JP2007316332A - Image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method by which a high-quality image is obtained, carrier adhesion is prevented and stable images can be produced over a long period of time. <P>SOLUTION: The image forming method includes at least a developing step of developing an electrostatic latent image using a developing unit housing a two-component developer including toner and a carrier, wherein a replenisher developer including at least a replenisher toner and replenisher carrier is replenished to the developing unit and carrier present in surplus is discharged from the developing unit. The replenisher developer includes 2-50 parts by mass of the replenisher toner based on 1 part by mass of the replenisher carrier. A photosensitive layer comprises a charge generating layer and a charge transport layer, the photosensitive layer has a specific total thickness, and the carrier and replenisher carrier have a specific volume-base 50% particle diameter (D50), a specific true specific gravity and a specific intensity of magnetization in a magnetic field of 1,000/4π (kA/m). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an image forming method used in electrophotography, electrostatic recording method, and electrostatic printing method.

  In general, in an image forming apparatus that records an image on a recording medium such as paper such as a copying machine or a printer, an electrophotographic system is employed as a system for recording the image on the recording medium.

  In the electrophotographic system, a photosensitive member having a photosensitive material coated on its surface is used as an electrostatic latent image carrier. First, after the surface of the photoconductor is uniformly charged, the surface of the photoconductor is irradiated with laser light, and a potential difference is given between the irradiated portion and the non-irradiated portion.

  Next, a toner image is formed on the surface of the photosensitive member by attaching the charged toner to the surface of the photosensitive drum in accordance with the potential using a developer having toner and carrier. Thereafter, the toner image is transferred to a recording medium, and the toner is fixed on the recording medium by heat, pressure, or the like to form an image.

  In the normal two-component development method, the toner in the developing device is consumed, and the replenishment of the shortage is performed with new toner, but the carrier is used continuously, so the development characteristics are deteriorated due to the deterioration of the carrier. There is a problem that the operation of periodically changing the developer in the developing device occurs. In response to this technical problem, a proposal has been made to replenish the replenishment toner and carrier at a fixed ratio, gradually replace the carrier in the developing device, whose development performance has deteriorated, with a new carrier, and eliminate these maintenance work. (For example, refer to Patent Document 1).

However, in the developing method described in Patent Document 1, since the replenishment developer including the carrier is replenished, there is a problem in the mixing property between the developer in the developing device and the replenishment developer. For example, when the mixing property is deteriorated, the charge amount of the developer may be uneven, and the development characteristics may be deteriorated.

  Recently, demands such as lower running costs of toner and photoreceptors with increasing image quality and speed of output devices have increased, and as a photosensitive drum used in the above electrophotographic system, due to the necessity of high resolution, A thin photosensitive layer is used, and on top of that, it is necessary to extend the life of the photosensitive drum in order to reduce the running cost. Therefore, the electrical, mechanical strength and wear resistance of the photosensitive member surface are improved. Is planned.

  Several proposals have been made to use a curable resin for the surface layer in order to achieve high resolution and high durability of the photoreceptor (see, for example, Patent Documents 2 and 3). When a curable resin is used for the surface layer, the mechanical strength is increased and it is difficult to scrape and scratches are less likely to occur than a thermoplastic resin, resulting in a longer life. Furthermore, a method for forming a protective layer using various energies (heat, ultraviolet rays, electron beams, etc.) on the surface layer of the photoreceptor has been proposed in order to achieve high durability including higher resolution of the photoreceptor (for example, See Example 1 of Patent Document 4).

  However, since such a thin film photoconductor has a large electrostatic capacity, the γ curve becomes large in the characteristics between the photoconductor potential and the image density. Or, by reducing the contrast potential, black and white copiers and printers can produce very sharp images. However, especially in full-color copiers and printers that require halftone high image quality, the gamma curve is very high in halftones. In some cases, it is difficult to reproduce halftones due to standing up, or color reproducibility becomes difficult due to a large change in density due to slight potential fluctuations.

On the other hand, there is also an approach from a developer for the purpose of improving image quality (see, for example, pages 2 to 3 of Patent Document 5). In order to improve image quality, the toner has a small particle size to define the particle size distribution, the carrier has a smaller particle size, and the shape is specified to provide excellent fluidity, resolution, gradation, and fine line reproducibility. Proposals for excellence have been made. Reducing the particle size of the toner and carrier is very effective for improving the image quality. However, when the above-described high-resolution thin-film photoconductor is used, gradation is taken (the γ curve is laid down). Therefore, it is necessary to increase the toner charge amount very much, and it may not be sufficient to satisfy the developability in that case, so-called toner separation from the carrier. In addition, when the toner charge amount is high, the counter charge tends to accumulate on the carrier, and the carrier tends to adhere to the photosensitive drum. In this case, if the carrier shape is indefinite, even if the photosensitive drum has a strong protective layer In some cases, the surface of the photosensitive drum is matted as the durability progresses, and the halftone portion is gritty.
Japanese Patent Publication No. 2-21591 JP 05-216249 A Japanese Patent Laid-Open No. 07-72640 JP 2003-345049 A Japanese Patent Laid-Open No. 06-332237

An object of the present invention is to provide an image forming method that solves the above-mentioned problems.
That is, an object of the present invention is to charge a conductive support and an electrophotographic photosensitive member having a photosensitive layer on the conductive support, and an exposure step of forming an electrostatic latent image on the photosensitive member. In an image forming method having at least a developing step of developing the electrostatic latent image using a developing device containing a two-component developer containing a toner and a carrier, a high-quality image is obtained and further carrier adhesion is prevented. Another object of the present invention is to provide an image forming method capable of outputting a stable image over a long period of time.

  As a result of intensive studies, the present inventors have found that the above requirements can be satisfied by an image forming method using an electrophotographic photosensitive member having a specific film thickness and a replenishment developer containing a specific toner and carrier. As a result, the present invention has been achieved.

The object of the present invention can be achieved by using the image forming method described in the following (1) to (6).
(1) a conductive support, a charging step for charging an electrophotographic photosensitive member having a photosensitive layer on the conductive support, an exposure step for forming an electrostatic latent image on the photosensitive member, a toner and a carrier, An image forming method comprising at least a developing step for developing the electrostatic latent image using a developing device containing a two-component developer containing a toner, wherein at least a replenishing toner and a replenishing carrier are provided to the developing device. The replenishment developer containing toner is replenished, and the excess carrier is discharged from the developing device. The replenishment developer contains 2 to 50 mass of replenishment toner per 1 part by mass of the replenishment carrier. The photosensitive layer has at least a charge generation layer and a charge transport layer, and the total thickness of the photosensitive layer is 5.0 μm to 15.0 μm. The volume-based 50% particle size (D50) of The true specific gravity of the carrier and the replenishment carrier is 2.5 to 4.2 g / cm ³ , and the magnetization of the carrier and the replenishment carrier in a magnetic field of 1000 / 4π (kA / m) An image forming method, wherein the strength of the ink is 40 to 70 Am ² / kg.

(2) The carrier and the replenishment carrier have an average circularity of 0.850 to 0.950, and contain 90% by number or more of particles having a circularity of 0.800 or more. Image forming method.

(3) The toner and the replenishing toner are characterized in that the light transmittance at a wavelength of 600 nm of a dispersion obtained by dispersing the toner in an aqueous solution containing 45% by volume of methanol is 30% to 80% (1) Or the image forming method according to (2).

(4) The average circularity of particles having an equivalent-circle diameter of 2.0 μm or more of the toner and the replenishing toner is 0.930 to 1.000, according to any one of (1) to (3) Image forming method.

(5) The carrier and the replenishment carrier are magnetic substance-containing resin carriers obtained by polymerizing a monomer for forming a binder resin in the presence of a magnetic substance (1) to (4) The image forming method according to any one of the above.

(6) The image forming method according to any one of (1) to (5), wherein the electrostatic latent image is formed using a semiconductor laser having a wavelength of 380 nm to 500 nm.

  According to the present invention, a high-quality image can be obtained by an image forming method using the replenishment developer containing the optimum replenishment toner and the optimum replenishment carrier with the film thickness of the electrophotographic photosensitive member being in the optimum range. Furthermore, carrier adhesion can be prevented and a stable image can be output over a long period of time.

The image forming method of the present invention comprises a conductive support, a charging step for charging an electrophotographic photosensitive member having a photosensitive layer on the conductive support, and an exposure step for forming an electrostatic latent image on the photosensitive member. And a developing step for developing the electrostatic latent image using a developing device containing a two-component developer containing a toner and a carrier, wherein the developing device includes at least a replenishing toner and The replenishment developer containing the replenishment carrier is replenished, and the excess carrier is discharged from the developing device. The replenishment developer supplies 2 replenishment toners to 1 part by mass of the replenishment carrier. To 50 parts by mass, the photosensitive layer has at least a charge generation layer and a charge transport layer, and the total thickness of the photosensitive layer is 5.0 μm to 15.0 μm, and the carrier and 50 based on volume of replenishment carrier % Particle size (D50) is 15 to 70 μm, the true specific gravity of the carrier and the replenishment carrier is 2.5 to 4.2 g / cm ³ , and 1000 / 4π (kA / The strength of magnetization under a magnetic field of m) is 40 to 70 Am ² / kg. As a result, a high-quality image can be obtained, carrier adhesion can be prevented, and a stable image can be output over a long period.

  In the present invention, an electrostatic latent image with high resolution can be obtained by setting the total film thickness of the photosensitive layer to 5.0 μm to 15.0 μm. This is because a high charge density can be maintained by increasing the electrostatic capacity of the surface of the photoreceptor. However, since the photosensitive member has a photosensitive layer on a conductive support, when it is used in a total film thickness within this range, charge injection tends to occur on the surface of the photosensitive member, and the carrier onto the photosensitive member Adhesion sometimes occurred. Therefore, by using the replenishment developer of the present invention, it is possible to prevent carrier adhesion to the photoreceptor and to output a stable image over a long period of time.

  The above carrier adhesion preventing effect is achieved by reducing the proportion of the carrier not covered with toner in the developer by supplying the developer to the developer while the toner is coated on the supply carrier. It is to do.

Further, by using the replenishment developer, it is possible to output an image with a stable toner charge amount and a small density fluctuation over a long period of time. This is because the carrier and the toner in the developing device can be mixed well by mixing the carrier in the replenishment developer in advance, and the toner can quickly hold the charge. Guessed.

As described above, by using the photoreceptor of the present invention and the replenishment developer, it is possible to faithfully reproduce a high-resolution electrostatic latent image and to obtain an image with reduced carrier adhesion. .
Furthermore, the volume-based 50% particle size (D50) of the carrier and the replenishment carrier is 15 to 70 μm, and the true specific gravity of the carrier and the replenishment carrier is 2.5 to 4.2 g / cm ³ . When the intensity of magnetization in the magnetic field of 1000 / 4π (kA / m) of the carrier and the replenishment carrier is 40 to 70 Am ² / kg, the gradation property faithful to the electrostatic latent image is maintained for a long time. Can be obtained over a wide range.

  This is because the 50% particle diameter and true specific gravity of the carrier are within the above ranges, so that even if the developer is stirred and mixed with a screw or the like, the load on the toner is small and adhesion of the toner to the carrier is suppressed. Is done. As a result, since the carrier can maintain the initial state, it is possible to obtain development that reproduces a high-resolution electrostatic latent image for a long period of time.

  In the case of the true specific gravity, since the difference in specific gravity with the toner is small, especially the coarse powder carrier can be easily pumped up to the developer collection port, and the carrier can be recovered (discharged) stably, and the recovered carrier has less fine powder. . As a result, the carrier granularity is maintained and high image quality is maintained over a long period of time.

Further, the replenishment developer contains 2 to 50 parts by mass of replenishment toner with respect to 1 part by mass of the replenishment carrier.
When the mass ratio of the replenishing toner is less than 2 parts by mass, the amount of toner to be replenished is relatively small, the charge amount of the toner becomes uneven, and there is a tendency to cause image defects such as white streaks. On the other hand, when the mass ratio exceeds 50 parts by mass, the replenishment effect of the replenishment carrier is difficult to be obtained, the performance of the developer is lowered, the durability is deteriorated, and the fog tends to increase.

  The photoreceptor used in the present invention has a photosensitive layer on a conductive support, the photosensitive layer has at least a charge generation layer and a charge transport layer, and the total thickness of the photosensitive layer is 5.0 μm to It is 15.0 μm. The photosensitive layer may further be provided with a protective layer in order to maintain durability.

  When the total film thickness of the photosensitive layer is less than 5.0 μm, the chargeability on the photoconductor is lowered with durability, and fogging occurs on the white background. On the other hand, if it exceeds 15.0 μm, it is difficult to obtain a high-resolution electrostatic latent image.

  The charge generation material used for the charge generation layer is not particularly limited, and a general material can be used. Examples of the charge generating material include selenium-tellurium, pyrylium, thiapyrylium dyes, and phthalocyanine compounds having crystal types such as α, β, γ, ε, and X types, anthanthrone pigments, dibenzpyrenequinone pigments, and pyranthrone pigments. , Trisazo pigments, disazo pigments, monoazo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanine pigments, and various central metals and crystal systems such as quinocyanine and A-Si (amorphous silicon).

In the charge generation layer, a binder resin can be used in addition to the charge generation material. Specific examples of the binder resin include polyester, polyurethane, polyacrylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, phenol resin, acrylic resin, silicone resin, epoxy resin, urea resin, allyl resin, alkyd resin, Examples thereof include polyamide-imide, polysulfone, polyallyl ether, polyacetal, butyral resin, and benzal resin.

  In the case where the charge generation layer contains a binder resin, the ratio of the charge generation material to the total mass of the binder resin and the charge generation material is preferably 0.1 to 100.0% by mass, more preferably 10. It is 0-80.0 mass%.

  The thickness of the charge generation layer is preferably 0.1 to 6.0 μm, more preferably 0.1 to 2.0 μm. The ratio of the charge generation material contained in the entire charge generation layer is preferably 10.0 to 100.0% by mass, more preferably 50.0 to 100.0% by mass.

  Examples of the charge transport material used in the charge transport layer include pyrene compounds, N-alkylcarbazole compounds, hydrazone compounds, N, N-dialkylaniline compounds, diphenylamine compounds, triphenylamine compounds, triphenylmethane compounds, pyrazoline compounds, styryl. Compounds and stilbene compounds.

  In addition to the charge transport material, a binder resin can be used in the charge transport layer. Specific examples of the binder resin include polyester, polyurethane, polyacrylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, and polyimide.

  When the charge transport layer is the outermost surface layer of the electrophotographic photosensitive member, the charge transport layer is cured or polymerized using a high energy ray or the like, a resin or monomer that is cured or polymerized, and further has a hole transport function. It is possible to use a resin or a monomer.

  When the charge transport layer contains a binder resin, the ratio of the charge transport material to the total mass of the binder resin and the charge transport material is preferably 0.1 to 100.0% by mass, more preferably 10.0. It is -80.0 mass%.

  If the thickness of the charge transport layer is too thin, the charging ability cannot be maintained. Preferably it is 5.0-14.9 micrometers, More preferably, it is 7.0-12.0 micrometers.

