JP2006301140A - Image forming apparatus, process cartridge, method for manufacturing electrophotographic photoreceptor, and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image of high image quality with an image forming apparatus using a combination of an electrophotographic photoreceptor of a predetermined configuration and a toner by a specific manufacturing method. <P>SOLUTION: The electrophotographic photoreceptor is obtained by stacking a charge generating layer 435 in which charge generating regions containing a charge generating material are dispersedly formed in a minute dot shape and a charge transport layer 437 containing a charge transport material in this order on a conductive support 431. The dispersed formation of the charge generating regions is carried out by jetting a coating liquid for the charge generating layer by a piezo system ink jet process. The space factor of the charge generating regions in the charge generating layer is set to a predetermined value of ≤90% and the dot pitch of the charge generating regions is made equal to the resolution of the image forming apparatus. The toner is obtained by suspension-polymerizing a polymerizable composition comprising a polymerizable monomer and a colorant in an aqueous medium. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention includes (1) an image forming apparatus such as a copying machine or a printer using an electrophotographic process using an electrophotographic photosensitive member having a specific structure and a toner manufactured by a specific synthesis method, and (2) the electrophotographic photosensitive member. The present invention relates to a process cartridge that includes a body and is detachably mounted on the image forming apparatus, (3) a method for manufacturing the electrophotographic photosensitive member, and (4) an image forming method that uses the electrophotographic photosensitive member and the toner.
In the present invention, in particular, the charge generation layer capable of obtaining high image quality is dispersed and formed in the form of dots as minute regions (the charge generation layer is formed by dispersing minute charge generation regions in the form of dots. The present invention relates to an electrophotographic photosensitive member and a method for producing the same.

Conventionally, the photoconductor used in the electrophotographic system includes a photoconductive layer mainly composed of selenium or a selenium alloy on a conductive support, and inorganic photoconductive materials such as zinc oxide and cadmium sulfide. Are generally known, such as those in which binder is dispersed in a binder, and those using an amorphous silicon-based material. However, cost, productivity, high degree of freedom in designing a photoreceptor, non-polluting, etc. Therefore, organic photoreceptors are widely used.
The organic electrophotographic photoreceptor includes a photoconductive resin typified by polyvinylcarbazole (PVK), a charge transfer complex type typified by PVK-TNF (2,4,7-trinitrofluorenone), Known are pigment-dispersed type typified by phthalocyanine-binder resin, and function-separated type photoconductors that use a combination of a charge generation material and a charge transport material. However, due to sensitivity, durability, and freedom of design, etc. A function-separated type photoreceptor in which a charge generation layer containing a charge generation material and a charge transport layer containing a charge transport material are laminated on a conductive support is common.
The mechanism of electrostatic latent image formation in this function-separated type photoreceptor is that when the photoreceptor is charged and irradiated with light, the light passes through the transparent charge transport layer and is absorbed by the charge generation material in the charge generation layer, The charge generation material that has absorbed the light generates charge carriers, which are injected into the charge transport layer, move in the charge transport layer according to an electric field, and neutralize the charge on the surface of the photoreceptor to neutralize the electrostatic latent. It forms an image. In function-separated type photoreceptors, it is known and useful to use a combination of a charge transport material having absorption mainly in the ultraviolet region and a charge generation material having absorption mainly from the visible region to the near infrared region. It is.

However, in the case of the above-described function-separated type photoreceptor, since the distance from the charge generation layer to the surface of the charge transport layer is long, there is a problem that the carrier is diffused during transport and the resolution is lowered. In other words, the carriers are attracted to the surface of the charge transport layer and transported, but at that time, they are also diffused in the lateral direction, the carrier diameter is larger than the beam spot diameter corresponding to one dot, and the adjacent image. The dot area is entered (see FIG. 1).
Furthermore, since the energy distribution of the exposure beam follows a Gaussian function (normal distribution), it will have a wide skirt, and carriers generated by the light at this skirt will easily diffuse into the adjacent image dot area, and the resolution will increase. Is a cause of lowering. FIG. 2 shows this, and shows the energy (I) distribution of an exposure beam of 600 dpi and a beam diameter of 68.9 μm. In the figure, when it has energy distribution of A and B, it becomes energy distribution C as a whole.
Further, in an electrophotographic image forming apparatus, the beam spot diameter of a laser beam for exposing a photosensitive drum (the diameter of a circle connecting regions showing an amount of light that is 1 / e ² of the peak value. E is the base of the natural logarithm. Are mostly in the range of 50 μm to 80 μm. When the resolution is 1200 dpi, the length per pixel is 21.2 μm, which is considerably smaller than the beam diameter. Since the beam diameter is determined by the wavelength of the laser, the focal length of the optical system, and the aperture diameter, reducing the beam diameter alone involves problems such as increasing the size of the device. There is a background that cannot be done.

  The problem that the beam spot diameter is larger than the length per pixel and the problem that occurs in the above-described function-separated type photoconductor (laminated photoconductor), that is, when the photocarrier passes through the charge transport layer. When combined with the problem that photocarriers diffuse into the surface area of the charge transport layer and enter adjacent pixel areas, conventional image forming apparatuses have a sharp electrostatic latent image (potential (charge (charge)). ) There is a problem that it is difficult to form an electrostatic latent image having a high contrast.

  When such an electrostatic latent image with a small potential contrast is formed through development, transfer, and fixing processes, the following phenomenon that leads to deterioration in image quality may occur. However, it became clear by the experiment which the present inventors conducted.

[First image quality degradation phenomenon: disappearance of fine lines]
When one dot line (thin line) is formed when the resolution is high (in the case of 1200 dpi), a phenomenon occurs in which the one dot line disappears and is not reproduced in the output image. Further, even when the resolution is small (in the case of 600 dpi), when half-dot (writing with a small value at the time of multi-value writing) writing is performed, fine lines disappear in the same manner and are not reproduced. Will occur. These thin line images and images having characteristics close to those exist as low-contrast images (images such as lines and characters that appear to be very light gray) even in general images. For this reason, even in a general image, a reduction in image quality such as a decrease in reproducibility of a low contrast image is caused.

[Second Image Quality Degradation Phenomenon: Abrupt Density Change at Highlight Area in Tone Image]
When a gradation image such as a photographic image or a graphics image is subjected to pseudo halftone processing with a high number of lines and output as an image, a highlight portion (an area having a reflection density of about 0 to 0.2) ) Causes a sudden change in density. In such a gradation image, such a sudden density change at the highlight portion causes a phenomenon called a pseudo contour that a gradation boundary that does not exist on the original image appears. Since the pseudo contour is an abnormal image that gives a sense of incongruity in a gradation image, it is a major factor in image quality degradation.

On the other hand, in an electrophotographic photoreceptor in which at least a photosensitive layer is formed on a conductive substrate, the photosensitive layer includes a charge generation region and a charge transport region, and the charge generation region is provided in the charge transport region. An electrophotographic photosensitive member characterized by a structure embedded in a hole is disclosed (for example, see Patent Document 1), but is expensive because the manufacturing process is complicated, and the surface layer has a region. Since they are separated from each other, adhesion of foreign matter, indentation and the like are likely to occur, and as a result, an abnormal image is likely to occur.
Further, in the function separation type photoreceptor in which the base, the carrier generation layer, and the carrier transport layer are sequentially laminated, a light shielding mask pattern layer that blocks a part of the image exposure light is provided at least on the surface of the carrier generation layer. An electrophotographic photoreceptor characterized by this is disclosed (for example, see Patent Document 2), but is also expensive due to the complicated manufacturing process, and contamination is caused by the material of the light-shielding mask pattern. As a result, problems in electrostatic characteristics arise.
Further, in the multilayer electrophotographic photosensitive member including a charge generation layer and a charge transport layer, the charge transport layer contains a photocurable resin and another resin component, and the photocurable resin is added when the charge transport layer is formed. By irradiating light in a wavelength region that can be cured in a lattice shape, a portion in which the content of the photocurable resin is larger than the unexposed portion is formed in a lattice shape, and the lattice-shaped exposed portion has surface resistance or volume resistance. An electrophotographic photosensitive member characterized in that it is an area larger than an unexposed portion is disclosed (for example, see Patent Document 3). However, since the manufacturing process is complicated, it is expensive. When a curable resin is used, the carrier mobility generally decreases, and the photoresponsiveness as a photoreceptor greatly decreases. Further, since the pattern is formed in a lattice pattern, it cannot be said that the effect of suppressing the reduction in resolution is great.
In addition, in an image forming apparatus that forms a visible image by charging, image exposure, and development on the surface of an image carrier on which a photoconductive photosensitive layer is formed, a minute region in which the potential is not attenuated with respect to the image exposure. An image forming apparatus characterized in that is formed in a dispersed manner in the photosensitive layer (see, for example, Patent Document 4), but improves the image density uniformity of solid images and graphics. Although it is effective, it is considered ineffective to improve the resolution. The production method is also formed by laser beam irradiation, and the process is complicated and the influence on the electrostatic properties of carbides generated by laser beam irradiation cannot be ignored.

In the above-described conventional technologies (Patent Documents 1 to 4), problems such as those already described (cost increase due to the complexity of the production method, reduction in durability due to non-uniformity of the light shielding pattern and the charge transport layer, and the like) It is not efficient enough not only to cause problems) but also to form an electrostatic latent image having a large potential contrast.
In the prior art described above, the generation ratio (so-called sensitivity) of photocarriers generated in the CGL (charge generation layer) is constant in any part of the CGL (any part of the unmasked part). In such a configuration, in combination with the current situation that the beam spot diameter cannot be actively reduced, the photocarriers generated in the unmasked portion are almost constant in the area where the mask is not applied. It becomes. In this case, the photocarrier generation region is slightly concentrated by the amount of the mask region, but the effect is limited to the size of the mask region. There has been a problem that an electrostatic latent image having a contrast high enough that the above-mentioned problems such as disappearance of fine lines and abrupt density change in a highlight portion of a gradation image do not occur.
For the above problem (problem in which an electrostatic latent image having a sufficiently high contrast cannot be formed), the mask area is further increased (the charge generation area is reduced), and the photocarrier generation location is set to one pixel. Improvement is also possible by limiting to the central part. However, in this case, there is a new problem that a so-called solid image (an image in which toner is uniformly attached to the entire region) cannot be obtained. This is because if the masked area is made large, the charge in this part cannot be canceled by writing, and toner cannot adhere to this part.

JP 2000-231203 A JP 2001-75301 A JP-A-11-258837 JP 11-338170 A

The present invention has been made in view of the above points, and an object of the present invention is to provide an electrophotographic photosensitive member that provides good image quality. It is another object of the present invention to provide an excellent electrophotographic photosensitive member production method which does not cause any problems in terms of electrostatic characteristics at low cost without using a complicated production method found in the past. In addition, the present invention provides an electrophotographic photoreceptor manufacturing method capable of achieving durability in terms of electrostatic characteristics because it does not go through complicated steps and does not have non-uniformity of a light shielding pattern or a charge transport layer. Objective.
Another object of the present invention is to propose an electrophotographic photosensitive member that can uniformly adhere toner to the entire surface of a solid image while forming an electrostatic latent image having a sufficiently large contrast. To do.
Another object of the present invention is to reduce toner consumption in the image forming process.
The present invention further includes (a) an image forming apparatus such as a copying machine or a printer using the electrophotographic photosensitive member and a toner manufactured by a specific synthesis method, and (b) the electrophotographic photosensitive member provided with the electrophotographic photosensitive member. The present invention provides a process cartridge that is detachably mounted on a forming apparatus, and (c) an image forming method using the electrophotographic photosensitive member and the toner.
In particular, the present invention provides an electrophotographic photosensitive member in which a charge generation layer is formed by dispersing minute charge generation regions that can obtain high image quality into dots, and a method for manufacturing the same.

That is, as a result of intensive investigations, the present inventors have found that the above problem can be solved by forming the charge generation layer as a minute region dispersed in dots as compared to the conventional electrophotographic photosensitive member and manufacturing method. I found it. Further, since the material itself constituting the present invention does not use a light-shielding material, a curable material, or the like, it can be used without changing from a conventional photoconductor, and uses a simple and accumulated photoconductor technology. As a result, it is possible to easily design a photoreceptor corresponding to high sensitivity and high image quality.
That is, according to the present invention, the above-described problem is solved by the present invention.
(1) In the image forming apparatus comprising: an electrophotographic photosensitive member; and a developing device that develops the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image. Comprises a charge generation layer and a charge transport layer containing a charge transport material on a conductive support, and the charge generation layer disperses minute charge generation regions having the charge generation material into dots. An image forming apparatus, wherein the toner is a toner produced by a chemical reaction in an aqueous medium.
(2) “In the charge generation layer of the electrophotographic photosensitive member, the occupation area ratio of the charge generation region formed in a dot shape is 90% or less, and the occupation area ratio represented by the following formula (1) ( X) The image forming apparatus as described in (1) above, wherein
η × J ≧ 0.01 × EXP (− (X−60 / 10) +0.002 (1)
(Η represents quantum efficiency, J represents exposure beam energy (J / m ² ), and “EXP” represents “exponential”) ”,
(3) The image forming apparatus according to (1) or (2), wherein the charge generation layer of the electrophotographic photosensitive member has a dot pitch of the charge generation region equal to a resolution of the image forming apparatus. "
(4) The above-mentioned (1) to (3), wherein the charge generation layer of the electrophotographic photosensitive member has an average particle size of a charge generation material contained in the charge generation region of 0.2 μm or less. Or an image forming apparatus according to any one of the above.
(5) The above (1) to (4), wherein the toner is a toner obtained by suspension polymerization of a polymerizable composition comprising a polymerizable monomer and a colorant in an aqueous medium. Or an image forming apparatus according to any one of the above.
(6) “The toner is formed into particles while reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium to form an adhesive substrate. The image forming apparatus according to any one of (1) to (4), wherein the image forming apparatus is provided.
(7) “The image forming apparatus according to any one of (1) to (6) above, wherein the toner has a volume average particle diameter of 4 to 8 μm.”
(8) The image forming apparatus according to any one of (1) to (7) above, wherein a ratio of a volume average particle size to a number average particle size in the toner is 1.10 to 1.25. . "
(9) “At least an electrophotographic photosensitive member carrying an electrostatic latent image and a developing unit for developing the electrostatic latent image formed on the electrophotographic photosensitive member using toner to form a toner image, The electrophotographic photosensitive member includes a charge generation layer and a charge transport layer containing a charge transport material on a conductive support, and the charge generation layer includes a microparticle having a charge generation material. And the toner is the toner described in the above (1), (5), (6), (7) or (8). To process cartridge. ",
(10) “A method for producing the electrophotographic photosensitive member according to any one of (1) to (4) above, wherein the charge generation region is formed by ejecting a charge generation layer coating solution by an inkjet method. A method for producing an electrophotographic photosensitive member, ”
(11) “The method for producing an electrophotographic photosensitive member according to (10) above, wherein the inkjet method is a piezo method.”
(12) "An electrostatic latent image forming step of forming an electrostatic latent image on an electrophotographic photosensitive member; a developing step of developing the electrostatic latent image with toner to form a toner image; and 5. An image forming method comprising a transfer step of transferring from an electrophotographic photosensitive member to a transfer medium, wherein the electrophotographic photosensitive member according to any one of claims 1 to 4 is used as the toner. 1), (5), (6), (7) or an image forming method using the toner described in (8).
Is achieved.

