JP2006221122A - Image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming apparatus capable of providing stable images regardless of long-term image forming operation. <P>SOLUTION: In the image forming apparatus 100, the distance X from a photoreceptor 40 to a developing sleeve 41 is 100-650 μm, a toner has a weight average particle diameter Dm of ≤6.5 μm, an external additive includes inorganic fine particles having a primary particle diameter D of 30-700 nm in an amount Z of 0.1-2.5 pts.wt. based on 100 pts.wt. of the toner, and a developer index Y1 represented by following expression (1) satisfies following expression (2); (1) Y1=306X<SP>2</SP>-374X+154-(4.7Z<SP>2</SP>+4Z) (where the unit of X is [mm] and the unit of Z is [pts.wt.] based on 100 pts.wt. of toner base weight), (2) 40≤Y1≤120. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an image forming apparatus that forms an image by an electrostatic copying process such as a copying machine, a facsimile machine, or a printer.

The electrostatic copying process of image formation, which is an electrophotographic method, develops an electrostatic latent image formed on a latent image carrier (photoreceptor) with toner containing a colorant, and the obtained toner image is transferred onto a transfer member. An image is obtained by fixing the latent image carrier with a heat roll or the like, and the latent image carrier is cleaned again to form an electrostatic latent image. The dry developer used in such electrophotography is a one-component developer using a toner in which a colorant or the like is blended in a binder resin, and a two-component developer in which a carrier is mixed with the toner. Broadly divided. However, the two-component developer is generally widely used because it is easier to control, including transport on the developer carrying member, toner charge amount in development, and correspondence to coloration.
However, in response to the recent demand for higher image quality, a reduction in toner particle size is being studied in order to improve faithful reproducibility of latent images and color reproducibility to increase the number of colors to be reproduced. However, in the image forming apparatus, it is difficult to transfer all the toner forming the image on the surface of the image carrier to the transfer material at the time of transfer, and it is inevitable that some toner remains on the image carrier. Further, the toner remaining on the image carrier after the transfer is not sufficiently removed from the image carrier before the next image formation on the image carrier. It interferes with the next image formation and deteriorates the image quality. For this reason, it is necessary to sufficiently clean the transfer residual toner every transfer.

Various cleaning devices have been proposed as cleaning means for this purpose. For example, there has been proposed a cleaning device that scrapes off and removes transfer residual toner with an edge of a cleaning blade made of an elastic material such as rubber that contacts the image carrier. This cleaning device is simple in structure and low in cost, and has an excellent function of removing transfer residual toner. For this reason, a cleaning device using a cleaning blade has already been widely used. However, this cleaning blade makes it difficult to clean the small particle size toner.
For this reason, for example, in Patent Document 1, in order to improve the developability, transferability, and cleaning properties of a small particle size toner, particles having an average particle size of 5 nm or more and less than 20 nm and particles having an average particle size of 20 nm or more and 40 nm or less are used. It is disclosed that two types of inorganic fine particles having different particle diameters are used in combination and added in a specific amount. This can initially provide high developability, transferability, and cleaning properties, but the force applied to the toner over time cannot be reduced, so external additives can easily be buried or peeled off. , Developability and transferability are greatly changed from the initial stage.

  On the other hand, Patent Document 3 and Patent Document 4 disclose that it is effective to use inorganic fine particles having a large particle diameter in order to improve such cleaning properties. However, since inorganic fine particles have a large true specific gravity, if the external additive particles are made large, the release of the external additive cannot be avoided due to the agitation stress in the developing device, and this causes adhesion to the photoreceptor. As a result, the problem of toner filming occurs. Further, the specific surface area is small and the charge amount is small as compared with the external additive having a small particle diameter, and it is difficult to control the charge amount of the toner. In addition, the fluidity of the toner and the developer decreases due to the liberation, and the amount of developer pumped onto the developer carrier decreases. This causes a problem that the density of the formed image is low because the amount of the developer is small.

Japanese Patent Laid-Open No. 3-100161 JP-A-7-28276 JP-A-9-319134

  Accordingly, the present invention has been made in view of the above problems, and an object thereof is to provide an image forming apparatus capable of providing a stable image regardless of a long-term image forming operation.

The features of the present invention, which is a means for solving the above problems, are listed below.
1. An image forming apparatus according to the present invention includes an image carrier that carries at least a latent image, and a developing device provided with a developer carrier that conveys a developer containing toner in the vicinity of the image carrier. In the forming apparatus, the image forming apparatus has a distance X between the image carrier and the developer carrier of 100 to 650 μm, and the toner has a weight average particle diameter Dm of 2.0 to 6.5 μm. The external additive contains inorganic fine particles having a primary particle size D of 30 to 700 nm and a prescription amount Z in the range of 0.1 to 2.5 parts by weight with 100 parts by weight of toner, and The developer index Y1 represented by the formula (1) is Y1 = 306X ² −374X + 154− (4.7Z ² + 4Z) (1) (where X is in [mm], and Z is in the toner base weight) Represents 100 parts by weight [parts by weight]), 40 ≦ And satisfies 1 ≦ 120 ... relationship of formula (2) (2).
2. The image forming apparatus of the present invention includes at least an image carrier that carries a latent image, and a developing device provided with a developer carrier that conveys a developer containing toner in the vicinity of the image carrier. In the image forming apparatus provided,
In the image forming apparatus, the distance X between the image carrier and the developer carrier is in the range of 100 to 650 μm, and the toner has a weight average particle diameter Dm in the range of 2.0 to 6.5 μm, The external additive contains inorganic fine particles having a primary particle diameter D of 30 to 700 nm, a prescription amount Z in the range of 0.1 to 2.5 parts by weight with 100 parts by weight of toner, and the following relational expression: (3) The developer index Y2 represented by (4) is Y2 = 306X ² −374X + 154− (4.7W ² + 4W) Formula (3), W = Z × (1.7 Log D−2.4) Formula (4) (where X is in [mm], Z is in [part by weight] with the toner base weight being 100 parts by weight, and D is in [mm]), 40 ≦ Y2 ≦ 120 ... which satisfies the relational expression (5) of the expression (5).
3. The image forming apparatus of the present invention is further characterized in that the ratio of the distance X and the weight average particle diameter Dm of the toner is in the range of 15-200.

  By the means for solving the above problems, the image forming apparatus of the present invention can stably convey the developer to the developing area regardless of the long-term image forming operation, and provides a high-quality image over time. be able to.

  The best mode for carrying out the present invention will be described below with reference to the drawings. Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.