The ratio of the amount of the charge transport material contained in the charge transport layer is preferably 20.0 to 100.0% by mass, more preferably 30.0 to 90.0% by mass.
Moreover, when providing a protective layer in the upper layer of an electric charge transport layer, the film thickness is 0.1-8.0 micrometers, More preferably, it is 0.1-7.0 micrometers. For this protective layer, it is possible to use a resin or monomer that cures and polymerizes using radiation or electron beams. Further, the protective layer may contain a conductive material such as a metal and its oxide, nitride, salt, alloy or carbon. Examples of such metal species include iron, copper, gold, silver, lead, zinc, nickel, tin, aluminum, titanium, antimony, and indium. Specifically, ITO, TiO ₂ , ZnO, SnO ₂ Al ₂ O ₃ or the like can be used. The conductive material is dispersed in the form of fine particles in the protective layer, and the particle size is preferably 0.001 to 5.000 μm, more preferably 0.010 to 1.000 μm. The amount added to is preferably 1.0 to 70.0 mass%, more preferably 5.0 to 50.0 mass%. A titanium coupling agent, a silane coupling agent, various surface activities, and the like may be used as the dispersant.

Various additives such as an antioxidant and a photodegradation inhibitor may be used for each layer constituting the photosensitive layer. Further, the outermost surface layer of the electrophotographic photosensitive member used in the present invention may contain various fluorine compounds, silane compounds, metal oxides or the like or fine particles thereof for the purpose of improving the lubricity and water repellency. . A dispersant or a surfactant may be used for the purpose of improving these dispersibility. The content of these additives in the outermost surface layer is preferably 1.0 to 70.0% by mass, more preferably 5.0 to 50.0% by mass.

A known support can be used as the conductive support used for the photoreceptor. For example, there are metals and alloys such as iron, copper, gold, silver, aluminum, zinc, titanium, lead, nickel, tin, antimony, and indium, or conductive materials such as oxides, carbon, and conductive polymers of the above metals. It can be used.
When the conductive material is molded as it is, it is deposited on the surface of the support member when it is used as a coating applied to the surface of the support member in order to form a conductive surface. In some cases, it may be processed by etching or plasma treatment. When a conductive material is used as a coating material, the support can be made of non-conductive materials such as paper and plastic as well as the metal and alloy.

As a layer structure of the photosensitive layer, a normal layer stack structure in which the charge generation layer / charge transport layer are stacked in this order from the conductive support side, and a reverse layer stack structure in which the charge transport layer / charge generation layer is stacked in this order from the conductive support side. Alternatively, any configuration of a single layer in which the charge generation material and the charge transport material are dispersed in the same layer can be employed.
In a single photosensitive layer, generation and movement of photocarriers are performed in the same layer, and the photosensitive layer itself is a surface layer. On the other hand, the laminated photosensitive layer has a structure in which a charge generation layer for generating photocarriers and a charge transport layer for moving the generated carriers are laminated.
The most preferable layer structure is a normal layer structure in which the charge generation layer / charge transport layer are laminated in this order from the conductive support side.
In this case, the charge transport layer is an electrophotographic photosensitive member that is an outermost surface layer containing a curable resin, or the charge transport layer is a laminated type of a non-curable first layer and a curable second layer. Any of the electrophotographic photoreceptors in which the curable second layer is the outermost surface layer is preferable.
In either case of a single layer or a laminate, a protective layer can be provided on the upper layer of the photosensitive layer. In this case, the protective layer preferably contains a curable resin.

  Furthermore, it is preferable to provide a conductive layer for the purpose of preventing interference fringes due to scattering when the support is coated with unevenness or defects, and when the image input is laser light. This can be formed by dispersing conductive powder such as carbon black, metal particles, and metal oxide in a binder resin.

  Further, an undercoat layer may be provided between the conductive support or the conductive layer and the photosensitive layer. The undercoat layer functions as a charge injection control or an adhesive layer at the interface between the layers. The undercoat layer is mainly composed of a binder resin, but may contain the metal or alloy, or oxides, salts, or surfactants thereof. Specific examples of the binder resin for forming the undercoat layer include polyester, polyurethane, polyacrylate, polyethylene, polystyrene, polybutadiene, polycarbonate, polyamide, polypropylene, polyimide, phenol resin, acrylic resin, silicone resin, epoxy resin, urea resin. , Allyl resin, alkyd resin, polyamide-imide, nylon, polysulfone, polyallyl ether, polyacetal, butyral resin, and the like. The thickness of the undercoat layer is preferably 0.1 to 7.0 μm, more preferably 0.1 to 2.0 μm.

Each of the above-described layers such as the outermost surface layer of the electrophotographic photosensitive member is the support itself or a layer that has already been formed on the support, or a composition such as a solution or dispersion containing the desired compound itself. It can be formed by a known method of adhering by a known method such as vapor deposition or coating, forming a film of the compound or composition, and curing the film. Among such known methods, the coating method is most preferable. The coating method can form films having various compositions in a wide range from a thin film to a thick film. Specifically, it is applied by bar coater, knife coater, dip coating, spray coating, beam coating, electrostatic coating, roll coater, attritor, powder coating, etc.

FIG. 1 shows a schematic configuration example of a general transfer type electrophotographic apparatus using the electrophotographic photosensitive member used in the present invention.
In FIG. 1, reference numeral 1 denotes an electrophotographic photosensitive member used in the present invention as an image carrier, which is driven to rotate at a predetermined peripheral speed in the direction of an arrow about an axis 1a. In the rotating process, the electrophotographic photosensitive member 1 is uniformly charged with a positive or negative predetermined potential on the surface of the outermost surface layer by the charging means 2 and then exposed to light image exposure (slit exposure / laser) by image exposure L in the exposure portion. Beam scanning exposure). As a result, electrostatic latent images corresponding to the exposure images are sequentially formed on the surface of the outermost surface layer of the electrophotographic photosensitive member.

The electrostatic latent image is then supplied with toner from the developing sleeve 3-1 by the developing means 3, and the developed toner image is transferred from the sheet feeding unit (not shown) by the transferring means 4 to the electrophotographic photosensitive member 1 and the transferring means. 4 are sequentially transferred onto the surface of the transfer material 7 taken out and fed in synchronism with the rotation of the electrophotographic photosensitive member 1.
The transfer material 7 that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means 8, and subjected to image fixing, and is output to the outside as a copy.
The surface of the electrophotographic photosensitive member 1 after the image transfer is cleaned by removing the transfer residual toner by the cleaning means 5 and further subjected to charge removal by the pre-exposure means 6 and repeatedly used for image formation.

Among the above-described components such as the photosensitive member, the developing unit, and the cleaning unit, a plurality of components are integrally coupled as an apparatus unit, and this unit is a process cartridge that is configured to be detachable from the apparatus body. May be. FIG. 2 shows an example of a process cartridge.
For example, the electrophotographic photosensitive member 1 and the cleaning unit 5 may be integrated into a single apparatus unit, and may be configured to be detachable using a guide unit such as a rail 12 of the apparatus body. At this time, the apparatus unit may be configured with a charging unit and / or a developing unit.
When the electrophotographic apparatus is used as a copying machine or a printer, the image exposure L is a reflected light or transmitted light from an original or a read signal of the original, and this signal is used to scan a laser beam, drive an LED array, or This is done by driving a liquid crystal shutter array. When used as a facsimile printer, image exposure is exposure for printing received data.

In the present invention, the electrostatic latent image is preferably exposed using a semiconductor laser having a wavelength of 380 nm to 500 nm to form an electrostatic latent image.
This is because the relationship between the spot diameter D and the wavelength λ is expressed by the following relational expression.
D = 1.22λ / NA (where NA represents the lens numerical aperture)

Specific examples of the semiconductor laser having a wavelength of 380 nm to 500 nm include a blue light emitting semiconductor laser (380 nm to 500 nm), and a laser spot using a similar optical system to a conventional red semiconductor laser (680 nm, 780 nm). It is possible to reduce the diameter to about ½.
In this way, a laser beam with a small diameter can be formed by using a semiconductor laser having a wavelength of 380 nm to 500 nm, and high-definition image recording can be performed particularly by performing area gradation control faithfully from highlight to halftone. , Particularly good gradation characteristics can be realized.
When this is applied to the present invention, it becomes possible to form a laser spot light latent image with a small diameter on the photoconductor, to obtain a high-quality image faithfully reproducing the latent image, further preventing carrier adhesion, and long-term This is preferable because a stable image can be output over a wide range.

  In the case of a semiconductor laser having a wavelength exceeding 500 nm, it is difficult to make the spot diameter smaller than a certain value from the relational expression D = 1.22λ / NA. Moreover, it is difficult to increase the output of a semiconductor laser having a wavelength of less than 380 nm, so that it has not been actually produced at present.

  The electrophotographic photosensitive member used in the present invention can be used not only in electrophotographic copying machines but also widely in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, liquid crystal printers, and laser plate making.

In the present invention, the volume-based 50% particle size (D50) of the carrier and the replenishment carrier is 15 to 70 μm, and the true specific gravity of the carrier and the replenishment carrier is 2.5 to 4.2 g / cm ³ , The carrier and the replenishment carrier have a magnetization strength of 40 to 70 Am ² / kg under a magnetic field of 1000 / 4π (kA / m).

The volume distribution standard 50% particle size (D50) of the carrier and the replenishment carrier is 15 to 70 μm, preferably 20 to 70 μm, and more preferably 25 to 60 μm. When the 50% particle size (D50) based on the volume distribution is within this range, the carrier adheres well to the photoreceptor over a long period of time, and a high image with good dot reproducibility can be obtained. .
When the above is less than 15 μm, the specific surface area of the carrier is increased and the miscibility with the toner is improved, but the carrier may adhere to the photoreceptor during development. When the 50% particle diameter (D50) based on the volume distribution of the carrier exceeds 70 μm, the stress applied to the toner increases, and the developability may be deteriorated.
The volume-based 50% particle size (D50) of the carrier can be adjusted to the above range by performing air classification or sieve classification.

The true specific gravity of the carrier and the replenishment carrier is 2.5 to 4.2 g / cm ³ , preferably 2.7 to 4.1 g / cm ³ , and more preferably 3.0 to 4. 0 g / cm ³ . When the true specific gravity is in this range, the carrier has good adhesion resistance to the photoreceptor over a long period of time, and a high image with good dot reproducibility can be obtained.
When the true specific gravity is less than 2.5 g / cm ³ , the toner is easily developed on the photoreceptor during development, and carrier adhesion may occur. When the true specific gravity of the carrier exceeds 4.2 g / cm ³ , the dot reproducibility during development deteriorates, and further, the stress on the developer in the developing device increases and the carrier may be deteriorated.
The true specific gravity of the carrier can be adjusted by appropriately selecting the type and amount of the element to be contained.

The magnetization strength of the carrier and the replenishment carrier is 40 to 70 Am ² / kg under a magnetic field of 1000 / 4π (kA / m). When the magnetization intensity of the carrier is within this range, the adhesion of the carrier to the photoconductor is good for a long time, and an image with good dot reproducibility can be obtained.
When the intensity of magnetization of the carrier is less than 40 Am ² / kg, it is easy to be developed on the photoreceptor during development, and carrier adhesion may occur. When the intensity of magnetization of the carrier exceeds 70 Am ² / kg, dot reproducibility during development deteriorates, and further, stress on the developer in the developing device increases and the carrier may be deteriorated. Further, the image may be disturbed by a magnetic brush on the developing carrier.
The magnetization intensity of the carrier can be adjusted by appropriately selecting the type and amount of the element contained.

The carrier and the replenishment carrier preferably contain 90% by number or more of particles having an average circularity of 0.850 to 0.950 and a circularity of 0.800 or more.
The average circularity of the carrier and the replenishment carrier is preferably 0.870 to 0.930, and more preferably 0.880 to 0.920. The average circularity is a coefficient representing the shape of the roundness of the particle, and is obtained from the maximum diameter of the particle and the measured particle projected area. If the average circularity is 1.000, it indicates a perfect sphere (perfect circle), and the smaller the value, the longer the shape or the more irregular the shape.

When the average circularity of the carrier and the replenishment carrier is 0.850 to 0.950, the carrier has sufficient carrier strength, excellent chargeability to the toner, and hardly damages the toner. Further, toner spent hardly occurs, the adhesion resistance of the carrier onto the photoreceptor is good, and the durability is excellent. When the average circularity is less than 0.850, it means that the particles have an irregular shape. In this case, the charge imparting property to the toner may be deteriorated, which is not preferable. On the other hand, when the average circularity exceeds 0.950, the specific surface area of the carrier becomes small, and the charge imparting property may be lowered. Further, when 90% by number or more of particles having a circularity of 0.800 or more are contained, it is preferable because the toner has uniform charge imparting properties.
When the number of particles having a circularity of 0.800 or more is less than 90% by number, the charge imparting property is deteriorated and the mixing property in the developing device is deteriorated, which is not preferable.
The average circularity of the carrier can be conveniently adjusted by applying a spheroidizing process using mechanical impact and heat.

The carrier and replenishment carrier used in the present invention (hereinafter simply referred to as carrier unless otherwise specified) are not particularly limited as long as the above physical properties are satisfied. For example, a so-called resin-impregnated carrier in which a porous magnetic body (including porous ferrite) is impregnated with a resin may be used, or a magnetic body-containing resin carrier in which a magnetic body is dispersed in a resin may be used. .
Among the above carriers, it is preferable to use a magnetic substance-containing resin carrier in which a magnetic substance is dispersed in a resin.

As a method for producing the magnetic substance-containing resin carrier, there is a method obtained by polymerizing monomers constituting the resin in the presence of the magnetic substance.
At this time, as monomers used for polymerization, in addition to vinyl monomers, bisphenols and epichlorohydrin for forming epoxy resins; phenols and aldehydes for forming phenol resins; urea resins are formed For example, urea and aldehydes for forming a melamine, and melamine and aldehydes for forming a melamine resin are included.

  For example, as a method for producing a magnetic substance-containing resin carrier using a phenol resin, phenols and aldehydes are polymerized in an aqueous medium containing phenols, aldehydes and a magnetic substance in the presence of a basic catalyst. Thus, a magnetic substance-containing resin carrier can be obtained. When a magnetic substance-containing resin carrier is manufactured by this method, the average circularity is easily adjusted to the above range, which is a preferable manufacturing method.

As the resin forming the magnetic substance-containing resin carrier, a phenol resin is preferable. Examples of phenols for producing the phenol resin include phenol, alkylphenols such as m-cresol, p-tert-butylphenol, o-propylphenol, resorcinol, bisphenol A, and a part of benzene nucleus or alkyl group. Examples thereof include compounds having a phenolic hydroxyl group such as halogenated phenols, all of which are substituted with chlorine atoms or bromine atoms. Of these, phenol (hydroxybenzene) is more preferable.
Examples of aldehydes for producing the phenol resin include formaldehyde and furfural in the form of either formalin or paraaldehyde. Of these, formaldehyde is particularly preferable.

  The molar ratio of aldehydes to phenols is preferably 1 to 4, particularly preferably 1.2 to 3. If the molar ratio of aldehydes to phenols is less than 1, particles are difficult to produce, and even if they are produced, the resin does not easily cure, so the strength of the particles produced tends to be weak. On the other hand, when the molar ratio of aldehydes to phenols is larger than 4, unreacted aldehydes remaining in the aqueous medium after the reaction tend to increase.

  Examples of the basic catalyst used in the condensation polymerization of phenols and aldehydes include those used in the production of ordinary resol type resins. Examples of such basic catalysts include aqueous ammonia, hexamethylenetetramine, and alkylamines such as dimethylamine, diethyltriamine, and polyethyleneimine. The molar ratio of these basic catalysts to phenols is preferably 0.02 to 0.30.

  As another method for producing the above magnetic substance-containing resin carrier, a vinyl-type or non-vinyl-type thermoplastic resin, a magnetic substance, and other additives are sufficiently mixed by a mixer, and then a heating roll, a kneader, and an extruder. There is a method in which a magnetic material-containing resin carrier core is obtained by melting and kneading using a kneader such as the above, and cooling and then pulverizing and classifying. At this time, it is preferable that the obtained magnetic substance-containing resin carrier core is spheroidized thermally or mechanically and used as a magnetic substance-containing resin carrier.