The present invention relates to an electrophotographic photosensitive member, a developing device for developing a latent electrostatic image formed on the electrophotographic photosensitive member with toner to form a toner image, and the toner image to be covered from the electrophotographic photosensitive member. In the image forming apparatus having a transfer device for transferring to a transfer medium, the electrophotographic photoreceptor comprises a charge generation layer and a charge transport layer containing a charge transport material on a conductive support, An image, wherein the charge generation layer is formed by dispersing minute charge generation regions having a charge generation material in the form of dots, and the toner is a toner produced by a chemical reaction in an aqueous medium. An invention related to a forming device,
More preferably, in the charge generation layer of the electrophotographic photosensitive member, the occupation area ratio of the charge generation region formed in a dot shape is 90% or less, and the occupation area ratio represented by the following formula (1) ( X) or more.
η × J ≧ 0.01 × EXP (− (X−60 / 10) +0.002 (1)
(Η represents quantum efficiency, and J represents exposure beam energy (J / m ² ).
Therefore, in the image forming apparatus and the image forming method of the present invention, in particular, it is possible to uniformly adhere toner to the entire surface even in a solid image while forming an electrostatic latent image having a sufficiently large contrast, and the toner has small particles. Since the molecular weight distribution is sharp in shape, it can be efficiently developed on the latent image, high image quality can be achieved, and toner consumption can be suppressed.

More specifically, even when an image is output by performing pseudo halftone processing with a high number of lines on a gradation image such as a photographic image or a graphics image, the highlight portion (the reflection density is 0). An image with good reproducibility can be obtained without a sudden density change in a region of about 0.2.
Further, by setting the area occupied by the charge generation region formed in a dot shape in the charge generation layer to 90% or less and within the range of the above formula (1), “good reproduction of fine lines” and “highlight” It is possible to obtain an image that is compatible with “stable density change in the area”. Even if it is placed on a solid black image, a sufficient image density can be obtained.
Further, the effect becomes more remarkable by making the dot pitch equal to the resolution of the image forming apparatus.
In addition, when the average particle size of the charge generation material contained in the charge generation region is 0.2 μm or less, dot reproducibility is improved, and unevenness of the entire image is reduced, and a good image can be obtained. .
In addition, by applying the charge generation layer using the ink jet method, it is possible to form dots with an extremely simple manufacturing apparatus and at a low cost as compared with the conventional case.
Further, by using the piezo method as the ink jet method, it is possible to prevent the charge generation layer coating solution which is easily deteriorated by heat from being deteriorated, and on the image which is a concern when applied by the foam jet recording method. Black spots can also be prevented, and the effects of the present invention can be brought out very well.

That is, the present invention relates to an electrophotographic photosensitive member, a developing device that develops an electrostatic latent image formed on the electrophotographic photosensitive member with a toner to form a toner image, and the toner image from the electrophotographic photosensitive member. In the image forming apparatus having a transfer device for transferring to a transfer medium, the electrophotographic photosensitive member includes a charge generation layer and a charge transport layer containing a charge transport material on a conductive support, The charge generation layer is formed by dispersing minute charge generation regions having a charge generation material in the form of dots, and the toner is a toner produced by a chemical reaction in an aqueous medium. Invention related to the device,
More preferably, in the charge generation layer of the electrophotographic photosensitive member, the occupation area ratio of the charge generation region formed in a dot shape is 90% or less, and the occupation area ratio represented by the above formula (1) ( X) or more of the invention.
According to such an invention, it is possible to obtain an image forming apparatus capable of uniformly depositing toner on the entire surface of a solid image while forming an electrostatic latent image having a sufficiently large contrast. Furthermore, in the present invention, since toner produced by a chemical reaction in an aqueous medium is used, since the molecular weight distribution is sharp with a small particle size, it can be efficiently developed on a latent image, and toner consumption is suppressed. Can do.

  The quantum efficiency η in the above formula (1) is calculated by the following formula (2).

Here, C is a capacitance per unit area of the photoreceptor, e is an elementary charge of electrons, J is monochromatic light energy, V is a surface potential, and t is time. The quantum efficiency η is a physical quantity independent of the film thickness and represents carrier generation efficiency (quantum efficiency of photoelectric conversion). The quantum efficiency η is calculated from the transient attenuation characteristics when exposed to monochromatic light (energy J per unit time) and the photoreceptor capacitance C, and is calculated by fitting to an electric field dependence equation, η = αE ^n. .

The measurement of the stationary beam light quantity J (the exposure beam energy is hereinafter referred to as the stationary beam light quantity) was performed as follows. An optical power meter (model 3292) manufactured by Yokogawa Electric Corporation was used for measurement of the amount of static beam. The probe (light receiving portion) of this optical power meter was placed at the laser beam imaging position (corresponding to the position where the photosensitive drum is placed) and set so that the laser beam was incident on the probe center. In this state, the output value of the optical power meter was recorded while the LD (laser diode) was continuously turned on, and the light amount was taken as a stationary beam amount.
When the occupation area ratio of the charge generation layer formed in the dot shape (charge generation region dispersed in the dot shape) is larger than 90%, an electrostatic latent image having a sufficiently large contrast can be formed. This is not possible, and the density changes rapidly in the highlight portion (region where the reflection density is about 0 to 0.2), and the effect of the present invention cannot be obtained.

The above formula (1) shown in the present invention is obtained from the reproducibility of isolated dots and the uniformity and density of a black solid image, and is obtained by conducting further experiments after examination from the following simulation. It is a thing.
The simulation method is as follows.
The relationship between the area occupied by the charge generation layer formed in a dot shape and the toner adhesion amount when the photosensitive member sensitivity and the exposure energy amount were varied was calculated by simulation.

It is known that the charge density distribution on the photoreceptor after exposure can be roughly grasped by using a PIDC curve. However, the difference in latent image distribution due to the effect that carriers generated in the CGL layer diffuse while moving through the CTL layer when the thickness of the photoconductor is changed, or in the vicinity of the CGL in the case of strong exposure. When analyzing the influence of the difference in latent image distribution caused by the recombination of positive and negative carriers with a PIDC curve, it is necessary to measure PIDC for each condition and for each film thickness. Further, it can be dealt with by actually measuring a PIDC curve at the time of a dot image, but it is impossible to measure a one-dot latent image distribution or potential distribution on a photoconductor with the current technology.
Therefore, the movement of carriers (charges) inside the photoconductor correctly takes into account the Coulomb repulsion between carriers, the recombination of carriers, and the mobility of carriers inside the photoconductor, and the latent image distribution and potential distribution are simulated. Need to predict.

The calculation method is described below. The calculation method consists of the following three steps.
(I) Calculation of latent image charge distribution The latent image charge distribution on the photoreceptor after exposure is calculated. The movement of the carrier (charge) inside the photoconductor is affected by the Coulomb repulsion between the carriers, recombination of the carriers, and the mobility of the carrier inside the photoconductor. Formation simulation is required.
The physical model used to calculate the latent image charge distribution consists of (1) calculation of exposure amount by a Gaussian laser beam, and (2) calculation of charge carrier generation and its transport process.
In the exposure amount calculation, the exposure amount distribution of a single stationary beam, that is, I (x, y) is expressed by the following equation (3).

(Where x-vt: distance from the laser center, y: distance from the laser center, ω: laser beam radius (1 / e ^{2 of} center intensity), P ₀ : laser power), and X direction It is calculated by integrating in the X direction for the moving distance (Vx · spotting time) during the lighting time.
When this amount of exposure is applied to the dot-like charge generation layer, only the portion where the charge generation region exists is actually exposed. Therefore, the region without the charge generation region (so-called non-charge) in the charge generation layer. The exposure distribution in the generation area) is deleted, and only the exposure distribution in the charge generation area is extracted, and this is used as the exposure distribution.
Next, the charge carrier generation (2) in OPC and the process of its transport are expressed by the Poisson equation (Expression (6)) of the following positive and negative carrier continuity expressions (Expression (4), Expression (5)): Ruled.

  Here, n, μ, E, Γ, R, ε, and e are the number density of carriers, mobility, electric field strength, amount of carriers generated per unit time, recombination coefficient per unit time of carrier, dielectric Rate and elementary charge. Subscripts p and n indicate positive and negative carriers, respectively.

Charge carriers were assumed to be generated uniformly in the layer, taking into account the thin CGL layer. For this reason, the carrier generation amount Γ is connected to the incident light intensity F, the quantum efficiency η, and the thickness d of the CGL layer in the following relationship.
Γ = β · η · F / (d · hυ) (7)
Here, β and hν are the light absorption efficiency in the CGL layer and the energy per photon of the laser beam, respectively.

In addition, the carrier recombination term of the second item on the right side of the above formulas (4) and (5) is used to explain that the amount of generated carriers decreases experimentally when positive and negative carriers coexist in the same vicinity. It has been introduced.
Among the above physical quantities, the light absorption coefficient β and the recombination coefficient R are calculated by performing experimental fitting from the surface potential at the time of black solid exposure.
Further, the quantum efficiency η is a value obtained from the equation (2) and is as described above.
Before the exposure, it is assumed that the photoreceptor is uniformly charged, and the charge amount on the surface of the photoreceptor is calculated. Thereafter, by calculating the above formula on the assumption that carriers are generated in the exposure region, the charge density distribution on the photoreceptor after exposure is calculated.

As a calculation method, a difference method regarding n _p , n _n , and φ was adopted. Here, φ represents a potential. The time forward difference (the following formulas (8) and (9)) is used for the continuous expression of charge carriers, that is, the time differential terms of the above formulas (4) and (5), and Uses the upstream differential method (the following equation (10)). Except for the time derivative term, a complete implicit method that evaluates implicitly is used.

  Here, δt, n, and n + 1 are a time step, a step number indicating the calculated current step, and a step number indicating the next future step, respectively.

The nonlinear algebraic equation thus obtained is calculated using a double iteration method. First, the entire three formulas (formulas (8) to (10)) are calculated using the successive approximation method. In this iteration, the equations (8) and (9) are variables other than those appearing in the time derivative term, for example, in equation (8), values other than n _p use values of known iteration results. First of all, this formula is calculated based on Successive Over Relaxation. The Poisson equation (formula (10)) performs the same calculation for φ. Iterates until the residual by the successive approximation method for the whole expression reaches a specified value. Here, designated values are designated for φ, n _n , and n _p, respectively, and are 5 × 10 ⁻³ , 1 × 10 ⁻² , and 1 × 10 ⁻² .

(II) Calculation of development electric field strength distribution The development electric field strength distribution is calculated from the latent image charge distribution on the photoreceptor obtained in (I) and the development conditions. It is assumed that the developing sleeve and the photoconductor are approximated by parallel plates, and the developer (carrier and toner) is uniformly filled between them. That is, the developer is treated as a uniform dielectric layer having an average dielectric constant. Here, the average dielectric constant is the product of the average dielectric constant and the vacuum dielectric constant, and the average dielectric constant ε ′ is ε ′ = a · ε _l + (1−a) (11)
It is obtained with. Here, ε _l is the relative dielectric constant of the carrier, and a is the proportion of the volume occupied by the carrier in the development nip.
The potential distribution can be obtained by solving the Poisson equation with the sleeve surface as the developing bias potential, the photosensitive member lower surface as the constant OV boundary condition, and the left and right boundaries as the periodic boundary conditions. At the surface of the photoreceptor E = −gradφ (12)
Is obtained, the development electric field strength distribution on the surface of the photoreceptor is obtained.

(III) Calculation of toner adhesion amount The toner adhesion amount is calculated from the electric field strength distribution obtained in (II) and the development conditions.

Here, k is a toner adhesion coefficient, v _r / v _p is a sleeve linear velocity ratio, 1 is a developing nip width, R is a carrier radius, ε ₀ is a dielectric constant, and q is a toner charge amount.

Beam spot diameter (main scanning x sub-scanning) 50 x 65 (μm)
Resolution 1200 dpi
Quantum efficiency 2.83 * 10 ^-5 * e ^0.5933 ("*" is a multiplication symbol)
Initial charging potential -650v
OPC film thickness 28μm
Power variable Image pattern 2 * 2 dots Charge generation area ratio x
Exposure energy y

FIG. 3 shows the relationship between the charge generation region area ratio and the toner adhesion amount obtained by the simulation.
As the charge generation region area ratio increases, the toner adhesion amount increases. Further, by increasing the exposure energy (a measurement line having a small gradient is a case where the exposure energy is small, and corresponds to a measurement line having a large gradient as the exposure energy increases), the toner adhesion amount increases.
Here, the relationship between the charge generation region area ratio x and the toner adhesion amount M is:
M = ax ² + bx + c (14)
Can be approximated.
Here, the coefficients a, b, and c can be approximated by a linear expression of Power. Therefore, the relationship between the charge generation area area ratio x and the toner adhesion amount M is M = a (p) x ² + b (p) x + c (15)
Can be expressed as
Here, since the toner adhesion amount per unit area is 0.45 mg / cm ² or more for the reproducibility of the black solid image and the image density required for the black solid image, the toner adhesion required amount is (16). In this equation, “*” is a multiplication symbol (the same applies hereinafter).

