cleaning blade without hindering the deformation at the tip of the cleaning blade (deformation caused by pressing against the photoreceptor). Can be stabilized.

The ratio of the free length of the cleaning blade to the elastic member is such that the free length of the cleaning blade is a and the free length of the elastic member is b, as shown in FIG. Designed for The free length is the length of a portion where each of the cleaning blade and the elastic member is not held by the support member 191.
As shown in FIG. 2, the distance from the end B of the support member 191 to the tip of each of the cleaning blade and the elastic member before deformation is shown.

Equation 1 0.1 <b / a ≦ 0.9 b / a falls within the above range, that is, when b / a exceeds 0.1 and 0.
By designing it to be 9 or less, the deformation of the tip of the cleaning blade (deformation caused by pressing against the photoreceptor) is not hindered, and the vibration of the cleaning blade is absorbed by the elastic member. It has been found that stable cleaning properties without toner slip-through can be realized. Furthermore, in the present invention, 0.3 to
0.8 is more preferable, and particularly preferably 0.5 to
0.6. On the other hand, if the value of b / a is 0.1 or less, toner slip through tends to occur, and b / a
If / a is greater than 0.9, blade turning is likely to occur.

The ratio of the thickness of the cleaning device the cleaning blade and the elastic member of the present invention t ₁ the thickness of the cleaning blade as shown in Figure 2, when the thickness of the elastic member and t _2, the formula 2 Designed to be satisfactory.

Equation 2 1/30 <t ₂ / t ₁ <2 t ₂ / t ₁ is set in the above range, that is, the value of t ₂ / t ₁ is more than 1/30 and less than 2. By doing so, it has been found that the cleaning blade and the elastic member are stably held by the support member 191, and that the vibration of the cleaning blade is absorbed by the elastic member, thereby achieving stable cleaning performance without causing blade turning or toner slip-through. . Furthermore, the value of t ₂ / t ₁ is 1 / 8-5 / 4,
Particularly preferably, it is 1/4 to 3/4. On the other hand, t ₂ / t ₁
Is less than 1/30, toner slip-through tends to occur, and when t ₂ / t ₁ is 2 or more, blade turning is likely to occur.

In the present invention, preferable values of the contact load P and the contact angle θ of the cleaning blade to the photoreceptor are P = 5 to 40 N / m and θ = 5 to 35 °.

The contact load P is a vector value in the normal direction of the pressing force P 'when the blade 126A is brought into contact with the photosensitive drum 121.

The contact angle θ is the angle between the tangent line X at the contact point A of the photosensitive member and the blade before deformation (indicated by a dotted line in the drawing). 172 is a fixing screw for fixing the support member 191, and 193 is a load spring.

The free length a of the cleaning blade
Represents the length of the tip point of the blade before deformation from the position of the end B of the support member 191 as shown in FIG. A preferred value of the free length is a = 6 to 15 mm. The thickness of the cleaning blade is preferably 0.5 to 10 mm.
Here, the thickness of the cleaning blade and the elastic member of the present invention indicates a direction perpendicular to the bonding surface of the support member 191 as shown in FIG.

The cleaning blade and the elastic member used in the present invention are preferably made of a rubber elastic body. The physical properties of the cleaning blade and the elastic member can be adjusted better by simultaneously controlling the rubber hardness and the rebound resilience. Sex can be controlled more effectively.

As another physical property of the cleaning blade, the hardness is 25 to 5 ° C. and the JISA hardness is 55 to 55 ° C.
A range of 90 is preferred. If it is smaller than 55, the cleaning performance tends to be reduced, and if it is larger than 90, the blade is easily inverted. The rebound resilience of the cleaning blade is preferably in the range of 25 to 80. When the rebound resilience exceeds 80, reversal of the blade is apt to occur, and 25
If it is less than this, the cleaning performance decreases. Young's modulus is 2
Those having a range of 94 to 588 N / cm ² are preferable.

If necessary, the cleaning blade may be spray-coated with a fluorine-based lubricant on the edge of the cleaning blade which comes into contact with the photoreceptor, or may be further provided on the edge of the cleaning blade over the entire width direction. It is preferable to apply a dispersion in which a fluorine-based polymer and a fluorine-based resin powder are dispersed in a fluorine-based solvent.

Next, the organic photoreceptor of the present invention will be described. In the present invention, an organic electrophotographic photoreceptor (organic photoreceptor) is an electrophotography constituted by providing an organic compound with at least one of a charge generation function and a charge transport function essential for the configuration of the electrophotographic photoreceptor. Photoreceptor means all known organic electrophotographic photoreceptors such as a photoreceptor composed of a known organic charge generating substance or organic charge transporting substance, and a photoreceptor having a charge generating function and a charge transporting function composed of a polymer complex. contains.