FIG. 1 is a schematic diagram showing the configuration of the image forming apparatus of the present invention. In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which the copying apparatus is placed, 300 is a scanner mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (ADF) mounted thereon.
The copying apparatus main body 100 has a tandem type in which four image forming units 18 each having an electrophotographic process such as charging, developing, and cleaning are arranged in parallel around a photosensitive member 40 as a latent image carrier. An image forming apparatus 20 is provided. Above the tandem type image forming apparatus 20, there is provided an exposure apparatus 21 that exposes the photoreceptor 40 with laser light based on image information to form a latent image. Further, an intermediate transfer belt 10 made of an endless belt member is provided at a position facing each photoreceptor 40 of the tandem type image forming apparatus 20. A primary transfer unit 62 for transferring the toner images of the respective colors formed on the photoconductor 40 to the intermediate transfer belt 10 is disposed at a position facing the photoconductor 40 via the intermediate transfer belt 10.
A secondary transfer device 22 that collectively transfers the toner images superimposed on the intermediate transfer belt 10 onto transfer paper conveyed from the paper feed table 200 is disposed below the intermediate transfer belt 10. The secondary transfer device 22 is configured by spanning a secondary transfer belt 24 that is an endless belt between two rollers 23, and is disposed by pressing against the support roller 16 via the intermediate transfer belt 10. The toner image on 10 is transferred onto a transfer sheet. A fixing device 25 for fixing the image on the transfer paper is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt.
The secondary transfer device 22 described above also has a sheet transport function for transporting the transfer paper after image transfer to the fixing device 25. Of course, a transfer roller or a non-contact charger may be arranged as the secondary transfer device 22, and in such a case, it is difficult to provide this sheet conveyance function together.
In the illustrated example, a reversing device 28 for reversing the transfer paper so as to record images on both sides of the transfer paper is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. .

FIG. 2 is an enlarged view of the image forming unit.
The developing device 4 of the image forming unit 18 uses a developer containing the above toner. The developing device 4 performs development using a two-component developer composed of toner and a carrier, and mainly includes a developer stirring tank 42 and a toner storage tank 43 provided above the developer stirring tank 42. A toner supply roller 44 for supplying toner from the toner storage tank 43 to the developer stirring tank 42 is provided between the toner storage tank 43 and the developer stirring tank 42, and the developer stirring tank 42 includes a casing. A stirring screw 45 as developer stirring means for stirring the developer is provided at the bottom, and a developing sleeve 41 for supporting the developer on the surface is provided at an opening facing the photoreceptor 40 of the casing. The agitating screw 45 replenishes the developer consisting of toner and carrier on the developing sleeve 41 while mixing and agitating the developer in the developer agitating tank 42. The developer replenished on the developing sleeve 41 is regulated to a predetermined thickness, and then conveyed to a developing region at a portion facing the photoconductor 40.
An optical sensor (not shown), which is a density detecting means for detecting the amount of toner developed on the photoconductor, is provided at a position facing the photoconductor on the downstream side of the developing region in the rotation direction of the photoconductor. The toner adhesion status is detected. Based on this detection signal, whether to continue or stop the stirring of the developer is determined, and a motor for driving a stirring screw 45 (not shown) is controlled. The agitation / mixing of the developer and toner in the developer agitation tank 42 by the agitation screw 45 uniformly mixes the developer and toner, and appropriately raises the charge amount of the developer. Since the developer in the developer agitation tank 42 is in a non-uniform state of toner density and chargeability at the time of warming up immediately after starting up the copying machine, the agitation of the developer by the rotation of the agitation screw 45 is started. The
In the developing device 4, the developer carrying member carries and conveys the developer, and an alternating electric field is applied at a position facing the photoconductor 40 to develop the latent image on the photoconductor 40. By applying the alternating electric field, the developer is activated, the toner charge amount distribution can be narrowed, and the developability can be improved.

The distance X between the photoreceptor 40 and the developing sleeve 41 is in the range of 100 to 650 μm, and the toner has a weight average particle diameter Dm of 6.5 μm or less and a low molecular weight linear polyester is added to the binder resin in an amount of 0.00. Inorganic fine particles containing 1 to 2.5 parts, external additives having a primary particle diameter D of 30 to 700 nm, and a prescription amount Z of 0.1 to 2.5 parts by weight with 100 parts by weight of toner And the developer index Y1 represented by the relational expression (1) is Y1 = 306X ² −374X + 154− (4.7Z ² + 4Z) (1) (where X is in [mm], Z Represents the [parts by weight] where the toner base weight is 100 parts by weight.), 40 ≦ Y1 ≦ 120, and satisfies the relational expression (2) of the expression (2).
The smaller the distance X is, the larger the electric field of the developing bias can be, so that the range is 100 to 650 μm. It is difficult to control practically below 100 μm. In particular, it is difficult to reduce the wave by the extrusion processing of the developing sleeve. On the other hand, if it exceeds 650 μmm, the developing bias electric field becomes small, and the image density is remarkably lowered.

The weight average particle diameter Dm of the toner is 6.5 μm or less. If the thickness exceeds 6.5 μm, the reproducibility of fine lines decreases, and in a full-color image, the color reproducibility decreases due to the appearance of graininess. However, at least 3 μm or more is preferable. If it is less than 3 μm, it is difficult to produce, and the cleaning property is deteriorated.
The toner contains 0.1 to 2.5 parts of low molecular weight linear polyester. The low molecular weight is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000. The weight average molecular weight (Mw) is preferably 1,000 to 50,000, more preferably 2,000 to 40,000, and particularly preferably 4,000 to 20,000. The number average molecular weights Mn and Mw can be measured by using gel permeation chromatography (GPC) with THF as a solvent. In addition, the linear polyester herein refers to a non-crosslinked type, which is soluble in a solvent such as THF, and has a bonding group other than an ester bond in the polyester resin, or is configured in the polyester resin. In this state, the resin components having different bonds are bound by a covalent bond, an ionic bond, or the like. Specifically, the polyester terminal is modified by introducing a functional group such as a carboxylic acid group or an isocyanate group that reacts with a hydroxyl group into the polyester terminal and further reacting with an active hydrogen-containing compound.
The content of the linear polyester is 0.1 to 2.5 parts by weight with respect to 100 parts by weight of the toner. If the amount is less than 0.1 parts by weight, the effect of increasing the fixing property is small. If the amount exceeds 2.5 parts by weight, the ratio of exposure to the toner surface increases, and an abnormal image may be formed by shifting to the carrier. .

  In addition, the toner includes inorganic fine particles in which the external additive has a primary particle diameter D of 30 to 700 nm, and a prescription amount Z is in the range of 0.1 to 2.5 parts by weight with 100 parts by weight of the toner, Furthermore, it preferably contains inorganic fine particles in the range of 1.0 to 2.5 parts by weight. As the external additive, inorganic fine particles such as a metal oxide, a metal carbide, a metal nitride, and a metal carbonate can be used. Specifically, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide Cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like. The external additive can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents that may contain alkyl groups, fluorinated alkyl groups, titanate coupling agents, coupling agents such as aluminum coupling agents, silicone oils, higher fatty acids, fluorine compounds and the like are preferable surface treatment agents. Can be mentioned.