Next, FIG. 4 shows the relationship between the charge generation region area ratio (DM ratio (%)) satisfying the toner adhesion amount M ≧ 0.45 mg / cm ² and the quantum efficiency * Energy.
It can be seen that the quantum efficiency * Energy and the area ratio of the charge generation region have a certain relationship regardless of the OPC type.
This is expressed by the following equation (17).

It can be seen that Here, two types of OPC were calculated with different resolutions, and a = 0.01, b = 60, and c = 0.002 were obtained.
The charge generation region area ratio x can be measured by using an optical microscope, a laser microscope, or the like.

Next, the ink jet method which is a manufacturing method used in the present invention will be described.
The ink jet method is a method used in an ink jet printer. Recently, an ink jet recording method using this ink jet method has begun to spread widely. This ink jet recording method is a printing method in which printing is performed by causing small droplets of an ink composition to fly and adhere to a recording medium such as paper. An ink jet recording apparatus using this method has a feature that a high-resolution and high-quality image can be printed at a high speed with a relatively inexpensive apparatus. For this reason, ink jet recording apparatuses have come to be used as digital printing machines, plotters, CAD output devices, and the like. In particular, since the ink jet recording apparatus can print a digitally processed sentence or image, it can store a document or an image original semipermanently and can print the contents. The ink jet recording apparatus can realize high analysis and high pixel printing by discharging ink composition droplets from a recording head under appropriate system processing.

  That is, the ink jet method can attach small droplets to a specific place so that photographic image quality can be output, and there is almost no loss as a liquid. Therefore, it is possible to form a high-quality coating film at low cost as a liquid. In addition, as used in digital equipment, the ON / OFF of droplet flight can be digitally controlled, so that liquid can be output and applied only where needed, and unnecessary parts can be easily removed. It can be uncoated. In addition, equipment such as nozzle heads used in the ink jet method can be easily obtained at low cost and with high quality and high stability due to the widespread use of ink jet printers. Does not require large-scale equipment. Further, as can be seen from the recent trend of inkjet printers, productivity can be dealt with by increasing the number of nozzles, and productivity can be easily improved.

  In addition, as an ink jet system used in the manufacturing method by the ink jet method of the present invention, a foaming jet type using an electrothermal transducer as an energy generating element, a piezo jet type using a piezoelectric element, or the like can be used. However, the piezo-type ink jet method only applies pressure to the ink and basically has no degradation effect on the ink, whereas the bubble-type ink-jet method instantaneously moves the micro heater embedded in the nozzle. In any case, since the ink is ejected by heating to 200 to 300 ° C. and generating bubbles, the ink has a deterioration action such as kogation. Due to the influence of this kogation, the background stain of the image may occur, and the piezo jet type is preferably used in consideration of the influence of heat or the like on the ink, that is, the coating liquid. Also, by changing the ink jet nozzle and pressurizing / heating time, the amount of ink per ink drop and the amount of ink applied per colored part can be set arbitrarily, so that charge generation is important in the present invention. It becomes possible to control the dot shape (diameter) of the layer.

(About electrophotographic photoreceptors)
Hereinafter, the electrophotographic photosensitive member used in the present invention will be described with reference to the drawings.
FIG. 6 shows a structure in which a charge generation layer (435) containing a charge generation material as a main component and a charge transport layer (437) containing a charge transport material are laminated on a conductive support (431). ing.
FIG. 7 shows a configuration in which an intermediate layer (433) is provided between the conductive support (431) and the charge generation layer (435) in FIG. (Although the charge generation layer shown in these drawings is drawn as a uniform layer, it is needless to say that the charge generation layer is actually formed by being dispersed in the form of dots as minute regions.)

Examples of the conductive support (431) include those having a volume resistance of 10 ¹⁰ Ω · cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, oxidation A method of extruding and drawing metal oxides such as indium by film deposition or sputtering, or coating a film or cylindrical plastic or paper, or a plate of aluminum, aluminum alloy, nickel, stainless steel, etc. After forming the tube, it is possible to use a tube subjected to surface treatment such as cutting, super-finishing, or polishing. Further, an endless nickel belt and an endless stainless steel belt disclosed in JP-A-52-36016 can also be used as the conductive support (431).
In addition, a material obtained by dispersing and coating conductive powder in an appropriate binder resin on the support can also be used as the conductive support (431) of the present invention. Examples of the conductive powder include carbon black, acetylene black, metal powder such as aluminum, nickel, iron, nichrome, copper, zinc, and silver, or metal oxide powder such as conductive tin oxide and ITO. It is done. The binder resin used at the same time is polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyvinylidene chloride, polyarylate resin, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinylcarbazole, acrylic resin, silicone resin, epoxy resin, Examples thereof include thermoplastic, thermosetting resins, and photocurable resins such as melamine resin, urethane resin, phenol resin, and alkyd resin. Such a conductive layer can be provided by dispersing and coating these conductive powder and binder resin in a suitable solvent such as tetrahydrofuran, dichloromethane, methyl ethyl ketone, and toluene.
Furthermore, it is electrically conductive by a heat-shrinkable tube containing the conductive powder in a material such as polyvinyl chloride, polypropylene, polyester, polystyrene, polyvinylidene chloride, polyethylene, chlorinated rubber, and Teflon (registered trademark) on a suitable cylindrical substrate. Those provided with a conductive layer can also be used favorably as the conductive support (431) of the present invention.

Next, the charge generation layer (435) is a layer mainly composed of a charge generation material, in which the charge generation material, the binder resin, or the like is dispersed or dissolved in an appropriate solvent, and this is formed on the conductive support or in the middle. It can be formed by coating and drying on the layer.
As the charge generation layer (435), a known charge generation material can be used, and representative examples thereof include phthalocyanine pigments such as titanyl phthalocyanine, vanadyl phthalocyanine, copper phthalocyanine, hydroxygallium phthalocyanine, and metal-free phthalocyanine, monoazo pigments, Known azo pigments such as disazo pigments, asymmetric disazo pigments, trisazo pigments, perylene pigments, perinone pigments, indigo pigments, pyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, quinone condensed polycyclic compounds, squalium pigments, etc. Materials, which are usefully used. These charge generating materials can be used alone or in combination of two or more.
In the charge generation layer (435), a charge generation material is dispersed in a suitable solvent together with a binder resin as necessary using a ball mill, attritor, sand mill, ultrasonic wave, etc., and this is applied onto a conductive support. And formed by drying. The particle size of the charge generation material is preferably 0.2 μm or less. In the case of 0.2 μm or more, since dots are not formed cleanly and uniformly, the resolution of isolated dots is lowered. In particular, the influence becomes significant when a high resolution of 1200 dpi or more and a writing system of a small diameter beam are used.
As the binder resin used for the charge generation layer (435) as necessary, polyamide, polyurethane, epoxy resin, polyketone, polycarbonate, silicone resin, acrylic resin, polyvinyl butyral, polyvinyl formal, polyvinyl ketone, polystyrene, polysulfone, poly -N-vinyl carbazole, polyacrylamide, polyvinyl benzal, polyester, phenoxy resin, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyphenylene oxide, polyamide, polyvinyl pyridine, cellulosic resin, casein, polyvinyl alcohol, polyvinyl pyrrolidone Etc. The amount of the binder resin is suitably 0 to 500 parts by weight, preferably 10 to 300 parts by weight with respect to 100 parts by weight of the charge generating material. The binder resin may be added before or after dispersion.
Examples of the solvent used here include isopropanol, acetone, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethyl cellosolve, ethyl acetate, methyl acetate, dichloromethane, dichloroethane, monochlorobenzene, cyclohexane, toluene, xylene, and ligroin. In particular, ketone solvents, ester solvents, and ether solvents are preferably used. These may be used alone or in combination of two or more.
The charge generation layer (435) is mainly composed of a charge generation material, a solvent, and a binder resin, and includes any additive such as a sensitizer, a dispersant, a surfactant, and silicone oil. May be.
As a coating method of the coating solution, methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating and the like can be used, but the ink jet method is preferable as shown in the present invention.
The thickness of the charge generation layer (435) is suitably about 0.01-5 μm, preferably 0.1-2 μm.

The charge transport layer (437) can be formed by dissolving or dispersing a charge transport material and a binder resin in a suitable solvent, and applying and drying the solution on the charge generation layer. Moreover, it is possible and useful to add one or two or more kinds of plasticizers, leveling agents, antioxidants, lubricants and the like as necessary.
As the solvent used here, tetrahydrofuran, dioxane, toluene, dichloromethane, monochlorobenzene, dichloroethane, cyclohexanone, methyl ethyl ketone, acetone and the like are used. These may be used alone or in combination of two or more.
As a coating method of the coating solution, methods such as dip coating, spray coating, beat coating, nozzle coating, spinner coating, ring coating, and the like can be used.
The charge transport material is classified into a hole transport material and an electron transport material. Examples of the electron transporting material include chloroanil, bromoanil, tetracyanoethylene, tetracyanoquinodimethane, 2,4,7-trinitro-9-fluorenone, 2,4,5,7-tetranitro-9-fluorenone, 2,4 , 5,7-tetranitroxanthone, 2,4,8-trinitrothioxanthone, 2,6,8-trinitro-4H-indeno [1,2-b] thiophen-4-one, 1,3,7-tri Examples thereof include electron-accepting substances such as nitrodibenzothiophene-5,5-dioxide and benzoquinone derivatives.
Examples of hole transport materials include poly-N-vinylcarbazole and derivatives thereof, poly-γ-carbazolylethyl glutamate and derivatives thereof, pyrene-formaldehyde condensates and derivatives thereof, polyvinylpyrene, polyvinylphenanthrene, polysilane, oxazole derivatives, Oxadiazole derivatives, imidazole derivatives, monoarylamine derivatives, diarylamine derivatives, triarylamine derivatives, stilbene derivatives, α-phenylstilbene derivatives, benzidine derivatives, diarylmethane derivatives, triarylmethane derivatives, 9-styrylanthracene derivatives, pyrazolines Derivatives, divinylbenzene derivatives, hydrazone derivatives, indene derivatives, butadiene derivatives, pyrene derivatives, bisstilbene derivatives, enamine derivatives, etc. Other known materials may be used. These charge transport materials may be used alone or in combination of two or more.
As the binder resin, polystyrene, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, styrene-maleic anhydride copolymer, polyester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, Polyvinylidene chloride, polyarylate, phenoxy resin, polycarbonate, cellulose acetate resin, ethyl cellulose resin, polyvinyl butyral, polyvinyl formal, polyvinyl toluene, poly-N-vinyl carbazole, acrylic resin, silicone resin, epoxy resin, melamine resin, urethane resin, Examples thereof include thermoplastic or thermosetting resins such as phenol resins and alkyd resins.
Moreover, it is preferable that the film thickness of a charge transport layer shall be 5-40 micrometers or less. The lower limit varies depending on the system to be used (particularly charging potential), but is preferably 5 μm or more.

A protective layer (not shown) may be formed on the charge transport layer (437) for the purpose of improving durability.
As the protective layer, for example, a layer containing a hole transporting hydroxyarylamine having a hydroxy functional group and a polyamide film forming binder capable of forming a hydrogen bond with the hydroxy functional group (Japanese Patent Laid-Open No. 7-253683) ), A hydroxyarylamine compound having a hydroxy functional group in a thermosetting polyamide resin, a curing catalyst, a film cured by heating after coating (US Pat. No. 5,670,291), an alkoxysilyl group A layer cured with a charge transport compound and an alkoxysilane compound (JP-A-3-191358), a cured layer using an organopolysiloxane and colloidal silica, and a conductive metal oxide and an acrylic resin ( JP-A-8-95280), a conductive metal oxide having a silicon functional group Layer cross-linked with acrylate (JP-A-8-160651), layer cross-linked with conductive metal oxide with photocurable acrylic monomer or oligomer (JP-A-8-184980), charge containing epoxy group A layer cured with a transporting compound (Japanese Patent Laid-Open No. 8-278645), a diamond-like carbon containing hydrogen, or a layer of crystalline carbon containing amorphous carbon or fluorine (Japanese Patent Laid-Open No. 9-101625, Kaihei 9-160268, JP-A-10-73945, a layer mainly composed of cyanoethyl pullulan (JP-A-9-90650), a layer obtained by crosslinking a silyl acrylate compound and colloidal silica (JP-A-9-319130). No.), a layer using a polycarbonate graft copolymer (Japanese Patent Laid-Open No. 10-630) 6), a layer obtained by curing colloidal silica particles and a siloxane resin (Japanese Patent Laid-Open No. 10-83094), a layer cured with a charge transport compound containing a hydroxy group and an isocyanate group-containing compound (Japanese Patent Laid-Open No. 10-177268). No. gazette).
The film thickness of the entire protective layer is 1 μm to 10 μm, preferably 2 to 6 μm. If the protective layer thickness is extremely thin, the uniformity of the film may be reduced or sufficient wear resistance may not be obtained.If the thickness is extremely thick, there is an effect of an increase in residual potential. In some cases, the resolution or dot reproducibility may decrease due to an increase in light transmittance.

