JP2005266383A - Toner for developing electrostatic charge image, full color toner kit, image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming apparatus wherein a toner has an appropriate strength, a wear amount of a cleaning blade is less and the toner corresponds to a low temperature fixing system, has satisfactory offset resistance, high charge properties and satisfactory charge rising properties and which is provided with high durability and low maintenance properties corresponding to the environment of high temperature and high humidity and low temperature and low humidity and to provide an image forming method. <P>SOLUTION: The toner for developing an electrostatic charge image comprises particles formed by dispersing oil drops of an organic solvent in which a toner composition containing a prepolymer is dissolved into an aqueous medium and then performing an extension reaction and/or a crosslinking reaction and has 0.100 to 1.00 kg/mm<SP>2</SP>strength in a fine compression tester and the ratio (kmax/kmin) of the maximum inclination value kmax to the minimum inclination value kmin of the inclination (force/displacement) to be the ratio of force to displacement of ≥20 in the range of 0 to 1 μm displacement in a strength displacement graph in the fine compression tester. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an electrostatic image developing toner, an electrostatic image developing developer, a full color toner kit, an image forming method, and an image forming apparatus.

In electrophotographic devices and electrostatic recording devices, toner is attached to an electrostatic latent image formed on a photoreceptor, transferred to a transfer material, and then fixed to the transfer material by heat to form a toner image. doing. Also, full-color image formation is generally performed by using four color toners of black, yellow, magenta, and cyan. Each toner is developed, and each toner layer is superimposed on a transfer material. To obtain a full-color image.
However, for users who are familiar with printing in general, images on full-color copiers are not yet satisfactory, and there is a demand for higher image quality that satisfies photography, high-definition, and high resolution. It is known to use a toner having a small particle size and a narrow particle size distribution to improve the image quality.

  Conventionally, an electrical or magnetic latent image has been visualized with toner. Toner used for electrostatic image development is generally colored particles in which a binder, a colorant, a charge control agent, and other additives are contained in a binder resin. There is a polymerization method. In the pulverization method, a colorant, a charge control agent, an offset preventing agent and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. According to the pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle. Therefore, when the above composition is actually pulverized into particles, a high-range particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, the particle size There is a disadvantage that the fine powder of 5 μm or less and the coarse powder of 20 μm or more must be removed by classification, resulting in a very low yield. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. The uneven dispersion of the compounding agent adversely affects the fluidity, developability, durability, image quality and the like of the toner.

  In recent years, in order to overcome these problems in the pulverization method, for example, toner particles are obtained by a suspension polymerization method (for example, see Patent Document 1). However, although the toner particles obtained by the suspension polymerization method are spherical, there is a disadvantage that the cleaning property is inferior. Development / transfer with a low image area ratio results in a small amount of residual toner, and poor cleaning does not pose a problem. However, images with a high image area ratio, such as photographic images, and untransferred images formed due to poor paper feed, etc. Toner may be generated on the photoconductor as untransferred toner, and if accumulated, the image may be soiled. In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. Also, the low temperature fixability is not sufficient, and a large amount of energy required for fixing is required, which is a problem. On the other hand, a method is disclosed in which resin fine particles obtained by an emulsion polymerization method are associated to obtain irregular toner particles (see, for example, Patent Document 2). However, in the toner particles obtained by the emulsion polymerization method, a large amount of the surfactant remains not only on the surface but also inside the particles even after the water washing step, and the environmental stability of the toner charging is impaired. The amount distribution is widened, and the background stain of the obtained image becomes poor. In addition, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, and the like, and the original charging ability cannot be exhibited.

On the other hand, in a fixing process by a contact heating method performed using a heating member such as a heat roller, release properties of toner particles (hereinafter referred to as “offset resistance”) to the heating member are required. Here, the offset resistance can be improved by the presence of a release agent on the toner particle surface. On the other hand, Patent Documents 3 and 4 disclose a method for improving offset resistance not only by containing resin fine particles in the toner particles but also by unevenly distributing the resin fine particles on the surface of the toner particles. Yes. However, there is a problem that the lower limit fixing temperature is increased and the low temperature fixing property, that is, the energy saving fixing property is not sufficient.
In addition, the following problems occur in the method of obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method. That is, when the release agent fine particles are associated with each other in order to improve the offset resistance, the release agent fine particles are taken into the toner particles, and as a result, the offset resistance can be sufficiently improved. Can not. Resin fine particles, release agent fine particles, colorant fine particles, etc. are randomly fused to constitute toner particles, so there is a variation in composition (content ratio of constituent components) and molecular weight of constituent resins among the obtained toner particles. As a result, the toner particles have different surface characteristics, and a stable image cannot be formed over a long period of time. Further, in a low-temperature fixing system that requires low-temperature fixing, there is a problem that fixing temperature range cannot be ensured because fixing inhibition occurs due to resin fine particles unevenly distributed on the toner surface.

On the other hand, a new production method called dissolution suspension method (EA; Emulsion-Aggregation method) has recently been proposed (for example, see Patent Document 5). This method is a method of granulating from a polymer dissolved in an organic solvent or the like, while the suspension polymerization method forms particles from monomers, and has advantages such as expansion of the resin selection range and polarity controllability. Cite. In addition, although the toner structure control (core / shell structure control) is mentioned as an advantage, the shell structure is a resin-only layer intended to reduce the exposure of pigments and wax to the surface, especially the surface. The state is not devised, nor is such a structure (see, for example, Patent Document 6). Therefore, although it has a shell structure, the toner surface is an ordinary resin and is not particularly devised, and when aiming at lower temperature fixing, it was not sufficient in terms of heat resistant storage stability and environmental charge stability, which was a problem. .
In addition, the suspension polymerization method, the emulsion polymerization method, and the dissolution suspension method generally use a styrene / acrylic resin, and the polyester resin has difficulty in particle formation, and the particle size, particle size distribution, and shape control. It was difficult. In addition, there was a limit to fixability when aiming at lower temperature fixing.

On the other hand, it is also known to use a polyester modified with a urea bond for the purpose of heat-resistant storage stability and low-temperature fixing (for example, see Patent Document 7). It was a problem because it was not sufficient in terms of environmental charge stability under severe conditions.
In the field of electrophotography, high image quality has been studied from various angles, and among them, the recognition that toner diameter reduction and spheroidization are extremely effective is increasing. However, as the diameter of the toner is reduced, the transferability and the fixing property are lowered, and a tendency to become a poor image is observed. On the other hand, it is known that transferability is improved by making the toner spherical (see, for example, Patent Document 8). Under such circumstances, further speeding up of image formation is desired in the field of color copiers and color printers. The “tandem method” is effective for speeding up (see, for example, Patent Document 9). The “tandem method” is a method of obtaining a full-color image on a transfer sheet by sequentially superimposing and transferring the image formed by the image forming unit on a single transfer sheet conveyed to a transfer belt. A tandem color image forming apparatus has a variety of transfer papers that can be used, has high quality of a full color image, and has excellent characteristics that a full color image can be obtained at a high speed. In particular, the characteristic that a full color image can be obtained at a high speed is a characteristic that is not found in other color image forming apparatuses. On the other hand, attempts have been made to achieve high speed while improving image quality using spherical toner. However, in order to cope with higher speeds, quick fixability is required, but a toner having both good fixability and low temperature fixability with a spherical toner has not been realized so far.

Also, high-temperature and high-humidity and low-temperature and low-humidity environments during storage and transportation after toner production are harsh conditions for the toner, and the toner does not aggregate even after storage in the environment, charging characteristics, fluidity, transferability, There is a demand for a toner having no deterioration in fixability or extremely low storage stability, but an effective means for these has not been found so far, particularly with a spherical toner.
It is also known to contain a fluorine-based compound in the toner as a charge control agent or the like as means for increasing the charging ability of the toner (particularly negatively charged toner) (Patent Documents 10, 11, etc.). However, in this method, the charging ability as a toner base is improved, but the good characteristics of the toner base are covered by the type and characteristics of the fluidizing agent added to the toner. This is a problem with fogging and toner scattering, and an effective method has been desired. On the other hand, inorganic fine particles using a fluorinated hydrophobizing agent are also known (Patent Document 12 and others), but for the purpose of reducing friction with the surface of the photoreceptor, there is no sufficient effect of improving the charge rise property, It was a problem in terms of environmental charge stability.

  An image forming apparatus that forms a predetermined latent image on a latent image holding body such as a photosensitive drum and forms an image using toner, such as an electrophotographic apparatus and an electrostatic recording apparatus, is a toner formed on the latent image holding body. Since an image cannot always be 100% transferred onto a support such as paper, a cleaning device is generally provided for removing residual toner on the latent image holding member. As a cleaning device, an elastic rubber blade is pressed against the surface of the latent image carrier to mechanically remove the residual toner, or a brush roller with a fine fiber plant is rotated at high speed to apply toner to the brush tip. A brush cleaning device that adheres and removes residual toner is known. However, when a blade cleaning device is used, the photosensitive drum may be worn due to friction with the cleaning blade, and image formation characteristics and life may be reduced. In order to solve such problems, image formation in which residual toner on a latent image carrier such as a photosensitive drum after transfer is collected in the developing device simultaneously with development by a developing device without using a cleaning device. A method (hereinafter referred to as “cleanerless image forming method”) is known from Patent Documents 13 and 14, and the like. On the other hand, as a toner used in a cleanerless image forming method, Patent Document 15 discloses a toner that defines an electrical resistance and a charge amount suitable for preventing a residual image due to a residual toner charge, and Patent Document 16 describes an image density and a toner. Toner having a suitable particle size distribution, shape and charge amount for achieving both cleaning properties, Patent Document 17 describes a shape for providing a suitable toner by a cleaner-less image forming method with less residual transfer toner. In Japanese Patent Application Laid-Open No. H11-260688, a specific toner and a spherical toner with a specified coverage are listed for image stabilization.