Further, the primary particle diameter D forming the aggregate of the external additive is in the range of 30 to 700 nm. This external additive imparts fluidity to the toner and facilitates toner replenishment. Moreover, the mixing property with the carrier can be improved, and the charge rising can be accelerated. Further, the presence of the toner on the toner surface becomes a part of the toner charge amount and contributes to the adjustment of the toner charge amount. Another effect of the addition of a large particle size external additive is that even if the toner is exposed to a high temperature during storage (less than 50 ° C.), the toners are not tightly packed together, so that the temperature is slowed down and the mass of the toners is reduced. Can be prevented. Further, even when heat is generated by stirring of the developing portion, it is difficult to promote the generation of toner lump. Further, even when a strong force is applied from the transfer member to the toner due to the spacer effect of the large particle size additive in the process of transferring the toner, the toner is hardly applied and the toner is not easily solidified. Therefore, in the case of a character image, voids (toner transfer failure) are less likely to occur, and high image quality can be achieved. The primary particle diameter D is measured by directly observing with SEM, STM or the like. At this time, when the primary particle diameter D is less than 30 nm, the amount embedded in the toner surface increases, the fluidity of the toner is reduced, and the amount conveyed to the development region by the developing sleeve is reduced. If it exceeds 700 nm, the amount released from the toner surface increases, and similarly, the amount conveyed to the developing area by the developing sleeve decreases. Furthermore, the fixing property to the transfer paper is insufficient and a cold offset may occur due to insufficient fixing. Furthermore, the surface of the fixing member can be easily damaged by the additive, and if the cleaning member is attached to the fixing member, the additive adheres to the cleaning member, and the wear of the surface of the fixing member is promoted using the article as a core. In addition, the pressure due to wear, the way of heat transmission, etc. tend to lead to poor fixing, and in addition, the cause of the winding of the transfer paper.
The prescription amount Z of the external additive is in the range of 0.1 to 2.5 parts by weight with 100 parts by weight of toner. If it is less than 0.1 parts by weight, it does not contribute to the fluidity of the toner. Further, the amount conveyed to the developing area by the developing sleeve is reduced.

Further, in the image forming apparatus of the present invention, the developer index Y1 represented by the relational expression (1) is Y1 = 306X ² −374X + 154− (4.7Z ² + 4Z) (1) (where X is a unit) The units [mm] and Z represent [parts by weight] in which the toner base weight is 100 parts by weight.), 40 ≦ Y1 ≦ 120 (2) satisfies the relational expression (2).
The amount of developer conveyed by the developing sleeve to the developing area is set in the range of 40 to 120 mg / cm ² . When the developer amount is less than 40 mg / cm ² , the image density is low because the developer does not come into contact with the photoreceptor 40 even when the distance X is 100 μm. When the developer amount exceeds 120 mg / cm ² , the developer conveyed on the developing sleeve is subjected to great stress, and an abnormal image is generated due to liberation of external additives and transfer of toner components. At this time, an image with a high image density can be obtained by setting this range, and by reducing the stress, the release of external additives and the migration of toner components are reduced, and the life of the developer is reduced. Can be extended.
At this time, Formula (1) is satisfied. The developer index Y1 must be balanced with the distance X and has the relationship shown in FIG. FIG. 3 is a graph showing the relationship between the distance X and the developer amount Y conveyed. The relationship of FIG. 3 is expressed as Y = 306X ² −374X + 154.
In addition, the developer amount decreases due to a long-term image forming operation. This is particularly affected by the prescription amount Z of the external additive. FIG. 4 is a graph showing the amount of decrease in the prescription amount Z of the external additive and the developer amount Y conveyed. The relationship of FIG. 4 is expressed as Y = 4.7Z ² + 4Z.
Therefore, in order to obtain a stable image over a long period of time, Y = 306X ² −374X + 154− (4.7Z ² + 4Z)... (1) representing the relationship between the ^two must be satisfied. By satisfying this expression (1), the developer index Y1 required for the distance X can be stably conveyed for a long time.
Furthermore, in the image forming apparatus of the present invention, the developer index Y2 represented by the following relational expressions (3) and (4) is Y2 = 306X ² −374X + 154− (4.7W ² + 4W) (Expression (3)) W = Z × (1.7 Log D-2.4) (4) (where X is in [mm], Z is in 100 parts by weight of toner base weight, [part by weight], D is in units) Represents [mm]), 40 ≦ Y2 ≦ 120, which satisfies the relational expression (5) of the expression (5).
The developer amount Y conveyed by the developing sleeve has an influence on the amount of decrease in the developer amount Y by the primary particle size D of the external additive as well as the prescription amount Z of the external additive. FIG. 5 is a graph showing the relationship between the primary particle diameter D of the external additive and the ratio of the developer amount Y to the decrease amount. As shown in FIG. 5, as the primary particle size D of the external additive increases, the amount of decrease increases. This relationship is shown by equations (3) and (4), and equation (5) is established by this relationship with equation (1).

  Further, the ratio (X / Dm) between the distance X and the weight average particle diameter Dm of the toner is in the range of 15 to 200. By setting this range, a better image can be obtained. When the ratio (X / Dm) is greater than 200, the amount of toner to be developed decreases. As a result, the amount of the external additive having a large particle size is also reduced, so that the toner collected at the tip of the blade is reduced in the amount of toner containing the large particle size external additive, resulting in poor cleaning. Further, since the development amount is small, a satisfactory image density cannot be obtained. When the ratio (X / Dm) is 15 or less, the external additive having a large particle diameter is easily embedded, and the toner collected at the tip of the blade contains less toner containing the external additive with a large particle diameter, resulting in poor cleaning. Further, since the amount of toner to be developed is too large, image flow, image rubbing, and fixing failure / transfer failure due to excessive toner layer generation occur.

In the image forming apparatus of the present invention, the developer is a two-component developer, the carrier has a weight average particle diameter Dm of 30 to 50 μm, and a toner concentration in the range of 3 to 15%. The carrier is a ferrite containing a divalent metal such as iron, magnetite, Mn, Zn, Cu, and preferably has a weight average particle diameter Dm of 30 to 100 μm, particularly preferably in the range of 30 to 50 μm. When the average particle size is less than 30 μm, carrier adhesion is likely to occur on the photoreceptor during development, and there is little repulsion between carriers, and the amount of developer conveyed is increased. If it exceeds 50 μm, the amount of developer conveyed is greatly reduced, and if it exceeds 100 μm, the mixing with the toner is low, and the charge amount of the toner is insufficient so that charging failure during continuous use tends to occur. In addition, Cu ferrite containing Zn is preferable because of high saturation magnetization, but can be appropriately selected according to the process of the image forming apparatus. The resin for coating the magnetic carrier is not particularly limited, and examples thereof include silicone resin, styrene-acrylic resin, fluorine-containing resin, and olefin resin. In the manufacturing method, the coating resin may be dissolved in a solvent, sprayed into a fluidized bed and coated on the core, or the resin particles are electrostatically attached to the core particles and then thermally melted for coating. It may be a thing. The resin to be coated has a thickness of 0.05 to 10 μm, preferably 0.3 to 4 μm.
Further, the toner concentration represented by the ratio between the toner amount and the developer amount is set in the range of 3 to 15%. When the toner concentration is less than 3%, the charge amount of the toner is high, and the toner amount conveyed to the development area is small and the image density is low. If it exceeds 15%, the charge amount of the toner is low, reversely charged toner is generated, and the background fog increases. At the same time, as the amount of the external additive increases, the amount of decrease over time increases.

