JP2009014844A - Toner, developer, developing device, process cartridge, image forming method and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner excellent in fluidity and capable of forming high-quality images for a long period of time, and to provide a developing device, a process cartridge, an image forming apparatus and an image forming method using the toner. <P>SOLUTION: The toner contains at least a binder resin, a colorant, a release agent and an external additive. Further, the toner contains: first toner particles composed of irregular toner base particles with addition of an external additive of large diameter particles and small diameter particles; and second toner particles composed of spherical toner base particles with addition of an external additive of the above large diameter particles and the above small diameter particles; in which the addition amount of the large diameter external additive in the first toner particles is larger than the addition amount of the large diameter external additive in the second toner particles. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic latent image used for image formation by an electrostatic copying process such as a copying machine, a facsimile machine, a printer, and the like, and a developer, a developing device, a process cartridge, and an image using the toner. The present invention relates to a forming method and an image forming apparatus.

In an image forming apparatus such as a copying machine, a printer, and a facsimile, an image forming method is used in which an electrostatic latent image by an electrophotographic method is visualized with toner of colored resin particles including a pigment. This image forming method can form images with high image quality at high speed, forms not only monochrome images but full-color images, and has durability and stability that can withstand long-term use. Yes.
Recently, the required image quality has increased, and further improvement has been demanded. In particular, high reproducibility for fine lines and fine dots is required for image quality, and for this, fine toner having a small particle diameter is used, and spherical toner is also used.

However, it is difficult to provide a sufficient charge amount with a so-called minute toner having a reduced particle size. Since the particles are small, the surface area is large, the van der Waals force is also large, the fluidity is lowered, and the frictional charging member is not sufficiently rubbed. For this reason, when a toner having a small particle diameter is used, problems such as toner scattering and fogging may occur. Further, since the adhesion to the photosensitive member becomes strong, there is a problem that sufficient cleaning becomes difficult with a cleaning method using an elastomer blade having a simple structure at a low cost.
In addition, the spherical toner (spherical toner) can be developed and reproduced with high reproducibility because it flies and moves faithfully to the electric field, and the same applies to the electric field in transfer. Highly efficient transfer. However, the spherical toner is easy to roll on the photosensitive member, and it is difficult to sufficiently clean it by a cleaning method using a blade.
In order to improve these problems, an external additive is used to control the adhesive force on the toner to improve the fluidity and adjust the charge amount (see, for example, Patent Documents 1 to 16).

Further, as an invention comprising an irregular toner and a spherical toner, for example, Patent Document 17 discloses an invention in which an irregular toner and a spherical toner are mixed to improve the cleaning property and transferability. The degree Sc / Sr (Sc: the area of a circle having the absolute maximum length of toner particles as a direct line, Sr: the actual projected area of the toner particles) is 1.0 to 1.3, and the amorphous toner is a styrene copolymer. In addition, silica is externally added as a fluidizing agent, and a spherical toner is prepared by a suspension polymerization method which is a known technique (see claims, paragraph 0012). Patent Document 18 discloses an invention in which an irregular toner and a spherical toner are mixed to improve the cleaning property and the transfer property (see claims, paragraphs 0005 to 0008). Patent Document 19 discloses an invention of an electrophotographic toner in which an irregular toner and a spherical toner are mixed to improve the cleaning property and transfer property. Further, it is described that the Sc / Sr value is in the range of 1.0 or more and 1.5 or less.
Patent Document 20 is filed by the applicant of the present application. In Patent Document 20, the first starting developing device contains mixed toner or amorphous toner of amorphous toner and spherical toner, and other developing devices include An invention in which spherical toner is accommodated, and a toner image composed of amorphous toner and spherical toner is formed and developed on the most upstream side image carrier by a first starting developing device at the time of non-image formation, thereby improving the cleaning property. Is disclosed.

JP-A-5-224456 JP 2001-340007 A JP 9-319135 A JP-A-10-207112 JP-A-11-143115 JP 2000-267343 A JP 2000-321812 A JP 2001-22119 A JP 2001-66820 A Japanese Patent Laid-Open No. 10-10773 JP 2001-147547 A JP 2001-166659 A JP-A-5-249741 JP-A-11-65163 Japanese Patent No. 2704766 Japanese Patent No. 3230006 JP-A-8-95286 JP-A-8-292595 JP-A-8-339094 JP 2005-338559 A

  As described above, even when an irregular toner and a spherical toner are used, if a developer is used for a long time, an external additive having a small particle size is added to the irregular toner base particles. For spherical toners, adding a large particle size external additive to the spherical toner base particles leaves the extremely difficult problem that the fluidity of the toner deteriorates as the cleaning properties by blade cleaning improve. ing. In addition, it is preferable to set the addition amount as small as possible within the range where the blade cleaning property and the toner fluidity can be maintained with the irregular shaped toner. Obtaining a toner having stable physical properties is a very difficult task.