Japanese Patent Laid-Open No. 9-43909 Japanese Patent No. 2537503 JP 2000-292773 A JP 2000-292978 A Japanese Patent No. 3141784 The 4th Joint Symposium of the Imaging Society of Japan / Electrostatic Society (2002.7.29) Japanese Patent Laid-Open No. 11-133667 JP 9-258474 A JP-A-5-341617 Japanese Patent No. 2942588 Japanese Patent No. 3102797 Japanese Patent No. 3057209 JP 59-133573 A JP 59-157661 A JP-A-5-2287 Japanese Patent Laid-Open No. 5-188737 JP-A-9-288373 Japanese Patent Laid-Open No. 10-20539

  Accordingly, it is an object of the present invention to (1) stably provide a toner having a proper toner strength and a small amount of wear of the cleaning blade, and (2) a low temperature while maintaining the cleaning property. To stably provide a toner, a developer, an image forming apparatus, and an image forming method that are compatible with the fixing system, have good offset resistance, and do not contaminate the fixing apparatus and the image. (3) The toner has a sufficiently high charging capability, good charge rise characteristics, and even if tens of thousands of images are output, there is little toner spent on the carrier, etc., and high chargeability and fluidity can be maintained. And to provide an image forming apparatus and an image forming method capable of obtaining an image quality with a sufficient image density and (4) toner having excellent environmental preservation (high temperature and high humidity, low temperature and low humidity). , To provide a developer, an image forming apparatus, and an image forming method, and (5) to form an image with less background stain (fogging) excellent in charging stability in a high temperature and high humidity and low temperature and low humidity environment, and To stably provide an image forming apparatus and an image forming method in which toner is less scattered in the machine. (6) Furthermore, as an image forming system, an image forming apparatus having high durability and low maintenance, It is to provide an image forming method stably.

The above-described problem is solved by (1) “a toner containing at least a colorant and a resin, in which an oil droplet of an organic solvent in which the toner composition containing a prepolymer is dissolved is dispersed in an aqueous medium. / Or consisting of particles formed by a crosslinking reaction, the strength in a micro compression tester is 0.100 to 1.00 kg / mm ² , and the displacement amount in the strength displacement graph in the micro compression tester is 0 to 1 μm Within the range, the ratio (kmax / kmin) of the maximum value slope kmax and the minimum value slope kmin of the gradient (force / displacement), which is the ratio of force and displacement, is 20 or more. toner",
(2) “The volume average particle diameter Dv of the toner is 4 to 6 μm, and the ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn is 1.00 to 1.25. The electrostatic image developing toner according to item (1),
(3) The electrostatic image developing toner according to (1) or (2) above, wherein at least the fine powder having a volume average particle diameter of 1 μm or less is 0 to 10% by weight. "
(4) “Toner for developing electrostatic image according to any one of items (1) to (3), wherein the toner has a circularity E of 0.92 to 0.99”. ,
(5) Any of the above items (1) to (4), wherein the toner has a circularity SF-1 value of 100 to 160 and a circularity SF-2 value of 100 to 150. The electrostatic image developing toner according to claim 1, "
(6) The electrostatic image development according to any one of (1) to (5) above, wherein the content of the wax in the toner is 3% to 8% in terms of weight. Toner ",
(7) “Electrostatic charge developing toner, wherein the binder resin of the electrostatic image developing toner according to any one of (1) to (6) includes at least a modified polyester resin” ,
(8) “Toner for developing electrostatic image according to any one of items (1) to (6), wherein the toner contains at least inorganic fine particles, and the inorganic fine particles are composed of at least two types”. ,
(9) “Toner for developing electrostatic image according to item (8), wherein the two kinds of inorganic fine particles are silica and titanium”.
Further, the above problem is that the electrostatic image developing toner according to any one of (10) and (1) to (9) of the present invention includes at least a magenta toner, a yellow toner, and a cyan toner. This is achieved by a “full-color toner kit”.
In addition, the above-mentioned problem is characterized in that it comprises the electrostatic charge image developing toner according to any one of (11) and (1) to (9) of the present invention and a carrier comprising magnetic particles. This is achieved by a “two-component developer for developing electrostatic image”.
In addition, the above-described problem is (12) “a process cartridge which integrally supports at least one of a developing unit and at least one unit selected from a photosensitive member, a charging unit, and a cleaning unit, and is detachable from an image forming apparatus main body. The developing means is the toner described in any one of (1) to (9), the full-color toner kit described in (10), or the development described in (11). It is achieved by a “process cartridge” characterized in that it holds the agent.
In addition, the above-described problems are solved by (13) “the toner according to any one of (1) to (9), the full-color toner kit according to (10), or the (11)- An image forming method comprising using the developer described in 1.
(14) The toner according to any one of (1) to (9), the full-color toner kit according to (10), or the developer according to (11) is used. And a tandem color image forming method characterized in that the printing speed is equivalent to A4 size and is 20 sheets / minute or more.
In addition, the above-described problems are solved by (15) “the toner according to any one of (1) to (9), the full-color toner kit according to (10), or the (11). This is achieved by an “image forming apparatus” in which a container filled with the developer described in the above item is loaded.

As a result of intensive studies to achieve the above-mentioned problems, in a toner including at least a colorant and a resin, an oil droplet of an organic solvent in which the toner composition containing the prepolymer is dissolved in an aqueous medium, the elongation reaction and / Or consisting of particles formed by a cross-linking reaction, the strength in the micro compression tester is 0.100 to 0.600 kg / mm ² , and the displacement amount in the strength displacement graph in the micro compression tester is a strength displacement graph. Within a range of 0 to 1 μm, the ratio of the maximum gradient kmax and the minimum gradient kmin (kmax / kmin), which is the ratio of force to displacement (force / displacement), is 20 or more. By using toner for developing electrostatic image, the amount of wear of the cleaning blade in the cleaning system is small and after outputting tens of thousands of images Excellent charging stability, little background stain (fogging), no toner scattering, excellent coloration, light resistance, transparency, color development, sharpness, color reproducibility, saturation, and gloss It was found that an image can be formed.
The mechanism is currently being elucidated, but the following can be inferred from some analysis data. The present invention is particularly effective for a toner formed by dispersing an oil droplet of an organic solvent in which a toner composition containing a prepolymer is dissolved in an aqueous medium and performing an elongation reaction and / or a crosslinking reaction. It is 0.100 to 0.600 kg / mm ² , and the gradient (force / displacement) is the ratio of force to displacement within the range of 0 to 1 μm in the amount of displacement in the strength displacement graph in the micro displacement tester in the strength displacement graph. When the ratio (kmax / kmin) between the maximum value slope kmmax and the minimum value slope kmin is 20 or more, the amount of wear of the cleaning blade can be reduced.

Further, in the micro compression tester of the toner, an inclination (force / displacement) that is a ratio of force to displacement is within a range of 0 to 1 μm in the displacement amount in the strength displacement graph in the micro displacement tester. The ratio (kmax / kmin) between the maximum value gradient kmmax and the minimum value gradient kmin has a region of 20 or more, and the strength is 0.100 to 0.600 kg / mm ² , preferably 0.200 to 0.600 kg / mm. ² and more preferably 0.470 to 0.600 kg / mm ² . When the strength is 0.100 kg / mm ² or less, the toner strength is not sufficient, and the blade is easily pulverized by the blade in the developing device, the stirring force or the friction force, and fine powder is generated. On the other hand, if the strength is 0.600 kg / mm ² or more, the toner is too hard and blade wear occurs, resulting in poor cleaning. In addition, the maximum gradient kmax and the minimum gradient of the gradient (force / displacement), which is the ratio of force to displacement, within a range of displacement of 0 to 1 μm in the displacement graph of the micro-compression testing machine in the displacement graph. A region where the ratio of kmin (kmax / kmin) is 20 or more is quite remarkable.

  Here, “the ratio between the maximum value slope kmmax and the minimum value slope kmin of the slope (force / displacement), which is the ratio of force and displacement, within a range of displacement of 0 to 1 μm in the strength displacement graph in the micro-compression tester. (A region where (kmax / kmin) is 20 or more "specifically refers to a compressive force of 0.002 to 0.002 when an applied compressive force is applied in a compression test using a micro compression tester MCT-W manufactured by Shimadzu Corporation. In the range of 0.05 gf / sec, especially in the range of 0.01 to 0.045 gf / sec. As shown in the graph, there is a region on the strength-displacement test result graph in which the displacement of the toner particles is drastically significant, that is, the gradient of force / displacement is within the range of the displacement amount within 1 μm in the strength displacement graph. The ratio of the maximum value to the minimum value means a region of 20 or more, and an example thereof will be more specifically shown later in FIGS. Such displacement in the toner of the present invention is usually in the range of 0.02 to 2.00 μm, more typically in the range of 0.03 to 1.50 μm. If the force is not increased, the displacement will not advance. The contact state between the residual toner and the cleaning blade in the cleaning process is dynamic, and in some cases involves impact such as striking. Therefore, the result of the compression test that is static and damage to the cleaning blade Although it seemed surprising that the degree of influence was related, the toner of the present invention is extremely effective in reducing the amount of wear on the cleaning blade. A range where the displacement amount in the graph is in the range of 0 to 1 μm, and the ratio (kmax / kmin) of the maximum value gradient kmax and the minimum value gradient kmin is 20 or more. It is a fact that is closely related to having Thus, the maximum inclination kmax of the inclination (force / displacement), which is the ratio of force to displacement, is within the range of 0 to 1 μm in the amount of displacement of the toner in the present invention in the strength displacement graph of the micro compression tester. In the region where the ratio of the minimum slope kmin (kmax / kmin) is 20 or more, there is no adhesive force or cohesive force at room temperature, and it is smooth, which is a conventionally preferred heat characteristic called sharp melt by heating at the time of fixing. It doesn't mean that.

  The ratio of the maximum slope kmax and the minimum slope kmin of the slope (force / displacement), which is the ratio of force and displacement, within the range of displacement in the strength-displacement graph in such a micro-compression testing machine (0-1 μm) In the toner of the present invention having a range of 20 or more (kmax / kmin), for example, an oil droplet of an organic solvent in which a toner composition containing a prepolymer is dissolved is dispersed in an aqueous medium, and an extension reaction and / or a crosslinking reaction is performed. It can be obtained by optimizing the material design and / or process design in the production of the toner composed of the particles formed by the above. Explaining in a non-limiting manner, the optimization of the material design includes adjustment of the composition and properties of the prepolymer, adjustment of the composition of the toner composition containing the prepolymer, adjustment of the type and amount of organic solvent, O / O in the W liquid system; adjustment of the W amount ratio, adjustment of the use amount and type of the elongation reaction agent and / or crosslinking reaction agent, etc. are included. Examples include adjustment of phase production conditions, adjustment of stirring conditions, adjustment of dispersion conditions in an O / W system, adjustment of reaction temperature, reaction time, and post-treatment time, and the like. As specifically shown in Fig. 5, it can be achieved only by adjusting the aging time and the solvent removal time.