  In the image forming apparatus of the present invention, the outer diameter of the photosensitive member is 50 mm or less, and the outer diameter of the developing sleeve is 20 mm or less. When the outer diameters of the photosensitive member and the developing sleeve are increased, the width of the developing region is increased. Therefore, even if the conveyed developer index Y1 is small, the development time is long, and thus the influence on the image is small. Therefore, when the outer diameter of the photosensitive member is 50 mm and the outer diameter of the developing sleeve exceeds 20 mm, it is not necessary to control the distance X and the developer index Y1.

In the image forming apparatus of the present invention, toner having an average circularity of 0.94 or more is used. Average circularity SR = (peripheral length of a circle having the same area as the particle projection area / perimeter length of the particle projection image) × 100%. Toner having a high degree of circularity is easily affected by the developing electric field, and is developed faithfully along the electric field of the electrostatic latent image. When reproducing minute latent image dots, fine line reproducibility is enhanced by dense and uniform development. In addition, toner with a high degree of circularity has a smooth surface and appropriate fluidity, so it is easily affected by the electric field, and is easily transferred faithfully along the electric field, resulting in a high transfer rate and a high-quality image. Can be obtained. However, if the average circularity of the toner is less than 0.94, faithful development and transfer with a high transfer rate cannot be performed. Therefore, the average circularity is preferably 0.94 or more.
This degree of circularity is thermally or mechanically spheroidized with toner produced by dry grinding. Thermally, for example, the spheronization treatment can be performed by spraying toner base particles together with a hot air stream on an atomizer or the like. In addition, a spheroidizing treatment can be performed by mechanically putting the mixture in a mixing machine such as a ball mill together with a mixed medium such as glass having a low specific gravity and stirring. However, in the thermal spheronization process, toner base particles that are aggregated and have a large particle diameter or in the mechanical spheronization process, fine powder is generated, so that a classification process is required again. In addition, in a toner manufactured in an aqueous solvent, the shape can be controlled by applying strong stirring in the process of removing the solvent.

The image forming apparatus of the present invention uses toner having a shape factor SF-1 in the range of 100 to 180 and a shape factor SF-2 in the range of 100 to 180.
FIG. 6 is a diagram schematically showing the shape of the toner for explaining the shape factor SF-1 and the shape factor SF-2.
The shape factor SF-1 indicates the ratio of the roundness of the toner shape, and is represented by the following formula (1). This is a value obtained by dividing the square of the maximum length MXLNG of the shape formed by projecting the toner on a two-dimensional plane by the figure area AREA and multiplying by 100π / 4.
SF-1 = {(MXLNG) ² / AREA} × (100π / 4) (1)
If the shape factor SF-1 of the toner is close to 100, the shape of the toner is close to a sphere, and the contact between the toner and the toner or between the toner and the photosensitive member becomes a point contact. -Adhesion force between the toners becomes weak and fluidity increases. Also, the adhesion force between the toner and the photosensitive member decreases, and the transfer rate increases. On the other hand, if the value of the shape factor SF-1 is greater than 180, the shape factor SF-1 becomes indefinite, which is not preferable because developability and transferability deteriorate.

The shape factor SF-2 indicates the ratio of the uneven shape of the toner, and is represented by the following formula (2). A value obtained by dividing the square of the perimeter PERI of the figure formed by projecting the toner on the two-dimensional plane by the figure area AREA and multiplying by 100π / 4.
SF-2 = {(PERI) ² / AREA} × (100π / 4) Expression (2)
The closer the value of SF-2 is to 100, the smoother the unevenness of the toner surface. In order to improve the cleaning property, it is preferable that the surface has moderate unevenness. However, when the shape factor SF-2 is larger than 180, the unevenness becomes conspicuous so that the toner is scattered on the image. This is not preferable because the image quality is lowered.
Specifically, the shape factor is measured by taking a photograph of the toner with a scanning electron microscope (S-800: manufactured by Hitachi, Ltd.) and introducing it into an image analyzer (LUSEX 3: manufactured by Nireco). Analyzed and calculated.

The image forming apparatus of the present invention uses a toner containing a release agent. Wax is used as a release agent. It became clear that the state of the wax in the toner greatly affects the releasability of the toner at the time of fixing, and the wax is finely dispersed in the toner and is in the vicinity of the surface inside the toner. The presence of a large amount makes it possible to obtain good fixing releasability, and it is preferable that the wax is dispersed in a long diameter of 1 μm or less. The content is in the range of 2 to 6 wt% with respect to the toner weight. If it is less than 2%, the releasability does not appear and the offset toner amount increases. On the other hand, if it exceeds 6%, the soft wax moves to the surface of the carrier by mixing and stirring with the carrier to change the chargeability, so that the image density may be lowered or background fogging may occur.
Known waxes can be used, and include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbons (paraffin wax, sazol wax, etc.); carbonyl group-containing waxes, and the like. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerine tribehenene. Polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (Trimellitic acid tristearyl amide, etc.); and dialkyl ketones (distearyl ketone, etc.). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat-resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause cold offset during fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability.

  In the image forming apparatus of the present invention, the toner comprises at least a binder resin, a chromatic colorant, and a release agent, and a pulverization method, a polymerization method (suspension polymerization, emulsion polymerization dispersion polymerization, emulsion aggregation, emulsion) Manufacturing methods such as meetings), but is not limited to these manufacturing methods. The toner of the present invention is preferably a toner having a small particle size and a nearly spherical shape so as to output a high-quality and high-definition image. As a method for producing such a toner, there are a suspension polymerization method, an emulsion polymerization method, a polymer suspension method and the like in which an oil phase is emulsified, suspended or aggregated in an aqueous medium to form toner base particles. Hereinafter, these toner manufacturing methods will be described.

(Suspension polymerization method)
A colorant, a release agent, and the like are dispersed in an oil-soluble polymerization initiator and a polymerizable monomer, and are emulsified and dispersed by an emulsification method in an aqueous medium containing a surfactant, other solid dispersant, and the like. At this time, the particle size of the release agent is controlled by conditions such as the stirring speed and temperature for dispersing the release agent. Then, after carrying out a polymerization reaction to form particles, a wet treatment for attaching inorganic fine particles to the toner particle surfaces in the present invention may be performed. At that time, it is preferable to treat the toner particles from which excess surfactant and the like are removed by washing.
Polymerizable monomers such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, acrylamide, methacrylamide, diacetone Functional groups can be introduced on the surface of toner particles by using a part of acrylate or methacrylate such as acrylamide or these methylol compounds, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate and other amino groups. .
Further, by selecting a dispersant having an acid group or a basic group as a dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

(Emulsion polymerization aggregation method)
A water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by an ordinary emulsion polymerization technique. Separately, a dispersion in which a colorant, a release agent having a controlled particle size and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, wet processing of the inorganic fine particles may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer that can be used in the suspension polymerization method.

(Polymer suspension method)
The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like. In the oil phase of the toner composition, a colorant such as a resin, a prepolymer, and a pigment, a release agent having a controlled particle size, a charge control agent, and the like are dissolved or dispersed in a volatile solvent.
An oil phase composed of a toner composition is dispersed in an aqueous medium in the presence of a surfactant, a solid dispersant and the like, and a prepolymer is reacted to form particles. Thereafter, wet processing of inorganic fine particles, which will be described later, may be performed.