Hereinafter, the constitution of the organic photoreceptor used in the present invention will be described. Conductive Support As the conductive support used in the photoreceptor of the present invention, any of a sheet shape and a cylindrical shape may be used, but in order to make the image forming apparatus compact, a cylindrical conductive support is used. Is more preferred.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

In the present invention, image blurring, streak-like or spot-like image defects in a high-temperature and high-humidity environment generated when an organic photoreceptor is used can be removed by using a cleaning blade with the elastic member attached thereto and a toner. It has been found that it is effective to add an external additive of fine particles having inorganic fine particles fixed to the surface of resin particles therein and to carry the external additive on the surface of a cleaning member (such as a cleaning blade) during cleaning. That is, by externally adding fine particles (hereinafter, also referred to as composite particles) having inorganic fine particles fixed on the surface of resin particles to the toner, the adsorbed components on the surface of the photoreceptor can be effectively removed, and image deletion, streaking, or spots It has been found that the problem of the occurrence of image defects can be solved, and the present invention has been completed.

Hereinafter, the toner used in the present invention will be described. The toner of the present invention has fine particles (composite particles) in which inorganic fine particles are fixed to at least the surface of resin particles on colored particles.
Since the inorganic fine particles are fixed on the surface of the composite particle which is a toner obtained by adding the toner, the toner has a high charge-imparting ability due to its effect. In addition, due to the inorganic fine particles on the surface, the photoreceptor has a polishing power and has high cleaning properties. Furthermore, since the resin particles are used as the core, it has a flexible structure, can reduce stress on the photoreceptor and the toner at the time of cleaning, and can be used as a fluidizing agent for the toner. Since burial can be suppressed, a stable image can be formed over a long period of time.

The resin particles of the composite particles include styrene resin particles, styrene acrylic resin particles, polyester resin particles, urethane resin particles and the like.

The composition of the resin particles is not particularly limited. Generally, vinyl-based organic fine particles are preferable. The reason for this is that it can be easily produced by a production method such as an emulsion polymerization method or a suspension polymerization method. Specifically, styrene, α-methylstyrene,
p-chlorostyrene, 3,4-dichlorostyrene, p-
Styrene such as phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pt-butylstyrene or styrene derivatives, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, methacrylic acid Methacrylic ester derivatives such as 2-ethylhexyl, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-acrylate
-Butyl, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, acrylate derivatives such as 2-ethylhexyl acrylate, ethylene, propylene, olefins such as isobutylene, vinyl chloride,
Vinyl halides such as vinylidene chloride, vinyl bromide, vinyl fluoride, and vinylidene fluoride; vinyl esters such as vinyl propionate and vinyl acetate; vinyl ethers such as vinyl methyl ether and vinyl ethyl ether;
Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl hexyl ketone; N-vinyl compounds such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl compounds such as vinyl naphthalene and vinyl pyridine; acrylonitrile; Methacrylonitrile, acrylamide, N-butylacrylamide,
N, N-dibutylacrylamide, methacrylamide,
There are acrylic acid and methacrylic acid derivatives such as N-butyl methacrylamide and N-octadecylacrylamide. These vinyl monomers can be used alone or in combination.

The resin particles can be produced by an emulsion polymerization method or a suspension polymerization method. The emulsion polymerization method is a method in which the above-mentioned monomer is added to water containing a surfactant and emulsified, followed by polymerization. As the surfactant, sodium dodecylbenzenesulfonate, polyvinyl alcohol, an ethylene oxide adduct, Any substance that is used as a surfactant such as alcohol sodium sulfate can be used and is not particularly limited.
Further, the use of a reactive emulsifier, a hydrophilic monomer, for example, polymerization with a persulfate initiator such as vinyl acetate or methyl acrylate, a method of copolymerizing a water-soluble monomer, a water-soluble resin, So-called non-emulsion polymerization methods such as a method using an oligomer, a method using a decomposable emulsifier, and a method using a cross-linkable emulsifier are also suitable. Examples of the reactive emulsifier include sulfonic acid salts of acrylic acid amide and salts of maleic acid derivatives. The non-emulsion polymerization method is not affected by the residual emulsifier, and is suitable when organic fine particles are used alone.

Polymerization initiators required for synthesizing resin particles include peroxides such as benzoyl peroxide and lauryl peroxide, and azo-based polymerization initiators such as azobisisobutyronitrile and azobisisovaleronitrile. Agents. The addition amount of these is preferably 0.1 to 2% by mass based on the monomer. If the amount is less than this, the polymerization reaction becomes insufficient, and the problem of residual monomer itself occurs. Further, when the amount is too large, a decomposition product of the polymerization initiator remains and affects the chargeability, and furthermore, the polymerization reaction is too early to cause a problem that the molecular weight becomes small. Further, in an emulsion polymerization method or the like, potassium persulfate, sodium thiosulfate, or the like can be used as a polymerization initiator.

In the preparation of the composite particles, inorganic fine particles are added to and mixed with the resin particles. Next, after the ordered mixture is formed and the inorganic fine particles are electrostatically attached to the surface of the resin particles, mechanical energy is applied to fix the inorganic fine particles to the surface of the resin particles. Here, the sticking means a sticking rate of 25 as described in JP-A-4-291352.
% Or more.

That is, the fixation ratio defines the state of fixation of the inorganic fine particles, and defines the state of embedding of the inorganic fine particles in the resin particles serving as nuclei. This sticking rate is specifically calculated by the following equation.