The toner has a volume average particle diameter Dv of 4 to 6 μm, and a ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn of 1.00 to 1.25. A developing toner is preferable because variations in strength in the toner are reduced.
In addition, by using an electrostatic charge image developing toner characterized in that the average circularity E of the toner particles is 0.92 to 0.99, unevenness of the toner surface can be controlled and transfer residue is reduced. Is more preferable.
By using a modified polyester resin as a binder resin in the toner, the toner strength becomes appropriate and can be detected within the scope of the present invention.
In addition, the toner contains at least inorganic fine particles, and the inorganic fine particles are composed of at least two kinds, so that it is preferable that the inorganic fine particles keep the toner strength within an appropriate range.
Further, in the high-speed image printing system, the margin of image quality stability is further reduced. However, the use of the toner of the present invention is more preferable because the image quality (background stain, toner scattering) and the like in high-speed printing are improved.
In addition, by using a two-component developer containing the toner and a carrier composed of magnetic particles, it is possible to further improve the charge rising property and to have a sufficiently sharp charge distribution amount. It is possible and more preferable.

The present invention relates to a toner particle containing at least a binder resin and a colorant, in which oil droplets of an organic solvent in which a toner composition containing a prepolymer is dissolved are dispersed in an aqueous medium, and then subjected to an extension reaction and / or a crosslinking reaction. The inorganic fine particles are contained in the production process to form the inorganic fine particles, and the inorganic fine particles are composed of at least two kinds. The strength in the micro compression tester is 0.100 to 0.600 kg / mm ^2. The ratio of the maximum slope kmax and the minimum slope kmin (kmax / kmin) of the slope (force / displacement), which is the ratio of force and displacement, is within the range of 0 to 1 μm in the displacement amount in the strength displacement graph in the machine. By using a spherical toner for developing an electrostatic charge image characterized by having 20 or more regions, the toner is stored at high temperature and high humidity after being stored for a long time in a high temperature and high humidity environment. It is possible to provide a toner, a developer, an image forming method, and an image forming apparatus in which even after outputting tens of thousands of images under an environment, there is little weakly charged and reversely charged toner excellent in charging stability, and no toner scattering occurs. Toner and developer that does not cause background stain (fogging) with little weakly charged and reversely charged toner with excellent charging stability even after outputting tens of thousands of images not only in normal temperature and normal humidity environment but also in low temperature and low humidity environment The image forming method and the image forming apparatus can be provided, and have sufficient colorability, light resistance, transparency, color development, sharpness, color reproducibility, saturation, and gloss even after outputting tens of thousands of images. The toner, developer, image forming method, and image forming apparatus can be provided with extremely excellent effects.

  Hereinafter, the present invention will be described in detail. Here, as long as the conditions regarding the electrostatic charge image developing toner used in the present invention, the production method and materials of the developer, and the overall system relating to the electrostatic charge image development process are satisfied, known ones can be used.

(Toner strength)
The toner strength in the present invention was measured by a micro compression tester (MCT-W, manufactured by Shimadzu Corporation). The micro-compression tester is a technique that automatically applies the test force to the sample fixed between the upper pressurization indenter and the lower pressurization plate at a constant increase rate by electromagnetic force, and automatically measures the deformation amount of the sample at this time. The force was measured at 0.100 gf and the loading speed was 0.004833 gf / sec.

(Average circularity E)
It is important that the toner in the present invention has a specific shape and shape distribution, and the average circularity E is preferably 0.90 to 0.99. A toner having an irregular shape of 0.90 or less, which is too far from a spherical shape, does not provide satisfactory transferability and high-quality images free from dust. On the other hand, if it exceeds 0.99, it becomes a perfect sphere, which is not preferable because of poor cleaning performance. As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. The average circularity E is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle. In order for the toner to form a high-definition image having a reproducibility with an appropriate density, the average circularity E is more preferably 0.94 to 0.99. If attention is paid to the ease of cleaning, it is more preferable that the particles having an average circularity E of 0.94 to 0.99 and a circularity E of less than 0.94 is 10% or less.

  The circularity E in the present invention can be measured as the average circularity E by a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

(Circularity SF-1, SF-2)
The shape factors SF-1 and SF-2, which are the circularity used in the present invention, are obtained by randomly sampling 300 SEM images of the toner obtained by measurement using an FE-SEM (S-4200) manufactured by Hitachi, Ltd. The image information was introduced into an image analysis apparatus (Luzex AP) manufactured by Nireco through an interface and analyzed, and values obtained from the following equations were defined as SF-1 and SF-2. The values of SF-1 and SF-2 are preferably values obtained by Luzex, but are not particularly limited to the FE-SEM device and the image analysis device as long as similar analysis results can be obtained.
Further, as shown in the following equation (2), the shape factor SF-2 indicates the ratio of the unevenness of the toner shape, and is the square of the perimeter PERI of the figure formed by projecting the toner onto a two-dimensional plane. Is divided by the graphic area AREA and multiplied by 100 / 4π. When the value of SF-2 is 100, there is no unevenness on the toner surface, and as the value of SF-2 increases, the unevenness of the toner surface becomes more prominent.
Further, 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.
When the value of SF-1 is 100, the shape of the toner becomes a true sphere, and becomes larger as the value of SF-1 increases.

  In the case of a true sphere, all become 100, and from a spherical shape to an indefinite shape as the value becomes larger than 100. In particular, SF-1 represents the shape of the entire toner (ellipse, sphere, etc.), and SF-2 is a shape factor indicating the degree of surface irregularities. However, “SF-1 is 100” naturally does not always match the above “circularity E1.00”.

(External additive)
As an external additive for assisting the developability, fluidity and chargeability of the colored particles obtained in the present invention and not impairing the cleaning property and the fixing property, it is more preferable to use organic and inorganic fine particles in combination. . As the external additive, in addition to oxide fine particles, inorganic fine particles or hydrophobic treated inorganic fine particles can be used in combination, but the average particle diameter of the hydrophobized primary particles is 1 to 100 nm, more preferably 5 nm to 70 nm. It is more desirable to contain at least one kind of inorganic fine particles. Further, it is more preferable that the hydrophobized primary particles contain at least one kind of inorganic fine particles having an average particle diameter of 20 nm or less and at least one kind of inorganic fine particles of 30 nm or more. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.
As long as the conditions are satisfied, known ones can be used. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide), fluoropolymers, and the like may be contained.

  Particularly suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H 1303 (above Hoechst), and R972, R974, RX200, RY200, R202, R805, and R812 (above Nippon Aerosil). Further, as titania fine particles, P-25 (Nippon Aerosil), STT-30, STT-65C-S (above Titanium Industry), TAF-140 (Fuji Titanium Industry), MT-150W, MT-500B, MT-600B MT-150A (taker above). Particularly, the hydrophobized titanium oxide fine particles include T-805 (Nippon Aerosil), STT-30A, STT-65S-S (above Titanium Industry), TAF-500T, TAF-1500T (above Fuji Titanium Industry), MT -100S, MT-100T (above Taka), IT-S (Ishihara Sangyo), etc.

In order to obtain hydrophobized oxide particles, silica particles, titania particles, and alumina particles, hydrophilic particles are treated with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.
Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, and amino-modified silicone. Oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic, methacryl-modified silicone oil, α-methylstyrene-modified silicone oil and the like can be used. Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica ash Examples thereof include stone, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Of these, silica and titanium dioxide are particularly preferred.

  The addition amount can be 0.1 to 5% by weight, preferably 0.3 to 3% by weight, based on the toner. The average particle size of the primary particles of the inorganic fine particles is 100 nm or less, preferably 3 nm or more and 70 nm or less. If it is smaller than 3 nm, the inorganic fine particles are buried in the toner, and its function is hardly exhibited effectively. On the other hand, if it is larger than 100 nm, the surface of the photoreceptor is not uniformly damaged, which is not preferable. In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, thermosetting resin And polymer particles.

  Such a fluidizing agent 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, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  The volume average particle diameter (Dv) of the toner of the present invention is more preferably 2 to 7 μm, and the ratio (Dv / Dn) to the number average particle diameter (Dn) is 1.25 or less, preferably 1.10 to 1.25. The dry toner is excellent in heat-resistant storage stability, low-temperature fixability, and hot offset resistance, and particularly excellent in image gloss when used in a full-color copying machine. Even if the toner balance is extended, the fluctuation of the toner particle diameter in the developer is reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Further, when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner filming on the developing roller and the toner thinning are performed. There was no fusion of toner to a member such as a blade, and good and stable developability and images were obtained even during long-term use (stirring) of the developing device. In particular, when inorganic fine particles that are surface-treated with at least both a fluorine-containing compound and a silicon-containing compound of the present invention are used as a fluidizing agent, the particle size distribution is reduced because the margin for filming is reduced due to the influence of fluorine groups. More preferred.

In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Also, when the volume average particle diameter is smaller than the range of the present invention, in the case of a two-component developer, the toner is fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier is reduced, or one-component development is performed. When used as an agent, filming of toner on the developing roller and fusion of toner to a member such as a blade for thinning the toner are likely to occur.
Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention.
On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.

(Modified polyester resin)
In the present invention, the following modified polyester resins can be used as the polyester resin. For example, a polyester prepolymer having an isocyanate group can be used. Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group, which is further reacted with a polyisocyanate (3). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; bisphenol And alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) to the polycarboxylic acid (2) is such that the equivalent ratio [OH] / hydroxyl group [OH] to carboxyl group [COOH] is satisfied in order to simultaneously satisfy both hot offset resistance and cleaning properties. [COOH] is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If it is less than 1 per molecule, the molecular weight of the modified polyester after crosslinking and / or elongation becomes low, and the hot offset resistance deteriorates.

(Crosslinking agent and extender)
In the present invention, amines can be used as a crosslinking agent and / or an extender. As amines (B), diamine (B1), triamine or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and amino groups of (B1) to (B5) (B6) etc. that are blocked. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), Examples include oxazoline compounds. Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).

  Furthermore, if necessary, the molecular weight of the modified polyester after completion of the reaction can be adjusted by using a terminator for crosslinking and / or elongation. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

(Unmodified polyester)
In the present invention, it is important not only to use the modified polyester (A) alone, but also to contain the unmodified polyester (C) as a toner binder component together with the (A). By using (C) in combination, the low-temperature fixability and the glossiness when used in a full-color apparatus are improved. Examples of (C) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (A), and preferred ones are also the same as (A). (C) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with, for example, a urethane bond. It is preferable that (A) and (C) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (A) and (C) preferably have similar compositions. When (A) is contained, the weight ratio of (A) to (C) is usually 5/95 to 75/25, preferably 10/90 to 25/75, more preferably 12/88 to 25/75, Especially preferably, it is 12 / 88-22 / 78. If the weight ratio of (A) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (C) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, the heat-resistant storage stability is deteriorated, and if it exceeds 10,000, the low-temperature fixability is deteriorated and the cleaning blade is liable to be damaged. The hydroxyl value of (C) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (C) is usually from 0.5 to 40, preferably from 5 to 35. By having an acid value, it tends to be negatively charged. Further, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.