The present invention maintains good cleaning performance, transferability, etc., and does not change the toner flowability, cleaning performance, transferability, and the amount of developer pumped onto the developing sleeve, so that the image density does not fluctuate and the flow is good. It is an object to obtain a toner capable of obtaining properties. Another object of the present invention is to obtain a developing device, a process cartridge, and an image forming apparatus that can obtain a high-quality image over a long period of time by using such a toner.

In order to solve the above problems, the present invention can include the following means.
(1) A toner containing at least a binder resin, a colorant, a release agent, and an external additive, wherein large-sized particles and small-sized particle external additives are added to the irregular toner base particles. A first toner particle; and a second toner particle obtained by adding the large particle size particle and the external additive of the small particle size particle to the spherical toner base particle, and the large particle in the first toner particle. The toner according to claim 1, wherein the additive amount of the external additive is larger than the additive amount of the large-diameter external additive in the second toner particles.
(2) The toner according to (1), wherein the circularity of the irregular toner base particles and the spherical toner base particles satisfy the following expressions, respectively.
0.85 ≦ circularity of irregular toner base particles ≦ 0.94,
0.95 ≦ Circularity of spherical toner base particles ≦ 0.99
(3) In the toner according to (1) or (2), the external additive of the large particle size particles added to the irregular toner base particles and the spherical toner base particles is 30 to 300 nm. The external additive of the diameter particle is 5 to 25 nm, and the amount of the external additive of the large particle size added to the irregular toner base particle is larger than the amount of the external additive of the small particle size, A toner characterized in that the amount of external additive of large particle size particles added to spherical toner base particles is smaller than the amount of external additive of small particle size particles.
(4) In the toner according to any one of (1) to (3), the amorphous toner base particles and spherical toner base particles have a weight average particle diameter of 4.0 to 9.5 μm, and the weight average particle diameter A toner having a ratio (D4 / Dn) of (D4) to number average particle diameter (Dn) in the range of 1.00 to 1.40.
(5) In the toner according to any one of (1) to (4), the shape factor SF-1 of the amorphous toner base particle toner is in the range of 150 to 190, and the shape factor SF-2 is 150 to 190. A toner having a spherical toner base particle toner having a shape factor SF-1 in the range of 100 to 147 and a shape factor SF-2 in the range of 100 to 147.
(6) The toner according to any one of (1) to (5), wherein the spherical toner base particles are obtained by a polymerization method.
(7) In the toner according to any one of (1) to (6), the first toner particles obtained by adding an external additive to the irregular toner base particles are 5 to 65 parts by weight, and 2. A toner characterized in that the second toner particle is 95 to 35 parts by weight (provided that the total amount of the first toner particles and the second toner particles is 100 parts by weight).
(8) A developer for developing an electrostatic latent image on an image carrier, comprising the toner according to any one of (1) to (7) and a magnetic carrier coated with a resin. Developer.
(9) A developing device arranged to face an image carrier that carries an electrostatic latent image, wherein the toner described in (7) or the developer described in (8) is used. Developing device.
(10) In the image forming method including at least a step of developing the electrostatic latent image on the image carrier with a developer and a step of cleaning the residual toner on the image carrier with a cleaning blade, development in the development step Is performed using the toner according to (7) or the developer according to (8), and the cleaning step is performed by blade cleaning.
(11) In a process cartridge that integrally supports an image carrier that carries an electrostatic latent image and at least a developing device that is disposed so as to face the image carrier, and that is detachable from an image forming apparatus main body, A process cartridge using the developing device described in (9) above.
(12) In an image forming apparatus including at least an image carrier that carries an electrostatic latent image and a developing device that is disposed to face the image carrier, the image forming apparatus is described in (9). An image forming apparatus using a developing device.