(Dry grinding method)
As an example of the pulverization system, a toner having at least a step of mechanically mixing raw materials including a binder resin, a charge control agent, and a colorant, a step of melt-kneading, a step of pulverizing, and a step of classifying A manufacturing method can be applied. Further, in order to improve the dispersibility of the colorant, the colorant may be mixed with other raw materials after the masterbatch treatment and processed to the next step.
The mixing step for mechanical mixing may be performed under normal conditions using a normal mixer using rotating wings, and is not particularly limited. When the above mixing process is completed, the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. Specific apparatuses for kneading the toner include batch type two rolls, a Banbury mixer and a continuous type twin screw extruder, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type twin screw manufactured by Toshiba Machine Co., Ltd. Extruder, KCK twin screw extruder, Ikegai Iron Works PCM type twin screw extruder, Kurimoto Iron Works KEX type twin screw extruder, continuous single screw kneader, such as Bus Etc. are preferably used. The melt-kneaded product obtained as described above is cooled and then pulverized. For pulverization, for example, coarsely pulverized using a hammer mill, a funnel plex or the like, and further, a fine pulverizer using a jet stream or mechanical pulverization A machine can be used. The pulverization is desirably performed so that the average particle diameter is 3 to 15 μm. Further, the particle size of the pulverized product is adjusted to 2.5 to 6.5 μm by a wind classifier or the like. Subsequently, the external additive is externally added to the toner particles, and the toner particles are coated on the surface of the toner particles while being crushed by mixing and stirring the toner particles and the external additive using a mixer.

  In this pulverized toner, a known binder resin can be used, but it is preferable to use a polyester resin from the viewpoint of improving the dispersibility of the pigment and obtaining an image of a wider color gamut. Furthermore, the polyester resin as the binder resin is composed of a linear polyester that does not contain a THF-insoluble component and a non-linear polyester that is a THF-insoluble component, thereby ensuring a wider fixing temperature range. By containing linear polyester and non-linear polyester, low-temperature fixability can be improved with linear polyester, and hot offset resistance can be improved with non-linear polyester. The dispersibility of the release agent must be improved. In order to improve the dispersibility of the release agent, it can generally be improved by controlling mechanical shearing and dispersion force during kneading, but in practice it is difficult to completely control shearing and dispersion. As a result, if the dispersion is improved, the shearing also proceeds, whereby the molecular weight is lowered by shearing, and the hot offset resistance by the non-linear polyester cannot be improved. However, since the dispersibility of the release agent and the colorant is improved by containing the hybrid resin, the necessity of controlling the mechanical energy for the dispersion is low, and only the control of shear is sufficient. Accordingly, the low temperature fixability can be improved with the linear polyester and the hot offset resistance can be improved with the non-linear polyester without impairing the gloss.

Among these, in particular, at least a binder resin and / or a binder resin precursor, a wax, and a colorant are dissolved or dispersed in an organic solvent or a polymerizable monomer to form particles in an aqueous medium. Toner is preferred. This is manufactured as follows.
1) A toner material solution is prepared by dispersing a colorant, unmodified polyester, a polyester prepolymer having an isocyanate group, and a release agent in an organic solvent.
In particular, a wax as a release agent is dissolved in an organic solvent and stirred here to form release agent particles. The particle size of the release agent particle can be controlled by stirring at this time. This is put into a binder resin and an organic solvent.
The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of an organic solvent is 0-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part.

2) The toner material liquid is emulsified in an aqueous medium in the presence of a surfactant and resin fine particles.
The aqueous medium may be water alone or an organic solvent such as alcohol (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.). It may be included.
The amount of the aqueous medium used relative to 100 parts by weight of the toner material liquid is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner material liquid is poor and a toner having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.

Further, in order to improve the dispersion in the aqueous medium, a dispersant such as a surfactant and resin fine particles is appropriately added.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine And the like.

Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-Hydroxyethyl) Perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.
Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Daikin Industries, Ltd.), Megafac F-110, F-120, F-113, F-191, F-812, F-833 (manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  Moreover, as the cationic surfactant, aliphatic quaternary ammonium such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt which has a right fluoroalkyl group is used. Salt, benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries) Smoke), Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products), Footage F-300 (Neos), and the like.

The resin fine particles are added to stabilize the toner base particles formed in the aqueous medium. For this reason, it is preferable to add so that the coverage existing on the surface of the toner base particles is in the range of 10 to 90%. For example, polymethyl methacrylate fine particles 1 μm and 3 μm, polystyrene fine particles 0.5 and 2 μm, poly (styrene-acrylonitrile) fine particles 1 μm, trade names are PB-200H (manufactured by Kao Corporation), SGP (manufactured by Soken Co., Ltd.), Techno Examples include polymer SB (manufactured by Sekisui Chemical Co., Ltd.), SGP-3G (manufactured by Sokensha), and micropearl (manufactured by Sekisui Fine Chemical Co., Ltd.).
In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.

As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxy Propyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl Nitrogen compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, poly Xoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.
The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

3) At the same time as the preparation of the emulsion, the amines (B) are added to cause a reaction with the polyester prepolymer (A) having an isocyanate group.
This reaction involves molecular chain crosslinking and / or elongation. The reaction time is selected depending on the reactivity between the isocyanate group structure of the polyester prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.

5) A charge control agent is injected into the toner base particles obtained above, and then inorganic fine particles such as silica fine particles and titanium oxide fine particles are externally added to obtain a toner.
The injection of the charge control agent and the external addition of the inorganic fine particles are performed by a known method using a mixer or the like.
Thereby, a toner having a small particle size and a sharp particle size distribution can be easily obtained. Furthermore, by giving strong agitation in the process of removing the organic solvent, the shape between the true spherical shape and the rugby ball shape can be controlled, and the surface morphology is also controlled between the smooth shape and the umeboshi shape. be able to.

  Further, the photosensitive member 40 and the developing device are integrally supported, and the process cartridge can be formed to be detachable from the image forming apparatus main body. In addition, the process cartridge may include a charging unit and a cleaning unit.

Example 1
A black toner was obtained according to the following toner formulation.
Binder resin: Polyester resin (Propylene oxide adduct of bisphenol A, polyester synthesized from terephthalic acid and succinic acid derivative): 100 parts Release agent: Carnauba wax: 5 parts
Charge control agent: Azo complex dye: 2 parts Colorant: Carbon black (# 44 Mitsubishi Chemical): 13 parts Pre-kneading with a mixer at the above-mentioned prescription amount. It is melt kneaded with a two-roll mill. Next, this was cooled, coarsely pulverized to about 0.5 to 3 mm, and then pulverized with an IDS type 2 jet pulverizer. Then, classification was performed to obtain a toner having an average particle diameter of 6.1 μm. To 100 parts by weight of the toner, 0.6 parts of silica fine powder (hexamethyldisilazane treatment) having an average particle diameter of 16 nm and 0.5 parts of silica fine powder (hexamethyldisilazane treatment) having an average particle diameter of 120 nm are used. The toner was prepared by mixing the external additive with a Henschel mixer and then sieving.