  The amount of the magnetic substance used in the magnetic substance-containing resin carrier is 70 to 95% by mass (more preferably 80 to 92% by mass) with respect to the magnetic substance-containing resin carrier. It is preferable for reducing the true specific gravity and ensuring sufficient mechanical strength. Furthermore, in order to adjust the magnetic properties of the magnetic substance-containing resin carrier, a part of the magnetic substance contained in the magnetic substance-containing resin carrier may be replaced with a nonmagnetic inorganic compound.

In addition, the nonmagnetic inorganic compound has a larger specific resistance value than the magnetic substance, and the number average particle diameter of the nonmagnetic inorganic compound is larger than the number average particle diameter of the magnetic substance in order to increase the specific resistance value of the carrier. preferable.
The magnetic substance is contained in an amount of 30 to 99% by mass with respect to the total amount of the magnetic substance and the nonmagnetic inorganic compound. In addition, it is preferable for adjusting the specific resistance value of the magnetic substance-containing resin carrier.

In the magnetic substance-containing resin carrier, the magnetic substance is preferably magnetite fine particles, or magnetic ferrite fine particles containing at least an iron element, and the nonmagnetic inorganic compound is hematite (α-Fe ₂ O ₃ ). Fine particles are more preferable in terms of making the dispersibility in the carrier uniform and adjusting the magnetic properties and true specific gravity of the carrier.

  The number average particle diameter of the magnetic material is preferably 0.02 to 2 μm from the viewpoint of making the particle surface state of the magnetic material-containing resin carrier uniform. The nonmagnetic inorganic compound preferably has a number average particle diameter of 0.05 to 5 μm, and the nonmagnetic inorganic compound has a particle diameter of 1.1 times or more larger than that of the magnetic substance. It is preferable for increasing the surface resistance value.

The surface of the magnetic substance-containing resin carrier is preferably coated with a coating material from the viewpoint of charge imparting properties and releasability. As a resin for forming the coating material, an insulating resin is preferably used. The insulating resin that can be used in this case may be a thermoplastic resin or a thermosetting resin.
Specific examples of the resin that forms the coating material include thermoplastic resins such as polystyrene, polymethyl methacrylate, acrylic resins such as styrene-acrylic acid copolymer, styrene-butadiene copolymer, and ethylene. -Vinyl acetate copolymer, polyvinyl chloride, polyvinyl acetate, polyvinylidene fluoride resin, fluorocarbon resin, perfluorocarbon resin, solvent-soluble perfluorocarbon resin, polyvinyl alcohol, polyvinyl acetal, polyvinyl pyrrolidone, petroleum resin, cellulose, cellulose acetate, Cellulose derivatives such as cellulose nitrate, methylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, novolac resin, low molecular weight polyethylene, saturated alkyl Riesuteru resin, polyethylene terephthalate, polybutylene terephthalate, polyarylates such aromatic polyester resins, polyamide resins, polyacetal resins, polycarbonate resins, polyethersulfone resins, polysulfone resins, polyphenylene sulfide resins, polyether ketone resins.
Thermosetting resins include phenolic resins, modified phenolic resins, maleic resins, alkyd resins, epoxy resins, acrylic resins, or unsaturated polyesters obtained by polycondensation of maleic anhydride, terephthalic acid and polyhydric alcohols, urea Resin, melamine resin, urea-melamine resin, xylene resin, toluene resin, guanamine resin, melamine-guanamine resin, acetoguanamine resin, gliptal resin, furan resin, silicone resin, polyimide, polyamideimide resin, polyetherimide resin, polyurethane resin Is mentioned.
The above-mentioned resins can be used alone or in combination. Further, it can be used by mixing a curing agent or the like with a thermoplastic resin and curing it. As a particularly preferable form, it is preferable to use a resin having a higher release property for a toner having a small particle diameter and containing a release agent.

  Furthermore, it is preferable that the coating material contains particles having conductivity and particles having charge controllability. Such a coating material contains the resin forming the coating material, or the monomer forming the resin with conductive particles or charge controllable particles, and the resin or monomer is magnetized by an appropriate method. It is preferable to coat the body-containing resin carrier. These particles are important in terms of soft and quick charging to a toner having a small particle size and low temperature fixability.

The conductive particles preferably have a specific resistance of 1 × 10 ⁸ Ωcm or less,
Furthermore, a specific resistance of 1 × 10 ⁶ Ωcm or less is more preferable. Specifically, the conductive particles are preferably particles containing at least one kind of particles selected from carbon black, magnetite, graphite, zinc oxide, and tin oxide. In particular, as the particles having conductivity, carbon black having good conductivity is preferable in terms of improving the charge imparting property (rise of charge amount) to the toner.

  It is preferable that the conductive particles have a number average particle size of 1 μm or less in order to prevent the particles from falling off from the carrier and to function as a uniform conductive site.

The particles having charge controllability include organometallic complex particles, organometallic salt particles, chelate compound particles, monoazo metal complex particles, acetylacetone metal complex particles, hydroxycarboxylic acid metal complex particles, and polycarboxylic acid. Examples thereof include metal complex particles and polyol metal complex particles. A charge control agent dispersed in the toner particles may be used. In order to improve the charge imparting property to the toner, it is possible to use resin particles having a functional group or inorganic particles treated with a treatment agent having a functional group. preferable.
Specifically, the particles having charge controllability include polymethyl methacrylate resin particles, polystyrene resin particles, melamine resin particles, phenol resin particles, nylon resin particles, silica particles, titanium oxide particles, and The particles preferably contain at least one kind of particles selected from alumina particles. Further, in the case of inorganic particles, it is preferable to use them after being treated with various coupling agents in order to develop charge controllability and conductivity.
The particles having charge control properties preferably have a number average particle diameter of 0.01 to 1.50 μm from the viewpoint of functioning as a uniform charging site.

The coating amount of the resin forming the coating material on the magnetic substance-containing resin carrier is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the magnetic substance-containing resin core. And, it is preferable for enhancing the durability of the carrier. The blending amount of the conductive particles and the charge controllable particles is preferably 0.1 to 30.0 parts by mass in total with respect to 100 parts by mass of the resin forming the coating material.
If the conductive particles or the charge controllable particles are added in an amount exceeding 30 parts by mass, the particles are difficult to disperse in the resin forming the coating material, and the particles are removed from the magnetic substance-containing resin carrier. May be separated. In particular, when carbon black is added, the toner may be contaminated with carbon black or the member may be contaminated as the durability increases.

  When the toner and the carrier are mixed and used as a two-component developer in the developing device, the mixing ratio of the toner and the carrier is 0.02 parts by mass to 0.35 parts by mass with respect to 1 part by mass of the carrier. It is preferably used in the range of parts by mass, more preferably 0.04 parts by mass to 0.25 parts by mass, and particularly preferably 0.05 parts by mass to 0.20 parts by mass. If the mixing ratio of the toner and the carrier is less than 0.02 parts by mass with respect to 1 part by mass of the carrier, the image density tends to decrease, and if it exceeds 0.35 parts by mass, fogging and scattering in the machine are likely to occur.

  In the present invention, the replenishment developer contains toner in a mass ratio of 2.0 to 50.0 parts by mass with respect to 1 part by mass of the carrier, and the toner and carrier in the replenishment developer If it is within the above range in the developing device, it can be mixed uniformly and efficiently, and it becomes a developer having a uniform charge distribution.

In the present invention, the toner and the replenishing toner have a light transmittance at a wavelength of 600 nm of a dispersion obtained by dispersing the toner in an aqueous solution containing 45% by volume of methanol, preferably 30% to 80%, more preferably. It is in the range of 35 to 70%, more preferably 35 to 60%.
When the transmittance (%) is in the above range, there is no image defect for a long period from the beginning, and high durability can be obtained. Further, it is possible to faithfully reproduce and develop a high-resolution electrostatic latent image on the photoreceptor of the present invention. This is considered to be due to the fact that the toner having such a transmittance is used during the development, thereby releasing from the carrier and developing efficiently.
Also, toner fusion and carrier adhesion to the surface of the photosensitive drum used in the present invention can be prevented. Further, it is possible to improve dot reproducibility and transfer efficiency when an image developed on the electrophotographic photosensitive member with toner is transferred to a transfer material.
In particular, when an electrostatic latent image is formed with a semiconductor laser having a wavelength of 380 nm to 500 nm, it is possible to realize good gradation characteristics particularly from highlight to halftone.

The toner and replenishing toner used in the present invention (hereinafter simply referred to as toner unless otherwise specified) may contain a wax in the toner. When the toner contains a wax, at least the wax is present on the toner surface. When the transmittance is less than 30%, the amount of wax on the toner surface is small, and a releasing effect at the time of fixing is hardly exhibited, and the effect of low-temperature fixability desired from the viewpoint of energy saving is reduced. When the transmittance exceeds 80%, a large amount of wax is present on the toner surface, and the wax is contaminated on the electrophotographic photosensitive member, causing toner fusion. Further, when fused on the developing sleeve, the resistance on the developing sleeve becomes high, and the effectiveness of the actual developing bias for development is lowered, and the image density is lowered and the developing durability may be deteriorated. Further, it may cause carrier adhesion to the surface of the photoreceptor. Thus, when the wax is contained in the toner, it is preferable to control the amount of wax on the toner surface.

The control of the amount of wax on the toner surface is particularly preferably used when the electrophotographic photoreceptor used in the present invention is used. When the transmittance is less than 30%, it means that the amount of wax on the toner surface is relatively reduced. In the cleaning process, the cleaning blade and the outermost surface of the electrophotographic photosensitive member when residual transfer toner is interposed The frictional resistance of the surface of the layer becomes high, and as a result, toner fusion occurs. On the other hand, when the transmittance exceeds 80%, the amount of wax on the toner surface increases, and at the same time, a lot of wax is released in the toner, so that the wax adheres directly to the surface of the outermost surface layer of the electrophotographic photosensitive member. As a result, toner fusion occurs. Also in the transfer process, the releasability from the photoreceptor is deteriorated, and the transfer efficiency is deteriorated. Also, the charge distribution of the toner particles becomes unstable, and the dot reproducibility for the latent image on the photoconductor deteriorates.
For this reason, in the image forming method using the electrophotographic photoreceptor used in the present invention, the light transmittance (%) at a wavelength of 600 nm of a dispersion in which toner is dispersed in an aqueous solution containing 45% by volume of methanol is controlled. Is particularly preferred. When the transmittance is in the range of 30 to 80%, toner fusion does not occur, toner with good dot reproducibility and good transfer efficiency can be obtained.

  Further, the amount of wax on the toner surface can be measured easily and with high accuracy by measuring the light transmittance (%) at a wavelength of 600 nm of a dispersion in which the toner is dispersed in an aqueous solution containing 45% by volume of methanol.

  In this measurement method, the toner is forcibly dispersed once in a methanol-water mixed solvent so that the characteristics of the surface wax amount of each toner particle can be easily obtained, and the transmittance after a certain time is measured. The amount of wax on the toner surface can be accurately grasped. In other words, if a large amount of hydrophobic wax is present on the toner surface, the toner dispersed in the solvent is difficult to wet and does not settle, resulting in high transmittance. Conversely, if the amount of wax on the toner surface is low, By showing the property, the transmittance becomes a small value.

The transmittance can be adjusted by the conditions and processing method of the spheroidizing treatment of the toner particles. Specifically, when the transmittance is less than 30%, the amount of wax on the toner surface may be increased, and when the transmittance exceeds 80%, the amount of wax on the toner surface may be decreased. The amount of wax can be adjusted, for example, by using heat in the spheroidization treatment of the toner surface.

  It is preferable that an average circularity of particles having an equivalent circle diameter of 2.0 μm or more of the toner is 0.930 to 1.000. When the toner having an average circularity in the above range is used in the image forming method of the present invention, it is preferable for achieving both transferability and developability. When the average circularity of the toner is lower than 0.930, the spheroidizing treatment is insufficient, the control of the presence of the release agent is insufficient, and the low-temperature fixability may be slightly lowered, and the transfer efficiency is lowered. Sometimes.

The toner has a weight average particle diameter (D4) of preferably 3.0 to 8.0 μm, and more preferably 4.0 to 6.0 μm in order to sufficiently satisfy dot reproducibility and transfer efficiency. If the weight average particle diameter of the toner is less than 3.0 μm, the yield of the toner particles during the spheronization treatment is reduced, and the specific surface area of the toner particles and the specific surface area of the toner are increased. It becomes difficult to uniformly control the temperature, and it may be impossible to achieve both low-temperature fixability and developability. In that case, toner fusing may occur on the surface of the photoreceptor. On the other hand, when the weight average particle diameter of the toner exceeds 8.0 μm, the scattering of the toner can be visually detected, and the dots when the spot of the electrostatic latent image has a minute spot diameter of 600 dpi or more are obtained. Reproducibility decreases. The weight average particle diameter of the toner can be adjusted by classifying the toner particles at the time of production.

  The toner used in the present invention preferably has a molecular weight distribution measured by gel permeation chromatography (GPC) of a resin component in the region of a molecular weight of 3,500 to 15,000. More preferably in the region of 000 to 13,000, and Mw / Mn is preferably 3.0 or more, more preferably 5.0 or more. When the main peak is in a region having a molecular weight of less than 3,500, the high temperature offset resistance of the toner decreases. On the other hand, when the main peak is in a region having a molecular weight of more than 15000, sufficient low-temperature fixability of toner and OHT permeability are lowered. Moreover, when Mw / Mn is less than 3.0, good offset resistance is reduced.

Further, the toner used in the present invention has a peak temperature of a maximum endothermic peak existing in a temperature range of 30 to 200 ° C. in an endothermic curve at a temperature rise measured by a differential scanning calorimetry (DSC) apparatus. It is preferable to be in the range of ° C. More preferably, it is in the range of 65 to 105 ° C, and particularly preferably in the range of 65 to 100 ° C.
When the peak temperature is less than 65 ° C., the storage stability of the toner deteriorates, and when the peak temperature exceeds 110 ° C., the dispersion of wax in the toner particles deteriorates, so that the amount of surface wax of the toner increases. The transmittance (%) in the 45% by volume aqueous methanol solution is large, which is not preferable.

  The wax is used in an amount of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin.

  In the endothermic curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) apparatus, the peak temperature of the maximum endothermic peak existing in the temperature range of 30 to 200 ° C. controls the type of wax used in the toner and the dispersion state. It is possible to adjust by.

  The toner used in the present invention preferably contains a binder resin, a colorant and a wax. The kind of the wax is not particularly limited. The binder resin is preferably a resin having at least a polyester unit.

  The above-mentioned “polyester unit” means a part derived from polyester. Specifically, as a component constituting the polyester unit, a divalent or higher alcohol monomer component and a divalent or higher carboxylic acid, a divalent or higher valent acid, Examples include acid monomer components such as carboxylic acid anhydrides and divalent or higher carboxylic acid esters.

For the toner used in the present invention, a resin having a polycondensation portion using a component constituting the polyester unit as a part of the raw material can be used.
The binder resin used in the toner is a polyester resin, a hybrid resin having a polyester unit and a vinyl polymer unit, a mixture of a hybrid resin and a vinyl polymer, or a mixture of a hybrid resin and a polyester resin. Or a resin selected from a mixture of a polyester resin, a hybrid resin, and a vinyl polymer, or a mixture of a polyester resin and a vinyl polymer.