In the photoreceptor of the present invention, an intermediate layer (433) can be provided between the conductive support (431) and the charge generation layer (435). The intermediate layer (433) generally has a resin as a main component, but these resins are resins having high solvent resistance with respect to general organic solvents in consideration of applying a photosensitive layer thereon with a solvent. It is desirable. Examples of such resins include water-soluble resins such as polyvinyl alcohol, casein, and sodium polyacrylate, alcohol-soluble resins such as copolymer nylon and methoxymethylated nylon, polyurethane, melamine resin, phenol resin, alkyd-melamine resin, and epoxy. Examples thereof include a curable resin that forms a three-dimensional network structure such as a resin. However, when the charge generation layer is dispersed in the form of dots as shown in the present invention, the intermediate layer contains a filler and is porous in order to improve the uniformity of size of the charge generation dots to be formed and to prevent bleeding. It preferably has a quality structure.
Further, fine powder pigments of metal oxides exemplified by titanium oxide, silica, alumina, zirconium oxide, tin oxide, indium oxide and the like may be added to the intermediate layer in order to prevent moire and reduce residual potential. These intermediate layers can be formed using an appropriate solvent and a coating method like the above-mentioned photosensitive layer. Furthermore, a silane coupling agent, a titanium coupling agent, a chromium coupling agent, or the like can be used as the intermediate layer of the present invention. Furthermore, various dispersing agents can be added. In addition, in the intermediate layer of the present invention, Al ₂ O ₃ is provided by anodic oxidation, organic matter such as polyparaxylylene (parylene), SiO ₂ , SnO ₂ , TiO ₂ , ITO, CeO _2, etc. Those provided with an inorganic material by a vacuum thin film forming method can also be used satisfactorily. However, the unevenness of the charge generation layer is likely to cause unevenness in the image, particularly non-uniformity of the halftone density. For this reason, the intermediate layer is porous in the micron order so that the coating solution does not bleed when the substrate adheres. Such an intermediate layer is desirable. The thickness of the intermediate layer is suitably from 0 to 5 μm.
In the photoreceptor of the present invention, another intermediate layer can be provided between the photosensitive layer and the protective layer. In the intermediate layer, a binder resin is generally used as a main component. Examples of these resins include polyamide, alcohol-soluble nylon, water-soluble polyvinyl butyral, polyvinyl butyral, and polyvinyl alcohol. As a method for forming the intermediate layer, a generally used coating method as described above is employed. In addition, about 0.05-2 micrometers is suitable for the thickness of an intermediate | middle layer.

(About toner)
Next, the toner of the present invention will be described. As the toner used in the present invention, any toner can be used as long as it is produced by a polymerization method. Among them,
(I) a toner obtained by suspension polymerization of a polymerizable composition comprising a polymerizable monomer and a colorant in an aqueous medium, or
(Ii) A toner obtained by reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium to form an adhesive base material in a particulate form. More preferably.

  Hereinafter, (i) a toner obtained by suspension polymerization of a polymerizable composition comprising a polymerizable monomer and a colorant in an aqueous medium will be described in detail.

"material"
(Monomer)
As the polymerizable monomer, a radically polymerizable monomer is an essential component, and a crosslinking agent can be used as necessary. Moreover, you may contain at least 1 type of the radically polymerizable monomer which has the following radically polymerizable monomer which has an acidic group, or a basic group.

(1) Radical polymerizable monomer The radical polymerizable monomer is not particularly limited, and a conventionally known radical polymerizable monomer can be used. Moreover, it can also be used combining 1 type (s) or 2 or more types.
Specifically, aromatic vinyl monomers, (meth) acrylic acid ester monomers, vinyl ester monomers, vinyl ether monomers, monoolefin monomers, diolefin monomers, halogenated olefin monomers, and the like can be used. . For example, aromatic vinyl monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, pn -Butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, 2,4- Examples thereof include styrene monomers such as dimethylstyrene and 3,4-dichlorostyrene and derivatives thereof. Examples of (meth) acrylic acid ester monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, Examples include hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like. Examples of vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl benzoate. Examples of vinyl ether monomers include vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl phenyl ether and the like. Examples of the monoolefin monomer include ethylene, propylene, isobutylene, 1-butene, 1-pentene, 4-methyl-1-pentene and the like. Examples of the diolefin monomer include butadiene, isoprene, chloroprene and the like. Examples of the halogenated olefin monomer include vinyl chloride, vinylidene chloride, and vinyl bromide.

(2) Crosslinking agent As the crosslinking agent, a radical polymerizable crosslinking agent may be added to improve the properties of the toner. Examples of the radical polymerizable crosslinking agent include those having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diallyl phthalate.

(3) Radical polymerizable monomer having acidic group or radical polymerizable monomer having basic group Radical polymerizable monomer having acidic group or radical polymerizable monomer having basic group includes, for example, carboxyl group-containing monomer, sulfone Amine-based compounds such as acid group-containing monomers, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts can be used.
Examples of the radical polymerizable monomer having an acidic group include carboxylic acid group-containing monomers such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, maleic acid monobutyl ester, and maleic acid monooctyl ester. Can be mentioned. Examples of the sulfonic acid group-containing monomer include styrene sulfonic acid, allyl sulfosuccinic acid, octyl allyl sulfosuccinate and the like. These may have a structure of an alkali metal salt such as sodium or potassium or an alkaline earth metal salt such as calcium.
Examples of the radically polymerizable monomer having a basic group include amine compounds such as dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and quaternary ammonium salts of the above four compounds, 3- Dimethylaminophenyl acrylate, 2-hydroxy-3-methacryloxypropyltrimethylammonium salt, acrylamide, N-butylacrylamide, N, N-dibutylacrylamide, piperidylacrylamide, methacrylamide, N-butylmethacrylamide, N-octadecylacrylamide, vinyl Pyridine, vinylpyrrolidone, vinyl N-methylpyridinium chloride, vinyl N-ethylpyridinium chloride, N, N-diary Examples thereof include rumethylammonium chloride and N, N-diallylethylammonium chloride.
As the radical polymerizable used in the present invention, the radical polymerizable monomer having an acidic group or the radical polymerizable monomer having a basic group is preferably used in an amount of 0.1 to 15% by mass based on the whole monomer. The agent is preferably used in the range of 0.1 to 10% by mass with respect to the total radical polymerizable monomer, although it depends on its characteristics.

[Chain transfer agent]
For the purpose of adjusting the molecular weight, it is possible to use a commonly used chain transfer agent. The chain transfer agent is not particularly limited, and mercaptans such as octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, and styrene dimer are used.

(Polymerization initiator)
The radical polymerization initiator used in the present invention is preferably oil-soluble in the suspension polymerization method.
Specific examples of the oil-soluble polymerization initiator include benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, cumene hydroperoxide, acetyl peroxide, and propionyl peroxide. Peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-valeronitrile), 2,2'-azobis-2-methylvaleronitrile, 2,2'-azobis Examples thereof include azobis-based polymerization initiators such as -2,4-dimethylvaleronitrile.
The polymerization temperature may be any temperature as long as it is equal to or higher than the lowest radical generation temperature of the polymerization initiator, but is preferably in a temperature range in which the half-life of the polymerization initiator is about 2 to 10 hours. Although the temperature range varies depending on the polymerization initiator, for example, a range of 50 ° C. to 90 ° C. is preferably used.
The addition amount of the polymerization initiator is determined by the molecular weight of the resin to be the final toner required, but is generally 0.1 to 10% by mass, preferably 0.2%, based on the radical polymerizable monomer. ˜5 mass%.

Further, as the dispersion stabilizer, those that can be easily removed in the final filtration and washing steps are preferable, and inorganic, hardly water-soluble dispersion stabilizers are particularly preferably used. Specific examples include calcium carbonate, tricalcium phosphate, aluminum oxide, barium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, titanium oxide, silicon oxide, and iron hydroxide. Particularly preferred dispersion stabilizers are Tricalcium phosphate. In addition to this poorly water-soluble inorganic dispersion stabilizer, a small amount of a surfactant may be used as a dispersion aid. In this case, any of nonionic, anionic, cationic and amphoteric systems can be used, but anionic surfactants are more preferred.
The dispersion stabilizer is used by being dispersed in an aqueous medium. In this case, it is preferable to use about 1 to 10% by mass with respect to the oil phase component to be dispersed. When the amount is less than this range, the dispersion stability is lowered and aggregation of particles occurs. In addition, when the amount is larger than this range, dispersion is promoted, so that a small particle size component is excessively generated.
Furthermore, it is preferable to add about 0.05 to 1% by mass of the surfactant with respect to the inorganic dispersion stabilizer. When the amount is less than this range, the effect of improving dispersion stability cannot be exhibited. On the other hand, when used beyond this range, emulsification of the radical polymerizable monomer occurs, so-called latex particles are generated in the system, and there is a problem that the particle size distribution is widened, and the surfactant is difficult to remove. There is a problem that causes moisture adsorption.

In addition, as a polymerization initiator used in the production method in which resin particles are prepared by so-called emulsion polymerization and then formed by salting out and fusing the resin particles, any polymerization initiator can be used as long as it is water-soluble. is there. For example, persulfate (potassium persulfate, ammonium persulfate, etc.), azo compounds (4,4′-azobis-4-cyanovaleric acid and salts thereof, 2,2′-azobis (2-amidinopropane) salt, etc.), A peroxide compound etc. are mentioned. Furthermore, the radical polymerization initiator can be combined with a reducing agent as required to form a redox initiator. By using a redox initiator, the polymerization activity is increased, the polymerization temperature is lowered, and the polymerization time can be further shortened.
The polymerization temperature may be any temperature as long as it is equal to or higher than the lowest radical generation temperature of the polymerization initiator. For example, a range of 50 ° C. to 90 ° C. is used. However, it is possible to perform polymerization at room temperature or higher by using a polymerization initiator that starts at room temperature, for example, a combination of hydrogen peroxide and a reducing agent (ascorbic acid or the like).

[Colorant]
Examples of the colorant include inorganic pigments and organic pigments. A conventionally well-known thing can be used as an inorganic pigment. Specific inorganic pigments are exemplified below.
Examples of the black pigment include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black, and magnetic powder such as magnetite and ferrite. These inorganic pigments can be used alone or in combination as required. Moreover, the addition amount of a pigment is 2-20 mass% with respect to a polymer, Preferably 3-15 mass% is selected. When used as a magnetic toner, the above-mentioned magnetite can be added. In this case, it is preferable to add 20 to 60% by mass in the toner from the viewpoint of imparting predetermined magnetic properties.
Conventionally known organic pigments can also be used. Specific organic pigments are exemplified below.
Examples of pigments for magenta or red include C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222. Examples of the orange or yellow pigment include C.I. I. Pigment orange 31, C.I. I. Pigment orange 43, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. And CI Pigment Yellow 138. Examples of pigments for green or cyan include C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. Pigment blue 60, C.I. I. And CI Pigment Green 7.
These organic pigments can be used alone or in combination as required. Moreover, the addition amount of a pigment is 2-20 mass% with respect to a polymer, Preferably 3-15 mass% is selected. The colorant can also be used after surface modification. As the surface modifier, conventionally known ones can be used, and specifically, silane coupling agents, titanium coupling agents, aluminum coupling agents and the like can be preferably used.

To the toner obtained in the present invention, so-called external additives can be added and used for the purpose of improving fluidity and improving cleaning properties. These external additives are not particularly limited, and various inorganic fine particles, organic fine particles and lubricants can be used.
A conventionally well-known thing can be used as an inorganic fine particle. Specifically, silica, titanium, alumina fine particles and the like can be preferably used. These inorganic fine particles are preferably hydrophobic. Specifically, as silica fine particles, for example, commercially available products R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., HVK-2150, H manufactured by Hoechst -200, commercially available products TS-720, TS-530, TS-610, H-5, MS-5 and the like manufactured by Cabot Corporation. Examples of the titanium fine particles include commercial products T-805 and T-604 manufactured by Nippon Aerosil Co., Ltd., commercial products MT-100S, MT-100B, MT-500BS, MT-600, MT-600SS, and JA- 1. Commercial products TA-300SI, TA-500, TAF-130, TAF-510, TAF-510T manufactured by Fuji Titanium Co., Ltd. Commercial products IT-S, IT-OA, IT-OB, IT- manufactured by Idemitsu Kosan Co., Ltd. OC etc. are mentioned. Examples of the alumina fine particles include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd. and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.
As the organic fine particles, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can be used. As this, a homopolymer such as styrene or methyl methacrylate or a copolymer thereof can be used.
Examples of lubricants include, for example, zinc stearate, aluminum, copper, magnesium, calcium, etc., zinc oleate, manganese, iron, copper, magnesium, etc., zinc palmitate, copper, magnesium, calcium, etc. Higher fatty acid metal salts such as zinc of linoleic acid, salts of calcium and the like, and zinc of ricinoleic acid, salts of calcium and the like.
The amount of these external additives added is preferably about 0.1 to 5% by mass with respect to the toner.

<Manufacturing process of suspension polymerization toner>
The process for producing the polymerized toner of the present invention comprises a step of dispersing and containing a polymerization initiator and components necessary for constituting the toner such as a pigment and a release agent in a radical polymerizable monomer, and dispersing the dispersion in water to form a toner. It consists of a step of dispersing into droplets having a particle size of a certain degree, a polymerization step, a step of removing the dispersion stabilizer and washing, filtering, and a drying step.
Dispersers used when dispersing the components constituting the toner such as pigments are not particularly limited, but preferably ultrasonic dispersers, mechanical homogenizers, pressure dispersers such as Manton Gorin and pressure homogenizers, sand grinders, etc. Examples thereof include a medium type disperser. In addition, since it is necessary to add a polymerization initiator, it is preferable to cool and disperse | distribute so that it may not receive to the influence of the heat at the time of dispersion | distribution.
Further, it is necessary to adjust the droplets formed when the dispersion liquid is dispersed in the aqueous medium so as to have a desired toner particle size. Examples of the dispersing device used in this case include a TK homomixer, a TK homojetter, a rotating double cylinder, and an ultrasonic disperser. When dispersion is performed, it is possible to form droplets having a desired dispersion diameter by observing the particle diameter of the dispersion liquid droplets with a microscope or the like and stopping the dispersion at a predetermined time. The toner of the present invention preferably has a volume average particle diameter of 3 to 9 μm. The volume average particle diameter of these toners can be measured using a Coulter Counter TA-II, Coulter Multisizer, SLAD1100 (Laser Diffraction Particle Size Measuring Device manufactured by Shimadzu Corporation) and the like. For Coulter Counter TA-II and Coulter Multisizer, those measured using a particle size distribution in the range of 2.0 to 40 μm using an aperture having an aperture diameter of 100 μm are shown.
In the polymerization step, polymerization is performed at a temperature higher than the decomposition temperature of the polymerization initiator. In general, the polymerization is preferably performed at about 50 to 90 ° C. After completion of the polymerization, it is preferable to add an acid in order to cool and remove the dispersion stabilizer. As the acid, hydrochloric acid, sulfuric acid and the like can be used. Thereafter, the toner can be obtained by filtering, washing with water and drying.