In the present invention, the glass transition point (Tg) of the toner is usually 40 to 70 ° C., preferably 45 to 55 ° C. If it is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the crosslinked and / or elongated polyester resin, the toner for developing an electrostatic charge image of the present invention exhibits good storage stability even when the glass transition point is low, as compared with known polyester-based toners. As the storage elastic modulus of the toner, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10000 dyne / cm ² is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or less, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and T (TG′−Tη) is preferably 0 ° C. or higher. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

(Coloring agent)
As the colorant of the present invention, known dyes and pigments can be used, such as carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G) , R), Tartrazine Lake, Quinoline Yellow Lake, Anthracene Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Faisley Red, Parachlor Ortoni Roaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Fu Talocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

  This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet cake of a coloring agent, is a method of mixing and kneading an aqueous paste containing water of a coloring agent together with a resin and an organic solvent, transferring the coloring agent to the resin side, and removing moisture and organic solvent components. Can be used as it is, so that it is not necessary to dry and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
Further, a wax may be contained together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. It is done. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, etc.); polyalkanol esters (trimellitic acid tristearyl, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). 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 a cold offset when 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. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent. May be.

(Resin fine particles)
In the present invention, resin fine particles can be contained as required. The resin fine particles used have a glass transition point (Tg) of 40 to 100 ° C., a weight average molecular weight of 9000 to 200,000 is more preferable, and as described above, the glass transition point (Tg) is less than 40 ° C., and When the weight average molecular weight is less than 9,000, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the glass transition point (Tg) is 100 ° C. or higher and / or the weight average molecular weight is 200,000 or higher, the resin fine particles inhibit the adhesiveness to the fixing paper, and the minimum fixing temperature increases.
More preferably, the residual ratio with respect to the toner particles is 0.5 to 5.0 wt%. When the residual ratio is less than 0.5 wt%, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the residual amount is 5.0 wt% or more, the resin fine particles are not present. The exudation of the wax is obstructed, the effect of releasing the wax cannot be obtained, and the occurrence of offset is observed.
The residual rate of the resin fine particles can be measured by analyzing a substance caused by the resin fine particles, not by the toner particles, using a pyrolysis gas chromatograph mass spectrometer, and calculating from the peak area. The detector is preferably a mass spectrometer, but is not particularly limited.
The resin fine particles may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide Examples thereof include resins, silicon-based resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.

  The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate polymer, Examples include styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

(Production method)
The toner binder can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group.

The dry toner of the present invention can be produced by the following method, but is not limited thereto.
(Toner production method in aqueous medium)
The aqueous phase used in the present invention is used by adding resin fine particles in advance. The water used for the aqueous phase may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.
The toner particles are obtained by forming a dispersion composed of a polyester prepolymer (A) having an isocyanate group dissolved or dispersed in an organic solvent in an aqueous phase and reacting with amines (B). As a method for stably forming a dispersion comprising a polyester prepolymer (A) in an aqueous phase, a composition of a toner raw material comprising a polyester prepolymer (A) dissolved or dispersed in an organic solvent in an aqueous phase is added. And a method of dispersing by shearing force. Polyester prepolymer (A) dissolved or dispersed in an organic solvent and other toner composition (hereinafter referred to as toner raw material), colorant masterbatch, release agent, charge control agent, unmodified The polyester resin or the like may be mixed when forming the dispersion in the aqueous phase, but after the toner raw material is mixed in advance and dissolved or dispersed in an organic solvent, the mixture is added to the aqueous phase and dispersed. Is more preferable. Further, in the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in the aqueous phase. After the particles are formed, It may be added. For example, after forming particles that do not contain a colorant, the colorant can be added by a known dyeing method.

  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. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. 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. Higher temperatures are preferred in that the dispersion of the polyester prepolymer (A) has a low viscosity and is easy to disperse.

  The amount of the aqueous phase used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts of the toner composition containing the polyester prepolymer (A). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino acids as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in the aqueous phase Alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, quaternary ammonium such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride Nonionic surfactants such as salt-type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N - Amphoteric surfactants such as ammonium betaine.

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- [omega-fluoroalkyl (C6 to C11). Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid and Metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctane sulfonic acid diethanolamide, N-propyl-N- (2 hydroxy ethyl) -Fluorooctanesulfonamide, 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, (Daikin Kogyo Co., Ltd.), MegaFac F-l0, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF- 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  Examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, benza Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) , Megafac F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.

  Moreover, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, etc. can be used as an inorganic compound dispersant which is hardly soluble in water.

  Further, 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 β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, 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, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Pinyl acetate, pinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, etc. Homopolymers or copolymers such as those having nitrogen atoms or heterocyclic rings thereof, polyoxyethylene, polyoxypropylene, polymers Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

In addition, when an acid such as calcium phosphate salt or an alkali-soluble one is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as washing with water after dissolving the calcium phosphate salt with an acid such as hydrochloric acid. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

  The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. 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.

In order to remove the organic solvent from the obtained emulsified dispersion, a method can be employed in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely evaporated and removed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide, combustion gas, or the like, particularly various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.
Further, as a method of removing the organic solvent, air can be blown away by a rotary evaporator or the like.
Thereafter, rough separation is performed by centrifugation, the emulsified dispersion is washed in a washing tank, and the drying process is repeated in a hot air drier. Finally, an aqueous solvent soda (containing a surfactant) in which the fluorine compound A is dispersed. In this case, the fluorine compound A is adhered to the surface of the toner, and then the solvent is removed and dried to obtain a toner base.

When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.
Mixing or giving mechanical impact force to the powder mixture after drying with different types of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles By immobilizing and fusing on the surface, it is possible to prevent detachment of foreign particles from the surface of the resulting composite particle.

Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.
Finally, external additives such as inorganic fine particles (especially including inorganic fine particles treated with fluorine-based compound B) and toner are mixed with a Henschel mixer, etc., and coarse particles are removed by ultrasonic sieving etc. to obtain the final toner. Get.

As other production methods, a polymerization method, a capsule method, or the like can be used. An outline of these production methods is described below.
<Polymerization method>
(1) A polymerizable monomer and, if necessary, a polymerization initiator, a colorant, a wax and the like are granulated in an aqueous dispersion medium.
(2) The granulated monomer composition particles are classified to an appropriate particle size.
(3) The monomer composition particles having a prescribed inner particle diameter obtained by the classification are polymerized.
(4) After removing the dispersant by appropriate treatment, the polymerization product obtained above is filtered, washed with water and dried to obtain base particles.

<Capsule method>
(1) A resin and, if necessary, a colorant are kneaded with a kneader or the like to obtain a molten toner core material.
(2) The toner core material is placed in water and stirred vigorously to form a fine particle core material.
(3) The above core material fine particles are put in a shell material solution, and a poor solvent is dropped while stirring, and encapsulated by covering the surface of the core material with a shell material.
(4) The capsule obtained as described above is filtered and dried to obtain base particles.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of carrier. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and polystyrene resins such as styrene-acrylic copolymer resins, Halogenated olefin resin such as polyvinyl chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, poly Hexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinyl fluoride Den and non-fluoride monomers including a fluoro such as terpolymers of, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(Intermediate transfer member)
In the present invention, an intermediate transfer member can also be used. One embodiment of the intermediate transfer member of the transfer system will be described.
FIG. 1 is a schematic configuration diagram of a copying machine according to the present embodiment. Around a photosensitive drum (hereinafter referred to as “photosensitive member”) (10) as an image carrier, a charging roller (20) as a charging device, an exposure device (30), a cleaning device (60) having a cleaning blade, a static elimination A neutralizing lamp (70) as a device, a developing device (40), and an intermediate transfer member (50) as an intermediate transfer member are provided. The intermediate transfer member (50) is suspended by a plurality of suspension rollers (51), and is configured to run endlessly in the direction of the arrow by a driving unit such as a motor (not shown). A part of the suspension roller (51) also serves as a transfer bias roller for supplying a transfer bias to the intermediate transfer member, and a predetermined transfer bias voltage is applied from a power source (not shown). A cleaning device (90) having a cleaning blade for the intermediate transfer member (50) is also provided. A transfer roller (80) is disposed as a transfer means for transferring the developed image to the transfer paper (100) as the final transfer material, facing the intermediate transfer member (50), and the transfer roller (80). Is supplied with a transfer bias by a power supply device (not shown). A corona charger (52) is provided around the intermediate transfer member (50) as a charge applying unit. The toner image on the transfer paper (100) passes through the transfer roller (80) and is then fixed by the fixing device (81).

  The developing device (40) includes a developing belt (41) as a developer carrying member, a black (hereinafter referred to as Bk) developing unit (45K) and yellow (hereinafter referred to as Yk) arranged around the developing belt (41). Development unit (45Y), magenta (hereinafter referred to as magenta) development unit (45M), and cyan (hereinafter referred to as C) development unit (45C). Further, the developing belt (41) is stretched between a plurality of belt rollers, and is configured to run endlessly in a direction of an arrow by a driving unit such as a motor (not shown), and a contact portion with the photoreceptor (10). Then, it moves at almost the same speed as the photoconductor (10).

  Since the configuration of each developing unit is common, the following description will be given only for the Bk developing unit (50Bk), and the other developing units (50Y), (50M), and (50C) will be described with reference to the Bk developing unit ( 50Bk), the parts corresponding to those in the unit are denoted by Y, M, C after the numbers given in the unit, and the description is omitted. The development unit (50Bk) includes a development tank (42Bk) that contains a high-viscosity, high-concentration liquid developer containing toner particles and a carrier liquid component, and a lower part that is a liquid developer in the development tank (42Bk). A drawing roller (43Bk) disposed so as to be immersed, and a coating roller (44Bk) for thinning the developer drawn from the drawing roller (43Bk) and applying it to the developing belt (41) Yes. The application roller (44Bk) has conductivity, and a predetermined bias is applied from a power source (not shown).

  In addition to the apparatus configuration shown in FIG. 1, the apparatus configuration of the copying machine according to the present embodiment includes a developing unit (45) for each color as shown in FIG. 2 around the photoreceptor (10). A device configuration may be provided.