The specific surface area of the resin particles is Sa, the specific surface area of the inorganic fine particles is Sb, the specific surface area of the composite particles after the inorganic fine particles are fixed on the surface of the resin particles is Sh, and the addition ratio of the inorganic fine particles to the resin particles is x. Then

[0074]

(Equation 1)

Is shown. The fixing rate is 25% or more and 10% or more.
Less than 0% is preferred. In particular, 40 to 80% is preferable.
If the sticking rate is less than 25%, the degree of sticking of the inorganic fine particles to the resin particles becomes low, and the inorganic fine particles existing on the surface are liberated. For this reason, if used repeatedly over a long period of time, the problem of damage to the photoreceptor due to release of inorganic fine particles occurs. The fixing rate can be adjusted by variously controlling the conditions in a manufacturing apparatus for fixing.

In the case of forming the ordered mixture, in the present invention, it is preferable to produce the resin particles at an atmosphere temperature equal to or lower than the glass transition temperature Tg of the resin constituting the surface of the resin particles. That is, when ordered mixture is formed at a temperature equal to or higher than Tg, coalescence of resin particles occurs.

The ratio between the inorganic fine particles constituting the composite particles and the resin particles as the nucleus depends on the respective particle diameters, and the inorganic fine particles may be added so as to uniformly cover the resin particles as the nucleus. Generally, 5-30 inorganic fine particles are used for the resin particles.
% By mass is preferred.

In the case of forming the ordered mixture, any apparatus can be used as long as it can uniformly and electrostatically attach the inorganic fine particles to the surface of the resin particle serving as a nucleus. For example, Henschel mixer, OM dither, Turbula mixer, Lodige mixer,
And a V-type mixer.

As mechanical energy applying devices for fixing inorganic fine particles electrostatically adhered to the surface, “Hybridizer” (manufactured by Nara Machinery Co., Ltd.) and “Freedom Mill” (Nara Machinery Co., Ltd.) modified from an impact type pulverizer are used. Manufactured by Seisakusho), "Ongmill" (manufactured by Hosokawa Micron), "Cryptron" (manufactured by Kawasaki Heavy Industries) and the like can be used. When the inorganic fine particles are fixed to the surface of the resin particles using the present apparatus, not only mechanical energy can be simply applied, but also heating or cooling can be performed from the outside. That is, when a mechanical impact force is applied in a device that rotates at a high speed, heat is generated by the energy of the collision, and the internal temperature rises. When the temperature inside the apparatus becomes higher than the Tg of the resin particles, there is a problem that fusion occurs inside the resin particles and aggregated particles are generated. For this purpose, it is necessary to perform cooling and control. On the other hand, when the internal temperature is lower than Tg by 30 ° C. or more, excessive energy is required for fixing, the collision energy increases, and problems such as crushing of resin particles occur. In order to solve this problem, it is necessary to raise the temperature to about Tg, and in this case, it is necessary to externally heat.

As a method of controlling the temperature from the outside, a method of circulating a heated medium through a jacket provided outside and controlling the temperature is preferable. The internal temperature is measured by the temperature of the circulating air measured by a thermometer installed at a portion for fixing the resin particles and the inorganic fine particles. The medium for circulation includes water or oil.

The charge amount of the composite particles is 1 to 40 μm in absolute value.
C / g is preferred. The charge amount can be controlled by controlling the chargeability of the inorganic fine particles adhered to the surface and controlling the chargeability of the resin particles serving as nuclei.

The number average particle diameter of the composite particles is 100 to 20.
It is preferably in the range of 00 nm, more preferably 200 to 1200 nm.
Is most preferably used. If it is less than 100 nm, the buffering effect of the cleaning blade on the toner and the photoreceptor is small, and the effect of preventing filming or the like is small.
On the other hand, if it is larger than 2000 nm, there is a problem that the composite particles are separated from the toner, and the scattered particles cause contamination of the band electrode and contamination of the transfer electrode, thereby causing image defects such as white stripes. The added amount of the composite particles is preferably 0.1 to 5.0% by mass in the toner (here, the total mass of the toner indicates the total mass including the composite particles and fine particles described later). Particularly preferably, it is 0.2 to 3.0% by mass, most preferably 0.4 to 1.5% by mass.

The following is an example of preparing composite particles. Titanium oxide 1 (number-average) obtained by using styrene / acrylic resin particles (methyl methacrylate: styrene 9: 1) having a number-average primary particle diameter of 0.3 μm and subjecting it to hydrophobic treatment with octyltrimethoxysilane as inorganic fine particles. Primary particle size =
15 nm). 17 parts by mass of inorganic fine particles are added to 100 parts by mass of resin particles, and the mixture is charged into an OM dither (manufactured by Nara Machinery Co., Ltd.). While mixing at 500 rpm for 3 minutes. The product temperature during mixing was 30 ° C. Observation of the obtained ordered mixture with a scanning electron microscope revealed that the inorganic fine particles were uniformly and electrostatically attached to the resin particle surfaces.

Next, this ordered mixture is put into a hybridizer (manufactured by Nara Machinery Co., Ltd.), and heated with circulating water at 45 ° C. as a medium from the outside of the apparatus in which the mechanical impact is repeatedly applied to the inorganic fine particles and the resin particles. While treating at a peripheral speed of 100 m / sec for 3 minutes, composite particles of the present invention were obtained. The internal temperature (product temperature) was 56 ° C. Further, the state of adhesion inside the machine was observed, and no particular adhesion was observed, which was favorable. Further, it was confirmed by scanning electron microscope observation that no union of resin particles was present.