<< Salting out, fusing type toner manufacturing process >>
The salting out and fusing type toner manufacturing process of the present invention includes emulsion polymerization to prepare resin particles or resin particles containing a colorant, and resin particles in an aqueous medium using the resin particle dispersion. The step of fusing the colorant particles or the resin particles containing the colorant, the step of filtering the obtained particles from an aqueous medium to remove the surfactant, the step of drying the obtained particles, and further drying An external additive addition step of adding an external additive or the like to the obtained particles. Here, the resin particles may be colored particles. Further, non-colored particles can also be used as the resin particles. In this case, after adding a colorant particle dispersion or the like to the resin particle dispersion, it can be further colored by fusing in an aqueous medium. it can.
In particular, as a method of fusing, a method of salting out using resin particles produced by the polymerization step and fusing is preferable. When non-colored resin particles are used, the resin particles and the colorant particles can be salted out in an aqueous medium and fused. In addition to the colorant and the release agent, a charge control agent that is a component of the toner can be added as particles in this step.
In addition, an aqueous medium here consists of water as a main component, and shows what the total amount of water is 50 mass% or more. Examples of those other than water include organic solvents that dissolve in water, and examples include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Alcohol organic solvents such as methanol, ethanol, isopropanol, and butanol, which are organic solvents that do not dissolve the resin, are particularly preferred.

The dispersing machine for dispersing the magnetic material is not particularly limited, but preferably an ultrasonic dispersing machine, a mechanical homogenizer, a pressure dispersing machine such as a manton gourin or a pressure homogenizer, a media type dispersion such as a sand grinder, a Getzman mill or a diamond fine mill. Machine. As the surfactant used here, the aforementioned surfactants can be used.
In the salting out / fusion step, a salting-out agent composed of an alkali metal salt, an alkaline earth metal salt, or the like is added as a flocculant having a critical coagulation concentration or more in water in which resin particles and magnetic particles are present. Next, it is a step of fusing at the same time as salting-out proceeds by heating the resin particles to the glass transition point or higher. In this step, an organic solvent that is infinitely soluble in water may be added, and a technique of effectively performing fusion by substantially reducing the glass transition temperature of the resin particles may be used. Here, the alkali metal salt and alkaline earth metal salt which are salting-out agents include lithium, potassium, sodium and the like as the alkali metal, and examples of the alkaline earth metal include magnesium, calcium, strontium and barium. Preferably, potassium, sodium, magnesium, calcium, and barium are used. Examples of the salt include chlorine salts, bromine salts, carbonates, sulfates and the like.

When the fusion of the present invention is carried out by salting out / fusion, it is preferable to make the time allowed to stand after adding the salting-out agent as short as possible. The reason for this is not clear, but there are problems that the aggregation state of the particles fluctuates depending on the standing time after salting out, the particle size distribution becomes unstable, and the surface property of the fused toner fluctuates. appear. The temperature for adding the salting-out agent needs to be at least the glass transition temperature of the resin particles. The reason for this is that if the temperature at which the salting-out agent is added is equal to or higher than the glass transition temperature of the resin particles, the salting-out / fusion of the resin particles proceeds rapidly, but the particle size cannot be controlled. There is a problem that particles having a particle size are generated. Although the range of this addition temperature should just be below the glass transition temperature of resin, generally it is 5-55 degreeC, Preferably it is 10-45 degreeC.
Moreover, in this invention, it is preferable to use the method of adding salting-out agent below the glass transition temperature of a resin particle, heating up as soon as possible after that, and heating it more than the glass transition temperature of a resin particle. The time until this temperature rise is preferably less than 1 hour. Further, although it is necessary to quickly raise the temperature, the rate of temperature rise is preferably 0.25 ° C./min or more. The upper limit is not particularly clear, but if the temperature is increased instantaneously, salting out proceeds rapidly, so there is a problem that particle size control is difficult, and 5 ° C./min or less is preferable.

  Here, the particle diameter of the toner obtained by fusing according to the present invention is preferably 3 to 9 μm in volume average particle diameter. The volume average particle diameter of these toners can be measured using a Coulter Counter TA-II, Coulter Multisizer, SLAD1100 (Laser Diffraction Particle Size Measuring Device manufactured by Shimadzu Corporation) and the like. In Coulter Counter TA-II and Coulter Multisizer, those measured using a particle size distribution in the range of 2.0 to 40 μm using an aperture having an aperture diameter of 100 μm are shown.

The toner obtained by fusing has a shape factor represented by the following formula within a range of 1.3 to 2.2 and a toner having a shape factor within a range of 1.5 to 2.0. The number of particles is preferably 80% by number or more. The shape factor of the toner is obtained by the following formula.
Shape factor = ((maximum diameter / 2) ² × π) / projection area

  This shape factor is obtained by taking a photograph in which the toner particles are magnified 500 times with a scanning electron microscope, and then analyzing the photographic image using “SCANNING IMAGE ANALYSER” (manufactured by JEOL Ltd.) based on this photograph. . At this time, the shape factor of the present invention is measured by the above formula using 500 toner particles. When the arithmetic average value of the shape factor is less than 1.3, the shape becomes spherical, so that the adhesion to a so-called photoconductor is increased, and defective cleaning tends to occur. Furthermore, since the toner is spherical, the toner is not easily transported to the development area, and a problem of image unevenness is likely to occur. On the other hand, when the shape factor exceeds 2.1, the irregularity becomes high, and when the mechanical stress is applied, the toner is crushed and the fine powder is easily generated. In component development, the developer carrying member and the developer layer regulating member are likely to be contaminated, and image defects such as fogging due to a decrease in toner chargeability are likely to occur. Furthermore, by making the toner particles having a shape factor in the range of 1.5 to 2.0 80% by number or more, the shape distribution can be made uniform, so that more spherical toner and more irregular shape can be obtained. Since the amount of toner present can be reduced, the aforementioned problems can be suppressed over a long period of time.

[Tonerization process]
In the toner forming step, the toner particles obtained above may be used as they are, but the above-mentioned external additives may be added for the purpose of improving fluidity, chargeability, and cleaning properties, for example. As a method for adding the external additive, a known mixing device such as a Turbuler mixer, a Henschel mixer, a Nauter mixer, or a V-type mixer can be used.
The toner may use a component such as a release agent or a charge control agent. As the mold release agent, low molecular weight polypropylene, low molecular weight polyethylene, carnawa wax, amide wax, natural wax and the like can be used. Similarly, various known charge control agents can be used. Specific examples include nigrosine dyes, naphthenic acid or higher fatty acid metal salts, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, salicylic acid metal salts or metal complexes thereof. These release agent and charge control agent particles preferably have a number average primary particle size of about 10 to 500 nm in a dispersed state.

Next, the toner of (ii), that is, an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in an aqueous medium to obtain an adhesive base material, which is obtained in the form of particles. The toner (hereinafter sometimes abbreviated as “(ii) toner”) will be described in detail.
The toner of (ii) is obtained in the form of particles while reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound to produce an adhesive base material in an aqueous medium, such as a pigment And, if necessary, other components such as a release agent, resin fine particles, non-reactive polyester resin, and charge control agent.

-Adhesive substrate-
The adhesive substrate is a polymer obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. It may contain at least other binders appropriately selected from known binder resins as necessary.

The weight average molecular weight of the adhesive substrate is not particularly limited and may be appropriately selected depending on the purpose. For example, 1,000 or more is preferable, and 2,000 to 10,000,000 is more preferable. 3,000 to 1,000,000 is particularly preferred.
When the weight average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.
There is no restriction | limiting in particular as glass transition temperature (Tg) of the said adhesive base material, According to the objective, it can select suitably, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable.
When the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.

There is no restriction | limiting in particular as a specific example of the said adhesive base material, According to the objective, it can select suitably, A polyester-type resin etc. are mentioned especially suitably.
There is no restriction | limiting in particular as said polyester-type resin, According to the objective, it can select suitably, For example, a urea modified polyester resin etc. are mentioned especially suitably.
The urea-modified polyester-based resin includes an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. In this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When the urea bond is less than 10, the hot offset resistance may be deteriorated.

Preferred specific examples of the urea-modified polyester resin include the following (1) to (10), that is,
(1) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate and uread with isophorone diamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid Mixtures with polycondensates,
(2) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and isophthalic acid with isophorone diisocyanate and uread with isophorone diamine, bisphenol A ethylene oxide 2-mole adduct and terephthalic acid Mixtures with polycondensates,
(3) A bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and a polyester prepolymer obtained by reacting a polycondensate of terephthalic acid with isophorone diisocyanate and urethanized with isophorone diamine, and bisphenol A ethylene A mixture of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and polycondensate of terephthalic acid,
(4) Bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct, and a polyester prepolymer obtained by reacting a polycondensate of terephthalic acid with isophorone diisocyanate and uread with isophorone diamine, and bisphenol A A mixture of propylene oxide 2 mol adduct and polycondensate of terephthalic acid,
(5) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, bisphenol A ethylene oxide 2-mole adduct, and terephthalate Mixtures with polycondensates of acids,
(6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A A mixture of propylene oxide 2 mol adduct and polycondensate of terephthalic acid,
(7) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate with urea and ethylenediamine 2 mol adduct and terephthalic acid Mixtures with condensates,
(8) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with diphenylmethane diisocyanate, and urethanized with hexamethylenediamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture with a polycondensate of
(9) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate was uread with hexamethylenediamine. Bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid,
(10) A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with toluene diisocyanate and uread with hexamethylenediamine, bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture with a polycondensate of
Etc. are preferable.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the B1-B5 blocked amino group (B6) include, for example, ketimines obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), or those obtained by blocking these (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
When the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be lowered. When the mixing equivalent ratio exceeds 3/1, the molecular weight of the urea-modified polyester resin becomes low. The hot offset resistance may be deteriorated.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. It can be appropriately selected from known resins and the like, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.
The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond-forming group in the urea bond-forming group-containing polyester resin (RMPE) is the isocyanate group, the polyester resin (RMPE) is particularly preferably exemplified by the isocyanate group-containing polyester prepolymer (A). It is done.

The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And those obtained by reacting the active hydrogen group-containing polyester resin with polyisocyanate (PIC).
There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol And a mixture with (TO). These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.

The trihydric or higher polyol (TO) is preferably a trihydric or higher polyhydric alcohol, for example, a trihydric or higher polyhydric aliphatic alcohol, a trihydric or higher polyphenol, or a trihydric or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the alkylene oxide adduct of the trihydric or higher polyphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trihydric or higher polyphenol.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tri- or higher valent polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, an isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TO) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.
As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

  The polyisocyanate (PIC) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic diisocyanates, araliphatic diisocyanates, and isocyanurates. And those blocked with phenol derivatives, oximes, caprolactams, and the like.

Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate and diphenyl ether-4,4′-diisocyanate. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, and the like.
These can be used alone or in combination of two or more.

As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing component are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and preferably 4/1 to 1.2 / 1. More preferred is 3/1 to 1.5 / 1.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

As an average number of the isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A), 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

--- Aqueous medium--
There is no restriction | limiting in particular as said aqueous medium, It can select suitably from well-known things, For example, water, a solvent miscible with this water, a mixture thereof, etc. are mentioned.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the cell solves include methyl cell solve. Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, cleaning improvers, fluidity imparting agents, mold release agents, colorants, non-reactive polyester resins, charge control Agents, magnetic materials and the like. These can be externally added to the toner.

  The cleaning improver is added to the toner in order to remove the toner after transfer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, polymethyl, etc. Examples include polymer fine particles produced by soap-free emulsion polymerization such as methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.

  Suitable examples of the fluidity-imparting agent include those similar to the fine particles described above. The fine particles are wet-added externally to the toner, and it is preferable to add the fluidity improver dry-type for the purpose of reinforcing the external addition effect of the fine particles.

The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used individually by 1 type and may use 2 or more types together.

The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 20% by mass, and more preferably 3 to 15% by mass.
When the content is less than 1% by mass, the coloring power may be insufficient, and when it exceeds 15% by mass, the fixability may be deteriorated.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-100 degreeC is especially preferable.
When the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and when it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.

There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable.
When the content exceeds 40% by mass, the fluidity of the toner may be lowered, and the durability of the developer may be lowered.

  The resin fine particles (as OMS) internally added to the toner are generally used for the purpose of controlling the toner shape (average circularity, particle size distribution, etc.). When the toner binder is generated and the toner particle shape is formed, the resin fine particles adhere to or bond to the surface of the particle shape.

The resin fine particles are preferably formed of a resin capable of forming an aqueous dispersion in an aqueous medium, and may be formed of a resin appropriately selected from known materials according to the purpose. May be a thermoplastic resin or a thermosetting resin.
Specific examples of the resin include vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin, etc. Is mentioned.
These may be used individually by 1 type and may use 2 or more types together. Among these, a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, and a mixture thereof are preferable because an aqueous dispersion of fine spherical resin fine particles can be easily prepared. The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer. For example, styrene- (meth) acrylic acid ester resin, styrene-butadiene copolymer, (meth) acrylic acid-acrylic acid ester. Examples thereof include a polymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, and a styrene- (meth) acrylic acid copolymer.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said resin fine particle, According to the objective, it can select suitably, For example, 40-100 degreeC is preferable and 60-80 degreeC is more preferable.
When the glass transition temperature (Tg) is less than 40 ° C., the storage stability of the toner deteriorates, and blocking may occur during storage of the toner and in the developing machine. Resin fine particles may interfere with adhesion to fixing paper, and the minimum fixing temperature may increase.

There is no restriction | limiting in particular as a weight average molecular weight (Mw) of the said resin fine particle, According to the objective, it can select suitably, For example, 9,000-500,000 are preferable, and 20,000-200,000 are more. preferable.
When the weight average molecular weight (Mw) is less than 9,000, the storage stability of the toner is deteriorated, and blocking may occur during storage of the toner and in the developing machine, exceeding 200,000. In addition, the resin fine particles may hinder the adhesion to the fixing paper, and the minimum fixing temperature may increase.