  Next, the operation of the copying machine according to the present embodiment will be described. In FIG. 1, the photosensitive member (10) is uniformly charged by the charging roller (20) while being driven to rotate in the direction of the arrow, and then the reflected light from the document is imaged and projected by an optical system (not shown) by the exposure device (30). Thus, an electrostatic latent image is formed on the photoconductor (10). This electrostatic latent image is developed by the developing device (40) to form a toner image as a visible image. The developer thin layer on the developing belt (41) is peeled off from the belt (41) in a thin layer state by contact with the photoreceptor in the developing region, and a latent image is formed on the photoreceptor (10). Transition to the part. The toner image developed by the developing device (40) is transferred to the intermediate transfer member (50) at a contact portion (primary transfer region) between the photosensitive member (10) and the intermediate transfer member (50) moving at a constant speed. (Primary transfer). When transferring three or four colors to be superimposed, this process is repeated for each color to form a color image on the intermediate transfer member (50).

  The corona charger (52) for applying an electric charge to the superimposed toner image on the intermediate transfer member, the photosensitive member (10) and the intermediate transfer member (in the rotation direction of the intermediate transfer member (50)). 50) on the downstream side of the contact facing portion and the upstream side of the contact facing portion between the intermediate transfer member (50) and the transfer paper (100). Then, the corona charger (52) gives the toner image a true charge having the same polarity as the charging polarity of the toner particles forming the toner image, so that the toner image can be satisfactorily transferred to the transfer paper (100). The toner image is sufficiently charged. The toner image is charged by the corona charger (52) and then transferred onto the transfer paper (100) conveyed in the direction of the arrow from a paper supply unit (not shown) by a transfer bias from the transfer roller (80). Batch transfer (secondary transfer). Thereafter, the transfer paper (100) onto which the toner image has been transferred is separated from the photoreceptor (10) by a separation device (not shown), and after being subjected to a fixing process by a fixing device (not shown), the transfer paper (100) is discharged from the device. On the other hand, after the transfer, the untransferred toner is collected and removed by the cleaning device (60), and the residual charge is discharged by the discharging lamp (70) in preparation for the next charging. The toner image on the transfer paper (100) passes through the transfer roller (80) and is then fixed by the fixing device (81).

As described above, the static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably from several Ωcm to 10 ³ Ωcm. When the volume resistance is set to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means hardly remains on the intermediate transfer member. Transfer unevenness can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

  The material of the intermediate transfer member is not particularly limited, and known materials can be used. An example is shown below. (1) A material having a high Young's modulus (tensile modulus) is used as a single-layer belt. PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT ( Polyalkylene terephthalate) blend material, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ETFE / PAT, PC / PAT blend material, carbon black dispersed thermosetting polyimide, and the like. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and registration is not likely to occur particularly during color image formation. (2) A belt having a two- or three-layer structure in which a belt having a high Young's modulus is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery thereof. Therefore, the line image has a performance capable of preventing the line image from being lost. (3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the width of the belt is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .

Conventionally, a fluorine-based resin, a polycarbonate resin, a polyimide resin, or the like has been used for the intermediate transfer belt, but in recent years, an elastic belt in which the entire belt layer or a part of the belt is used as an elastic member has been used. The transfer of a color image using a resin belt has the following problems.
A color image is usually formed with four color toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer receives pressure by passing through the primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and the secondary transfer (transfer from the intermediate transfer belt to the sheet), and the cohesive force between the toners increases. When the cohesive force between the toners increases, the phenomenon of missing characters in the characters and missing edges in the solid portion image tends to occur. Since the resin belt has high hardness and does not deform in accordance with the toner layer, the toner layer is easily compressed, and the character dropout phenomenon is likely to occur.
Recently, there is an increasing demand for forming full-color images on various papers, for example, Japanese paper, intentionally irregularities, and forming images on paper. However, a paper with poor smoothness is liable to generate toner and voids at the time of transfer, and transfer loss is likely to occur. When the transfer pressure at the secondary transfer portion is increased to improve the adhesion, the condensing power of the toner layer is increased, and the above-described character void is generated.

  The elastic belt is used for the following purposes. The elastic belt is deformed corresponding to the toner layer and the paper having poor smoothness at the transfer portion. In other words, since the elastic belt deforms following local irregularities, the paper does not have excessive flatness and has good adhesion without excessively increasing the transfer pressure on the toner layer. The transfer image with excellent uniformity can be obtained.

  The elastic belt resin is polycarbonate, fluorine resin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer. Polymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer and styrene-phenyl acrylate copolymer), styrene-methacrylic acid ester copolymer (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-phenyl methacrylate copolymer) Coalesce etc.), styrene-α-chloroacryl Styrenic resin (monopolymer or copolymer containing styrene or styrene-substituted product), methyl methacrylate resin, butyl methacrylate resin, acrylic resin, such as methyl phosphate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer Ethyl acid resin, butyl acrylate resin, modified acrylic resin (silicone modified acrylic resin, vinyl chloride resin modified acrylic resin, acrylic / urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate Polymer, rosin-modified maleic resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, ionomer resin, polyurethane resin, silicone resin, ketone resin, Len - ethyl acrylate copolymer, it may be used xylene resin and polyvinyl butyral resin, polyamide resin, one kind or two kinds or more selected from the group consisting of modified polyphenylene oxide resin. However, it is a matter of course that the material is not limited to the above materials.

  Elastic rubbers and elastomers include butyl rubber, fluorine rubber, acrylic rubber, EPDM, NBR, acrylonitrile-butadiene-styrene rubber, natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene Terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, silicone rubber, fluoro rubber, polysulfide rubber, polynorbornene rubber, hydrogenated Selected from the group consisting of nitrile rubber, thermoplastic elastomer (eg polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide, polyurea, polyester, fluororesin) It is possible to use one kind or two or more elements. However, it is a matter of course that the material is not limited to the above materials.

  There are no particular restrictions on the conductive agent for adjusting the resistance value. For example, carbon black, graphite, metal powder such as aluminum and nickel, tin oxide, titanium oxide, antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite Conductive metal oxides such as oxides (ATO) and indium oxide-tin oxide composite oxides (ITO), and conductive metal oxides are coated with insulating fine particles such as barium sulfate, magnesium silicate and calcium carbonate But you can. Of course, the conductive agent is not limited thereto.

  The surface layer material and the surface layer are required to prevent contamination of the photoconductor by the elastic material, reduce the surface friction resistance to the transfer belt surface, reduce the adhesion of the toner, and improve the cleaning property and the secondary transfer property. . For example, materials that use one or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and increase lubricity, such as powders of fluororesins, fluorine compounds, fluorocarbons, titanium dioxide, silicon carbide, etc. Can be used by dispersing one or more kinds of particles, particles or particles having different particle sizes, and by forming a fluorine-rich layer on the surface by heat treatment like a fluorine-based rubber material, the surface energy can be increased. It is also possible to use a smaller one.

The method for manufacturing the belt is not limited.
Centrifugal molding method in which material is poured into a rotating cylindrical mold to form a belt Spray coating method in which a liquid paint is sprayed to form a film Dipping method in which a cylindrical mold is immersed in a solution of the material and pulled up Inner mold, outer mold There is a method of wrapping a compound around a cylindrical mold and performing vulcanization polishing, but this is not a limitation, and it is common to manufacture belts by combining multiple manufacturing methods. is there.

As a method for preventing elongation as an elastic belt, there are a method of forming a rubber layer in a core resin layer with little elongation, a method of putting a material for preventing elongation into the core layer, and the like, but it is not particularly related to the production method.
Materials constituting the core layer for preventing elongation include, for example, natural fibers such as cotton and silk, polyester fibers, nylon fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, One or two selected from the group consisting of synthetic fibers such as polyurethane fibers, polyacetal fibers, polyfluoroethylene fibers and phenol fibers, inorganic fibers such as carbon fibers, glass fibers and boron fibers, and metal fibers such as iron fibers and copper fibers A woven or thread-like material can be formed using more than one seed. Of course, the material is not limited to the above.
The yarn may be twisted in any manner, such as one or a plurality of filaments twisted, a single twisted yarn, various twisted yarns, a double yarn or the like. Further, for example, fibers of a material selected from the above material group may be blended. Of course, the yarn can be used after being subjected to an appropriate conductive treatment.
On the other hand, the woven fabric can be any woven fabric, such as knitted weave, and of course, a woven fabric that is interwoven can also be used, and naturally it can be subjected to a conductive treatment.

The production method for providing the core layer is not particularly limited, for example, a method of providing a woven fabric woven in a cylindrical shape on a mold and the like, and providing a coating layer thereon, the woven fabric woven in a cylindrical shape is a liquid rubber And a method of providing a coating layer on one side or both sides of the core layer, and a method of winding a thread spirally around a mold at an arbitrary pitch and providing a coating layer thereon.
The thickness of the elastic layer depends on the hardness of the elastic layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur in the surface layer. In addition, it is not preferable that the thickness is too large (e.g., about 1 mm or more) because the amount of expansion and contraction becomes large and the image is stretched.

(Tandem type color image forming device)
The present invention can also be used as a tandem color image forming apparatus. An example of an embodiment of a tandem type color image forming apparatus will be described. In the tandem type electrophotographic apparatus, as shown in FIG. 3, images on the respective photosensitive members (301) are sequentially transferred onto a sheet (s) conveyed by a sheet conveying belt (303) by a transfer device (302). As shown in FIG. 4, the image on each photoconductor (401) is transferred to the intermediate transfer member (404) by the primary transfer device (402) and sequentially transferred to the intermediate transfer member. (404) There is an indirect transfer type in which the above image is collectively transferred to a sheet (s) by a secondary transfer device (405). The transfer device (405) is a transfer conveyance belt, but there are also roller shapes and methods.

Comparing the direct transfer type and the indirect transfer type, the former is the upstream side of the tandem type image forming apparatus (T) in which the photoconductors (1) are arranged, and the downstream side. Therefore, the fixing device (407) must be arranged on the sheet, and there is a disadvantage that the fixing device (407) is enlarged in the sheet conveying direction.
On the other hand, the latter can set the secondary transfer position relatively freely.
The sheet feeding device (406) and the fixing device (407) can be arranged so as to overlap the tandem type image forming device (T), which is advantageous in that the size can be reduced.
In the former, in order not to increase the size in the sheet conveying direction, the fixing device (407) is arranged close to the tandem type image forming apparatus (T). Therefore, the fixing device (407) cannot be disposed with a sufficient margin that allows the sheet (s) to bend, and an impact (particularly thick sheet) occurs when the leading edge of the sheet (s) enters the fixing device (407). The fixing device (407) affects upstream image formation due to the difference in speed between the sheet conveyance speed when passing through the fixing device (407) and the sheet conveyance speed by the transfer conveyance belt. There are easy drawbacks.

On the other hand, in the latter case, the fixing device (407) can be disposed with a sufficient margin that the sheet (s) can be bent, so that the fixing device (407) hardly affects the image formation. be able to.
In view of the above, recently, an indirect transfer type of tandem type electrophotographic apparatus has attracted attention.