On the other hand, the carrier adjusted the coating liquid by the following prescription.
Silicone resin SR2411 (Toray Dow Corning) 300 parts Toluene

1200 parts The above solution was put into a rotating disk type fluidized bed coating apparatus together with 5 kg of ferrite carrier having an average particle size of 50 μm to coat the carrier. Thereafter, the coating was taken out from the apparatus and heated at 250 ° C. for 2 hours to age the film. In order to test by setting on a copying machine, a developer was prepared by weighing the toner and carrier so that the toner density was 5% and the total amount of toner and carrier was 1000 g. For evaluation, a part of Imagiono 450 (Ricoh Copier) was modified to set the distance between the latent image carrier and the developer carrier to 0.5 mm. Then, a developer was set in the developing section of Imagiono 450 (Ricoh Copier). Then, a test of passing 50000 (50K) sheets was performed. The results are shown in Table 2.

(Examples 2 to 11)
As shown in Table 1, the particle size and amount of the external additive, the distance between the latent image carrier and the developer carrier, and the toner particle size were changed. The results are shown in Table 2.
(Example 12)
In Example 1, the carrier is replaced with a ferrite carrier having an average particle size of 30 μm, and the developer is measured by weighing the toner and carrier in Example 1 to a total amount of 1000 g so that the toner concentration is 12%. Table 2 shows the results of the test performed in the same manner as in Example 1 except that was created.
(Example 13)
Example 6 is the same as Example 6 except that the developer was prepared by weighing the toner to a total amount of 1000 g using the toner and carrier of Example 6 so that the toner concentration was 3.1%. The results of testing in the same way as in Table 2 are as follows.
(Example 14)
In Example 1, the toner was prepared by using a linear polyester having a softening temperature of 110 ° C. and an acid value of 17 as the binder resin of the toner. Other than that, the same test as in Example 1 was carried out in the same manner, and the results are shown in Table 2.

(Example 15)
It is obtained by crosslinking and / or extending in a water-based solvent a toner material liquid in which at least a polyester prepolymer having a functional group containing a nitrogen atom, polyester, a colorant, and a release agent are dispersed in an organic solvent. The constituent material and manufacturing method of the toner will be described.
(1. Example of black toner)
~ Synthesis of organic fine particle emulsion ~
Production Example 1
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, 110 butyl acrylate Parts and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Furthermore, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and an aqueous dispersion of vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). [Fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 58 ° C., and the weight average molecular weight was 130,000.

-Adjustment of aqueous phase-
Production Example 2
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7): Sanyo Chemical Industries, Ltd. and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 7 hours under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 44 parts of trimellitic anhydride into the reaction vessel, and add 3 parts at 180 ° C at normal pressure. By reacting for a time, [low molecular weight polyester 1] was obtained. [Low molecular polyester 1] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, Tg of 43 ° C., and an acid value of 25.

~ Synthesis of intermediate polyester ~
Production Example 4
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 7 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight percentage of 1.53%.

~ Synthesis of ketimine ~
Production Example 5
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

~ Synthesis of master batch (MB) ~
Production Example 6
1200 parts of water, 540 parts of carbon black (manufactured by Printex 35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5],
1,200 parts of polyester resin was added, mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), the mixture was kneaded at 130 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1]. .

~ Creation of oil phase ~
Production Example 7
In a container in which a stir bar and a thermometer were set, 378 parts of [Low molecular weight polyester 1], Carnauba WAX 10O part, 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw Material Solution 1] Transfer 1324 parts to a container and use a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.) to feed 1 kg / hr of liquid, 6 m / sec of disk peripheral speed, and 80% by volume of 0.5 mm zirconia beads. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

~ Emulsification⇒Desolvation ~
Production Example 8
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at 13,000 rpm for 25 minutes to obtain [Emulsion Slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 1].

~ Washing⇒Drying ~
Production Example 9
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 1OO parts of 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (10 minutes at 12,000 rpm) and filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [filter cake 1]. It was.
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer. To 100 parts of the base toner, zinc salicylate (E-84: manufactured by Orient Chemical Co., Ltd.) was mixed at a ratio of 0.6 part by a mixer. And sieved with a mesh of 75 μm, volume average particle size (Dv) 6.1 μm, number average particle size (Dn) 5.5 μm, Dv / Dn = 1.1, average circularity = 0.97, shape factor SF A toner having -1 = 135 and a shape factor SF-2 = 118 was obtained.

(1. Yellow toner example)
~ Synthesis of organic fine particle emulsion ~
Production Example 1
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, 110 butyl acrylate Parts and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Furthermore, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and an aqueous dispersion of vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). [Fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 58 ° C., and the weight average molecular weight was 130,000.

-Adjustment of aqueous phase-
Production Example 2
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7): Sanyo Chemical Industries, Ltd. and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 7 hours under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 44 parts of trimellitic anhydride into the reaction vessel, and add 3 parts at 180 ° C at normal pressure. By reacting for a time, [low molecular weight polyester 1] was obtained. [Low molecular polyester 1] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, Tg of 43 ° C., and an acid value of 25.

~ Synthesis of intermediate polyester ~
Production Example 4
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 7 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight percentage of 1.53%.

~ Synthesis of ketimine ~
Production Example 5
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

~ Synthesis of master batch (MB) ~
Production Example 6
1200 parts of water, C.I. I. Pigment Yellow 180 (PV
540 parts of Fast Yellow HG (Clariant)) and 1200 parts of polyester resin are added, mixed with a Henschel mixer (made by Mitsui Mining Co., Ltd.), the mixture is kneaded at 130 ° C. for 1 hour using two rolls, rolled and cooled with a pulverizer. Grinding to obtain [Masterbatch 1].

~ Creation of oil phase ~
Production Example 7
In a container in which a stir bar and a thermometer were set, 378 parts of [Low molecular weight polyester 1], Carnauba WAX 10O part, 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw Material Solution 1] Transfer 1324 parts to a container and use a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.) to feed 1 kg / hr of liquid, 6 m / sec of disk peripheral speed, and 80% by volume of 0.5 mm zirconia beads. Pigment yellow and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

~ Emulsification⇒Desolvation ~
Production Example 8
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at 13,000 rpm for 25 minutes to obtain [Emulsion Slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 1].

~ Washing⇒Drying ~
Production Example 9
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 1OO parts of 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (10 minutes at 12,000 rpm) and filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [filter cake 1]. It was.
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer. To 100 parts of the base toner, zinc salicylate (E-84: manufactured by Orient Chemical Co., Ltd.) was mixed at a ratio of 0.6 part by a mixer. And sieved with a mesh of 75 μm, volume average particle size (Dv) 6.1 μm, number average particle size (Dn) 5.5 μm, Dv / Dn = 1.1, average circularity = 0.97, shape factor SF A toner having -1 = 133 and a shape factor SF-2 = 116 was obtained.

(1. Example of magenta toner)
~ Synthesis of organic fine particle emulsion ~
Production Example 1
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, 110 butyl acrylate Parts and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Furthermore, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and an aqueous dispersion of vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). [Fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 58 ° C., and the weight average molecular weight was 130,000.

-Adjustment of aqueous phase-
Production Example 2
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7): Sanyo Chemical Industries, Ltd. and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 7 hours under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 44 parts of trimellitic anhydride into the reaction vessel, and add 3 parts at 180 ° C at normal pressure. By reacting for a time, [low molecular weight polyester 1] was obtained. [Low molecular polyester 1] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, Tg of 43 ° C., and an acid value of 25.