There is no restriction | limiting in particular as an average particle diameter of the said resin fine particle, According to the objective, it can select suitably, For example, 5-500 nm is preferable and 30-300 nm is more preferable.
When the average particle size is less than 5 nm, particle size controllability may be lowered, and when it exceeds 500 nm, the particle size distribution may be broad.

There is no restriction | limiting in particular as content in the said toner of the said resin fine particle, Although it can select suitably according to the objective, For example, 0.5-5.0 mass% is preferable, 1.0-3.0 The mass% is more preferable.
Note that the content of the resin fine particles in the toner can be measured by various methods, and substances or functional groups caused only by the resin fine particles are analyzed using, for example, a pyrolysis gas chromatograph mass spectrometer. By doing so, it can be calculated from the peak area.

The non-reactive polyester resin can be contained in the toner for the purpose of improving low-temperature fixability, glossiness and the like.
The non-reactive polyester resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, the same non-reactive polyester resin as the urea bond-forming group-containing polyester resin, that is, polyol (PO) And a polycondensate of polycarboxylic acid (PC). The non-reactive polyester resin is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. The non-reactive polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure that is compatible with each other. From the viewpoint of heat resistance and hot offset resistance.

There is no restriction | limiting in particular as a weight average molecular weight of the said non-reactive polyester resin, According to the objective, it can select suitably, For example, it is 1,000-30, as measured by GPC (gel permeation chromatography). 000 is preferable, and 1,500 to 15,000 is more preferable.
When the weight average molecular weight is less than 1000, the offset property may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.

  As an acid value of the said non-reactive polyester resin, 1-50 are preferable and 5-30 are more preferable. Generally, it becomes easy to be negatively charged by giving the toner an acid value.

When the non-reactive polyester resin is contained in the toner, the mixed mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the non-reactive polyester resin (PE) is 5 / 95-80 / 20 is preferable, 5 / 95-30 / 70 is more preferable, and 5 / 95-25 / 75 is still more preferable.
When the mixing mass ratio of the non-reactive polyester resin (PE) exceeds 95, the hot offset resistance may deteriorate, and when it is less than 20, the low-temperature fixability may deteriorate.

The charge control agent is not particularly limited and may be appropriately selected from known materials according to the purpose. However, since a color tone may change when a colored material is used, a material that is colorless to nearly white is used. Preferably, for example, nigrosine dye, triphenylmethane dye, chromium-containing metal complex dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt (including fluorine-modified quaternary ammonium salt), alkylamide And a simple substance of phosphorus or a compound thereof, a simple substance of tungsten or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include bontron 03 of a nigrosine dye, bontron P-51 of a quaternary ammonium salt, and bontron S-34 of a metal-containing azo dye. , Oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302 TP-415 (made by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (Above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Japan) Ritto Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, sulfonate group, a carboxyl group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with each component of the toner when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner varies depending on the type of the toner binder, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally defined. For example, with respect to 100 parts by mass of the toner binder, 0.1-10 mass parts is preferable and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the chargeability may be insufficient. When the content is more than 10 parts by mass, the chargeability of the toner becomes excessively large, and the developer fluidity is reduced. The concentration may decrease.

  There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone. The toner production method (ii) includes at least an adhesive base material generation step, and further includes other steps appropriately selected as necessary.

-Adhesive substrate production process-
In the adhesive base material generation step, the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are dispersed in the aqueous medium and reacted to form an adhesive base material while producing a toner. It is a process to obtain.
In the adhesive substrate generation step, for example, preparation of an aqueous medium phase, preparation of an organic solvent phase, emulsification / dispersion, and others (synthesis of a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound, Synthesis of active hydrogen group-containing compounds).

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The organic solvent phase is prepared in the organic solvent by the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, the pigment, the mold release agent, the charge control agent, and the non-reacting agent. It can be carried out by dissolving or dispersing a toner raw material such as a reactive polyester resin.
In the toner raw material, components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound are added when the resin fine particles are dispersed in the aqueous medium in the preparation of the aqueous medium phase. You may add and mix in an aqueous medium, or when adding the said organic solvent phase to the said aqueous medium phase, you may add to the said aqueous medium phase with this organic solvent phase.

The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner raw material, and can be appropriately selected according to the purpose, and has a boiling point of less than 150 ° C. in terms of ease of removal. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner raw materials, and 60-140 mass parts is. More preferably, 80-120 mass parts is still more preferable.

The emulsification / dispersion can be performed by emulsifying / dispersing the previously prepared organic solvent phase in the previously prepared aqueous medium phase. In the emulsification / dispersion, when the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction, the adhesive base material is generated.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). The organic solvent phase is emulsified and dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are extended in the aqueous medium phase. Or (2) the organic solvent phase is emulsified and dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion, and the aqueous medium It may be generated by extending or cross-linking both in the phase, or (3) the active solvent containing the organic solvent phase after being added and mixed in the aqueous medium. The compound was added to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  As the reaction conditions for generating the adhesive substrate by subjecting the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound to an extension reaction or a crosslinking reaction by the emulsification / dispersion, There is no limitation, and it can be appropriately selected according to the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, preferably 2 Time to 24 hours are more preferable, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, In an aqueous medium phase, a polymer capable of reacting with the active hydrogen group-containing compound dissolved or dispersed in the organic solvent (for example, the isocyanate group-containing polyester prepolymer (A)), the pigment, the release agent, Examples thereof include a method in which the toner raw material such as the charge control agent and the non-reactive polyester resin is added and dispersed by a shearing force.
The dispersion is not particularly limited as a method thereof, and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction type. Examples thereof include a disperser, a high-pressure jet disperser, and an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the number of revolutions, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the number of revolutions is 1000 -30000 rpm is preferred, 5000-20000 rpm is more preferred, and the dispersion time is preferably 0.1-5 minutes in the case of a batch system, and the dispersion temperature is preferably 0-150 ° C. under pressure, -98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

In the emulsification / dispersion, the usage amount of the aqueous medium is preferably 50 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner raw material.
When the amount used is less than 50 parts by mass, the toner raw material is poorly dispersed, and toner particles having a predetermined particle size may not be obtained. When the amount exceeds 2,000 parts by mass, the production cost is high. May be.

In the emulsification / dispersion, it is preferable to use a dispersant as necessary from the viewpoint of sharpening the particle size distribution and performing stable dispersion.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable.

  Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like.

  Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nihon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M); F-824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products); Footgent F-300 (manufactured by Neos).

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and compounds containing carboxyl groups, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.

  Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like.

  Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In the emulsification / dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.
In the emulsification / dispersion, a catalyst for the elongation reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

In this way, the obtained toner particles are mixed with particles such as the release agent and the charge control agent, or further applied with a mechanical impact force so that the particles such as the release agent are separated from the surface of the toner particles. Can be prevented from desorbing.
As a method of applying the mechanical impact force, for example, a method of applying an impact force to the mixture by a blade rotating at high speed, an appropriate collision between particles or composite particles by introducing the mixture into a high-speed air stream and accelerating the mixture is accelerated. The method of making it collide with a board etc. are mentioned. As an apparatus used in this method, for example, an ong mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.), and a pulverization air pressure are lowered, a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

Here, a specific example of a preferable production method of the toner (ii) will be shown.
-Adhesive substrate production process-

-Preparation of aqueous medium phase (aqueous phase)-
In a reaction vessel equipped with a stirrer and a thermometer, water, sodium salt of ethylene oxide methacrylate adduct sulfate, styrene, methacrylic acid, and ammonium persulfate were charged and stirred for 15 minutes at 400 rpm. An emulsion of is obtained. The emulsion is heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, a 1% by mass ammonium persulfate aqueous solution is added to the reaction solution and aged at 75 ° C. for 5 hours to give a vinyl resin ( An aqueous dispersion (hereinafter, abbreviated as “fine particle dispersion”) of a styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) is prepared. Thereafter, water, the fine particle dispersion, a 48.5 mass% aqueous solution of sodium dodecyl diphenyl ether disulfonate, and ethyl acetate are mixed and stirred to prepare a milky white liquid (hereinafter abbreviated as “aqueous phase”).

--Synthesis of prepolymer (polymer capable of reacting with the active hydrogen group-containing compound)-
Put a bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 3-mole adduct, terephthalic acid, adipic acid, and dibutyltin oxide in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and normal pressure. After reacting at 230 ° C. for 8 hours and further reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, trimellitic anhydride is put into the reaction vessel and reacted at 180 ° C. for 2 hours at normal pressure. Thus, a low molecular weight polyester is synthesized.
Thereafter, the low molecular weight polyester, isophorone diisocyanate, and ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours to produce a prepolymer (the active hydrogen A polymer capable of reacting with the group-containing compound).

--Synthesis of ketimine (the active hydrogen group-containing compound)-
Isophoronediamine and methyl ethyl ketone are charged into a reaction vessel equipped with a stir bar and a thermometer, and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).

-Preparation of organic solvent phase-
Charge the low molecular weight polyester, synthetic ester wax (pentaerythritol tetrabehenate) and ethyl acetate into a reaction vessel equipped with a stirrer and a thermometer, heat up to 80 ° C. with stirring, and keep at 80 ° C. for 5 hours. After holding, cool to 30 ° C. over 1 hour. Next, ethyl acetate is charged into the reaction vessel and mixed for 1 hour to obtain a raw material solution.
The obtained raw material solution is transferred to a reaction vessel and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec. Then, the wax is dispersed under the condition of 3 passes. Next, a 65% by mass ethyl acetate solution of the low molecular weight polyester is added to the dispersion, and the mixture is dispersed once by a bead mill under the same conditions as described above to prepare an organic solvent phase.

--Emulsification / Dispersion--
The organic solvent phase, the prepolymer (low molecular weight polyester), and the ketimine compound are put in a reaction vessel, mixed at 5,000 rpm for 1 minute using a TK homomixer (made by Tokushu Kika), and then in the reaction vessel. The aqueous phase is added to the mixture, and the mixture is mixed for 20 minutes at a rotational speed of 13,000 rpm using a TK homomixer, and emulsified and dispersed to prepare an emulsified slurry. Next, the emulsified slurry is put into a reaction vessel equipped with a stirrer and a thermometer, the solvent is removed at 30 ° C. for 8 hours, and the emulsified slurry is allowed to stand at 50 ° C. for 6 hours.

The emulsified slurry after standing is filtered under reduced pressure, and then ion-exchanged water is added to the filter cake, followed by mixing with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), followed by filtration. 10 mass% sodium hydroxide aqueous solution is added to the filter cake obtained here, ultrasonic vibration is given, and it mixes with TK homomixer (rotation speed 12,000 rpm for 30 minutes), Then, it filters under reduced pressure. This ultrasonic alkali cleaning is performed again (twice ultrasonic alkali cleaning). 10 mass% hydrochloric acid is added to the filter cake obtained here, and after mixing with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), the mixture is filtered. Ion exchanged water was added to the filter cake obtained here, and the mixture was mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes) and then filtered twice to obtain a filter cake. The filter cake obtained here is dried at 45 ° C. for 48 hours with a circulating drier, and sieved with a mesh having an opening of 75 μm, whereby toner particles can be obtained.
The obtained toner particles are mixed with hydrophobic silica and hydrophobic titanium oxide using a Henschel mixer, whereby the toner (ii) of the present invention can be produced.

  According to the above toner manufacturing method, the toner of (ii) is efficiently manufactured. The shape, size, etc. of the toner of the present invention are not particularly limited and can be appropriately selected according to the purpose. The average circularity, volume average particle diameter, volume average particle diameter as follows. And the number average particle diameter (volume average particle diameter / number average particle diameter), thermal characteristics, and the like are preferable.

The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected area as the shape of the toner by the circumference of the actual particles. For example, 0.940 to 0.960 is preferable, and 0.945 to 0 is preferable. .955 is more preferred. The particles having an average circularity of less than 0.94 are preferably 10% or less.
When the average circularity is less than 0.940, a satisfactory transferability and a high-quality image free from dust may not be obtained. When the average circularity exceeds 0.960, image formation employing blade cleaning or the like is employed. In the system, defective cleaning occurs on the photoconductor and transfer belt, and in the case of image formation with a high image area ratio such as photographic images, an untransferred image is formed due to poor paper feed, etc. As a result, the accumulated toner may become a transfer residual toner on the photoconductor, which may cause background smearing of the image, or may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.

The average circularity is measured by, for example, an optical detection band method in which a suspension containing toner particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.).
The volume average particle diameter of the toner is preferably 4 to 8 μm, for example.
When the volume average particle size is less than 4 μm, in a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, leading to a decrease in the charging ability of the carrier, or as a one-component developer. When used, it tends to cause toner filming to the developing roller and toner fusion to a member such as a blade for thinning the toner. On the other hand, if it exceeds 8 μm, the resolution is high. It becomes difficult to obtain high-quality images.

The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is, for example, preferably 1.25 or less, and more preferably 1.10 to 1.25.
When the ratio (volume average particle diameter / number average particle diameter) exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and the toner particles when the toner balance during development is performed. Variation in diameter may be large. On the other hand, if it is less than 1.10, it is preferable in terms of stabilizing the behavior of the toner and making the charge amount uniform, but the toner may not be sufficiently charged or the cleaning property may be deteriorated. is there.

  The volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) are, for example, a particle size measuring instrument ““ Coulter Counter TAII ”manufactured by Coulter Electronics Co., Ltd. Can be measured.

(Developer)
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.

  There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. Further, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D50)) of 20 to 200 μm, and more preferably 40 to 100 μm.
When the average particle diameter (volume average particle diameter (D50)) is less than 10 μm, in the distribution of carrier particles, the fine powder system increases, the magnetization per particle is lowered, and carrier scattering may occur. If the thickness exceeds 150 μm, the specific surface area may be reduced and toner scattering may occur. In the case of a full color with many solid portions, the reproduction of the solid portions may be particularly poor.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, fluorine And a copolymer of vinylidene fluoride and vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 99% by mass Is preferable, and 93-97 mass% is more preferable.
Since the developer of the present invention contains the toner of the present invention, when an image is formed using the toner, a high-definition and high-quality image can be obtained while maintaining excellent blade cleaning properties. can get.