It is preferable to use a fluidizing agent for fine particles of 5 to 49 nm together with the composite particles. Preferred as such a fluidizing agent are silica, alumina, titania, zirconia and the like.

The amount of the fluidizing agent added is 0.1% in the toner.
To 3.0% by mass, preferably 0.3 to 2.5% by mass. If added beyond this range, there is a problem that the fine particles themselves are released, and the scattered particles cause contamination of the band electrode and contamination of the transfer electrode, which causes image defects such as white stripes. Furthermore, since the fine particles are present in the toner in a free state, they cause damage to the photoreceptor, and damage the photoreceptor, so-called black spots and white spots. On the other hand, if it is too small, the fluidity of the toner becomes insufficient, and it is difficult to form a good image.

The above particle size is a number average primary particle size, which is magnified 2000 times by transmission electron microscope observation,
0 particles are observed and are shown by image analysis.

The inorganic fine particles and the fluidizing agent of the composite particles are preferably subjected to a hydrophobic treatment. When performing the hydrophobizing treatment, it is preferable to perform hydrophobizing treatment with a so-called coupling agent such as various titanium coupling agents and silane coupling agents, and silicone oil, and further, aluminum stearate, zinc stearate, and calcium stearate. Hydrophobization treatment with a higher fatty acid metal salt such as described above is also preferably used.

In addition to the fine particle external additives, a lubricant may be added to the toner of the present invention. For example, salts of zinc, aluminum, copper, magnesium, calcium, etc. of stearic acid, zinc, manganese, iron, copper, salts of magnesium, etc. of oleic acid, zinc, copper, magnesium of palmitic acid,
Metal salts of higher fatty acids such as salts of calcium and the like, salts of zinc and linoleic acid such as calcium, salts of ricinoleic acid such as zinc and calcium and the like. The amount of these lubricants added
It is preferably about 0.1 to 5% by mass based on the toner. [Tonerization Step] As a method of adding the external additive, various known mixing apparatuses such as a turbulent mixer, a Henschel mixer, a Nauter mixer, and a V-type mixer can be used.

The toner may contain a material capable of imparting various functions as a toner material in addition to the colorant and the release agent. Specific examples include a charge control agent. These components can be added at the stage of producing the colored particles at the stage of the toner (also referred to as colored particles) before adding the external additive. The colored particles may be produced by a conventional pulverization method or may be produced by a polymerization method.

In the case of producing colored particles by a pulverization method, a release agent and a charge control agent can be added at the stage of kneading the resin and the pigment. On the other hand, when producing by a polymerization method, a method of adding at the stage of resin polymerization, a method of adding simultaneously with a pigment and the like at a resin particle aggregation stage after resin particle production, and the like can be mentioned.

As the release agent in the polymerization method, it is preferable to use various known ones which can be dispersed in water. Specifically, polypropylene,
Examples include olefin waxes such as polyethylene, modified products thereof, natural waxes such as carnauba wax and rice wax, and amide waxes such as fatty acid bisamide. It has already been mentioned that these are preferably added as release agent particles and are preferably salted out / fused together with the resin or colorant.

Similarly, various known charge control agents in the polymerization method, which can be dispersed in water, can be used. Specifically, a nigrosine dye,
Examples include metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, quaternary ammonium salt compounds, azo-based metal complexes, salicylic acid metal salts or metal complexes thereof.

The particles of the release agent and the charge control agent preferably have a number average primary particle diameter of about 10 to 500 nm in a dispersed state.

Hereinafter, the toner (colored particles) produced by the polymerization method preferably used in the present invention will be described.

As the toner applied to the present invention, a polymerized toner having a relatively uniform particle size distribution and shape of individual toner particles is preferable. Here, the term “polymerized toner” means a toner obtained by forming a toner binder resin and forming the toner shape by polymerization of a raw material monomer of the binder resin and a subsequent chemical treatment. More specifically, it means a toner obtained through a polymerization reaction such as suspension polymerization and emulsion polymerization and, if necessary, a step of fusing particles together after the polymerization reaction.

The polymerized toner used in the present invention is preferably a toner having a specific shape. Hereinafter, the polymerized toner that can be preferably used in the present invention will be described.

The preferred polymerized toner applicable to the present invention is a toner having a shape coefficient in the range of 1.2 to 1.6 in which the number of toner particles is at least 65% by number and a coefficient of variation of the shape coefficient of 1
6% or less. It has been found that the use of the polymerized toner having such characteristics can stabilize the vibration of the cleaning blade and exhibit excellent cleaning performance.

The stability of the vibration of the cleaning blade also depends on the particle size of the toner particles. The smaller the particle size, the higher the adhesion to the image carrier, so that the vibration tends to be excessive, and Has a high probability of slipping through the cleaning blade. However, when the toner particle diameter is large, such slip-through is reduced,
The problem that image quality, such as resolution, falls occurs.

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

Further, by using toner particles having no corners at 50% by number or more and controlling the number variation coefficient in the number and particle size distribution at 27% or less, excellent cleaning properties and fine line reproducibility and high quality are obtained. Image quality can be formed over a long period of time.