The hybrid resin is formed by a transesterification reaction between a polyester unit component and a vinyl polymer unit obtained by polymerizing a monomer component having a carboxylic acid ester group such as (meth) acrylic acid ester. A graft copolymer (or block copolymer) in which a polymer is a trunk polymer and a polyester unit is a branched polymer.

  As the divalent or higher alcohol monomer component as the polyester unit component, specifically, as the divalent alcohol monomer component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, Polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2. 0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, bisphenol A alkylene such as polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane Oxide adduct, ethylene glycol, diethylene glycol, triethylene glycol, 1,2- Lopylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, Examples include dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, and hydrogenated bisphenol A.

  Examples of the trivalent or higher alcohol monomer component include sorbit, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Is mentioned.

  The divalent carboxylic acid monomer component which is the polyester unit component includes aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid. Acids or anhydrides thereof; succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof; .

Examples of the trivalent or higher carboxylic acid monomer component include trimellitic acid, pyromellitic acid, polyvalent carboxylic acid such as benzophenone tetracarboxylic acid and its anhydride, and the like.
Examples of other monomers include polyhydric alcohols such as oxyalkylene ethers of novolak type phenol resins.
Among them, in particular, a bisphenol derivative represented by the following general formula (A) is a dihydric alcohol monomer component, and a carboxylic acid component comprising a divalent or higher carboxylic acid or an acid anhydride thereof or a lower alkyl ester thereof ( For example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) are used as acid monomer components, and resins obtained by condensation polymerization with these polyester unit components have good charging characteristics. Therefore, it is preferable.

（式中、Ｒはエチレン又はプロピレン基を示し、ｘ，ｙはそれぞれ１以上の整数であり、
かつｘ＋ｙの平均値は２〜１０である。）

(In the formula, R represents an ethylene or propylene group, x and y are each an integer of 1 or more,
And the average value of x + y is 2-10. )

The binder resin used in the toner is preferably a resin having at least a polyester unit, and more preferably, the polyester unit component contained in the total binder resin is 30% by mass with respect to the total binder resin. % Or more is preferable for exhibiting the effects of the present invention. More preferably, it is 40 mass% or more, Most preferably, it is 50 mass% or more.
When the amount of the polyester unit component contained in the total binder resin is 30% by mass or more with respect to the total binder resin, it is preferable in terms of fixability and charging stability.

  The following are mentioned as a vinyl-type monomer for producing | generating the vinyl-type polymer unit or vinyl-type polymer used for the said hybrid resin. Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene and derivatives thereof such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene Class: Vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride Vinyl halides such as; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, Α-methylene aliphatic monocarboxylic acid esters such as dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, acrylic Propyl acid, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chlore acrylate , Acrylic esters such as phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl compounds such as N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  In addition, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester unsaturated dibasic acid half ester; dimethylmaleic acid, dimethyl fumaric acid unsaturated dibasic acid ester; acrylic acid, meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, the α, β-unsaturated acid and lower fatty acids And monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

  The vinyl polymer or vinyl polymer unit used in the hybrid resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups, but the crosslinking agent used in this case is Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,4-butanediol. Examples include diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate; linked by an alkyl chain containing an ether bond. Diacrylate Examples of the compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds. Examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond include, for example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate Polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing acrylates of the above compounds with methacrylate.

  Polyfunctional cross-linking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallylcia Examples include nurate and triallyl trimellitate.

  The hybrid resin preferably contains a monomer component capable of reacting with both resin components in the vinyl polymer or unit and / or the polyester resin or unit. Among the monomers constituting the polyester resin or unit, those capable of reacting with the vinyl polymer or unit include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid and itaconic acid, or anhydrides thereof. It is done. Among the monomers constituting the vinyl polymer or unit, those capable of reacting with the polyester resin or unit include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method for obtaining a reaction product of a vinyl polymer and a polyester resin, either a polymer or a resin containing a monomer component capable of reacting with each of the vinyl polymer and the polyester resin listed above is present. A method obtained by polymerizing one or both of the polymers or resins is preferred.

Examples of the polymerization initiator used for producing the vinyl polymer or vinyl polymer unit include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-methoxy-). 2,4-dimethylvaleronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobis Isobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo- 2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide , Ketone peroxides such as cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydro Peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, deca Noyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-toluoyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxide -Bonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl per Oxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t- Butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxy Oxy hexahydro terephthalate, di -t- butyl peroxy azelate and the like.

As a manufacturing method of the said hybrid resin component, the following (1)-(6) can be mentioned, for example.
(1) A method in which a vinyl polymer, a polyester resin, and a hybrid resin component are blended after production. The blend is produced by dissolving and swelling in an organic solvent (for example, xylene) and then distilling off the organic solvent. The hybrid resin component is synthesized by separately producing a vinyl polymer and a polyester resin, dissolving and swelling in a small amount of an organic solvent, adding an esterification catalyst and an alcohol, and performing a transesterification reaction by heating. The ester compound used can be used.
(2) A method of producing a hybrid resin component having a polyester unit and a vinyl polymer unit by producing and reacting a polyester resin in the presence of the vinyl polymer after production. The hybrid resin component is produced by a reaction between a vinyl polymer (a vinyl monomer can be added if necessary) and a polyester monomer (alcohol, carboxylic acid) and / or a polyester resin. Also in this case, an organic solvent can be appropriately used.
(3) A method of producing a hybrid resin component having a polyester unit and a vinyl polymer unit by producing and reacting a vinyl polymer in the presence of the polyester resin after production. The hybrid resin component is produced by a reaction between a polyester resin (a polyester monomer can be added if necessary) and a vinyl monomer and / or a vinyl polymer.
(4) After the vinyl polymer and the polyester resin are produced, the hybrid resin component is produced by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) in the presence of these polymer units. Also in this case, an organic solvent can be appropriately used.
(5) After producing a hybrid resin component having a polyester unit and a vinyl polymer unit, by adding a vinyl monomer and / or a polyester monomer (alcohol, carboxylic acid) and performing an addition polymerization and / or a condensation polymerization reaction. A vinyl polymer and / or polyester resin, or further a hybrid resin component is produced. In this case, as the hybrid resin component having the polyester unit and the vinyl polymer unit, those produced by the production methods (2) to (4) can be used, and if necessary, by a known production method. What was manufactured can also be used. Furthermore, an organic solvent can be used as appropriate.
(6) By mixing a vinyl monomer and a polyester monomer (alcohol, carboxylic acid, etc.) and continuously performing addition polymerization and condensation polymerization reaction, a vinyl polymer, a polyester resin, a polyester unit and a vinyl polymer unit are obtained. A hybrid resin component is produced. Furthermore, an organic solvent can be used as appropriate.
In the production methods (1) to (6) above, the vinyl copolymer unit and / or the polyester unit can use a plurality of polymer units having different molecular weights and cross-linking degrees.

  In the present invention, the vinyl polymer or vinyl polymer unit means a vinyl homopolymer, a vinyl copolymer, a vinyl monopolymer unit, or a vinyl copolymer unit.

  Examples of the wax used in the toner include the following. Oxides of aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or the like Block copolymers of these products: Deoxidized part or all of fatty acid esters such as carnauba wax, behenic ester behenate wax, and montanic acid ester wax, and fatty acid esters such as deoxidized carnauba wax Things. In addition, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brandic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and seryl alcohol Saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid; and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, seryl alcohol, Esters of alcohols such as merisyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid Saturated fatty acid bisamides such as amide, ethylene bislauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N ′ dioleyl Unsaturated fatty acid amides such as sebacic acid amides; Aromatic bisamides such as m-xylene bisstearic acid amide and N, N ′ distearyl isophthalic acid amides; calcium stearate, calcium laurate, zinc stearate, magnesium stearate, etc. Aliphatic metal salts (generally referred to as metal soaps); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides and many others Price Lumpur partial ester; methyl ester compounds having hydroxyl groups obtained by and hydrogenated vegetable oils and the like.

Examples of the wax particularly preferably used in the present invention include aliphatic hydrocarbon waxes and esterified products which are esters of fatty acids and alcohols. For example, low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure with Ziegler catalyst or metallocene catalyst under low pressure; alkylene polymer obtained by thermal decomposition of high molecular weight alkylene polymer; synthesis containing carbon monoxide and hydrogen A synthetic hydrocarbon wax obtained from the distillation residue of hydrocarbons obtained from the gas by the age method or by hydrogenating them is preferred. Furthermore, what carried out the fractionation of the hydrocarbon wax by the use of the press perspiration method, the solvent method, the vacuum distillation or the fractional crystallization method is more preferably used. Hydrocarbons as the base are synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (mostly two or more multi-component systems) [for example, the Jintole method, the hydrocol method (with a fluid catalyst bed). Hydrocarbon compounds synthesized by use); hydrocarbons with up to several hundred carbon atoms obtained by the age method (using the identified catalyst bed) in which a large amount of wax-like hydrocarbons can be obtained; alkylene such as ethylene by Ziegler catalyst Polymerized hydrocarbons are preferred because they are linear hydrocarbons with little branching, small and long saturation. In particular, a wax synthesized by a method that does not rely on polymerization of alkylene is also preferred from its molecular weight distribution. Paraffin wax is also preferably used.

  As the colorant used in the toner, known dyes and / or pigments are used. Although the pigment alone may be used, it is more preferable from the viewpoint of the image quality of the full-color image that the combination of the dye and the pigment improves the sharpness.

  Examples of the color pigment for magenta toner include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perlin compounds. Specifically, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 254, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the magenta toner dye include C.I. I solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic dyes such as basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28 may be mentioned.

  Examples of the color pigment for cyan toner include C.I. I. Pigment Blue 1, 2, 3, 7, 15: 2, 15: 3, 15: 4, 16, 17, 60, 62, 66; I. Bat Blue 6, C.I. I. Examples include Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on a phthalocyanine skeleton having a structure represented by the following formula (B).

〔式中、ｎは１〜５の整数を示す。〕

[In formula, n shows the integer of 1-5. ]

  Examples of the colored pigment for yellow include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal compounds, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 155, 168, 174, 180, 181, 185, 191, C.I. I. Bat yellow 1, 3, 20 and the like. In addition, C.I. I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6 and Solvent Yellow 162 can also be used.

  As the black colorant used for the toner, carbon black, iron oxide, and a toner that is toned in black using the yellow / magenta / cyan colorant shown above can be used.

In the above toner, it is preferable to use a toner obtained by mixing a colorant with a binder resin in advance and forming a master batch. Then, the colorant can be favorably dispersed in the toner by melt-kneading this colorant master batch and other raw materials (binder resin, wax, etc.).
When a colorant is mixed with the binder resin to make a master batch, even if a large amount of colorant is used, the dispersibility of the colorant is not deteriorated, and the dispersibility of the colorant in the toner particles is improved. Excellent color reproducibility such as color mixing and transparency. Further, a toner having a large covering power on the transfer material can be obtained. Further, since the dispersibility of the colorant is improved, it is possible to obtain an image having excellent durability stability of toner chargeability and maintaining high image quality.

  The amount of the colorant used in the toner is preferably 0.1 to 15.0 parts by mass, and 0.5 to 12.0 parts by mass with respect to 100 parts by mass of the binder resin in terms of color reproducibility and developability. Part is more preferable, and 2.0 to 10.0 parts by mass is most preferable.

  A known charge control agent can be used for the toner in order to stabilize its chargeability. The charge control agent varies depending on the type of charge control agent and the physical properties of other toner constituent materials, but generally 0.1 to 10.0 parts by mass per 100 parts by mass of the binder resin is preferably contained in the toner. More preferably, 0.1 to 5.0 parts by mass are contained. As such a charge control agent, there are known one that controls the toner to be negatively charged and one that controls the toner to be positively charged. One or two kinds of various kinds of charge control agents are used depending on the kind and use of the toner. The above can be used.

  Examples of the negatively chargeable charge control agent include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds, calixes. Arene etc. can be used. As the positively chargeable charge control agent, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, an imidazole compound, or the like can be used. The charge control agent may be added internally or externally to the toner.

  In particular, the charge control agent used in the toner is preferably an aromatic carboxylic acid metal compound that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount.

  The toner can be used for the purpose of improving the performance of the toner by pulverizing and classifying and then mixing a fluidizing agent, a transfer aid, a charge stabilizer and the like with a mixer such as a Henschel mixer.

In the present invention, inorganic fine particles having a number average particle diameter of 0.06 μm to 0.30 μm are preferably added to the toner particles for the purpose of improving transferability.
As the inorganic fine particles, one or more kinds selected from titanium oxide fine particles, alumina fine particles, and silica fine particles can be used. When the inorganic fine particles have a number average particle size of 0.06 μm to 0.30 μm, it can function as an appropriate spacer between the toner surface and the photoreceptor, and good transferability without toner scattering can be obtained.
When the number average particle diameter of the inorganic fine particles is less than 0.06 μm, the effect of the spacer on the toner and the photoreceptor is small, and the effect of improving transferability is not seen. When the number average particle diameter of the inorganic fine particles exceeds 0.30 μm, the adhesion force of the inorganic fine particles to the toner is weakened, and the inorganic fine particles are released from the toner and scattered, thereby deteriorating the fog.

The surface of the inorganic fine particle is more preferably subjected to a hydrophobic treatment. The inorganic fine particles may be oil-treated.
Examples of the method of hydrophobizing the surface of the inorganic fine particles include a method of chemically or physically treating the inorganic fine particles with an organosilicon compound that reacts or physically adsorbs with the inorganic fine particles.

A preferable method for the hydrophobic treatment is a method in which silica fine particles produced by vapor phase oxidation of a silicon halogen compound are treated with an organosilicon compound. Examples of such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchloro. Silane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisilo Xan, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane having 2 to 12 siloxane units per molecule and having one hydroxyl group each in Si located at the terminal. These are used alone or in a mixture of two or more.
The content of the inorganic fine particles is preferably 0.8 to 8.0 parts by mass, and more preferably 1.0 to 4.0 parts by mass with respect to 100 parts by mass of the toner.

  As the fluidizing agent, any fluidizing agent can be used as long as it can increase the fluidity before and after the addition. For example, fluorinated resin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, titanium oxide fine powder, alumina fine powder, wet process silica, fine process silica such as dry process silica, silane compound, and organic Examples thereof include treated silica that has been surface-treated with a silicon compound, a titanium coupling agent, silicone oil, and the like.

The dry process silica is a fine powder produced by vapor phase oxidation of a silicon halogen compound, and is referred to as so-called dry process silica or fumed silica, and is manufactured by a known technique. For example, the production method uses a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction equation is the following equation (2).
(2): SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl
In this production process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride or titanium chloride together with silicon halogen compounds. . The particle size is preferably within the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably, silica fine powder within the range of 0.002 to 0.200 μm is used.

  In the case of titanium oxide fine powder, fine particles of titanium oxide obtained by low-temperature oxidation (thermal decomposition, hydrolysis) of sulfuric acid method, chlorine method, volatile titanium compounds such as titanium alkoxide, titanium halide and titanium acetylacetonate are used. As the crystal system, any of anatase type, rutile type, mixed crystal type thereof, and amorphous type can be used.

  And if it is alumina fine powder, buyer method, improved buyer method, ethylene chlorohydrin method, underwater spark discharge method, organoaluminum hydrolysis method, aluminum alum pyrolysis method, ammonium aluminum carbonate pyrolysis method, aluminum chloride flame Alumina fine powder obtained by a decomposition method is used. As the crystal system, α, β, γ, δ, ξ, η, θ, κ, χ, ρ type, mixed crystal type, amorphous type, α, δ, γ, θ, mixed crystal can be used. A mold or an amorphous material is preferably used.