  The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Process cartridge)
The process cartridge of the present invention uses an electrostatic latent image carrier (electrophotographic photosensitive member) carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer. Development means for forming a visible image by developing at least, and further having other means appropriately selected as necessary.
The electrostatic latent image carrier (electrophotographic photosensitive member) includes a charge generation layer having at least a charge generation material on a conductive support, and a charge transport layer containing at least a charge transport material. It is formed by being dispersed in the form of dots as minute regions.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably detachably provided in the electrophotographic apparatus of the present invention described later.

Here, as the process cartridge, for example, as shown in FIG. 8, a photosensitive member 101 is incorporated, and in addition, a charging unit 102, an exposure unit 103, a developing unit 104, a transfer material (paper or the like) 105, and a cleaning unit 107. , The transfer means 108 and the like, and other members as necessary.
The photoreceptor 101 includes a support and a photosensitive layer including a charge generation layer, a charge transport layer, and a cross-linked charge transport layer in this order on the support. As described above, a known charging member is used as the charging member 102. When a high-definition image is formed, the electric field strength of the photoreceptor is 30 V / μm or more (60 V / μm or less, preferably 50 V / μm or less. ) To give a corona discharge.
A light source capable of writing with high resolution is used for the exposure means 103. An arbitrary charging member (preferably scorotron charging) is used for the charging means 102.

  The electrophotographic image forming apparatus of the present invention is constructed by integrally connecting the above-described photosensitive member and components such as a developing device and a cleaning device as a process cartridge, and this unit is configured to be detachable from the apparatus main body. May be. In addition, a process cartridge is formed by integrally supporting at least one of a charger, an image exposure device, a developing device, a transfer or separation device, and a cleaning device together with a photosensitive member, and a single unit that is detachable from the apparatus main body. It is good also as a structure which can be attached or detached using guide means, such as a rail of an apparatus main body.

(Image forming method and image forming apparatus)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, a developing unit, and a transfer unit, and further, other units appropriately selected as necessary, for example, a neutralizing unit, a recycling unit, and a control unit. Means and the like.
The image forming method of the present invention includes at least a development process and a transfer process, and further includes other processes appropriately selected as necessary, for example, a static elimination process, a recycling process, a control process, and the like.

The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit. Details will be described below.
The electrostatic latent image bearing member (electrophotographic photosensitive member) of the present invention can be applied to general electrophotographic apparatuses such as copying machines, laser printers, LED printers, and liquid crystal shutter printers. The present invention can be widely applied to apparatuses such as applied displays, recording, light printing, plate making and facsimile.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back surface side of the electrostatic latent image carrier may be adopted.
In addition, when the image forming apparatus is used as a copying machine or a printer, image exposure is performed by irradiating a photosensitive member with reflected light or transmitted light from a document, or by reading a document with a sensor and generating a signal according to this signal. This is performed by irradiating light to the photosensitive member by scanning the beam, driving the LED array, or driving the liquid crystal shutter array.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, the toner or developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developing unit capable of contacting or non-contacting the toner or the developer with the electrostatic latent image is provided, and includes the toner container according to the present invention. More preferred is a developing device.

  For the developing device, a dry development system is usually used. Further, it may be a single color developing device or a multicolor developing device. For example, a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller. Preferred examples include those possessed.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrostatically attracted by the static force. It moves to the surface of the electrostatic latent image carrier. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier.

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the electrostatic latent image carrier using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.
The transfer unit (the primary transfer unit and the secondary transfer unit) has at least a transfer unit that peels and charges the visible image formed on the electrostatic latent image carrier to the recording medium side. Is preferred. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

-Fixing process and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressurizing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

-Cleaning process and cleaning means-
In the cleaning step, the electrostatic latent image carrier is cleaned using a cleaning unit. Examples of the cleaning means include a cleaning blade, a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.

  Here, the cleaning means will be described. FIG. 9 is a schematic cross-sectional view of the cleaning mechanism used in the present invention. In the present invention, known cleaning conditions and blade materials can be used. At this time, it is preferable to use the photoconductor in contact with the counter in the rotational direction of the photoconductor.

In FIG. 9, the contact load P is a vector value in the normal direction of the pressure contact force when the cleaning blade 71 is brought into contact with the photosensitive member 10. Further, the contact angle θ represents an angle formed between a tangent at the contact point of the photoconductor 10 and the blade before deformation. The cleaning blade free length L represents the length of the blade tip point before the deformation from the end of the support member 72.
P is preferably 5 to 50 g / cm as a preferable value of the contact load P and the contact angle θ of the cleaning blade 71 to the photosensitive member 10. θ is preferably 5 to 35 °. The cleaning blade free length L is preferably 3 to 15 mm. The thickness of the cleaning blade is preferably 0.5 to 10 mm.

  Examples of the material of the rubber blade used in the blade cleaning method include urethane rubber, silicone rubber, fluorine rubber, chloroprene rubber, butadiene rubber, and the like. Among these, urethane rubber is particularly preferable.

  In the present invention, the reversal of the blade can be effectively suppressed by simultaneously controlling the hardness and rebound resilience of the rubber blade. The JISA hardness at 25 ± 5 ° C. of the rubber blade is preferably 65-80. When the JISA hardness is less than 65, the blade may be easily reversed, and when it exceeds 80, the cleaning performance may be deteriorated. The impact resilience of the rubber blade is preferably 20 to 75%. If the impact resilience exceeds 75%, the blade may be easily reversed, and if it is less than 20%, the cleaning performance may deteriorate.

  Here, both the JISA hardness and the resilience can be measured based on the vulcanized rubber physical test method of JIS K6301.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralizing means is not particularly limited and may be appropriately selected from known neutralizers as long as it can apply a neutralizing bias to the latent electrostatic image bearing member. Preferably mentioned.

The recycling step is a step of recycling the electrophotographic color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. PET for OHP A base or the like can also be used.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 10 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is formed between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is arranged between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 10, for example, the charging roller 20 uniformly charges the photosensitive drum 10. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 11 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 10, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 11, the same components as those in FIG. 10 are denoted by the same reference numerals.

Another aspect of carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to the drawings. The tandem image forming apparatus shown in FIGS. 12 and 13 (FIG. 13 is a partially enlarged view of FIG. 12) is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 12. An intermediate transfer body cleaning device 17 for removing residual toner on the intermediate transfer body 50 is disposed in the vicinity of the support roller 15. The intermediate transfer body 50 stretched by the support roller 14 and the support roller 15 is a tandem type in which four image forming means 18 of yellow, cyan, magenta, and black are arranged in parallel and facing each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full color image (color copy) using the tandem image forming apparatus will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem image forming apparatus. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem image forming apparatus, as shown in FIGS. Each of the photoconductors 10 (the black photoconductor 10K, the yellow photoconductor 10Y, the magenta photoconductor 10M, and the cyan photoconductor 10C), the charger 60 that uniformly charges the photoconductor, and each color image information An exposure unit that exposes the photoconductor for each color image-corresponding image (indicated by symbol L in FIG. 13) and forms an electrostatic latent image corresponding to each color image on the photoconductor, A developing device 61 that develops the electrostatic latent image with each color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner; A transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a photoconductor cleaning device 63, and a static eliminator 64 are provided, and each monochrome image (black) is based on the image information of each color. Image, yellow image, magenta image, and cyan image) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feeding roller 150 is rotated to feed out sheets (recording paper) on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the paper discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57. In the image forming apparatus and the image forming method of the present invention, the electrophotographic photosensitive member comprises a charge generation layer having at least a charge generation material on a conductive support, and a charge transport layer containing at least a charge transport material. The generation layer is formed as fine regions dispersed in dots, and the toner is a toner manufactured by a polymerization method, so that a high-quality image can be formed and the amount of toner adhesion can be small.

EXAMPLES Next, although this invention is demonstrated based on an Example, this invention is not limited by these Examples.
(Photoreceptor configuration)
Intermediate layer An intermediate layer coating solution having the following formulation was prepared.
"Interlayer coating liquid"
Polyamide resin (CM8000, manufactured by Toray Industries, Inc.) 2 parts Methanol 58 parts n-Butanol 40 parts This coating solution is dip-coated on an aluminum drum having a diameter of 30 mm and a length of 340 mm, dried at 120 ° C. for 20 minutes, and a film thickness of 0 An intermediate layer of 3 μm was prepared.

Charge generation layer Next, a charge generation layer coating solution having the following formulation was prepared.
10 parts by weight of a trisazo pigment represented by the following chemical formula (1) is added to a resin solution in which 4 parts by weight of polyvinyl butyral (BM-2: manufactured by Sekisui Chemical Co., Ltd.) is dissolved in 150 parts by weight of cyclohexanone, and dispersed for 72 hours by a ball mill. Was done. After the completion of dispersion, 250 parts by weight of cyclohexanone and 200 parts by weight of 2-butanone were added and dispersed for 3 hours to prepare a charge generation layer coating solution. This coating solution was applied onto the intermediate layer in the form of dots under the following conditions and dried at 120 ° C. for 20 minutes to form a charge generation layer (both ends 10 mm uncoated portion).

Although some unevenness was observed due to bleeding and spreading of the coating solution, the coating solution was satisfactorily coated without any roughness or unevenness of the coating film. Moreover, since the coating width was controlled, the uncoated part was not wiped off, and the defect due to wiping (thickening of the coating film thickness at the end, splashing at the time of wiping) was good. The amount of coating solution used was about 0.5 ml.
The particle diameter of the charge generation material after dispersion was 0.07 μm. The particle size was measured by centrifugal sedimentation using CAPA-700 manufactured by Horiba.
In the present invention, the coating was performed by modifying a commercially available Seiko Electronic Industry IP-4000 A0 printer (compatible with oil-based pigment ink). A piezo type recording head was used. The ink in the ink cartridge can be replaced. In addition, the aluminum drum was remodeled so that it could be rotated at the ink adhering part and paper position. In addition, coating by the ink jet method can be controlled from a personal computer. The coating width, liquid discharge amount (which changes the size of the dots), and dot spacing were controlled by a personal computer.

Charge Transport Layer Next, a charge transport layer coating liquid having the following chemical formula (2) was prepared.

7 parts by weight of the charge transport material represented by the chemical formula (2) and 10 parts by weight of polycarbonate (Z type: viscosity average molecular weight 50,000) were dissolved in 100 parts by weight of tetrahydrofuran to prepare a charge transport layer coating solution. This coating solution was dip-coated on the charge generation layer, dried at 130 ° C. for 20 minutes, and a charge transport layer having a thickness of 20 μm was applied to produce the photoreceptor 1 of the example.
Next, a developer was prepared according to Production Example 1.

(Production Example 1)
-Preparation of toner-
-Preparation of aqueous medium phase (aqueous phase)-
The following raw materials were charged into a reaction vessel equipped with a stir bar and a thermometer, and stirred at 400 rpm for 15 minutes to obtain a white emulsion.
Water 683 parts Sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30"; manufactured by Sanyo Chemical Industries) 11 parts Styrene 138 parts Methacrylic acid 138 parts Ammonium persulfate 1 part

The obtained emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% by mass ammonium persulfate aqueous solution was added to the reaction solution, and the mixture was aged at 75 ° C. for 5 hours, and the vinyl resin (styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate sodium salt was added. An aqueous dispersion (hereinafter referred to as “fine particle dispersion 1”) was prepared.
The obtained “fine particle dispersion 1” had a volume average particle size of 0.14 μm as measured with a laser diffraction particle size distribution analyzer (“LA-920”; manufactured by Horiba, Ltd.). Further, a part of the obtained “fine particle dispersion 1” was dried to isolate the resin component. The glass transition temperature (Tg) of the resin component was 152 ° C.
Thereafter, 990 parts of water, 80 parts of the fine particle dispersion, 40 parts of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate ("Eleminol MON-7"; manufactured by Sanyo Chemical Industries Ltd.), and 90 parts of ethyl acetate are mixed. Stirring to prepare a milky white liquid (hereinafter referred to as “aqueous phase 1”).

--Synthesis of low molecular weight polyester 1--
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 220 parts of bisphenol A ethylene oxide 2-mole adduct, 561 parts of bisphenol A propylene oxide 3-mole adduct, 218 parts of terephthalic acid, 48 parts of adipic acid, And 2 parts of dibutyltin oxide were allowed to react at 230 ° C. for 8 hours under normal pressure. Next, the reaction solution was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg, and then 45 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. Molecular polyester 1 ”was synthesized.
The obtained “low molecular weight polyester 1” had a number average molecular weight (Mn) of 2500, a weight average molecular weight (Mw) of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25. .

--Synthesis of prepolymer 1 (polymer capable of reacting with the active hydrogen group-containing compound)-
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 Part and 2 parts of dibutyltin oxide were allowed to react at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15 mHg for 5 hours, and the "intermediate polyester 1" was synthesize | combined.
The obtained “intermediate polyester 1” has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, The hydroxyl value was 51.
Then, 411 parts of the “intermediate polyester 1”, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Thus, prepolymer 1 was synthesized.
The free isocyanate content of the obtained prepolymer 1 was 1.53% by mass.

--Synthesis of ketimine compound 1 (the active hydrogen group-containing compound)-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize ketimine compound 1.
The amine value of the obtained ketimine compound (the active hydrogen group-containing compound) was 418.

-Preparation of masterbatch (MB)-
40 parts of carbon black (manufactured by Cabot, Regal 400R), binder resin (polyester resin: manufactured by Sanyo Chemical Industries, RS-801, acid value = 10, weight average molecular weight (Mw) = 20000, Tg = 64 ° C.) 60 parts and 30 parts of water were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. The mixture was kneaded for 45 minutes with two rolls set at a roll surface temperature of 13 ° C. and then pulverized to a size of 1 mm in diameter with a perparizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch 1.