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

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

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

As the polymerized toner, the shape factor is 1.
The content of toner particles in the range of 2 to 1.6 is preferably at least 65% by number, more preferably at least 70% by number.

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

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

The coefficient of variation of the shape factor of the polymerized toner is calculated from the following equation. Coefficient of variation = [S / K] × 100 (%) [where S represents the standard deviation of the shape factor of 100 toner particles, and K represents the average value of the shape factor. The variation coefficient of the shape factor is preferably 16% or less, and more preferably 14% or less. Coefficient of variation of shape factor is 1
When the content is 6% or less, the gap of the transferred toner layer is reduced, the fixing property is improved, and the offset hardly occurs. Further, the charge amount distribution becomes sharp, and the image quality is improved.

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

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

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

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

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

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

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

The toner particles having no corners mean toner particles having substantially no projections on which electric charges are concentrated or projections which are easily worn by stress, that is, as shown in FIG. 3 (a). When the major axis of the toner particle T is L, a circle C having a radius (L / 10) is rolled inward while being in contact with the peripheral line of the toner particle T at one point. Is substantially outside the toner T, is referred to as “toner particles without corners”. “Cases that do not substantially protrude” refer to cases where there are no more than one protrusion having a protruding circle. In addition, "the major axis of the toner particles"
The term “width” refers to the width of a particle at which the distance between the parallel lines becomes maximum when the projected image of the toner particles on the plane is sandwiched between two parallel lines. FIGS. 3B and 3C show projected images of the toner particles having corners, respectively.

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

The proportion of toner particles having no corners is preferably at least 50% by number, more preferably at least 70% by number.
When the ratio of the toner particles having no corners is 50% by number or more, it is difficult to generate fine particles due to stress with the developer conveying member, and so-called excessively adherent toner to the surface of the developer conveying member. Can be prevented, contamination of the developer conveying member can be suppressed, and the charge amount can be sharpened. In addition, the amount of toner particles that are easily worn or broken and the number of toner particles having a portion where charges are concentrated are reduced, the charge amount distribution is sharpened, the chargeability is stabilized, and good image quality can be formed over a long period of time.

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

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

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

When the number average particle diameter is 3 to 8 μm, it is possible to reduce the presence of a toner having an excessively high adhesion to the developer conveying member or a toner having a low adhesion to the developer conveying member in the fixing step. In addition to being able to stabilize for a long period of time, the transfer efficiency is increased, the image quality of halftone is improved, and the image quality of fine lines and dots is improved.

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

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

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

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

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

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

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

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

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

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

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

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

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

When the emulsion polymerization method is used, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and salts thereof, and hydrogen peroxide.

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

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

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

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

The amount of the coagulant added may be at least the critical coagulation concentration, but is preferably at least 1.2 times the critical coagulation concentration.
More preferably, it is better to add 1.5 times or more.

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

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

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

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

As the colorant used in the toner, any of carbon black, magnetic substance, dye, pigment and the like can be used arbitrarily. Examples of the carbon black include channel black, furnace black, acetylene black, thermal black, lamp black and the like. used. As the magnetic material, ferromagnetic metals such as iron, nickel and cobalt, alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys which do not contain ferromagnetic metals but show ferromagnetism by heat treatment, For example, an alloy of a type called a Heusler alloy such as manganese-copper-aluminum, manganese-copper-tin, chromium dioxide, or the like can be used.

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

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

Further, low molecular weight polypropylene (number average molecular weight = 1500 to 9000), low molecular weight polyethylene or the like may be added as a fixing property improving agent.

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

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

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

First, a reaction apparatus preferably used for producing a polymerized toner will be described. FIGS. 4 and 5 are a perspective view and a cross-sectional view, respectively, showing an example of the polymerization toner reaction device. In the reaction apparatus shown in FIGS. 4 and 5, a rotating shaft 3 is suspended from the center of a vertical cylindrical stirring tank 2 having a heat exchange jacket 1 mounted on the outer peripheral portion. A lower-stage stirring blade 40 disposed close to the bottom surface of the tank 2 and a higher-stage stirring blade 50 are provided. The upper-stage stirring blade 50 is disposed at an intersection angle α that precedes the rotation direction with respect to the lower-stage stirring blade 40. When producing the toner of the present invention, the intersection angle α is preferably less than 90 degrees (°). The lower limit of the intersection angle α is not particularly limited, but is preferably about 5 ° or more, and more preferably 10 ° or more. When a three-stage stirring blade is provided, the intersection angle α between adjacent stirring blades is set.
Is preferably less than 90 degrees.

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

In FIGS. 4 and 5, arrows indicate the direction of rotation, 7 is an upper material inlet, 8 is a lower material inlet, 9
Is a turbulent flow forming member for effective stirring.

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

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

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

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

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

As a stirring tank used for producing a polymerization toner for associating or fusing resin particles, the same stirring tank as used in the above-mentioned suspension polymerization method can be used. In this case, it is necessary not to provide an obstacle such as a baffle plate that forms a turbulent flow in the stirring tank.

The shape of the stirring blade is not particularly limited as long as it forms a laminar flow and does not form a turbulent flow. However, a continuous surface such as a rectangular plate shown in FIG. It is preferably formed and may have a curved surface. << Developer >> The toner used in the present invention may be a one-component developer or a two-component developer, but is preferably a two-component developer.