The fluidizing agent used in the present invention preferably has a specific surface area by nitrogen adsorption measured by BET method of 30 m ² / g or more, preferably 50 m ² / g or more from the viewpoint of fluidity imparting property. The fluidizing agent is used in an amount of 0.1 to 8.0 parts by weight, preferably 0.1 to 4.0 parts by weight, based on 100 parts by weight of the toner.

  Next, a procedure for producing the toner and developer used in the present invention will be described. The toner used in the present invention is obtained by mixing a binder resin, a colorant, a wax, and an arbitrary material as raw materials, then melt-kneading, cooling and pulverizing, and pulverizing the pulverized product as necessary. Alternatively, it may be produced by performing a classification treatment and mixing the fluidizing agent as necessary.

Specific examples are shown below.
First, in the raw material mixing step, at least a resin and a colorant are weighed and mixed as toner internal additives, and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer.

  Further, the toner raw materials blended and mixed as described above are melt-kneaded to melt the resins, and the colorant and the like are dispersed therein. In the melt-kneading step, for example, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. In recent years, single-screw or twin-screw extruders have become mainstream due to the advantage of being capable of continuous production, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw extruder manufactured by Toshiba Machine Co., Ltd. A twin screw extruder manufactured by Kay Sea Kay, a co-kneader manufactured by Buss, etc. are generally used. Furthermore, the colored resin composition obtained by melt-kneading the toner raw material is rolled by a two-roll roll after melt-kneading, and then cooled through a cooling step of cooling by water cooling or the like.

  In general, the cooled colored resin composition obtained above is then pulverized to a desired particle size in a pulverization step. In the pulverization step, first, coarse pulverization is performed with a crusher, a hammer mill, a feather mill or the like, and further, pulverization is performed with a kryptron system manufactured by Kawasaki Heavy Industries, Ltd., a super rotor manufactured by Nisshin Engineering Co., Ltd. or the like. After that, if necessary, classification is performed using a classifier such as an inertia class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.) or a centrifugal class turbo turbo (manufactured by Hosokawa Micron Co., Ltd.), and the weight average particle diameter A 3.0 to 8.0 μm classified product is obtained.

If necessary, surface modification and spheronization may be performed using, for example, a hybridization system manufactured by Nara Machinery Co., Ltd. or a mechano-fusion system manufactured by Hosokawa Micron. In such a case, if necessary, a sieving machine such as a wind-type sieve high voltor (manufactured by Shin Tokyo Machine Co., Ltd.) may be used. Furthermore, as a method of externally adding the external additive, a predetermined amount of classified toner and various known external additives are blended, and a high-speed stirrer that gives a shearing force to the powder such as a Henschel mixer or a super mixer is removed. A method of stirring and mixing can be used as an accessory.

In the production of the toner used in the present invention, the surface modification step is not particularly limited as long as the state of presence of the release agent on the surface of the toner can be appropriately adjusted, but in particular the batch shown in FIG. In order to produce the toner of the present invention, it is preferable to use a surface modification device of the formula. Specifically, a surface modifying apparatus used in the surface modifying step and a toner manufacturing method using the surface modifying apparatus will be specifically described with reference to the drawings.

FIG. 3 shows an example of a surface modification apparatus used in the present invention.
The batch-type surface reforming apparatus shown in FIG. 3 includes a cylindrical main body casing 30, a top plate 43 installed on the upper portion of the main body casing so as to be openable and closable; a fine powder discharge portion 44 having a fine powder discharge casing and a fine powder discharge pipe; A cooling jacket 31 through which cooling water or antifreeze can be passed; a plurality of square disks 33 on the upper surface, which are attached to the central rotating shaft in the main body casing 30 as surface modification means, in a predetermined direction Dispersion rotor 32, which is a disk-like rotating body that rotates at high speed; liner 34 that is fixedly arranged around dispersion rotor 32 at a constant interval and that has a large number of grooves on the surface facing dispersion rotor 32 A classification rotor 35 for continuously removing fine powder and ultrafine powder having a predetermined particle size or less in the finely pulverized product; cold air inlet 4 for introducing cold air into the main body casing 30; A charging pipe having a raw material charging port 37 and a raw material supplying port 39 formed on the side surface of the main body casing 30 for introducing finely pulverized material (raw material); discharging toner particles after the surface modification treatment to the outside of the main body casing 30; A product discharge pipe having a product discharge port 40 and a product extraction port 42 for opening and closing; an openable and closable raw material installed between the raw material input port 37 and the raw material supply port 39 so that the surface modification time can be freely adjusted A supply valve 38; and a product discharge valve 41 installed between the product discharge port 40 and the product extraction port 42.

The surface of the liner 34 has grooves as shown in FIGS. 7A and 7B, which is preferable for efficiently modifying the surface of the toner particles. As shown in FIGS. 5A and 5B, the number of the rectangular disks 33 is preferably an even number in consideration of the rotational balance.
The classifying rotor 35 shown in FIGS. 3, 4 and 8 is preferably rotated in the same direction as the rotation direction of the dispersion rotor 32 in order to increase the efficiency of classification and the efficiency of surface modification of toner particles. The fine powder discharge pipe has a fine powder discharge port 45 for discharging fine powder and ultrafine powder removed by the classification rotor 35 to the outside of the apparatus.

  The surface modifying apparatus further includes, as shown in FIGS. 6A and 6B, a cylindrical guide ring 36 as a guide means having an axis perpendicular to the top plate 43 in the main body casing 30. Have. The upper end of the guide ring 36 is provided at a predetermined distance from the top plate, and the guide ring 36 is fixed to the main casing 30 by a support so as to cover at least a part of the classification rotor 35. The lower end of the guide ring 36 is provided at a predetermined distance from the rectangular disk 33 of the dispersion rotor 32. In the surface modification apparatus, a space between the classification rotor 35 and the dispersion rotor 32 is guided into a first space 47 outside the guide ring 36 and a second space 48 inside the guide ring 36. Divided by 36. The first space 47 is a space for guiding the finely pulverized product and the surface-modified particles to the classification rotor 35, and the second space guides the finely pulverized product and the surface-modified particles to the dispersion rotor. It is a space for. A gap between the plurality of rectangular disks 33 installed on the dispersion rotor 32 and the liner 34 is a surface modification zone 49, and the classification rotor 35 and a peripheral portion of the classification rotor 35 are classification zones 50. .

As shown in FIG. 8, the finely pulverized product introduced into the raw material hopper 380 passes through the quantitative feeder 315, enters the apparatus from the raw material supply port 37 through the raw material supply port 37 through the raw material supply port 38. Supplied. In the surface reforming apparatus, the cold air generated by the cold air generating means 319 is supplied into the main body casing from the cold air introduction port 46, and the cold water from the cold water generating means 320 is supplied to the cold water jacket 31, Adjust the temperature to a predetermined temperature. The supplied finely pulverized product swirls in the first space 47 outside the cylindrical guide ring 36 by the swirl flow formed by the suction air volume by the blower 364, the rotation of the dispersion rotor 32, and the rotation of the classification rotor 35. However, classification processing is performed by reaching the classification zone 50 in the vicinity of the classification rotor 35. The direction of the swirl flow formed in the main body casing 30 is the same as the rotation direction of the dispersion rotor 32 and the classification rotor 35.

  Fine powder and super fine powder to be removed by the classification rotor 35 are sucked from the slit (see FIG. 4) of the classification rotor 35 by the suction force of the blower 364, and then passed through the fine powder discharge port 45 and the cyclone inlet 359 of the fine powder discharge pipe. 369 and bug 362. The finely pulverized product from which fine powder and ultrafine powder have been removed reaches the surface modification zone 49 in the vicinity of the dispersion rotor 32 via the second space 48, and the square disk 33 (hammer) provided in the dispersion rotor 32 and the main body. The surface modification treatment of the particles is performed by the liner 34 provided in the casing 30. The particles subjected to the surface modification reach the classification rotor 35 again while turning along the guide ring 36, and fine particles and ultrafine particles are removed from the surface-modified particles by the classification rotor 35 classification. . After the treatment for a predetermined time, the product discharge valve 41 is opened, and the surface-modified toner particles from which fine powder and super fine powder having a predetermined particle diameter or less are removed are taken out from the surface reforming apparatus. The toner particles adjusted to a predetermined weight average particle diameter, adjusted to a predetermined particle size distribution, and further surface-modified to a predetermined circularity are transferred to an external additive adding step by the toner particle transport means 321. The

  The surface reforming apparatus used in the present invention includes a dispersion rotor 32, a finely pulverized product (raw material) input unit 39, a classification rotor 35, and a fine powder discharge unit from the lower side in the vertical direction. Therefore, normally, the drive portion (motor or the like) of the classification rotor 35 is provided further above the classification rotor 35, and the drive portion of the dispersion rotor 32 is provided further below the dispersion rotor 32. The surface reforming apparatus used in the present invention is a finely pulverized product (raw material) classified into a classification rotor, such as a TSP classifier (manufactured by Hosokawa Micron Corporation) having only a classification rotor 35 described in JP-A-2001-259451. It is difficult to supply from the vertically upward direction of 35.

  In the present invention, it is preferable that the tip peripheral speed of the classifying rotor 35 having the largest diameter is 30 to 120 m / sec. The tip circumferential speed of the classification rotor is more preferably 50 to 115 m / sec, and further preferably 70 to 110 m / sec. If it is slower than 30 m / sec, the classification yield tends to decrease, and the amount of ultrafine powder tends to increase in the toner particles. If it is faster than 120 m / sec, the problem of increased vibration of the device is likely to occur.

  Furthermore, it is preferable that the tip peripheral speed of the portion with the largest diameter of the dispersion rotor 32 is 20 to 150 m / sec. The tip peripheral speed of the dispersion rotor 32 is more preferably 40 to 140 m / sec, and further preferably 50 to 130 m / sec. When it is slower than 20 m / sec, it is difficult to obtain surface-modified particles having sufficient circularity, which is not preferable. When the speed is higher than 150 m / sec, particles are likely to be fixed inside the apparatus due to the temperature rise inside the apparatus, and the classification yield of the toner particles is likely to be lowered. By setting the tip peripheral speeds of the classification rotor 35 and the dispersion rotor 32 in the above range, the classification yield of the toner particles can be improved and the surface modification of the particles can be performed efficiently.

In the toner production method used in the present invention, it is preferable that the finely pulverized product (raw material) supplied to the raw material charging port 37 of the surface modifying device has a specific particle size distribution. Furthermore, it is preferable that the amount of ultra fine powder of toner particles (surface modified particles) after being processed by the surface modifying device is controlled to a predetermined amount. In the present invention, the finely pulverized product has a weight average particle diameter of 2.5 to 8.0 μm, and a ratio of particles having a weight average particle diameter of 4.0 μm or less is 50 to 80% by number, and toner particles obtained The weight average particle diameter of (surface modified particles) is 3.0 to 8.0 μm, and the ratio of particles (fine powder) having a weight average particle diameter of 4.0 μm or less is 5 to 40% by number. Toner having a circle equivalent diameter of 0.6 μm or more and less than 2.0 μm (small particles) in a particle size distribution based on the number of particles having an equivalent circle diameter of 0.6 μm or more and 400 μm or less as measured by a flow particle image measuring apparatus for particles The proportion of particles is preferably 0 to 15% by number.

  The particle size distribution of the finely pulverized product affects the classification efficiency. When there are many fine particles in the finely pulverized product, the classification time becomes long, and even particles that do not need to be classified and removed are removed by classification, which may cause a reduction in classification yield. Furthermore, the cohesiveness of the finely pulverized product becomes high when classification is performed, and it may be difficult to remove the ultrafine powder that should be removed from the toner particles, and the resulting toner is likely to be fogged.

  Therefore, when the weight average particle size of the finely pulverized product is smaller than 2.5 μm, the cohesiveness between the particles becomes high and efficient classification may be difficult. On the other hand, when the weight average particle size of the finely pulverized product is larger than 8.0 μm, it is not preferable because the obtained toner is difficult to form a clear image quality. On the other hand, when the ratio of particles having a weight average particle diameter of 4.0 μm or less is less than 50% by number, it is difficult to form a clear image with the obtained toner. On the other hand, if the proportion of particles having a weight average particle diameter of 4.0 μm or less is more than 80% by number, the cohesiveness of the finely pulverized product becomes high and it becomes difficult to obtain a good classification yield. Furthermore, when the proportion of particles having a weight average particle size of 4.0 μm or less is more than 80% by number, small particles in the finely pulverized product tend to increase, which is not preferable. The proportion of particles having a weight average particle size of 4.0 μm or less in the finely pulverized product is preferably 55 to 75% by number.

  In the particle size distribution based on the number of particles having an equivalent circle diameter of 0.6 μm or more and 400 μm or less, which is measured by a flow type particle image measuring apparatus for toner particles processed by the surface modification device, the equivalent circle diameter is 0. It is preferable to control the ratio of toner particles (small particles) of 6 μm or more and less than 2.0 μm to a range of 0 to 15% by number. When the ratio of toner particles having an equivalent circle diameter of 0.6 μm or more and less than 2.0 μm is more than 15% by number, the obtained toner is not preferable because fog phenomenon easily occurs. When the ratio of toner particles having an equivalent circle diameter of 0.6 μm or more and less than 2.0 μm is more than 15% by number when the electrophotographic photoreceptor used in the present invention is used, Toner fusion or toner adhesion to the carrier deteriorates, which is not preferable. The ratio of toner particles having an equivalent circle diameter of 0.6 μm or more and less than 2.0 μm is more preferably 13% by number or less.

Further, the developer containing the toner and the carrier may be manufactured by mixing with a mixing device after manufacturing the toner. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, and a Nauter mixer. By using these apparatuses, the toner and the carrier are uniformly mixed, and the mixing property of the replenishment developer and the developer in the developing device is improved.

FIG. 9 shows an example of a developing device used in the present invention.
In the present invention, development is performed while supplying a replenishment developer containing a replenishment toner and a replenishment carrier to the developing device, and excess carrier inside the developing device is discharged from the developing device. Next, the flow of the developer in the image forming apparatus using the replenishment developer will be described with reference to FIG. As the electrostatic latent image on the photoreceptor is developed with toner, the toner in the developing device 102 is consumed. A toner density detection sensor (not shown) detects that the toner in the developing device is low, and the replenishment developer is supplied from the replenishment developer container 101 to the developing device 102. The excess carrier in the developing device moves to the developer recovery container 104. The developer collection container 104 may collect the toner collected by the cleaning device 103 together.

  A suitable method for measuring physical properties related to the present invention will be described below.