~ Synthesis of intermediate polyester ~
Production Example 4
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 7 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight percentage of 1.53%.

~ Synthesis of ketimine ~
Production Example 5
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

~ Synthesis of master batch (MB) ~
Production Example 6
1200 parts of water, C.I. I. Pigment Red 122 Hostaperm Pink E (Clarint)) 540 parts,
1,200 parts of polyester resin was added, mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), the mixture was kneaded at 130 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1]. .

~ Creation of oil phase ~
Production Example 7
In a container in which a stir bar and a thermometer were set, 378 parts of [Low molecular weight polyester 1], Carnauba WAX 10O part, 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw Material Solution 1] Transfer 1324 parts to a container and use a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.) to feed 1 kg / hr of liquid, 6 m / sec of disk peripheral speed, and 80% by volume of 0.5 mm zirconia beads. Pigment Red and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

~ Emulsification⇒Desolvation ~
Production Example 8
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at 13,000 rpm for 25 minutes to obtain [Emulsion Slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 1].

~ Washing⇒Drying ~
Production Example 9
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 1OO parts of 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (10 minutes at 12,000 rpm) and filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [filter cake 1]. It was.
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer. To 100 parts of the base toner, zinc salicylate (E-84: manufactured by Orient Chemical Co., Ltd.) was mixed at a ratio of 0.6 part by a mixer. Then, sieved with a mesh of 75 μm, volume average particle size (Dv) 6.1 μm, number average particle size (Dn) 5.5 μm, Dv / Dn = 1.1, average circularity = 0.97 shape factor SF− A toner having 1 = 123 and a shape factor SF-2 = 117 was obtained.

(1. Cyan toner example)
~ Synthesis of organic fine particle emulsion ~
Production Example 1
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, 110 butyl acrylate Parts and 1 part of ammonium persulfate were added and stirred at 3800 rpm for 30 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Furthermore, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and an aqueous dispersion of vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). [Fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 110 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The Tg of the resin was 58 ° C., and the weight average molecular weight was 130,000.

-Adjustment of aqueous phase-
Production Example 2
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7): Sanyo Chemical Industries, Ltd. and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl Add 2 parts of tin oxide, react at 230 ° C for 7 hours under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 44 parts of trimellitic anhydride into the reaction vessel, and add 3 parts at 180 ° C at normal pressure. By reacting for a time, [low molecular weight polyester 1] was obtained. [Low molecular polyester 1] had a number average molecular weight of 2,300, a weight average molecular weight of 6,700, Tg of 43 ° C., and an acid value of 25.

~ Synthesis of intermediate polyester ~
Production Example 4
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 7 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 9700, Tg of 54 ° C., an acid value of 0.5, and a hydroxyl value of 52.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight percentage of 1.53%.

~ Synthesis of ketimine ~
Production Example 5
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 4 and a half hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 417.

~ Synthesis of master batch (MB) ~
Production Example 6
1200 parts of water, C.I. I. Pigment Blue 15: 3 (Lionol Blue FG-7351 (Toyo Ink)) 540 parts,
1,200 parts of polyester resin was added, mixed with a Henschel mixer (Mitsui Mining Co., Ltd.), the mixture was kneaded at 130 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1]. .

~ Creation of oil phase ~
Production Example 7
In a container in which a stir bar and a thermometer were set, 378 parts of [Low molecular weight polyester 1], Carnauba WAX 10O part, 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. It was cooled to 30 ° C at 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw Material Solution 1] Transfer 1324 parts to a container and use a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.) to feed 1 kg / hr of liquid, 6 m / sec of disk peripheral speed, and 80% by volume of 0.5 mm zirconia beads. Pigment Blue and WAX were dispersed under the conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

~ Emulsification⇒Desolvation ~
Production Example 8
[Pigment / WAX Dispersion 1] 749 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 2.9 parts in a container and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 2 minutes After mixing, 1200 parts of [Aqueous Phase 1] was added to the container and mixed with a TK homomixer at 13,000 rpm for 25 minutes to obtain [Emulsion Slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 7 hours to obtain [Dispersion slurry 1].

~ Washing⇒Drying ~
Production Example 9
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 1OO parts of 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (10 minutes at 12,000 rpm) and filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [filter cake 1]. It was.
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer. To 100 parts of the base toner, zinc salicylate (E-84: manufactured by Orient Chemical Co., Ltd.) was mixed at a ratio of 0.6 part by a mixer. Then, sieved with a mesh of 75 μm, volume average particle size (Dv) 6.1 μm, number average particle size (Dn) 5.5 μm, Dv / Dn = 1.1, average circularity = 0.97 shape factor SF− A toner having 1 = 128 and a shape factor SF-2 = 115 was obtained.
For each of the yellow, magenta, cyan and black toners of each color, 1.6 parts of silica fine powder (hexamethyldisilazane treatment) with an average particle diameter of 16 nm and an average particle diameter of 120 nm with respect to 100 parts by weight of each toner. After mixing 0.8 parts of silica fine powder (hexamethyldisilazane treatment) and 0.5 part of titanium oxide fine powder (isobutyltrimethoxysilane treatment) having an average particle size of 15 nm with a Henschel mixer, the mixture is sieved. Toner was created. A developer was prepared by weighing each toner so that the toner density was 7% and the carrier of Example 1 to a total amount of 1000 g. In order to evaluate, a part of IPSIO Color 8000 (Ricoh Copier) was remodeled, the distance between the latent image carrier and the developer carrier was 0.45 mm, the outer diameter of the image carrier was 30 mm, and the developer carrier The outer diameter was set to 20 mm. Then, a developer was set in the developing unit. The 50,000 (50K) sheets were tested. The results are shown in Table 2.

(Example 16)
A color toner was obtained according to the following toner formulation.
Binder resin: Polyester resin (Propylene oxide adduct of bisphenol A, polyester synthesized from terephthalic acid and succinic acid derivative): 100 parts Charge control agent: Zinc salicylate (Bontron E84, Orient Chemical): 2 parts Colorant: Yellow Colorant: C.I. I. Pigment Yellow 180 (PV
Fast Ye low HG (Clariant)): 5 parts
Magenta colorant: C.I. I. Pigment Red 57: 1 (Lionol Red 6B FG-4215 (Toyo Ink)): 4 parts
Cyan colorant: C.I. I. Pigment Blue 15: 3 (Lionol
BlueFG-7351 (Toyo Ink)): 2 parts
Black colorant: Carbon black (# 44 Mitsubishi Chemical): 7.5 parts Each toner is preliminarily kneaded with a mixer at each prescribed amount. It is melt kneaded with a three-roll mill. Next, this was cooled, coarsely pulverized to about 0.5 to 3 mm, and then pulverized with an IDS type 2 jet pulverizer. Then, classification was performed to obtain a toner having an average particle diameter of 6.1 μm. For each of the yellow, magenta, cyan, and black toners of each color, 1.3 parts of silica fine powder (hexamethyldisilazane treatment) with an average particle diameter of 16 nm and an average particle diameter of 120 nm with respect to 100 parts by weight of the toner. After mixing 0.7 parts of silica fine powder (hexamethyldisilazane treatment) and 0.8 parts of titanium oxide fine powder (isobutyltrimethoxysilane treatment) with an average particle size of 15 nm with a Henschel mixer, the toner is removed by sieving. Created.