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

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

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

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

[0167]

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

The following photoconductors were produced as the photoconductors used in the examples. Preparation of Photoreceptor 1 <Undercoat layer> Titanium chelate compound (TC-750: manufactured by Matsumoto Pharmaceutical Co., Ltd.) 30 g Silane coupling agent (KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.) 17 g 2-propanol 150 ml Coating was performed so as to have a dry film thickness of 0.5 μm on a cylindrical conductive support.

<Charge Generation Layer> Y-type titanyl phthalocyanine (the maximum peak angle of X-ray diffraction by Cu-Kα characteristic X-ray is 27.3 at 2θ) 60 g Silicon-modified butyral resin (X-40-1211M: manufactured by Shin-Etsu Chemical Co., Ltd.) ) 700 g of 2-butanone (2000 ml) were mixed and dispersed for 10 hours using a sand mill to prepare a charge generation layer coating solution. This coating solution was applied on the undercoat layer by a dip coating method to form a charge generation layer having a dry film thickness of 0.2 μm.

<Charge Transport Layer> Charge transport substance [N- (4-methylphenyl) -N- {4- (β-phenylstyryl) phenyl} -p-toluidine] 225 g Polycarbonate (viscosity average molecular weight 30,000) 300 g 6 g of an antioxidant (Sanol LS2626: manufactured by Sankyo Co., Ltd.) and 2,000 ml of dichloromethane were mixed and dissolved to prepare a charge transport layer coating solution. This coating solution was applied on the charge generation layer by a dip coating method to form a charge transport layer having a dry film thickness of 20 μm.

Preparation of Photoreceptor 2 Photoreceptor 2 was prepared in the same manner as for Photoreceptor 1, except that the polycarbonate in the charge transport layer of Photoreceptor 1 was replaced with polycarbonate having a viscosity average molecular weight of 80,000.

The toner used in the present invention was prepared below. 10. Preparation of Colored Particles 1 and 2 (Example of Emulsion Polymerization Method) 0.90 kg of sodium n-dodecyl sulfate and pure water
Add 0 l and stir to dissolve. To this solution, add Regal 330
1.20 kg of R (carbon black manufactured by Cabot Corporation) was gradually added, and the mixture was stirred well for 1 hour, and then continuously dispersed for 20 hours using a sand grinder (medium type disperser). This is referred to as “colorant dispersion liquid 1”. A solution composed of 0.055 kg of sodium dodecylbenzenesulfonate and 4.0 l of ion-exchanged water is referred to as “anionic surfactant solution A”.

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

A 100 l GL (glass lining) reactor equipped with a temperature sensor, a cooling pipe,
3.41 kg of AX emulsion (polypropylene emulsion having a number average molecular weight of 3,000: number average primary particle size = 120 nm / solid concentration = 29.9%), the whole amount of “anionic surfactant solution A” and “nonionic surfactant solution B” Add the whole amount and start stirring. Next, ion-exchanged water 4
Add 4.0 l.

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

The glass transition temperature of the resin particles in the latex-A was 57 ° C., the softening point was 121 ° C., and the molecular weight distribution was as follows:
It was 0 nm.

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

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

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

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

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

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

100 l of S with temperature sensor, cooling tube, nitrogen introduction device, particle size and shape monitoring device
In a US reactor, add the latex-A = 2 prepared above.
0.0 kg, latex-B = 5.2 kg, colorant dispersion 1 = 0.4 kg, and ion-exchanged water 20.0 kg are stirred. Then, the mixture was heated to 40 ° C., and sodium chloride solution G and isopropanol (manufactured by Kanto Chemical Co., Ltd.) 6.00 k
g, Nonionic surfactant solution H are added in this order. Then, after leaving it for 10 minutes, the temperature was started and the liquid temperature was 8
The temperature is raised to 5 ° C. in 60 minutes, and heated and stirred at 85 ± 2 ° C. for 0.5 to 3 hours to grow the particle size while salting out / fusing.
Next, 2.1 l of pure water is added to stop the particle size growth.

Into a 5 liter reaction vessel equipped with a temperature sensor, a cooling pipe, and a device for monitoring particle size and shape, 5.0 kg of the above-prepared fused particle dispersion was placed.
The shape was controlled by heating and stirring at ± 2 ° C. for 0.5 to 15 hours. Thereafter, the mixture is cooled to 40 ° C. or less and the stirring is stopped. Next, classification is performed in the liquid by a centrifugal sedimentation method using a centrifugal separator, and the liquid is filtered through a sieve having openings of 45 μm, and the filtrate is used as an associated liquid. Next, non-spherical particles in the form of a wet cake were collected by filtration from the associated liquid using a Nutsche. afterwards,
It was washed with ion-exchanged water.

The non-spherical particles were dried at a suction temperature of 60 ° C. using a flash jet drier, and then dried at a temperature of 60 ° C. using a fluidized bed drier. In the monitoring of the salting-out / fusion step and the shape control step, the number of rotations of the stirring and the heating time are controlled to control the variation coefficient of the shape and the shape coefficient. Was adjusted to obtain colored particles 1 and 2 shown in Table 1.