<Carrier particle size distribution and circularity>
The 50% particle size (D50) and average circularity based on the volume distribution of the carrier are measured as follows using, for example, a multi-image analyzer (manufactured by Beckman Coulter).
A solution obtained by mixing about 1% NaCl aqueous solution and glycerin at 50% by volume: 50% by volume is used as the electrolytic solution. Here, the NaCl aqueous solution may be prepared using primary sodium chloride, and may be, for example, ISOTON (registered trademark) -II (manufactured by Coulter Scientific Japan). Glycerin may be a special grade or first grade reagent.
To the electrolytic solution (about 30 ml), 0.1 to 1.0 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 minute with an ultrasonic disperser (for example, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios)) to obtain a dispersion.
Using a 200 μm aperture and a 20 × lens as the aperture, the equivalent circle diameter and circularity are calculated under the following measurement conditions.
Average luminance within measurement frame: 220 to 230
Measurement frame setting: 300
SH (threshold): 50
Binarization level: 180
The electrolytic solution and the dispersion liquid are put into a glass measuring container, and the concentration of carrier particles in the measuring container is set to 5 to 10% by volume. Stir the contents of the glass measuring container at the maximum stirring speed. The sample suction pressure is 10 kPa. When the carrier specific gravity is large and the sedimentation is likely to occur, the measurement time is 15 to 30 minutes. Further, the measurement is interrupted every 5 to 10 minutes to replenish the sample solution and the electrolytic solution-glycerin mixed solution.
The number of measurements is 2000. After the measurement is finished, the main body software removes a defocused image, aggregated particles (multiple simultaneous measurements), etc. on the particle image screen.
The circularity and equivalent circle diameter of the carrier are calculated from the following formulas (I) and (II).
Formula (I): Circularity = (4 × Area) / (MaxLength ² × π)
Formula (II): equivalent circle diameter = √ (4 · Area / π)
Here, “Area” is the projected area of the binarized carrier particle image, and “MaxLength” is defined as the maximum diameter of the carrier particle image. The equivalent circle diameter is represented by the diameter of a perfect circle when “Area” is the area of the perfect circle. The equivalent circle diameter is divided into 4 to 100 μm in 256, and is used by logarithmically displaying on a volume basis. Using this, the 50% particle size (D50) based on volume distribution is obtained. The average circularity is obtained by adding the circularity of each particle and dividing by the total number of particles. FIG. 10 shows an example of a graph of measurement results of carrier 1 obtained by carrier manufacturing 1 described later. The “arithmetic average value” in the “circularity arithmetic statistical value” section in the figure indicates the average circularity.

<True specific gravity of carrier>
The true specific gravity of the carrier used in the present invention can be measured using a dry automatic densimeter autopycnometer (manufactured by Yuasa Ionics).

<Strength of magnetization of carrier>
The intensity of the magnetization of the carrier used in the present invention can be measured by the following procedure according to the description in the instruction manual using an oscillating magnetic field type magnetic property automatic recording device BHV-30 manufactured by Riken Denshi Co., Ltd. it can. The cylindrical plastic container is filled with the carrier sufficiently densely, while an external magnetic field of 1000 / 4π (kA / m) (1000 oersted) is created, and the magnetization moment of the carrier filled in the container is measured in this state. . Further, the actual mass of the carrier filled in the container is measured to determine the magnetization strength (Am ² / kg) of the carrier.

<Transmissivity in 45% by volume methanol aqueous solution>
(1) Preparation of toner dispersion An aqueous solution having a volume mixing ratio of methanol and water of 45:55 is prepared. 10 ml of this aqueous solution is placed in a 30 ml sample bottle (Nippon Denka Glass: SV-30), 20 mg of toner is immersed on the liquid surface, and the bottle lid is capped. Then, shake for 5 seconds at 150 reciprocations / minute with a Yayoi-type shaker (model: YS-LD). At this time, the angle of shaking is such that the shaking column moves 15 degrees forward and 20 degrees backward, assuming that the vertical (vertical) of the shaker is 0 degree. And it is shaken once each forward and backward, and when returning to just above, it counts as one reciprocation.
The sample bottle is fixed to a fixing holder (with the sample bottle lid fixed on the extension at the center of the column) attached to the tip of the column. After removing the sample bottle, the dispersion after standing for 30 seconds is used as a dispersion for measurement.
(2) Transmittance (%) measurement The dispersion obtained in (i) was placed in a 1 cm square quartz cell, and the spectrophotometer MPS2000 (manufactured by Shimadzu Corporation) was used, and 10 minutes after the cell was placed in the apparatus. The light transmittance (%) at a wavelength of 600 nm of the dispersion is determined. The transmittance (%) is obtained by the following formula (I).
(I): Transmittance (%) = I / I ₀ × 100
(In the formula, I ₀ represents an incident light beam, and I represents a transmitted light beam.)

<Measurement of average circularity of toner and amount of super fine powder>
The equivalent circle diameter, circularity, and frequency distribution of the toner are used as a simple method for quantitatively expressing the shape of the toner particles. In the present invention, the flow type particle image measuring device “FPIA-2100 type” is used. ”(Manufactured by Sysmex Corporation), and calculation is performed using the following formulas (I) and (II).
Formula (I): equivalent circle diameter = (particle projected area / π) ^1/2 × 2
Formula (II): Circularity = (perimeter of a circle having the same area as the particle projection area) / (perimeter of the particle projection image)
Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define. The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm). In the present invention, the circularity is an index indicating the degree of unevenness of the toner particles, and is 1.000 when the toner particles are completely spherical. The more complicated the surface shape, the smaller the circularity.
The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following formula (III), where ci is the circularity (center value) at the dividing point i of the particle size distribution and m is the number of measured particles. Is done.

In addition, “FPIA-2100”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity. 1.0 is divided into classes equally divided every 0.01, and the average circularity is calculated using the center value of the division points and the number of measured particles.
As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more. In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the in-machine temperature of the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocus is performed using 2 μm latex particles every 2 hours.
To measure the shape of the toner particles, the flow type particle image measuring device is used, and the concentration of the dispersion is readjusted so that the color toner particle concentration at the time of measurement is 3000 to 10,000 particles / μl. Measure more than one. After the measurement, this data is used to cut data less than 2 μm, and the average circularity of the toner particles is obtained.
Furthermore, “FPIA-2100”, which is a measuring apparatus used in the present invention, improves the magnification of the processed particle image as compared with “FPIA-1000” conventionally used for calculating the shape of the toner. Further, the accuracy of toner shape measurement has been improved by improving the processing resolution of the captured image (256 × 256 → 512 × 512), thereby achieving more reliable capture of fine particles. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA 2100 that can obtain information on the shape more accurately is more useful.

<Measurement of particle size distribution of toner and finely pulverized product>
As a measuring device, Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Inc.) is used. As the electrolytic solution, an about 1% NaCl aqueous solution is used. As the electrolytic solution, an electrolytic solution prepared using primary sodium chloride or, for example, ISOTON (registered trademark) -II (manufactured by Coulter Scientific Japan) can be used.
As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolyte solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser (for example, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios Co., Ltd.), and the measurement is performed using a 100 μm aperture as the aperture. The volume and number of the sample are measured for each channel by the apparatus, and the volume distribution and number distribution of the sample are calculated, and the weight average particle diameter (D4) of the sample is obtained from the obtained distribution. Are 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8.00 μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 00 to 40.30 μm are used.

<Measurement of molecular weight of toner by GPC>
The molecular weight of the toner by gel permeation chromatography (GPC) is measured under the following conditions.
Resin prepared by stabilizing the column in a heat chamber at 40 ° C., and flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min to the column at this temperature to adjust the sample concentration to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 to 200 μl of a THF sample solution. An RI (refractive index) detector is used as the detector. As a column, in order to accurately measure a molecular weight region of 10 ^{3 to} 2 × 10 ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, μ-styragel 500, 103, 104, 105 manufactured by Waters And combinations of shodex KA-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko KK are preferable.
In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical
Co. Ltd. Alternatively, Toyo Soda Kogyo Co., molecular weight of ^{6 × 10 2, 2.1 × 10} 3, 4 × 10 3, 1.75 × 10 4, 5.1 × 10 4, 1.1 × 10 5, 3.9 × 10 ⁵ , 8.6 × 1
It is appropriate to use those having 0 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ and at least about 10 standard polystyrene samples.

<Measurement of maximum endothermic peak of wax and toner>
The maximum endothermic peak of the wax and toner can be measured according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring device) and DSC2920 (TA Instruments Japan).
As a measuring method, 5 to 20 mg, preferably 10 mg of a measurement sample is accurately weighed. This is put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10 ° C./min and normal temperature and normal humidity within a measurement temperature range of 30 to 200 ° C. In this temperature raising process, an endothermic peak in the temperature range of 30 to 200 ° C. is obtained. When there are a plurality of peaks, the highest endothermic peak is the one having the highest height from the baseline in the region above the endothermic peak due to the resin.

<Measurement of film thickness of photoconductor>
The film thickness of each photoconductor can be measured using a film thickness meter (FISCHERSCOPE MMS: manufactured by FISCHER) according to the description in the instruction manual.

<Measurement of spot diameter of electrostatic latent image>
The spot diameter of the electrostatic latent image can be measured and adjusted using a beam analyzer manufactured by Melles Griot Co., Ltd. according to the description in the instruction manual. The spot diameter indicates a diameter at a light amount of 1 / e ² from a peak light amount of a laser optical spot having a Gaussian distribution.

<Number average particle diameter of magnetic substance, number average particle diameter of particles having charge controllability and number average particle diameter of inorganic fine particles>
The number average particle diameter of the fine particles is obtained by randomly extracting 500 or more particles having a particle diameter of 5 nm or more with a scanning electron microscope (50,000 times), measuring the long axis and the short axis with a digitizer, and averaging them. The number average particle size is calculated from the particle size that becomes the peak of the particle size distribution of 500 or more particles (from the histogram of the column divided every 10 nm).

Specific examples of the present invention will be described below, but the present invention is not limited to these examples.
<Electrophotographic photosensitive member production example 1>
The electrophotographic photoreceptor 1 was produced as follows. First, an aluminum cylinder (aluminum alloy specified by JIS A3003) having a length of 381 mm, an outer diameter of 84 mm, and a thickness of 3 mm was produced by cutting. When the surface roughness of this cylinder was measured in the direction of the rotation axis, Rzjis = 0.08 μm. This cylinder is subjected to ultrasonic cleaning in pure water containing a detergent (trade name: Chemicol CT, manufactured by Tokiwa Chemical Co., Ltd.), followed by a step of washing away the detergent, and further ultrasonic cleaning in pure water. And degreased.
60 parts by mass of titanium oxide powder (trade name: Kronos ECT-62, manufactured by Titanium Industry Co., Ltd.) having a coating film of tin oxide doped with antimony, titanium oxide powder (trade name: titone SR-1T, 堺Chemical Co., Ltd.) 60 parts by mass, resol type phenol resin (trade name: Phenolite J-325, Dainippon Ink & Chemicals, Inc., solid content 70%) 70 parts by mass, 2-methoxy-1-propanol A slurry composed of 50 parts by mass and 50 parts by mass of methanol was dispersed with a ball mill for about 20 hours to obtain a dispersion. The average particle size of the filler contained in this dispersion was 0.25 μm.
The dispersion thus prepared was applied onto the aluminum cylinder by a dipping method, and the aluminum cylinder coated with the dispersion was heated and dried for 48 minutes in a hot air dryer adjusted to 150 ° C. The liquid coating film was cured to form a conductive layer having a film thickness of 15 μm. The film thickness was measured using a film thickness meter (FISCHERSCOPE MMS manufactured by FISCHER).
Next, 10 parts by mass of a copolymer nylon resin (trade name: Amilan CM8000, manufactured by Toray Industries, Inc.) and 30 parts by mass of a methoxymethylated nylon resin (trade name: Toresin EF30T, manufactured by Teikoku Chemical Industry Co., Ltd.) were added to methanol 500. A solution dissolved in a mixed solution of parts by weight and 250 parts by weight of butanol is dip-coated on the conductive layer, and the aluminum cylinder coated with the solution is put in a hot air dryer adjusted to 100 ° C. for 22 minutes. By heating and drying, the coating film of the solution was cured to form an undercoat layer having a film thickness of 0.45 μm.
Next, 4 parts by mass of a hydroxygallium phthalocyanine pigment having strong peaks at 7.4 ° and 28.2 ° with a Bragg angle of 2θ ± 0.2 ° in a CuKa line diffraction spectrum, a polyvinyl butyral resin (trade name: ESREC BX-1) , Manufactured by Sekisui Chemical Co., Ltd.) and a mixed solution consisting of 90 parts by mass of cyclohexanone was dispersed in a sand mill for 10 hours using glass beads having a diameter of 1 mm, and then 110 parts by mass of ethyl acetate was obtained. Was added to prepare a charge generation layer coating solution. The coating liquid is dip-coated on the undercoat layer, and the aluminum cylinder coated with the coating liquid is charged in a hot air dryer adjusted to 80 ° C. for 22 minutes and dried by heating. A charge generation layer having a thickness of 0.20 μm was formed by curing the coating film of the liquid.
Next, 35 parts by mass of a triarylamine compound represented by the following structural formula (I)

And 50 parts by mass of bisphenol Z-type polycarbonate resin (trade name: Iupilon Z400, manufactured by Mitsubishi Engineering Plastics Co., Ltd.) in 320 parts by mass of monochlorobenzene and 50 parts by mass of dimethoxymethane, Prepared. The coating liquid is dip-coated on the charge generation layer, and the aluminum cylinder coated with the coating liquid is heated and dried in a hot air dryer adjusted to 100 ° C. for 40 minutes to obtain the coating liquid. By curing the coating film, a first charge transport layer having a thickness of 8 μm was formed.
Next, 30 parts by mass of a hole transporting compound having a polymerizable functional group represented by the following structural formula (II)

After dissolving in 35 parts by mass of 1-propanol and 35 parts by mass of 1,1,2,2,3,3,4-heptafluorocyclopentane (trade name: Zeolora H, manufactured by Nippon Zeon Co., Ltd.), 0 made of PTFE The solution was subjected to pressure filtration with a .5 μm membrane filter to prepare a second charge transport layer coating solution as a curable surface layer (protective layer). This coating solution was applied onto the first charge transport layer by a dip coating method to form a coating film for the second charge transport layer as a curable surface layer. Thereafter, the coating film was irradiated with an electron beam in nitrogen under conditions of an acceleration voltage of 150 kV and a dose of 15 kGy to obtain an aluminum cylinder (electrophotographic photosensitive member) in which the coating film was cured. Subsequently, a heat treatment was performed for 90 seconds under the condition that the temperature of the electrophotographic photosensitive member was 120 ° C. The oxygen concentration at this time was 10 ppm. Furthermore, the electrophotographic photosensitive member was heat-treated in a hot air dryer adjusted to 100 ° C. in the atmosphere for 20 minutes to form a curable surface layer having a thickness of 4.5 μm. The total film thickness of the photoreceptor 1 was 12.7 μm. Table 1 shows the film thickness and total film thickness of each layer of the obtained photoreceptor 1.

<Electrophotographic photosensitive member production examples 2 to 6>
In the electrophotographic photoreceptor production example 1, the charge generation layer, the charge transport layer, and the protective layer were adjusted to have the thicknesses shown in Table 1 to prepare photoreceptors 2 to 6. Table 1 shows the film thickness and the total film thickness of each layer of the obtained photoreceptors 2 to 6.

<Carrier production example 1>
For magnetite powder having a number average particle size of 0.30 μm and (magnetization strength of 75 Am ² / kg under a magnetic field of 1000 / 4π (kA / m)) and hematite powder having a number average particle size of 0.30 μm, respectively. 4.0% by mass of a silane coupling agent (3- (2-aminoethylaminopropyl) trimethoxysilane) was added and mixed and stirred at 100 ° C. or higher in a container to treat each fine particle.