  In this type of color electrophotographic apparatus, as shown in FIG. 4, the transfer residual toner remaining on the photoconductor (401) after the primary transfer is removed by the photoconductor cleaning device (408) to remove the photoconductor (408). 401) The surface was cleaned and prepared for another image formation. Further, the transfer residual toner remaining on the intermediate transfer body (404) after the secondary transfer is removed by the intermediate transfer body cleaning device (409) to clean the surface of the intermediate transfer body (404), and in preparation for the image formation again. It was.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
FIG. 5 shows another embodiment of the present invention, which is a tandem indirect transfer type electrophotographic apparatus. In the figure, reference numeral (600) is a copying apparatus main body, (700) is a paper feed table on which it is placed, (800) is a scanner mounted on the copying apparatus main body (600), and (900) is an automatic document feeder mounted thereon. (ADF). The copying machine main body (600) is provided with an endless belt-shaped intermediate transfer member (510) in the center.
Then, as shown in FIG. 5, in the illustrated example, it is wound around three support rollers (514), (515), and (516) so that it can be rotated and conveyed clockwise in the figure.
In this illustrated example, an intermediate transfer body cleaning device (517) for removing residual toner remaining on the intermediate transfer body (510) after image transfer is provided on the left of the second support roller (515) among the three.
Further, among the three, on the intermediate transfer member (510) stretched between the first support roller (514) and the second support roller (515), yellow, cyan and magenta are arranged along the transport direction. The black image forming means (518) are arranged side by side to constitute a tandem image forming apparatus (520).

An exposure apparatus (521) is further provided on the tandem image forming apparatus (520) as shown in FIG. On the other hand, a secondary transfer device (522) is provided on the opposite side of the intermediate transfer member (510) from the tandem image forming device (520). In the example shown in the figure, the secondary transfer device (522) is configured such that a secondary transfer belt (524), which is an endless belt, is stretched between two rollers (523). 3 is pressed against the support roller (516), and the image on the intermediate transfer member (510) is transferred to the sheet.
Next to the secondary transfer device (522), a fixing device (525) for fixing the transferred image on the sheet is provided. The fixing device (525) is configured by pressing a pressure roller (527) against a fixing belt (526) which is an endless belt.
The secondary transfer device (522) described above is also provided with a sheet conveyance function for conveying the sheet after image transfer to the fixing device (525). Of course, as the secondary transfer device (522), a transfer roller or a non-contact charger may be arranged. In such a case, it is difficult to provide this sheet conveying function together.

In the illustrated example, a sheet is recorded under such a secondary transfer device (522) and a fixing device (525) in order to record an image on both sides of the sheet in parallel with the tandem image forming device (520). A sheet reversing device (528) for reversing is provided.
Now, when making a copy using this color electrophotographic apparatus, the document is set on the document table (530) of the automatic document feeder (900). Alternatively, the automatic document feeder (900) is opened, a document is set on the contact glass (532) of the scanner (800), and the automatic document feeder (900) is closed and pressed.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder (900), the document is transported and moved onto the contact glass (532), and then the other contact glass (532). When the document is set on the scanner, the scanner (800) is immediately driven to travel on the first traveling body (533) and the second traveling body (534). Then, the first traveling body (533) emits light from the light source, and the reflected light from the document surface is further reflected toward the second traveling body (534) and reflected by the mirror of the second traveling body (534). The image is then placed in the reading sensor (536) through the imaging lens (535) and the content of the original is read.
When a start switch (not shown) is pressed, one of the support rollers (514), (515), and (516) is driven to rotate by the drive motor (not shown), and the other two support rollers are driven to rotate. The transfer body (510) is rotated and conveyed. At the same time, the individual image forming means (518) rotates the photoconductor (540) to form black, yellow, magenta, and cyan single-color images on each photoconductor (540). Then, along with the conveyance of the intermediate transfer member (510), the monochrome images are sequentially transferred to form a composite color image on the intermediate transfer member (510).

On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers (542) of the paper feed table (700) is selectively rotated, and one of paper feed cassettes (544) provided in multiple stages in the paper bank (543). The sheet is fed out from the sheet, separated one by one by the separation roller (545), put into the sheet feeding path (546), and conveyed by the conveying roller (547) to the sheet feeding path (548) in the copying machine main body (600). Guide and stop against the registration roller (549).
Alternatively, the sheet feeding roller (550) is rotated to feed out the sheets on the manual feed tray (551), separated one by one by the separation roller (552), and put into the manual sheet feeding path (553). ) And stop.
Then, the registration roller (549) is rotated in synchronization with the composite color image on the intermediate transfer member (510), and the sheet is fed between the intermediate transfer member (510) and the secondary transfer device (522). The image is transferred by the next transfer device (522) to record a color image on the sheet.

The sheet after image transfer is conveyed by the secondary transfer device (522) and sent to the fixing device (525). The fixing device (525) applies heat and pressure to fix the transferred image, and then the switching claw. It is switched at (555), discharged by the discharge roller (556), and stacked on the discharge tray (557). Alternatively, it is switched by the switching claw (555) and put into the sheet reversing device (528), where it is reversed and guided again to the transfer position, and after the image is recorded also on the back surface, the discharge tray (556) discharges the discharge tray ( 557) to discharge above.
On the other hand, the intermediate transfer member (510) after image transfer is removed by an intermediate transfer member cleaning device (517) to remove residual toner remaining on the intermediate transfer member (510) after image transfer, and a tandem image forming device (520). To prepare for image formation again.
Here, the registration roller (549) is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.

  In the tandem image forming apparatus (520) described above, the individual image forming means (618) includes, for example, a charging device (660) around a drum-shaped photoconductor (640) as shown in FIG. ), A developing device (661), a primary transfer device (662), a photoconductor cleaning device (663), a charge removal device (664), and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to this. Here, “parts” indicates parts by weight. 7 is an intensity displacement graph obtained by measuring the intensity-displacement state of the toner of the example, and FIG. 8 is obtained by measuring the intensity-displacement state of the toner of the comparative example. Intensity displacement graphs and strength displacement graphs (commercial products 1 to 5) obtained by measuring the strength-displacement states of various conventional commercial toners including commercially available toners by the applicant are shown.

(Evaluation of two-component developer)
When evaluating an image with a two-component developer, a ferrite carrier having an average particle diameter of 35 μm coated with a silicone resin at an average thickness of 0.5 μm is used as follows, and toner 7 of each color is used with respect to 100 parts by weight of the carrier. The developer was prepared by uniformly mixing and charging the parts by weight using a tumbler mixer of the type in which the container rolls and stirs.

(Carrier production)
・ Core material Mn ferrite particles (weight average diameter: 35 μm) 5000 parts ・ Coating material Toluene 450 parts Silicone resin SR2400
(Made by Toray Dow Corning Silicone, nonvolatile content 50%) 450 parts Aminosilane SH6020 (made by Toray Dow Corning Silicone) 10 parts Carbon Black 10 parts The coating material is dispersed with a stirrer for 10 minutes to prepare a coating solution, The coating liquid and the core material were put into a coating apparatus for coating while forming a swirling flow in which a rotating bottom plate disk and a stirring blade were provided in the fluidized bed, and the coating liquid was applied onto the core material. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to obtain the carrier.

(Evaluation item)
1) Particle size The toner particle size was measured with Coulter Multisizer II. As a measuring method, first, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersing agent to 100 to 150 ml of an electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated.

2) Average circularity E
The average circularity E can be measured by a flow type particle image analyzer FPIA-2100 (Sysmex Corporation). As a specific measuring method, 0.3 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 120 ml of water from which impure solids have been removed in advance, and about 0.2 g of a measurement sample is added. Add. The suspension in which the sample is dispersed is obtained by performing a dispersion treatment with an ultrasonic disperser for about 2 minutes, and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of about 5000 / μl.

3) Circularity SF-1, SF-2
300 toner SEM images obtained by measurement with Hitachi FE-SEM (S-4200) were randomly sampled, and the image information was sent to the Nireco image analyzer (Luzex AP) via the interface. It was introduced and analyzed.

4) Cleanability The transfer residual toner on the photosensitive member that has passed the cleaning process after outputting 100 sheets is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.), measured with a Macbeth reflection densitometer RD514 type, and blanked. Evaluation was made with a difference of less than 0.005 as ◎, 0.005 to 0.010 as ○, 0.011 to 0.02 as Δ, and more than 0.02 as X.

5) Charging stability Using an evaluation machine that was tuned by remodeling Ricoh's IPSiO Color 8200 into an oil-less fixing system, an image area ratio 7% chart continuous output test for 100,000 sheets was performed using each toner. Changes in charge amount were evaluated. 1 g of developer was weighed and the change in charge amount was determined by the blow-off method. When the change in charge amount was 5 μc / g or less, ◎ was given when it was 10 μc / g or less, and Δ was given when it exceeded 10 μc / g.

6) Image density Using an evaluation machine tuned by remodeling Ricoh's IPSiO Color 8200 to an oilless fixing system, the amount of adhesion is 0.5 ± 0.1 mg / cm ^{2 on} plain paper transfer paper (Ricoh type 6200). After outputting the solid image, the image density was measured by X-Rite (manufactured by X-Rite). An image density of 1.5 or more was evaluated as ◎, a value less than 1.5 1.35 or more as ◯, a value less than 1.35 as 1.2 or more as Δ, and a value less than 1.2 as X.

7) Image graininess and sharpness Using an evaluation machine that was tuned by remodeling Ricoh's IPSiO Color 8200 into an oilless fixing method, a photographic image was output in a single color, and the degree of graininess and sharpness was visually evaluated. . From the good ones, the evaluations were ◎, ○, Δ, and X.並 is equivalent to offset printing, ◯ is slightly worse than offset printing, Δ is much worse than offset printing, and X is very bad compared to conventional electrophotographic images.

8) Fog In an environment with a temperature of 35 ° C and a humidity of 95%, using an evaluation machine that has been tuned by remodeling the Ricoh IPSiO Color 8200 to an oil-less fixing system, an image area ratio of 7% charts and continuous output of 100,000 sheets The degree of toner contamination on the background of the transfer paper after the endurance test was visually evaluated (loupe). From the good ones, the evaluations were ◎, ○, Δ, and X. ◎ indicates that the toner is not observed at all and is in a good state, ○ indicates that the contamination is slightly observed and does not cause a problem, △ indicates that the contamination is slightly observed, and X indicates that the contamination is not within the allowable range. There is a problem.