Preparation of Colored Particles 3 (Example of Suspension Polymerization Method) Styrene = 165 g, n-butyl acrylate = 35
g, carbon black = 10 g, metal di-t-butylsalicylate = 2 g, styrene-methacrylic acid copolymer = 8 g, paraffin wax (mp = 70 ° C.) = 20
g was heated to 60 ° C. and uniformly dissolved and dispersed at 12,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.).
To this, 2,2'-azobis (2,4-
(Valeronitrile) = 10 g was added and dissolved to prepare a polymerizable monomer composition. Then, 710 g of ion-exchanged water
Was added with 450 g of a 0.1 M aqueous sodium phosphate solution, and TK was added.
While stirring with a homomixer at 13000 rpm, 1.
68 g of 0M calcium chloride was gradually added to prepare a suspension in which tricalcium phosphate was dispersed. The polymerizable monomer composition was added to this suspension, and the mixture was added to a TK homomixer.
The mixture was stirred at 0000 rpm for 20 minutes to granulate the polymerizable monomer composition. Thereafter, a reactor (crossing angle α is 45 °) having a stirring blade configuration as shown in FIG.
The reaction was performed at 〜95 ° C. for 5 to 15 hours. Tricalcium phosphate is dissolved and removed with hydrochloric acid, and then, using a centrifuge,
Classification was performed in the liquid by centrifugal sedimentation, followed by filtration, washing and drying.

By monitoring during the polymerization, controlling the liquid temperature, the number of rotations of the stirring, and the heating time, the variation coefficient of the shape and the shape coefficient are controlled. By adjusting the coefficient, colored particles 3 shown in Table 1 below were obtained.

[0188]

[Table 1]

The coloring particles 1 to 3 and the fluidizing agent and composite particles shown in Tables 3 and 4 below were added as shown in Table 2, and mixed with a Henschel mixer under a rotation condition of 30 m / sec. To 9 were produced.

[0190]

[Table 2]

[0191]

[Table 3]

* Titanium oxide 1: titanium oxide treated with octyltrimethoxysilane (number average primary particle diameter = 15 nm) * Titanium oxide 2: titanium oxide treated with zinc stearate (number average primary particle diameter = 20 nm) * Titanium oxide 3: stearin Zinc oxide-treated titanium oxide (number average primary particle size = 40 nm)

[0193]

[Table 4]

Preparation of Developer A toner having a toner concentration of 6% was prepared by mixing each of “Toner 1” to “Toner 9” with a ferrite carrier coated with a silicone resin and having a volume average particle diameter of 60 μm. Used for evaluation. This developer is referred to as “developer 1” to “developer 9” corresponding to the toner.

Preparation of Combination of Cleaning Blade and Elastic Member Fourteen combinations of cleaning blade and elastic member used in the cleaning device were prepared as shown in Table 5. The cleaning blade and the elastic member were bonded with a double-sided tape.

[0196]

[Table 5]

Cleaning Condition A cleaning blade having a free length of 9 mm was brought into contact with the photoreceptor by a weight load method in the counter direction with respect to the rotation direction so as to have a linear pressure of 20 (N / m).

Evaluation Konica 7 digital copier manufactured by Konica Corporation was used as the evaluation machine.
075 (corona charging, laser exposure, reversal development, electrostatic transfer, nail separation, cleaning blade, cleaning auxiliary brush roller adoption process), the photoconductor, developer and cleaning described in Table 6 were used in the copying machine. The evaluation was performed by mounting a combination of devices. For cleaning performance and image evaluation, an original image in which a character image having a pixel ratio of 7%, a photograph of a person's face, a solid white image, and a solid black image were equally divided into quarters each was copied to A4 neutral paper. Environmental conditions are considered to be the most severe high temperature and high humidity environment (30 ℃, 80%
(RH), 100,000 sheets were continuously copied, and evaluated using a character image, a halftone, a solid white image, and a solid black image. The evaluation items and evaluation criteria are shown below.

[0199]

[Table 6]

Evaluation Criteria Image blur (evaluated due to a decrease in the resolution of the character image) ：: No image blur occurs until 100,000 copies are completed. Δ: Minor image blur occurs until 100,000 copies are completed. ×: Significant image blur occurs before 100,000 copies are completed (characters cannot be decoded). Cleanability (10,000 copies are continuously made on A3 paper after 30,000, 50,000 and 100,000 copies are completed. Judgment based on whether or not cleaning failure has occurred in a solid white portion) ：: No filming occurs due to slippage of toner up to 100,000 sheets △: No filming occurs due to slippage of toner up to 50,000 sheets ×: Toner is less than 30,000 sheets Filming caused by slip-through etc. Blade turning ○: No blade turning during copying 100,000 sheets ×: Blade turning during copying 100,000 sheets Overall image quality (initial and 1 Was assessed after ten thousand copies) ○:. Initial and 100,000 copies after both character image is clearly,
The halftone image is reproduced smoothly and is good. Δ: Good at the initial stage, but image blur or roughness is slightly observed in the character image after copying 100,000 sheets or the halftone image.

×: Image blur or roughness is noticeable in the character image or halftone image after 100,000 copies.