・ Phenol 10 parts by mass ・ Formaldehyde solution 6 parts by mass (formaldehyde 40% by mass, methanol 10% by mass, water 50% by mass)
・ Processed magnetite 75 parts by mass ・ Processed hematite 9 parts by mass

Phenol resin produced by putting the above material, 5 parts by weight of 28% by weight ammonia water and 20 parts by weight of water into a flask, raising the temperature to 85 ° C. over 30 minutes while stirring and mixing, and allowing the polymerization reaction to proceed for 3 hours. Was cured. Thereafter, the cured phenol resin was cooled to 30 ° C., water was further added, the supernatant was removed, the precipitate was washed with water, and then air-dried. Subsequently, this was dried under reduced pressure (5 mmHg or less) at a temperature of 60 ° C. to obtain a spherical magnetic substance-containing resin carrier core 1 in which the magnetic substance was dispersed.
As a coating material, a copolymer of methyl methacrylate and perfluorooctyl acrylate (copolymerization ratio (mass% ratio) 9: 1, weight average molecular weight 45,000) is used, and this is the magnetic substance-containing resin core 1 100 at the time of coating. A carrier coat solution containing 10% by mass of the copolymer of methyl methacrylate and perfluorooctyl acrylate was prepared using a mixed solvent of methyl ethyl ketone and toluene as a solvent so as to be 2 parts by mass with respect to parts by mass. In addition, 1.5 parts by mass of melamine resin (number average particle size 0.2 μm) and 0.5 parts by mass of carbon black (number average particle size 30 nm, DBP oil absorption 50 ml / 100 g) may be added to the carrier coat solution using a homogenizer. Mix. Next, the magnetic material-containing resin core 1 is added to the mixed solution, and a solvent is volatilized at 70 ° C. while continuously applying a shear stress to the mixed solution. Copolymer with octyl acrylate was coated.
The resin-coated magnetic material-containing resin core 1 coated with a copolymer of methyl methacrylate and perfluorooctyl acrylate is heat-treated by stirring at 100 ° C. for 2 hours, cooled, crushed, and classified with a 200 mesh sieve. The volume-based 50% particle size (D50) is 35 μm, the true specific gravity is 3.7 g / cm ³ , the magnetization intensity is 50 Am ² / kg under a magnetic field of 1000 / 4π (kA / m), and the average circularity is 0. A carrier 1 having a ratio of particles of 923 and circularity of 0.800 or more to 94% by number was obtained. Table 2 shows the physical properties of Carrier 1 thus obtained.

<Carrier production example 2>
With respect to the magnetite powder having a number average particle size of 0.20 μm and (magnetization strength of 70 Am ² / kg under a magnetic field of 1000 / 4π (kA / m)), 6.0% by mass of a silane coupling agent (3 -(2-aminoethylaminopropyl) trimethoxysilane) was added, and each fine particle was treated by mixing and stirring at 100 ° C. or higher in a container.

・ Phenol 10 parts by mass ・ Formaldehyde solution 6 parts by mass (formaldehyde 40% by mass, methanol 10% by mass, water 50% by mass)
・ 84 parts by mass of magnetite processed

Phenol resin produced by putting the above materials, 6 parts by mass of 28% by mass ammonia water and 20 parts by mass of water into a flask, raising the temperature to 85 ° C. over 30 minutes while stirring and mixing, and carrying out a polymerization reaction for 3 hours. Was cured. Thereafter, the cured phenol resin was cooled to 30 ° C., water was further added, the supernatant was removed, the precipitate was washed with water, and then air-dried. Subsequently, this was dried under reduced pressure (5 mmHg or less) at a temperature of 60 ° C. to obtain a spherical magnetic substance-containing resin carrier core 2 in which the magnetic substance was dispersed.
As a coating material, a copolymer of methyl methacrylate and perfluorooctyl acrylate (copolymerization ratio (mass% ratio) 9: 1, weight average molecular weight 45,000) is used, and this is the magnetic substance-containing resin core 1 100 at the time of coating. A carrier coat solution containing 10% by mass of the copolymer of methyl methacrylate and perfluorooctyl acrylate was prepared using a mixed solvent of methyl ethyl ketone and toluene as a solvent so as to be 2 parts by mass with respect to parts by mass. In addition, 1.5 parts by mass of melamine resin (number average particle size 0.2 μm) and 0.5 parts by mass of carbon black (number average particle size 30 nm, DBP oil absorption 50 ml / 100 g) may be added to the carrier coat solution using a homogenizer. Mix. Next, the magnetic material-containing resin core 2 is put into the mixed solution, and the solvent is volatilized at 70 ° C. while continuously applying a shear stress to the mixed solution. Copolymer with octyl acrylate was coated.
The resin-coated magnetic body-containing resin core 2 coated with a copolymer of methyl methacrylate and perfluorooctyl acrylate is heat-treated by stirring at 100 ° C. for 2 hours, cooled, crushed, and classified with a 200 mesh sieve. 50% particle size on volume basis (D50) 6
8 μm, true specific gravity 4.1 g / cm ³ , magnetization ratio 68Am ² / kg under magnetic field of 1000 / 4π (kA / m), average circularity 0.890, ratio of particles having a circularity of 0.800 or more 86% by number of carrier 2 was obtained. The physical properties of the obtained carrier 2 are shown in Table 2.

<Carrier Production Example 3>
A mixture of Fe ₂ O ₃ ; 50 mol%, MnO; 10.0 mol%, MgO; 40 mol% was mixed for 10 hours using a ball mill. The obtained mixture was calcined at 800 ° C. for 2 hours, and the calcined mixture was pulverized with a ball mill. The average particle size of the obtained pulverized product was 0.2 μm.
To the obtained pulverized product, water (300% by mass with respect to the pulverized product), polyvinyl alcohol (5% by mass with respect to the pulverized product), and NaHCO ₃ (3% by mass with respect to the pulverized product) are added, and further a spray dryer. Was granulated. The granulated product was sintered at 980 ° C. for 10 hours, then pulverized and further classified to obtain a Mn—Mg ferrite carrier core. The volume-based 50% particle size (D50) of this Mn—Mg ferrite carrier core was 40 μm.
T unit in which all organic groups are methyl groups: 12 parts by mass of siloxane formulated so that D units in which all organic groups are methyl groups = 85: 15, and 0.3 parts by mass of γ-aminopropyltrimethoxysilane, A mixed solution of 200 parts by mass of toluene was added to 100 parts by mass of the carrier core, and the solvent was removed by drying under reduced pressure while stirring and mixing with a solution vacuum kneader. The obtained particles were baked at 140 ° C. for 2 hours to obtain Carrier 3. The volume-based 50% particle size (D50) of the carrier 3 is 40 μm, the true specific gravity is 2.6 g / cm ³ , the strength of magnetization under a magnetic field of 1000 / 4π (kA / m) is 42 Am ² / kg, and the average circle Carrier 3 having a degree of 0.830 and a ratio of particles having a circularity of 0.800 or more of 75% by number was obtained. Table 2 shows the physical properties of the carrier 3.

<Carrier Production Example 4>
These metal oxide particles were weighed so that the molar ratio was Fe ₂ O ₃ ; 75 mol%, MnO; 5.0 mol%, MgO; 20 mol%, and mixed using a ball mill. The obtained mixed powder was calcined, pulverized by a ball mill, further granulated by a spray dryer, sintered, and further classified to obtain a Mn—Mg ferrite carrier core. The volume-based 50% particle size (D50) of this Mn—Mg ferrite carrier core 4 was 15 μm.
T unit in which all organic groups are methyl groups: 20 parts by mass of siloxane formulated so that D units in which all organic groups are methyl groups = 85: 15, and 0.5 parts by mass of γ-aminopropyltrimethoxysilane, A mixed solution of 200 parts by mass of toluene was added to 4100 parts by mass of the carrier core, and the solvent was removed by drying under reduced pressure while stirring and mixing with a solution vacuum kneader. The obtained particles were baked at 140 ° C. for 2 hours to obtain carrier 4. The volume-based 50% particle size (D50) of the carrier 4 is 15 μm, the true specific gravity is 4.3 g / cm ³ , the strength of magnetization under a magnetic field of 1000 / 4π (kA / m) is 72 Am ² / kg, and the average circle Carrier 4 having a degree of particles of 0.800 and a circularity of 0.800 or more was 71% by number. Table 2 shows the physical properties of the obtained carrier 4.

<Carrier Production Example 5>
A mixture of Fe ₂ O ₃ ; 40 mol%, MnO; 20.0 mol%, MgO; 40 mol% was mixed for 10 hours using a ball mill. The obtained mixture was calcined at 800 ° C. for 2 hours, and the calcined mixture was pulverized with a ball mill. The average particle size of the obtained pulverized product was 0.2 μm.
To the obtained pulverized product, water (300% by mass with respect to the pulverized product), polyvinyl alcohol (7% by mass with respect to the pulverized product), and NaHCO ₃ (4% by mass with respect to the pulverized product) were added, and further a spray dryer. Was granulated. The granulated product was sintered at 980 ° C. for 10 hours, then pulverized and further classified to obtain a Mn—Mg ferrite carrier core. The volume-based 50% particle size (D50) of this Mn—Mg ferrite carrier core was 72 μm.
T unit in which all organic groups are methyl groups: 8 parts by mass of siloxane formulated so that D units in which all organic groups are methyl groups = 85: 15, and 0.2 parts by mass of γ-aminopropyltrimethoxysilane, A mixed liquid of 200 parts by mass of toluene was added to 100 parts by mass of the carrier core, and the solvent was removed by drying under reduced pressure while stirring and mixing with a solution vacuum kneader. The obtained particles were baked at 140 ° C. for 2 hours to obtain carrier 5. The volume-based 50% particle diameter (D50) of the carrier 5 is 72 μm, the true specific gravity is 2.4 g / cm ³ , the magnetization intensity is 38 Am ² / kg under a magnetic field of 1000 / 4π (kA / m), and the average circle Carrier 5 having a degree of 0.826 and a ratio of particles having a circularity of 0.800 or more of 86% by number was obtained. The physical properties of the obtained carrier 5 are shown in Table 2.

<Binder resin production example 1>
(Example of hybrid resin production)
As a material for the vinyl polymer unit, 2.0 mol of styrene, 0.21 mol of 2-ethylhexyl acrylate, 0.14 mol of fumaric acid, 0.03 mol of α-methylstyrene dimer, and 0.05 mol of dicumyl peroxide are added dropwise. Put in. Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 7.0 mol, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) as materials for the polyester unit ) 3.0 mol of propane, 3.0 mol of terephthalic acid, 1.9 mol of trimellitic anhydride, 5.0 mol of fumaric acid and 0.2 g of dibutyltin oxide were put in a 4-liter four-necked flask made of glass. A thermometer, a stirring rod, a condenser, and a nitrogen introducing tube were attached to the four-necked flask, and the four-necked flask was placed in a mantle heater. Next, after the inside of the four-necked flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and the monomer and polymerization of the vinyl polymer unit were performed from the previous dropping funnel while stirring at a temperature of 145 ° C. The initiator was added dropwise over 4 hours. Next, the obtained product was heated to 200 ° C. and reacted for 4 hours to obtain a hybrid resin. Regarding the molecular weight of this hybrid resin by GPC, the weight average molecular weight (Mw) was 50,000, the number average molecular weight (Mn) was 4000, and the peak molecular weight was 8,000.

<Toner production example 1>
-100 parts by weight of the above hybrid resin-5 parts by weight of paraffin wax (melting point 75 ° C)-0.5 parts by weight of 1,4-di-t-butylsalicylic acid aluminum compound-C.I. I. Pigment Blue 15: 3 5 parts by mass After the above materials were thoroughly mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Chemical Co., Ltd.), a twin-screw kneader (PCM-30 type, Kneaded by Ikekai Tekko Co., Ltd. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The obtained crushed material was finely pulverized using a collision type airflow pulverizer (for example, a jet mill pulverizer IDS2 type manufactured by Nippon Pneumatic Industry Co., Ltd.) using a high-pressure gas. The obtained finely pulverized product had a weight average particle diameter of 4.9 μm and an average circularity of 0.915.
Next, using the surface modification apparatus shown in FIG. 3 for the finely pulverized product obtained, 1.3 kg is charged into the surface modification apparatus at a time, and the number of rotations of the classification rotor 35 is 7300 rpm to remove the fine particles. However, the surface treatment was performed for 70 seconds at a rotation speed of the dispersion rotor 32 of 4000 rpm (rotational peripheral speed 130 m / sec) (after the finely pulverized product was charged through the raw material supply port 39, the product was discharged after 70 seconds of treatment. The valve 41 was opened and taken out as a processed product).
At this time, in this embodiment, ten square disks 33 are installed on the upper part of the dispersion rotor 32, the distance between the guide ring 36 and the square disk 33 on the dispersion rotor 32 is 30 mm, and the dispersion rotor 32 and the liner 34 are arranged. Was set at 5 mm. The blower air volume was 14 m ³ / min, the temperature of the refrigerant passed through the jacket and the cold air temperature T1 were −20 ° C.
As a result of repeated operation for 20 minutes in this state, the temperature T2 behind the classification rotor 35 was stabilized at 27 ° C. The cyan toner particles obtained after the surface treatment had a weight average particle diameter of 5.4 μm, an average circularity of 0.940, and a classification yield of 82%.
Furthermore, using a mesh surface fixed wind sieve high voltor (NR-300, manufactured by Shin Tokyo Machine Co., Ltd .: air brush attached to the back of the wire mesh), this has a diameter of 30 cm, an opening of 29 μm, and an average diameter of the wire Was provided with a 30 μm wire mesh, and the cyan toner powder was supplied to the wire mesh with an air flow of 5 Nm ³ / min to obtain cyan toner particles from which coarse particles were separated.
To 100 parts by mass of the obtained cyan toner particles, as inorganic fine particles, 1.0 part by mass of titanium oxide having a number average particle diameter of 40 nm and hydrophobized and 1.5 parts by mass of amorphous having a number average particle diameter of 110 nm. Silica was externally added to obtain toner 1 (cyan toner).
The obtained toner 1 had a weight average particle diameter of 5.8 μm and an average circularity of 0.940 in particles having an equivalent circle diameter of 2.0 μm or more. Furthermore, the light transmittance at a wavelength of 600 nm of a dispersion obtained by dispersing 20 mg of the toner 1 in an aqueous solution containing 45% by volume of methanol was 50%. Table 3 shows the physical properties of Toner 1 thus obtained.

<Toner Production Example 2>
Toner 2 (cyan toner) was obtained in the same manner as in Toner Production Example 1, except that the rotational speed of the dispersion rotor was changed to 3000 rpm under the production conditions of the surface modification device. Table 3 shows the physical properties of Toner 2 thus obtained.

<Toner Production Example 3>
Toner 3 (cyan toner) was obtained in the same manner as in Toner Production Example 1 except that the rotational speed of the dispersion rotor was changed to 6000 rpm under the production conditions of the surface modification device. Table 3 shows the physical properties of Toner 3 thus obtained.

<Toner Production Example 4>
Toner 4 (cyan toner) was obtained in the same manner as in Toner Production Example 1 except that the rotational speed of the dispersion rotor was changed to 5000 rpm under the production conditions of the surface modification device. Table 3 shows the physical properties of Toner 4 thus obtained.

<Toner Production Example 5>
In Toner Production Example 1, the obtained finely pulverized product was further classified with an air classifier (for example, Elbow Jet Classifier manufactured by Matsubo Co., Ltd.) without using a surface modifying apparatus, and a weight average particle size of 5.8 μm Cyan toner particles were obtained.
To 100 parts by mass of the obtained cyan toner particles, as inorganic fine particles, 0.8 parts by mass of titanium oxide having a number average particle diameter of 40 nm and hydrophobized and 1.2 parts by mass of amorphous having a number average particle diameter of 110 nm. Silica was externally added to obtain toner 5 (cyan toner). Table 3 shows the physical properties of Toner 5 thus obtained.

<Toner Production Example 6>
The cyan toner particles obtained in Toner Production Example 5 were subjected to surface modification at 4000 rpm using a mechano-fusion system (manufactured by Hosokawa Micron) equipped with a cooling mechanism such as a chiller unit to obtain toner 6 (cyan toner). Table 3 shows the physical properties of Toner 6 thus obtained.