9) Toner scattering In an environment where the temperature is 35 ° C. and the humidity is 95%, using an evaluation machine that has been tuned by remodeling the IPSiO Color 8200 made by Ricoh into an oil-less fixing system, an image area ratio 7% chart 100000 continuous images using each toner The toner contamination state in the copying machine after the output durability test was visually evaluated. ◎ indicates that the toner is not observed at all and is in a good state, ○ indicates that the contamination is slightly observed and does not cause a problem, △ indicates that the contamination is slightly observed, and X indicates that the contamination is not within the allowable range. There is a problem.

10) Environmental preservability Weigh 10 g of toner, put it in a 20 ml glass container, tap the glass bottle 100 times, leave it in a thermostatic chamber set at 55 ° C. and 85% humidity, and then leave it for 24 hours. The penetration was measured with The toner stored in a low-temperature and low-humidity (10 ° C., 15%) environment was similarly evaluated for penetration, and the value with the lower penetration was employed in a high-temperature and high-humidity and low-temperature and low-humidity environment.
From good ones, ◎: 20 mm or more, ○: 15 mm or more and less than 20 mm,
Δ: 10 mm to less than 15 mm, X: less than 10 mm,
It was.

11) Color vividness After 100,000 sheets of 50% image area image charts were run and output in the monochromatic mode, the color vividness was visually evaluated on an image output on Ricoh 6200 paper. ◎, ○, Δ, and X in order of goodness.

12) Color reproducibility After running 100,000 image charts of 50% image area in monochromatic mode, the color reproducibility was visually evaluated on the image output on Ricoh 6200 paper. ◎, ○, Δ, and X in order of goodness.

13) Gloss After running 100,000 image charts of 50% image area in monochrome mode, the image output to 6200 paper made by Ricoh is used to measure the gloss meter (VG-1D) (made by Nippon Denshoku). The light projection angle and the light reception angle were adjusted to 60 °, and the S and S / 10 switch SWs were adjusted to S, and the measurement was performed after 0 preparation and standard setting using a standard plate.
From those having good glossiness, ◎: 13 or more, ○: 5 or more and less than 13,
Δ: 2 or more to less than 5 and X: less than 2.

14) Light resistance After running 100,000 sheets of an image chart of 50% image area in monochromatic mode, the image output to Ricoh 6200 paper is converted into 10,000 images by XENONTESTER XW-150 (manufactured by Shimadzu Corporation). The image after irradiation for 15 hours was observed, and light resistance was evaluated according to the following criteria.
A: Almost no change.
○: Slightly changes.
Δ: Slightly changes.
X: It changes considerably.

(Example 1)
~ Synthesis of organic fine particle emulsion ~
Production Example 1
In a reaction vessel equipped with a stirrer and a thermometer, water 683 parts, sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, butyl acrylate 110 Part and 1 part of ammonium persulfate were added and stirred at 6400 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. Further, 30 parts of a 1% aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 6 hours, and then 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 dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) 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 2 parts of tin oxide was 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. Then 44 parts of trimellitic anhydride was added to the reaction vessel, and 3 parts at 180 ° C. and normal pressure. The reaction was performed for a while to obtain [Low molecular weight polyester 1]. [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 24.

~ Synthesis of intermediate polyester ~
Production Example 4
In a reaction vessel equipped with a cooling pipe, 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 Part and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. at normal pressure for 7 hours, 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 degrees for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

~ Synthesis of ketimine ~
Production Example 5
In a reaction vessel equipped with a stirrer 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
Add 1200 parts of water, 540 parts of carbon black (Printex35 Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] and 1200 parts of polyester resin, and mix with a Henschel mixer (Mitsui Mining Co., Ltd.). After kneading at 130 ° C. for 1 hour using two rolls, rolling and cooling and pulverizing with a pulverizer, [Masterbatch 1] was obtained.

~ 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 polyester 1], 100 parts of Carnauba WAX, and 947 parts of ethyl acetate were charged, heated to 80 ° C. with stirring, and kept at 80 ° C. for 5 hours. Cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. 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 the above-described bead mill 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 50 minutes to obtain [Emulsion Slurry 1].
[Emulsion slurry 1] was put into a container in which a stirrer and a thermometer were set, and the solvent was removed for 8th time at 30 ° C., followed by aging 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,
(I): 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.
(II): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (I), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(III): 100 parts of 10% hydrochloric acid was added to the filter cake of (II), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then 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. Thereafter, sieved with a mesh of 75 μm, [Toner Base Particle 1] was obtained.
The strength and physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3. The intensity displacement graph is shown in FIG.

(Example 2)
In Example 1, a toner was obtained in the same manner as in Example 1 except that the low molecular polyester synthesis step was changed to the following conditions. The strength and physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3. The intensity displacement graph is shown in FIG.

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 724 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were subjected to polycondensation under normal pressure at 230 ° C. for 7 hours. Reaction was performed at a reduced pressure of ˜15 mmHg for 5 hours to obtain [Low molecular polyester 2].
[Low molecular polyester 2] had a number average molecular weight of 2300, a weight average molecular weight of 6700, a peak molecular weight of 3800, a Tg of 43 ° C. and an acid value of 4.

(Example 3)
In Example 1, a toner was obtained in the same manner as in Example 1 except that the oil phase preparation step was changed to the following conditions. The strength and physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3. The intensity displacement graph is shown in FIG.

~ Creation of oil phase ~
Production Example 10
In a container equipped with a stir bar and a thermometer, 378 parts of [low molecular weight polyester 1], 100 parts of carnauba / rice wax (weight ratio 7: 3) WAX, and 947 parts of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining at 80 ° C. for 4 hours, it was cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 2].
[Raw material solution 2] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 7 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by 4 passes using a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 2]. The solid content concentration of [Pigment / WAX Dispersion 2] (130 ° C., 30 minutes) was 50%.

Example 4
A toner was obtained in the same manner as in Example 1 except that the steps from emulsification to solvent removal were changed to the following conditions. The strength and physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3.

~ 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 10 minutes to obtain [Emulsified Slurry 2].
[Emulsion slurry 2] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 6 hours, aging was carried out at 45 ° C. for 5 hours to obtain [Dispersed slurry 2].

(Example 5)
A toner was obtained in the same manner as in Example 1 except that the steps from emulsification to solvent removal were changed to the following conditions. The strength and physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3. The intensity displacement graph is shown in FIG.

~ 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 40 minutes to obtain [Emulsified Slurry 3].
[Emulsion slurry 3] 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 5 hours to obtain [Dispersion slurry 3].

(Example 6)
In Example 1, a toner was obtained in the same manner as in Example 1 except that the low molecular polyester synthesis step was changed to the following conditions. The strength and physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3. The intensity displacement graph is shown in FIG.

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 500 parts of bisphenol A ethylene oxide 2-mole adduct and 500 parts of terephthalic acid were subjected to polycondensation under normal pressure at 230 ° C. for 7 hours. Reaction was performed at a reduced pressure of ˜15 mmHg for 5 hours to obtain [Low molecular weight polyester 3]. [Low molecular weight polyester 3] had a number average molecular weight of 2300, a weight average molecular weight of 6700, a peak molecular weight of 3800, a Tg of 43 ° C. and an acid value of 10.

(Example 7)
A toner was obtained in the same manner as in Example 1 except that the steps from emulsification to solvent removal were changed to the following conditions. The strength and physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3. The intensity displacement graph is shown in FIG.

~ 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 [Aqueous Phase 1] 1200 parts are added to the container. The mixture was mixed for 1 hour at a rotational speed of 13,000 rpm to obtain [Emulsion slurry 4].
[Emulsion slurry 4] 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 10 hours to obtain [Dispersed slurry 4].

(Example 8)
A toner was obtained in the same manner as in Example 1 except that the following conditions were changed in Example 1. The strength and physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3.

~ Synthesis of low molecular weight polyester ~
Production Example 3
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 724 parts of bisphenol A ethylene oxide 2-mole adduct and 276 parts of terephthalic acid were subjected to polycondensation under normal pressure at 230 ° C. for 7 hours. Reaction was performed at a reduced pressure of ˜15 mmHg for 5 hours to obtain [Low molecular polyester 2]. [Low molecular polyester 2] had a number average molecular weight of 2300, a weight average molecular weight of 6700, a peak molecular weight of 3800, a Tg of 43 ° C. and an acid value of 4.

~ Creation of oil phase ~
Production Example 7
In a container in which a stir bar and a thermometer are set, 378 parts of [low molecular weight polyester 2], carnauba / rice wax (weight ratio 7: 3) WAX 100 parts, 947 parts of ethyl acetate are charged, and the temperature is raised to 80 ° C. with stirring. After maintaining at 80 ° C. for 4 hours, it was cooled to 30 ° C. in 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 3].
[Raw Material Solution 3] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 7 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 2] was added, followed by 4 passes using a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 3]. The solid content concentration of [Pigment / WAX Dispersion 3] (130 ° C., 30 minutes) was 50%.

(Comparative Example 1)
<First step>
-Preparation of dispersion (1)-
Styrene ... 370g
nButyl acrylate ... 30g
Acrylic acid ... 8g
Dodecanethiol ... 24g
Carbon tetrabromide ... 4g
The above mixture was dissolved and ionized with 6 g of a nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and 10 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC). Dispersed in 550 g of exchange water, dispersed in a flask, emulsified, slowly mixed for 10 minutes, and then charged with 50 g of ion exchange water in which 4 g of ammonium persulfate was dissolved. While stirring in the flask, the contents were heated in an oil bath until the temperature reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a dispersion (1) was prepared by dispersing resin particles having an average particle size of 155 nm, a glass transition point of 59 ° C., and a weight average molecular weight (Mw) of 12,000.

-Preparation of dispersion (2)-
Styrene ... 280g
n-Butyl acrylate ... 120g
Acrylic acid ... 8g
The above mixture was dissolved, and 6 g of a nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and 12 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) were ionized. Dispersed in 550 g of exchange water, dispersed in a flask, emulsified, and slowly mixed for 10 minutes, charged with 50 g of ion exchange water in which 3 g of ammonium persulfate was dissolved, and after nitrogen replacement, While stirring in the flask, the contents were heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. The average particle size was 105 nm, the glass transition point was 53 ° C., and the weight average molecular weight (Mw) was 550. A dispersion liquid (2) was prepared by dispersing resin particles having a molecular weight of 1,000.

-Preparation of colorant dispersion (1)-
Carbon black ... 50g
(Cabot Corporation: Mogal L)
Nonionic surfactant ... 5g
(Sanyo Kasei Co., Ltd .: Nonipol 400)
Ion exchange water ... 200g
The above is mixed, dissolved, and dispersed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to disperse a colorant (carbon black) having an average particle size of 250 nm (carbon black) 1) was prepared.