The magnitude of the vibration of the cleaning blade The method of measuring the magnitude of the vibration When the sensor of the acceleration detector NP-3210 manufactured by Ono Sokki Co., Ltd. is attached to the support member to which the cleaning blade is joined, and the photoconductor rotates at a constant speed. Is read by the sensor for 10 seconds, and the output data from the sensor is subjected to arithmetic processing by an “ONO SOKKI CF6400 4-channel intelligent FF analyzer” to obtain an average value of the amplitude of the vibration, which is obtained as the magnitude of the vibration of the blade. It was expressed in terms of (μm).

Photoreceptor Film Thickness Amount The photoreceptor film thickness reduction was determined as the difference between the average thickness of the photoreceptor measured at the start of the actual printing evaluation and at the end of 100,000 sheet copying, and was taken as the film thickness reduction.

Method of Measuring Film Thickness The film thickness of the photosensitive layer is measured at random at 10 places with a uniform film thickness portion, and the average value is defined as the film thickness of the photosensitive layer. The film thickness measuring device is an eddy current type film thickness measuring device EDDY560C (HELMUT
FISCHER GMBTE CO).

Other Evaluation Conditions The other evaluation conditions using the digital copying machine Konica 7075 were set as follows.

Charging Conditions Charger: Scorotron charger, initial charging potential was -750
V Exposure conditions Exposure amount is set so that the exposure portion potential is -50V.

Developing condition DC bias; -550 V Transfer condition Transfer pole; Corona charging system The evaluation results are shown in Table 7.

[0208]

[Table 7]

As can be seen from Table 7, the combination No. satisfying the requirements of the present invention. 1-8, 10-14, and 17
Nos. 19 to 19 have no image blur, have good cleaning properties, and have a small thickness loss. On the other hand, the combination No. In No. 9, the image blur was remarkably generated. In Nos. 15, 21, and 22, the vibration of the cleaning blade was not effectively absorbed, the cleaning property was reduced, and the image was blurred. In Nos. 16 and 20, the vibration of the cleaning blade was excessive, and the blade was turned up.

[0210]

As is clear from the above embodiment, by implementing the present invention in which the cleaning blade having the elastic member and the developer are combined, the residual toner on the organic photoreceptor can be turned up by the blade or the toner can pass through. It is possible to provide an image forming method and an image forming apparatus which can be effectively removed without occurrence and have good overall image quality.

[Brief description of the drawings]

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

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

FIG. 3A is an explanatory diagram illustrating a projected image of a toner particle having no corner, and FIGS. 3B and 3C are explanatory diagrams illustrating a projected image of a toner particle having a corner.

FIG. 4 is a perspective view showing an example of a polymerization toner reaction device.

FIG. 5 is a sectional view showing an example of a polymerization toner reaction device.

FIG. 6 is a schematic diagram showing a specific example of the shape of a stirring blade.

[Explanation of symbols]

121 Photoconductor 122 Charger 123 Developing device 124 Transfer device 125 Separator 126 Cleaning device 126A Cleaning blade 126B Elastic member 127 PCL (precharge lamp) 130 Exposure optical system 191 Support member a Free length of cleaning blade b Free length of elastic member the thickness of the thickness t ₂ the elastic members of t ₁ the cleaning blade

Claims (6)

[Claims] 1. An electrostatic latent image formed on an organic photoreceptor,
An image forming method, comprising: developing with a developer containing toner, transferring a toner image visualized by the development from an organic photoconductor to a transfer material, and removing a toner remaining on the organic photoconductor. Wherein the cleaning blade is in contact with the elastic member on the surface opposite to the surface in contact with the organic photoreceptor, and the free length a of the cleaning blade and the free length b of the elastic member satisfy the relationship of Formula 1; An image forming method, wherein the toner used as the agent is a toner obtained by adding fine particles obtained by fixing inorganic fine particles on the surface of resin particles to colored particles. Formula 1 0.1 <b / a ≦ 0.9 2. An electrostatic latent image formed on an organic photoreceptor,
An image forming method, comprising: developing with a developer containing toner, transferring a toner image visualized by the development from an organic photoconductor to a transfer material, and removing a toner remaining on the organic photoconductor. Wherein the cleaning blade is in contact with the elastic member on the surface opposite to the surface in contact with the organic photoreceptor, and the thickness t ₁ of the cleaning blade and the thickness t ₂ of the elastic member satisfy the relationship of Expression 2, and An image forming method, wherein the toner used for the developer is a toner obtained by adding fine particles obtained by fixing inorganic fine particles on the surface of resin particles to colored particles. Equation 2 1/30 <t ₂ / t ₁ <2 3. The image forming method according to claim 1, wherein the number average particle diameter of the fine particles having inorganic fine particles fixed on the surface of the resin particles is 100 nm to 2000 nm. 4. The toner according to claim 1, wherein the amount of the fine particles is 0.1%.
The image forming method according to any one of claims 1 to 3, wherein the amount is from 3.0 to 3.0% by mass. 5. The toner further comprises a number average primary particle size of 5
The image forming method according to any one of claims 1 to 4, wherein 0.1 to 3.0% by mass of a fluidizing agent having a thickness of from 49 to 49 nm is added to the toner. 6. An image forming apparatus using the image forming method according to claim 1.