<Toner Production Example 7>
In Toner Production Example 1, C.I. I. Pigment Blue 15: 3 5 parts by mass, C.I. I. Pigment Red 1212 Toner 7 (magenta toner) was obtained in the same manner except that the amount was changed to 5 parts by mass. Table 3 shows the physical properties of Toner 7 thus obtained.

<Toner Production Example 8>
In Toner Production Example 1, C.I. I. Pigment Blue 15: 3 5 parts by mass, C.I. I. Toner 8 (yellow toner) was obtained in the same manner except that the pigment yellow 74 was changed to 5 parts by mass. Table 3 shows the physical properties of Toner 8 thus obtained.

<Toner Production Example 9>
In Toner Production Example 1, C.I. I. Pigment Blue 15: 3 Toner 9 (black toner) was obtained in the same manner except that 5 parts by mass of carbon black was changed to 5 parts by mass of carbon black. Table 3 shows the physical properties of Toner 9 thus obtained.

<Toner Production Example 10>
To 710 parts by mass of ion-exchanged water, 450 parts by mass of 0.12M-Na ₃ PO ₄ aqueous solution was added and the aqueous solution obtained by heating to 60 ° C. was obtained using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). And stirred at 15,000 rpm. To this, 68 parts by mass of 1.2M-CaCl ₂ aqueous solution was gradually added to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .
The following materials: Styrene 160 parts by mass n-butyl acrylate 40 parts by mass Behenic acid behenyl ester wax (maximum endothermic peak temperature 72 ° C.)
20 parts by mass, 1,4-di-t-butylsalicylic acid aluminum compound 0.5 parts by mass, saturated polyester (terephthalic acid-propylene oxide modified bisphenol A; acid value 15, peak molecular weight 6000) 10 parts by mass I. Pigment Blue 15: 3 10 parts by mass

Was heated to 60 ° C., and uniformly dissolved and dispersed at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). In this, 10 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.
The obtained polymerizable monomer composition was put into the aforementioned aqueous medium. The obtained mixture was stirred at 15,000 rpm for 10 minutes at 60 ° C. in a nitrogen atmosphere using a TK homomixer to granulate the polymerizable monomer composition. Then, it heated up at 80 degreeC, stirring with a paddle stirring blade, and was made to react for 10 hours. After completion of the polymerization reaction, the remaining monomer was distilled off under reduced pressure. After cooling, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ . The resulting solution was filtered, and the filtered product was washed with water and dried to obtain cyan toner particles. The cyan toner particles had a weight average particle diameter of 6.0 μm, and the average circularity of particles having an equivalent circle diameter of 2.0 μm or more was 0.985.
To 100 parts by mass of the obtained cyan toner particles, as inorganic fine particles, 1.0 part by mass of titanium oxide having a number average particle diameter of 40 nm and hydrophobized and 1.5 parts by mass of amorphous having a number average particle diameter of 110 nm. Silica was externally added to obtain toner 10 (cyan toner).
The obtained toner 10 (cyan toner) had a weight average molecular weight (Mw) of 90000, a number average molecular weight (Mn) of 40000, and a peak molecular weight of 30000.
The obtained toner 10 had a weight average particle diameter of 6.0 μm and an average circularity of 0.985 in particles having an equivalent circle diameter of 2.0 μm or more. Further, the light transmittance at a wavelength of 600 nm of a dispersion obtained by dispersing 20 mg of the toner 10 in an aqueous solution containing 45% by volume of methanol was 20%. Table 3 shows the physical properties of Toner 10 thus obtained.

<Toner Production Example 11>

Dispersion A
-Styrene 350 parts by mass-n-butyl acrylate 100 parts by mass-Acrylic acid 25 parts by mass-t-dodecyl mercaptan 10 parts by mass

The above composition was mixed and dissolved to prepare a monomer mixture.
100 parts by weight of a paraffin wax dispersion with a melting point of 75 ° C. (solid content concentration 30%, dispersed particle size 0.14 μm, wax Mw = 500, Mn = 380) Anionic surfactant 1.2 parts by weight (first Kogyo Seiyaku Co., Ltd .: Neogen SC)
・ 0.5 parts by weight of nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400)
・ Ion-exchanged water 1530 parts by mass

The above composition was dispersed in a flask, and heating was started while performing nitrogen substitution. When the liquid temperature reached 70 ° C., a solution prepared by dissolving 6.56 parts by mass of potassium persulfate with 350 parts by mass of ion-exchanged water was added thereto. While maintaining the liquid temperature at 70 ° C., the monomer mixture is charged and stirred, the liquid temperature is raised to 80 ° C., and emulsion polymerization is continued for 6 hours. Liquid A was obtained. Thus, the particles in the obtained dispersion have a number average particle size of 0.16 μm, a glass transition point of solid content of 60 ° C., a weight average molecular weight (Mw) of 15,000, and a peak molecular weight of 12, 000. Paraffin wax was contained in the polymer in an amount of 6% by mass. As a result of observing a thin piece of this solid content with a transmission electron microscope, it was confirmed that the polymer particles included the wax particles.

Dispersion B
・ C. I. Pigment Blue 15: 3 12 parts by mass / Anionic surfactant 2 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-86 parts by mass of ion-exchanged water The above composition was mixed and dispersed using a bead mill (for example, Ultra Apex Mill, manufactured by Kotobuki Industries Co., Ltd.) to obtain Colorant Dispersion Liquid B.
300 parts by mass of the dispersion A and 25 parts by mass of the dispersion B were charged into a 1 liter separable flask equipped with a stirrer, a cooling tube and a thermometer, and stirred. As a flocculant, 180 parts by mass of a 10% sodium chloride aqueous solution was dropped into this mixed solution, and the flask was heated to 54 ° C. while stirring the inside of the flask. After maintaining at 48 ° C. for 1 hour, it was confirmed by observation with an optical microscope that aggregated particles having a diameter of about 5 μm were formed.
In the subsequent fusion process, after adding 3 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC), the stainless steel flask was sealed and stirring was continued using a magnetic seal. While heating to 100 ° C., it was held for 3 hours. Then, after cooling, the reaction product was filtered, washed thoroughly with ion exchange water, and then dried to obtain cyan toner particles 11.
To 100 parts by mass of the obtained cyan toner particles 11, as inorganic fine particles, the number average particle diameter is 40 nm and the hydrophobically treated 1.0 part by mass of titanium oxide and the number average particle diameter is 110 nm.
The toner 11 (cyan toner) was obtained by externally mixing 1.5 parts by mass of amorphous silica.
The obtained toner 11 (cyan toner) had a weight average molecular weight (Mw) of 150,000 and a peak molecular weight of 12,000.
The obtained toner 11 had a weight average particle diameter of 5.0 μm and an average circularity of 0.958 in particles having an equivalent circle diameter of 2.0 μm or more. Further, the light transmittance at a wavelength of 600 nm of a dispersion obtained by dispersing 20 mg of the toner 11 in an aqueous solution containing 45% by volume of methanol was 10%. Table 3 shows the physical properties of Toner 11 thus obtained.

<Example 1>
10 parts by mass of the toner 1 obtained in the toner production example 1 and 90 parts by mass of the carrier 1 obtained in the carrier production example 1 are mixed by a V-type mixer, and a start developer stored in a developing device is first prepared. Obtained. Similarly, 90 parts of the toner 1 obtained in the toner production example 1 and 10 parts of the carrier 1 obtained in the carrier production example 1 were mixed by a V-type mixer to obtain a replenishment developer 1. Table 4 shows the blending ratio of the toner with respect to 1 part by mass of the carrier of the obtained start developer 1 and replenishment developer 1.
Using these start developer 1 and replenishment developer 1, a Canon full-color copier, iRC6800 remodeling machine (specifically, the laser beam with a wavelength of 405 nm was changed to a spot diameter of 30 nm × 30 nm, and the resolution was It was changed to 1200 dpi, and modified so that an electrostatic latent image was formed and image exposure was possible.The photoconductor was changed to the photoconductor 1), and normal temperature and humidity (NN) (23 ° C., 50%). RH), high temperature and high humidity (HH) (30 ° C., 90% RH), low temperature and low humidity (NL) (15 ° C., 5% RH), endurance image evaluation (A4 landscape, 20% printing ratio, 100,000) Sheet). The items for image output evaluation after 100,000 sheets are passed and the evaluation criteria are shown below.

(1) Dot reproducibility (end of durability (after 1 sheet) and after 100,000 sheets)
A halftone image was formed using the developer and the modified machine, this image was visually observed, and the dot reproducibility of the image was evaluated based on the following criteria. The formed halftone image is a halftone image when the 48th density in the 256 gradation display in which 0 is solid white and 256 is solid black.
(Evaluation criteria)
A: Smooth and smooth.
B: I don't feel a lot of rustling.
C: Although there is a slight feeling of roughness, it is at a level where there is no practical problem.
D: There is a feeling of roughness.
E: There is a very rough feeling.

(2) Fog (initial durability (after 1 sheet) and after 100,000 sheets)
The average reflectance Dr (%) of plain paper before image printing was measured by a reflectometer (“REFLECTOMETER MODEL TC-6DS” manufactured by Tokyo Denshoku Co., Ltd.).
At the beginning of the endurance, a solid white image was printed on plain paper by changing Vd every 50V so that Vback was 0V to 300V. Further, after endurance output, a solid white image (Vback: 150 V) was drawn on plain paper. The reflectivity Ds (%) of the imaged solid white image was measured. The fog (%) was calculated from the obtained Dr and Ds (initial and subsequent durability) using the following formula. The obtained fog was evaluated according to the following evaluation criteria.
Fog (%) = Dr (%)-Ds (%)
(Evaluation criteria)
A: 0.5% or less: No problem at all.
B: 0.6 to 1.0%: A little can be confirmed by gazing.
C: 1.1 to 2.0%: Level that can be visually observed but is not problematic in practice D: 2.1 to 3.0%: Fog is slightly noticeable E: 3.1% or more: Fog is clearly confirmed

(3) Carrier adhesion (after initial durability (after 1 sheet) and after 100,000 sheets)
A halftone image is formed on the paper using the developer and the modified machine, and the number of carriers present is counted with an optical microscope within an area of 1 cm ² on the halftone image.
(Evaluation criteria)
A: 0 to 5 pieces: Very inconspicuous and very good.
B: 6-10 pieces: Good.
C: 11 to 20: Although the attached carrier can be seen, it is at a level where there is no practical problem.
D: 21-30 pieces: In the morning, a cleaning failure occurs at startup.
E: 31 or more: The carrier adhering on the image is conspicuous, causing vertical streaks, which is a problem.
Table 5 shows the evaluation results of (1) to (3) in the durability evaluation. In Table 5, the results are shown in the order of the evaluation results at the initial stage of durability → the evaluation results after 100,000 sheets.

<Examples 2-4, 11-15>
Evaluations (1) to (3) were performed under the same conditions as in Example 1 except that the toner, carrier, photoreceptor, replenishment developer, and start developer were changed to those shown in Table 4.

<Examples 5 to 10 and Comparative Examples 1 to 7>
Change the laser beam of Canon full-color copier and iRC6800 modified machine to a laser beam with a wavelength of 405 nm, change the spot diameter to 50 nm x 50 nm and resolution to 1200 dpi, and form an electrostatic latent image so that image exposure can be performed (1) to (3) were evaluated under the same conditions as in Example 1 except that modification was made and the toner, carrier, photoreceptor, replenishment developer, and starter developer shown in Table 4 were changed. . The results are shown in Table 5.

1 is a schematic view of an electrophotographic apparatus of the present invention. 1 is a schematic view of an electrophotographic apparatus having a process cartridge of the present invention. In the toner production method of the present invention, the finely pulverized product is classified and surface-modified, and the surface is preferably used in a process for obtaining surface-modified toner particles having a suitable particle size distribution. The schematic sectional drawing of an example of a reformer. (A) The schematic horizontal projection of a classification rotor, (B) The schematic sectional drawing of a classification rotor. (A) The horizontal projection figure of a dispersion | distribution rotor, (B) The rough vertical projection surface figure of a dispersion | distribution rotor. (A) The figure for demonstrating the diameter of a guide ring, (B) The perspective view of the support body of a guide ring and a guide ring. (A) The schematic horizontal projection figure of a liner, (B) The partial explanatory drawing of a liner. FIG. 4 is a partial flowchart for explaining a method for producing toner used in the present invention. FIG. 3 is a schematic diagram illustrating a flow of a developer in an image forming apparatus using a replenishment developer. It is an example of the graph of a measurement result about the particle size distribution and circularity of the carrier of this invention. The left axis shows the frequency of particle size based on the number as a bar graph. The degree of circularity is shown as a dot on the right axis.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Electrophotographic photoreceptor 1a Axis 2 Charging means 3 Developing means 3-1 Developing sleeve 4 Transfer means 5 Cleaning means 6 Pre-exposure means 7 Transfer material 8 Image fixing means 12 Rail L Image exposure 30 Main body casing 31 Cooling jacket 32 Dispersing rotor 33 Square disk 34 Liner 35 Classification rotor 36 Guide ring 37 Raw material inlet 38 Raw material supply valve 39 Raw material supply port 40 Product outlet 41 Product outlet valve 42 Product outlet 43 Top plate 44 Fine powder outlet 45 Fine powder outlet 46 Cold air inlet 46 47 First space 48 Second space 49 Surface reforming zone 50 Classification zone 315 Constant supply machine 319 Cold air generating means 320 Cold water generating means 321 Toner particle transport means 359 Cyclone inlet 362 Bug 364 Blower 369 Cyclone 380 Raw material hopper
DESCRIPTION OF SYMBOLS 101 Replenishment developer storage container 102 Developing device 103 Cleaning apparatus 104 Developer collection container

Claims (6)

A conductive support, a charging step for charging an electrophotographic photosensitive member having a photosensitive layer on the conductive support, an exposure step for forming an electrostatic latent image on the photosensitive member, and a toner and a carrier. An image forming method comprising at least a developing step of developing the electrostatic latent image using a developing device containing a two-component developer,
The developer is replenished with a replenishment developer containing at least replenishment toner and a replenishment carrier, and excess carrier is discharged from the developer.
The replenishment developer contains 2 to 50 parts by mass of replenishment toner with respect to 1 part by mass of the replenishment carrier.
The photosensitive layer has at least a charge generation layer and a charge transport layer;
The total thickness of the photosensitive layer is 5.0 μm to 15.0 μm;
The volume-based 50% particle size (D50) of the carrier and the replenishment carrier is 15 to 70 μm,
The true specific gravity of the carrier and the replenishment carrier is 2.5 to 4.2 g / cm ³ ;
An image forming method, wherein the carrier and the replenishment carrier have a magnetization intensity of 40 to 70 Am ² / kg under a magnetic field of 1000 / 4π (kA / m).   2. The image formation according to claim 1, wherein the carrier and the replenishing carrier have an average circularity of 0.850 to 0.950 and contain 90% by number or more of particles having a circularity of 0.800 or more. Method.   2. The light transmission rate at a wavelength of 600 nm of a dispersion obtained by dispersing the toner in an aqueous solution containing 45% by volume of methanol is 30% to 80%. The image forming method according to claim 2. 4. The image formation according to claim 1, wherein an average circularity of particles having an equivalent circle diameter of 2.0 μm or more of the toner and the replenishing toner is 0.930 to 1.000. 5. Method.   5. The magnetic substance-containing resin carrier obtained by polymerizing a monomer for forming a binder resin in the presence of a magnetic substance, the carrier and the replenishment carrier. The image forming method according to item.   The image forming method according to claim 1, wherein the electrostatic latent image is formed using a semiconductor laser having a wavelength of 380 nm to 500 nm.

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