-Preparation of organic solvent phase (oil phase)-
In a reaction vessel equipped with a stir bar and a thermometer, 378 parts of the above-mentioned “low molecular polyester 1”, 110 parts of carnauba wax, 22 parts of CCA (“salicylic acid metal complex E-84”; manufactured by Orient Chemical Industries), and ethyl acetate 947 parts were charged, and the temperature was raised to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of “Masterbatch 1” and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain “Raw material solution 1”.
1324 parts of the obtained “raw material solution 1” was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Corporation), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, The carbon black and carnauba wax of “Raw Material Solution 1” were dispersed in 3 passes under the condition that 80% by volume of 5 mm zirconia beads were filled. Next, 1324 parts of a 65% by mass ethyl acetate solution of “low molecular weight polyester 1” was added to the dispersion. One pass was performed in a bead mill under the same conditions as described above, and the mixture was dispersed to prepare “organic solvent phase 1”.
The solid content concentration of the obtained organic solvent phase was 50% by mass.

--Emulsification / Dispersion--
Into a reaction vessel, 648 parts of “organic solvent phase 1”, 154 parts of “prepolymer 1”, and 6.6 parts of “ketimine compound 1” are charged. K. After mixing for 1 minute at 5,000 rpm using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), 1200 parts of “Aqueous Phase 1” was added to the reaction vessel. K. Using a homomixer, mixing was carried out at a rotational speed of 13,000 rpm for 20 minutes to carry out emulsification and dispersion to prepare “emulsified slurry 1”.
Next, “emulsified slurry 1” was charged into a reaction vessel equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours. Thereafter, the “emulsified slurry 1” was aged at 45 ° C. for 4 hours.
The obtained “emulsified slurry 1” had a volume average particle size of 5.95 μm and a number average particle size of 5.45 μm.

--- Washing and drying--
100 parts of “emulsified slurry 1” after aging was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, and T.P. K. After mixing with a homomixer (10 minutes at 12,000 rpm), the mixture was filtered. 100 parts of a 10% by mass sodium hydroxide aqueous solution was added to the filter cake obtained here, and T.F. K. After mixing with a homomixer (rotating at 12,000 rpm for 30 minutes), an operation of filtration under reduced pressure (hereinafter referred to as “ultrasonic alkali cleaning”) was performed twice. 100 parts of 10% by mass hydrochloric acid was added to the filter cake obtained here, and T.W. K. After mixing with a homomixer (10 minutes at 12,000 rpm), the mixture was filtered. To the filter cake obtained here, 300 parts of ion exchange water was added. K. After mixing with a homomixer (rotating at 12,000 rpm for 10 minutes), filtration was performed once to obtain “filter cake 1”. The “filter cake 1” obtained here was dried at 45 ° C. for 48 hours with a circulating drier and sieved with a mesh having a mesh size of 75 μm, whereby “toner 1” of Production Example 1 was obtained.

  The resulting toner of Production Example 1 had a volume average particle diameter Dv of 6.07 μm, a number average particle diameter Dn of 5.50 μm, and Dv / Dn = 1.10. Moreover, the average circularity measured by the following method was 0.950.

<Average circularity>
The average circularity of the toner was measured using a flow particle image analyzer (“FPIA-2100”; manufactured by Toa Medical Electronics Co., Ltd.). Specifically, 0.1 to 0.5 ml of a surfactant (alkylbenzene sulfonate) as a dispersant was added to 100 to 150 ml of water from which impure solids had been removed in advance. Next, 0.1 to 0.5 g of each toner was added and dispersed. The obtained dispersion was subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape and distribution of the obtained toner were measured at a dispersion concentration of 3000 to 10,000 / μl. The average circularity was calculated from these measurement results.

(Production Example 2)
-Preparation of toner-
In Production Example 1, “Toner 2” of Production Example 2 was produced in the same manner as in Production Example 1, except that the ultrasonic alkali cleaning in the washing / drying step was performed twice. The obtained toner of Production Example 2 had a volume average particle diameter Dv of 6.03 μm, a number average particle diameter Dn of 5.52 μm, and Dv / Dn = 1.09. The average circularity was 0.955.

Example 1
A combination of the photoreceptor 1 and the toner of Production Example 1 was referred to as Example 1.

In the above, the photosensitive member shaken in the range of 100% (photosensitive member in which CGL is not formed in a normal dot shape) to 60% (region in which solid ID can be secured from the above simulation result) as the area occupancy rate of the CGL dot portion. A drum was prototyped, and the resulting photoconductor was used to output an image for evaluation of image quality.
As for image output, paying attention to two items of “good reproduction of fine lines” and “stable density change in highlight portion”, the following image output experiments were performed respectively. First, “good reproduction of fine lines” was evaluated visually using an image pattern with 400 lines shown in FIG. 5 using an image output experimental machine with a resolution of 1200 dpi described below. The case where a 400-line line image was reproduced was marked as ◯, and the case where a 400-line line image was not reproduced was marked as x. Whether or not the 400-line line image is set as a criterion for determination is based on the outline of the character part (not to become a rattling outline) and the color of the character when a low-contrast character / color character is printed with a printer. This is set as a substitute characteristic for reproducing both items such as reproducibility (which can reproduce the desired color).

Next, with respect to “stable density change in the highlight portion”, an 8-bit Tiff image data including patches of 0 to 256 gradations (15 mm square) is used by using an image output experimental machine with a resolution of 1200 dpi described below. On the other hand, image data for output (data after pseudo halftone processing) prepared in advance with dither processing (screen screen number of about 170 lines, screen angle 45 degrees, line screen type, quantization number 2 bits, resolution 1200 dpi) is prepared in advance. In addition, image output is performed using the output image data. The evaluation of the output image was performed using the result of measuring the reflection density (ID value) of the highlight portion (data 0 to 32) with a spectral reflection densitometer (model 938 manufactured by X-Rite). A linear equation is approximated with respect to the relationship between the reflection density value and the input data value, and a case where the value of R ² is 0.95 or more is evaluated as ◯, and a case where the value of R ² is less than 0.95. X. The condition that the R ² value of linear approximation is 0.95 or more in the highlight portion (data 0 to 32) set as the determination criterion here is an abnormal image called a pseudo contour in a gradation image. This is set as a substitute characteristic to reproduce well without occurrence.

  Next, an experimental machine used for image output will be described. This experimental machine is an experimental machine modified on the basis of Ricoh's Ipsio Color 5100, and is mainly a modified writing unit. In this experimental machine, a four-channel LD array in which four light emitting points (laser diodes) are formed in a line on one chip is used as an LD element. Thereby, a resolution of 1200 dpi was realized. In this experimental machine, the optical element and the aperture are adjusted so that the beam diameter is 50 (main scanning direction) × 65 (sub-scanning direction) μm on the photosensitive member position. The amount of the stationary beam of the laser beam is adjusted and set by measurement using the above-described optical power meter.

Next, an image output experiment and results thereof will be described. The prototype photoconductor used in the experiment was manufactured by the method described above (photosensitive member configuration). (CGM is trisazo pigment: structural formula (A).) At this time, the area occupied by the charge generation layer is in the range of 100 to 60% at 1200 dpi while variously adjusting the coating conditions of the coating liquid of the ink jet printer. Prototype photoconductor drums were produced by changing the above.
Using the photoconductor drum produced in this way, the image output is performed while changing the amount of the stationary beam of the laser, and the above two items (“400 line line image reproduction”, “Highlight portion are expressed by a linear expression) Tables 1 and 2 below show the results of the evaluation of the approximation and the R ² value of 0.95 or more.
In addition, the numerical value shown under (circle) of Table ^{2 is} the value of said R2 (same also about Table 5 and Table 6).

  From the results of Tables 1 and 2, when the occupation area ratio of the charge generation layer is 90% or less, the improvement to the “problem to be solved by the invention” as described in the section of the prior art is improved. It turns out that it is possible. Further, when the occupation area ratio of the charge generation layer is equal to or greater than a certain relationship (described separately), solid ID = 1.4 or more can be ensured, and good image quality can be realized.

  Next, the results of outputting a comprehensive test chart including image quality elements such as a highlight portion, a low-contrast character portion, and a solid portion using some of the conditions evaluated above are shown in Table 3. is there.

  In Tables 1 and 2, it can be seen that high-quality images can be obtained even in the output results of the comprehensive test chart under the conditions where good results can be obtained.

Example 2
A combination of the photoreceptor 1 and the toner of Production Example 2 was referred to as Example 2. The results evaluated in the same manner as in Example 1 are shown in Tables 4 and 5 below.
The overall evaluation chart is the same as in Table 3.

(Production Example 3)
-Preparation of pulverized toner-
100 parts of styrene acrylic resin, 8 parts of carbon black, and 4 parts of low molecular weight polypropylene (number average molecular weight (Mn) = 3600) are melted and kneaded by a known method, and then pulverized and classified to give a volume average particle diameter Dv. “Toner 3” of Production Example 3 was produced by a pulverization method having a particle size of 7.2 μm, a number average particle diameter Dn of 4.22 μm, and Dv / Dn = 1.71. The average circularity measured in the same manner as in Production Example 1 was 0.930. A combination of the photoreceptor 1 and the toner of Production Example 3 was referred to as Comparative Example 1.
Table 6 below shows the results of evaluating “stable change in density at highlight portion” in the same manner as in Example 1.

FIG. 6 is a diagram showing that a carrier diameter is larger than a beam spot diameter corresponding to one dot and enters an adjacent image dot region in a conventional laminated photoreceptor. In the exposure beam energy distribution, it is a diagram showing the case of 600 dpi and a beam diameter of 68.9 μm. FIG. 4 is a diagram illustrating a relationship between a charge generation layer area ratio and a toner adhesion amount in the invention. FIG. 6 is a graph showing a relationship between a charge generation layer area ratio (DM ratio) satisfying a toner adhesion amount M ≧ 0.45 mg / cm ² and quantum efficiency * Power in the present invention. It is explanatory drawing (at the time of resolution 1200 dpi) of a 400 line image pattern. 1 is a configuration diagram of an electrophotographic photoreceptor in the present invention. 3 is another structural drawing of the electrophotographic photosensitive member in the present invention. It is a schematic explanatory drawing which shows an example of the process cartridge of this invention. It is a schematic explanatory drawing which shows an example of the cleaning means used by this invention. It is a schematic explanatory drawing which shows an example which enforces the image forming method of this invention with the image forming apparatus of this invention. It is a schematic explanatory drawing which shows the other example which implements the image forming method of this invention with the image forming apparatus of this invention. FIG. 2 is a schematic explanatory diagram illustrating an example in which the image forming method of the present invention is carried out by the image forming apparatus (tandem color image forming apparatus) of the present invention. FIG. 13 is a partially enlarged schematic explanatory diagram of the image forming apparatus of FIG. 12.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Constant current source 55 Switching claw 56 Discharging roller 57 Discharging tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 71 Cleaning blade 72 Support member 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming apparatus 101 Photoconductor 102 Charging means 103 Exposure 104 Developing means 105 Transfer body 106 Transfer means 107 Cleaning means 120 Tandem type developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Away rollers 146 feed path 147 transport rollers 148 feed path 150 copier main body 200 feeder table 300 Scanner 400 automatic document feeder (ADF)
431 Conductive support 433 Intermediate layer 435 Charge generation layer 437 Charge transport layer

Claims (12)

  In an image forming apparatus comprising: an electrophotographic photosensitive member; and a developing device that develops an electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image, the electrophotographic photosensitive member has a conductive property. A charge generation layer and a charge transport layer containing a charge transport material are provided on a support, and the charge generation layer is formed by dispersing minute charge generation regions having a charge generation material in a dot shape. An image forming apparatus, wherein the toner is a toner produced by a chemical reaction in an aqueous medium. In the charge generation layer of the electrophotographic photosensitive member, the occupation area ratio of the charge generation region formed in a dot shape is 90% or less, and the occupation area ratio (X) represented by the following formula (1) is greater than or equal to The image forming apparatus according to claim 1, wherein the image forming apparatus is provided.
η × J ≧ 0.01 × EXP (− (X−60 / 10) +0.002 (1)
(Η represents quantum efficiency, and J represents exposure beam energy (J / m ² ).)   The image forming apparatus according to claim 1, wherein the charge generation layer of the electrophotographic photosensitive member has a dot pitch of the charge generation region equal to a resolution of the image forming apparatus.   4. The image according to claim 1, wherein the charge generation layer of the electrophotographic photosensitive member has an average particle diameter of a charge generation material contained in the charge generation region of 0.2 μm or less. 5. Forming equipment.   5. The image according to claim 1, wherein the toner is a toner obtained by suspension polymerization of a polymerizable composition comprising a polymerizable monomer and a colorant in an aqueous medium. Forming equipment.   The toner is formed into particles while reacting an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium to form an adhesive substrate. The image forming apparatus according to claim 1.   7. The image forming apparatus according to claim 1, wherein the toner has a volume average particle diameter of 4 to 8 [mu] m.   The image forming apparatus according to claim 1, wherein a ratio of a volume average particle size to a number average particle size in the toner is 1.10 to 1.25.   An electrophotographic photosensitive member carrying an electrostatic latent image, and a developing means for developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image. The electrophotographic photoreceptor comprises a charge generation layer and a charge transport layer containing a charge transport material on a conductive support, and the charge generation layer has a minute charge generation region having a charge generation material. A process cartridge, wherein the toner is the toner described in claim 1, 5, 6, 7 or 8.   5. The method for producing an electrophotographic photosensitive member according to claim 1, wherein the charge generation region is formed by ejecting a charge generation layer coating liquid by an ink jet method. A method for producing a photographic photoreceptor. The method for producing an electrophotographic photosensitive member according to claim 10, wherein the ink jet method is a piezo method. An electrostatic latent image forming step for forming an electrostatic latent image on the electrophotographic photosensitive member, a developing step for developing the electrostatic latent image with toner to form a toner image, and the toner image on the electrophotographic photosensitive member. In the image forming method including the transfer step of transferring from the toner to the transfer medium, the electrophotographic photosensitive member according to any one of claims 1 to 4 is used as the toner. An image forming method using the toner described in 6, 7 or 8, respectively.

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