-Preparation of release agent dispersion (1)-
Paraffin wax ... 50g
(Nippon Seiwa Co., Ltd .: HNP0190, melting point 85 ° C.)
Cationic surfactant ... 5g
(Manufactured by Kao Corporation: Sanizol B50)
Ion exchange water ... 200g
The above was heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50), and then dispersed with a pressure discharge homogenizer to disperse a release agent having an average particle size of 550 nm. A release agent dispersion (1) was prepared.

-Preparation of aggregated particles-
Dispersion (1) ... 120g
Dispersion liquid (2) ... 80g
Colorant dispersion (1) ... 30g
Release agent dispersion (1) 40g
Cationic surfactant ... 1.5g
(Manufactured by Kao Corporation: Sanizol B50)
The above was mixed and dispersed in a round stainless steel flask using a homogenizer (manufactured by IKA: Ultra Turrax T50), and then heated to 48 ° C. while stirring the inside of the flask in an oil bath for heating. After maintaining at 48 ° C. for 30 minutes, it was confirmed by observation with an optical microscope that aggregated particles (volume: 95 cm ³ ) having an average particle diameter of about 5 μm were formed.

<Second step>
-Preparation of adhered particles-
To this, 60 g of the dispersion liquid (1) as the resin-containing fine particle dispersion liquid was gradually added. The volume of the resin particles contained in the dispersion (1) is 25 cm ³ . And the temperature of the heating oil bath was raised to 50 degreeC, and was hold | maintained for 1 hour.

<Third step>
Then, after adding 3 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC), the stainless steel flask was sealed, and stirring was continued using a magnetic seal up to 105 ° C. Heated and held for 3 hours. Then, after cooling, the reaction product was filtered, washed thoroughly with ion-exchanged water, and then dried.

<4th process>
Thereafter, the fluorine compound A (2) was adhered to the toner surface in an aqueous solvent soda in which the fluorine compound A (2) was dispersed, and then dried at 45 ° C. for 48 hours in a circulating drier. Thereafter, the mixture was sieved with a mesh having an opening of 75 μm to obtain a toner base.
The strength and physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3. The intensity displacement graph is shown in FIG.

(Comparative Example 2)
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube and reacted at 230 ° C. for 8 hours at normal pressure. The reaction was further carried out at a reduced pressure of 10 to 15 mmHg for 5 hours, followed by cooling to 160 ° C., and 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Subsequently, it cooled to 80 degreeC and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours, and the isocyanate containing prepolymer (1) was obtained. Next, 267 parts of the prepolymer (1) and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a urea-modified polyester (1) having a weight average molecular weight of 64,000. In the same manner as above, 724 parts of bisphenol A ethylene oxide 2 mol adduct, 138 parts of terephthalic acid and 138 parts of isophthalic acid were polycondensed at 230 ° C. for 6 hours under normal pressure, and then reacted for 5 hours at a reduced pressure of 10 to 15 mmHg. An unmodified polyester (a) having a peak molecular weight of 2300, a hydroxyl value of 55, and an acid value of 1 was obtained. 200 parts of urea-modified polyester (1) and 800 parts of unmodified polyester (a) are dissolved and mixed in 1000 parts of a mixed solvent of ethyl acetate / MEK (1/1), and an ethyl acetate / MEK solution of toner binder (1) is mixed. Got. In a reaction vessel equipped with a condenser, a stirrer and a thermometer, 942 parts of water and 58 parts of a 10% suspension of hydroxyapatite (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) are placed, and the toner binder (1 1000 parts of ethyl acetate / MEK solution was added and dispersed. The temperature was raised to 98 ° C., the organic solvent was distilled off, and after cooling, filtered from water, washed and dried to obtain the toner binder (1) of the present invention. The toner binder (1) had a Tg of 52 ° C., a Tη of 123 ° C., and a TG ′ of 132 ° C.
100 parts of the toner binder (1), 7 parts of glycerin tribehenate and 4 parts of cyanine blue KRO (manufactured by Sanyo Dye Co., Ltd.) were converted into a toner by the following method. First, after premixing using a Henschel mixer (FM10B manufactured by Mitsui Miike Chemical Co., Ltd.), the mixture was kneaded using a biaxial kneader (PCM-30 manufactured by Ikegai Co., Ltd.). Subsequently, the mixture was finely pulverized using a supersonic jet pulverizer, Labo Jet (manufactured by Nippon Pneumatic Industry Co., Ltd.), and then classified by an airflow classifier (MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.). Thereafter, the fluorine compound A (2) was adhered to the toner surface in an aqueous solvent soda in which the fluorine compound A (2) was dispersed, and then dried at 45 ° C. for 48 hours in a circulating drier. Thereafter, the mixture was sieved with a mesh having an opening of 75 μm to obtain a toner base.
The strength and physical properties of the obtained toner are shown in Table 2, and the evaluation results are shown in Table 3. The intensity displacement graph is shown in FIG.

1 is a schematic configuration diagram illustrating an example of an embodiment of an image forming apparatus of the present invention. It is a schematic block diagram which shows the other example of embodiment of the image forming apparatus of this invention. 1 is a schematic configuration diagram illustrating an example of an embodiment of a tandem image forming apparatus. FIG. 6 is a schematic configuration diagram illustrating another example of an embodiment of a tandem image forming apparatus. 1 is a schematic configuration diagram illustrating an example of a tandem indirect transfer type image forming apparatus. 1 is a partially enlarged view of an image forming apparatus according to the present invention. It is a figure showing the intensity displacement graph (gram) of the Example of this invention. It is a figure showing the intensity displacement graph (gram) of the comparative example of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Photoconductor 20 Charging roller 30 Exposure apparatus 40 Developing apparatus 41 Developing belt 42 Developing tank 43 Pumping roller 44 Coating roller 45 Developing unit 50 Intermediate transfer body 51 Suspension roller 52 Corona charger 60 Cleaning device 70 Static elimination lamp 80 Transfer roller 81 Fixing means 90 Cleaning Device 100 Transfer Paper 301 Photoconductor 302 Transfer Device 303 Sheet Conveying Belt 306 Conveying Path 307 Fixing Roller 401 Photosensitive Member 402 Transfer Device 403 Sheet Conveying Belt 404 Intermediate Transfer Member 405 Secondary Transfer Device 406 Paper Feed Device 407 Fixing Device 408 Cleaning Device 409 Intermediate transfer member cleaning device 410 Exposure device 510 Intermediate transfer member 514 Support roller 515 Second support roller 516 Third support roller 517 Cleaning device 518 Image forming means 520 Tandem image forming device 521 Exposure device 522 Secondary transfer device 523 Roller 524 Secondary transfer belt 525 Fixing device 526 Fixing belt 527 Pressure roller 528 Reversing device 530 Document table 532 Contact glass 533 First traveling member 534 Second traveling member 535 Imaging lens 536 Reading sensor 540 Photoconductor 542 Paper feed roller 543 Paper bank 544 Paper feed cassette 545 Separation roller 546 Paper feed path 547 Transport roller 548 Paper feed path 549 Registration roller 550 Paper feed roller 551 Manual feed tray 552 Separation roller 553 Manual feed Paper path 555 Switching claw 556 Discharge roller 557 Discharge tray 562 Primary transfer device 600 Copying device main body 610 Intermediate transfer belt 640 Photoconductor 660 Charging device 661 Developing device 662 Primary transfer device 663 Photoconductor cleaning Device 664 Neutralizing device 665 Development area 666 Toner storage unit 667 Toner supply unit 672 Developing roller 673 Toner amount supply regulating means 676 Cleaning roller 677 Toner removal roller 678 Removal toner collection roller 700 Feeding table 800 Scanner 900 Automatic document feeder (ADF)
L Exposure apparatus S Conveying sheet T Tandem type image forming apparatus

Claims (15)

In a toner containing at least a colorant and a resin, the toner is composed of particles formed by dispersing oil droplets of an organic solvent in which a toner composition containing a prepolymer is dissolved in an aqueous medium, and by an extension reaction and / or a crosslinking reaction. The ratio of force to displacement is within the range of 0 to 1 μm in the displacement amount in the strength displacement graph in the micro compression tester and the strength in the micro compression tester is 0.100 to 1.00 kg / mm ^2. A toner for developing an electrostatic charge image, wherein a ratio (kmax / kmin) of a maximum value slope kmax and a minimum value slope kmin of the inclination (force / displacement) is 20 or more. The volume average particle diameter Dv of the toner is 4 to 6 μm, and the ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn is 1.00 to 1.25. The toner for developing an electrostatic image according to the description. 3. The electrostatic image developing toner according to claim 1, wherein at least a fine powder having a volume average particle diameter of 1 μm or less of the toner is 0 to 10% by weight. 4. 4. The electrostatic image developing toner according to claim 1, wherein the toner has a circularity E of 0.92 to 0.99. 5. The electrostatic image developing toner according to claim 1, wherein the toner has a circularity SF-1 value of 100 to 160 and a circularity SF-2 value of 100 to 150. 6. The toner for developing an electrostatic charge image according to claim 1, wherein the content of the wax inside the toner is 3% to 8% in terms of weight. 7. The electrostatic charge developing toner according to claim 1, wherein the binder resin of the electrostatic charge image developing toner contains at least a modified polyester resin. The toner for developing an electrostatic charge image according to claim 1, wherein the toner contains at least inorganic fine particles, and the inorganic fine particles comprise at least two kinds. 9. The electrostatic image developing toner according to claim 8, wherein the two kinds of inorganic fine particles are silica and titanium. 10. A full-color toner kit, wherein the electrostatic image developing toner according to claim 1 contains at least magenta toner, yellow toner, and cyan toner. A two-component electrostatic charge image developing developer comprising the electrostatic charge image developing toner according to claim 1 and a carrier comprising magnetic particles. A process cartridge that integrally supports a developing unit and at least one unit selected from a photosensitive member, a charging unit, and a cleaning unit and is detachable from the main body of the image forming apparatus, wherein the developing unit includes: A process cartridge that holds the toner according to claim 9, the full-color toner kit according to claim 10, or the developer according to claim 11. An image forming method using the toner according to claim 1, the full-color toner kit according to claim 10, or the developer according to claim 11. The toner according to any one of claims 1 to 9, the full-color toner kit according to claim 10, or the developer according to claim 11 is used, and the printing speed is equivalent to A4 size and is 20 sheets / minute or more. A tandem type color image forming method. An image forming apparatus comprising a container filled with the toner according to claim 1, the full color toner kit according to claim 10, or the developer according to claim 11.

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