On the other hand, the carrier adjusted the coating liquid by the following prescription.
Silicone resin SR2411 (Toray Dow Corning) 300 parts Toluene
1200 parts The above solution was put into a rotating disk type fluidized bed coating apparatus together with 5 kg of ferrite carrier having an average particle size of 50 μm to coat the carrier. Thereafter, the coating was taken out from the apparatus and heated at 250 ° C. for 2 hours to age the film. In order to test by setting on a copying machine, a developer was prepared by weighing the total amount of the initial agent toner and the carrier to 1000 g so that the toner density was 5%. In order to evaluate, a part of IPSIO Color 8000 (Ricoh Copier) was remodeled, the distance between the latent image carrier and the developer carrier was 0.45 mm, the outer diameter of the image carrier was 30 mm, and the developer carrier The outer diameter was set to 20 mm. Then, a developer was set in the developing unit. After that, a test of passing 50000 (50K) sheets was performed. The results are shown in Table 2.

(Comparative Example 1)
Table 2 shows the same results as in Example 1 except that in the toner formulation, silica fine powder having an average particle size of 120 nm (hexamethyldisilazane treatment) and 0.5 part are not added. The result was as follows. (As the primary particle size D of the external additive is not added in the range of 30 to 700 nm, the cleaning property is poor due to the toner slipping through the cleaning portion by continuous copying, and the transfer failure is poor because the external additive is embedded in the toner particles. It occurs remarkably.)

(Comparative Example 2)
Example 1 was the same as Example 1 except that the silica fine powder (hexamethyldisilazane treatment) having an average particle size of 120 nm in the toner formulation was changed from 0.5 to 3.5 parts. However, the results shown in Table 2 were obtained. (Since the addition of 3.5 parts of the external additive having a primary particle size D of 30 to 700 nm is not caused by the toner being slipped from the cleaning part by continuous copying, the charge amount is not increased. (Because of the decrease, the background stains and the toner scattering are large. The external additive adheres to the latent image carrier and the toner transfer property is not good. Also, the developer amount is greatly reduced.)

1 is a schematic diagram illustrating a configuration of an image forming apparatus of the present invention. It is the figure which expanded and showed the image formation means. It is a graph which shows the relationship between distance X and developer index Y1 conveyed. It is a graph which shows the fall amount of the formulation amount Z of the external additive and the developer index Y2 conveyed. It is a graph which shows the relationship between the primary particle size D of an external additive, and the ratio with respect to the fall amount of the developer index | exponent Y2. It is the figure which represented typically the shape of the toner in order to demonstrate shape factor SF-1 and shape factor SF-2.

Explanation of symbols

4 Developing Device 41 Developing Sleeve 42 Developer Stirring Tank 43 Toner Storage Tank 44 Toner Supply Roller 45 Stirring Screw 10 Intermediate Transfer Belt (Intermediate Transfer Body)
18 Image forming means 21 Exposure device 22 Secondary transfer device 25 Fixing device 251 Fixing roller 252 Pressure roller 255 Coating roller 256 Fixing roller cleaning roller 257 Pressure roller cleaning roller 258 Temperature sensor 259 Supply roller 260 Molded body 40 Photosensitive body (latent Image carrier)
62 Primary transfer means 100 Copying device main body 200 Paper feed table 300 Scanner 400 Automatic document feeder

Claims (12)

An image forming apparatus comprising: an image carrier that carries at least a latent image; and a developing device provided with a developer carrier that conveys a developer containing toner in the vicinity of the image carrier.
In the image forming apparatus, the distance X between the image carrier and the developer carrier is in the range of 100 to 650 μm,
The toner has a weight average particle diameter Dm in the range of 2.0 to 6.5 μm,
The external additive contains inorganic fine particles having a primary particle size D of 30 to 700 nm and a prescription amount Z in the range of 0.1 to 2.5 parts by weight with 100 parts by weight of toner, and
The developer index Y1 represented by the relational expression (1) satisfies the following relational expression (2):
Y1 = 306X ² −374X + 154− (4.7Z ² + 4Z) (1)
(However, the unit of X represents [mm], and the unit of Z represents [part by weight] with the toner base weight being 100 parts by weight.)
40 ≦ Y1 ≦ 120 Formula (2)
An image forming apparatus. An image forming apparatus comprising: an image carrier that carries at least a latent image; and a developing device provided with a developer carrier that conveys a developer containing toner in the vicinity of the image carrier.
In the image forming apparatus, the distance X between the image carrier and the developer carrier is in the range of 100 to 650 μm,
The toner has a weight average particle diameter Dm in the range of 2.0 to 6.5 μm,
The external additive contains inorganic fine particles having a primary particle size D of 30 to 700 nm and a prescription amount Z in the range of 0.1 to 2.5 parts by weight with 100 parts by weight of toner, and
The developer index Y2 represented by the following relational expressions (3) and (4) satisfies the following relational expression (5):
Y2 = 306X < ² > -374X + 154- (4.7W < ² > + 4W) ... Formula (3)
W = Z × (1.7 Log D−2.4) (4)
(However, the unit of X is [mm], the unit of Z is [part by weight] with the toner base weight being 100 parts by weight, and the unit of D is [mm].)
40 ≦ Y2 ≦ 120 (5)
An image forming apparatus. The image forming apparatus according to claim 1, wherein
The ratio between the distance X and the weight average particle diameter Dm of the toner is in the range of 15 to 200. The image forming apparatus according to any one of claims 1 to 3,
The image forming apparatus, wherein the developer is a two-component developer, and has a carrier weight average particle diameter Dm of 30 to 50 μm and a toner concentration of 3 to 15%. The image forming apparatus according to claim 1,
In the image forming apparatus, the outer diameter of the image carrier is 15 to 50 mm or less, and the outer diameter of the developer carrier is 5 to 20 mm or less. The image forming apparatus according to claim 1,
The image forming apparatus uses toner having an average circularity of 0.94 or more. The image forming apparatus according to claim 1,
The image forming apparatus uses a toner containing a release agent. The image forming apparatus according to claim 1,
In the image forming apparatus, the toner contains a binder resin and a colorant, and uses a toner obtained by melting, kneading, and dry pulverizing. The image forming apparatus according to claim 1,
The image forming apparatus uses toner granulated in an aqueous solvent. The image forming apparatus according to claim 9.
The toner forms particles in an aqueous medium by dissolving or dispersing at least a binder resin and / or a binder resin precursor, wax, and a chromatic colorant in an organic solvent or a polymerizable monomer. An image forming apparatus. The image forming apparatus according to claim 8,
The image forming apparatus uses the toner having a shape factor SF-1 in the range of 100 to 180 and a shape factor SF-2 in the range of 100 to 180. The image forming apparatus according to claim 1,
The image forming apparatus, wherein the image forming apparatus is a process cartridge that can be attached to and detached from a main body.

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