  According to the present invention, the irregular toner (first toner) has a large particle size external additive and a small particle size external additive so that the developer can be used for a long time. However, the external additive having a small particle size makes it difficult for the additive to be buried inside the amorphous toner base particle, and the external additive having a large particle size and the small particle size are added to the surface of the amorphous toner base particle. Since the external additive is mixed, the toner fluidity can be maintained well. The spherical toner (second toner) has an external additive having a large particle diameter, so that the blade cleaning property is improved, but the toner fluidity tends to deteriorate accordingly. Further, the external additive is less likely to adhere to the surface of the spherical toner base particles than the amorphous toner. Therefore, it is preferable to set the addition amount as small as possible within the range in which the blade cleaning property and the toner fluidity can be maintained. In this way, the cleaning property, the transfer property, etc. are maintained satisfactorily. Toner fluidity, cleanability, transferability, and the amount of developer pumped onto the developing sleeve do not change, so the toner does not change the image density and can obtain good fluidity. It is possible to provide a developing device, a process cartridge, and an image forming apparatus that can obtain an image of the above.

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

  The toner of the present invention is a toner for developing an electrostatic latent image, and includes at least a binder resin, a colorant, a release agent, and an external additive. The toner particles used in the toner of the present invention are produced by a production method such as a pulverization method or a polymerization method (suspension polymerization, emulsion polymerization, dispersion polymerization, emulsion aggregation, emulsion association, etc.). Not limited to.

  As an example of the pulverization method, first, constituent materials such as a binder resin, a pigment or dye as a colorant, a charge control agent, a release agent, and other additives are sufficiently mixed by a mixer such as a Henschel mixer. Then, the components are thoroughly kneaded using a thermal kneader such as a batch-type two-roll, three-roll, Banbury mixer, continuous twin-screw extruder, continuous single-screw kneader, etc. Cut. The toner kneaded product after cutting is crushed, coarsely pulverized using a hammer mill, etc., and further pulverized by a fine pulverizer or mechanical pulverizer using a jet stream, and a classifier or Coanda effect using a swirling airflow Is classified to a predetermined particle size by a classifier using

  Examples of the polymerization toner include a suspension polymerization toner, or a toner composition containing at least a polymer having an active hydrogen group, polyester, a colorant, and a release agent in the presence of resin fine particles in an aqueous medium. It is preferable to use a toner that has undergone crosslinking and / or elongation reaction, an emulsion polymerization toner, or the like.

As the external additive, inorganic fine particles and organic fine particles can be used.
As the inorganic fine particles, metal compounds such as oxides, nitrides, carbides and carbonates are used. Specifically, silicon oxide (silica), aluminum oxide (alumina), titanium oxide (titania), zinc oxide, zirconium oxide, cerium oxide, tungsten oxide, manganese oxide, barium titanate, strontium titanate, titanate Examples thereof include oxides such as magnesium, calcium carbonate, and potassium carbonate, silicon nitride, aluminum nitride, and the like, nitrides such as carbon nitride, and carbides such as nitrogen carbide. In particular, oxides of silicon, titanium, and aluminum are preferably used.
Organic fine particles include polymer fine particles such as vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization. , Polymer particles of melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin.

  Such an external additive can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, 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. It is done.

  The particle diameter of the external additive having a large particle size added to the amorphous toner base particles is 30 to 300 nm. If it is 30 nm or less, the toner is easily buried in the toner base by stirring the developer. When the thickness is 300 nm or more, the cleaning property is improved, but it is easily released by stirring the developer. The external additive having a large particle size is 0.8 to 4.0 parts by weight, more preferably 0.9 to 3.7 parts by weight, based on 100 parts by weight of the amorphous toner base particles. Further, in the case of an external additive having a small particle diameter of 5 to 25 nm, 0.2 to 2.0 parts by weight, more preferably 0.3 to 1 part by weight with respect to 100 parts by weight of amorphous toner base particles. 8 parts by weight.

  The external additive having a large particle size of 30 to 300 nm and added to the spherical toner base particles is 0.2 to 1.3 parts by weight, more preferably 0.3 parts per 100 parts by weight of the spherical toner base particles. -1.1 parts by weight. The particle diameter of the external additive having a small particle size added to the spherical toner base particles is 5 to 25 nm. If it is less than 5 nm, fluidity is hardly imparted and it is easily embedded in the toner base. Above 25 nm, the developer is likely to be liberated by stirring. The addition amount of the external additive having a small particle diameter is 0.7 to 1.7 parts by weight, more preferably 0.8 to 1.4 parts by weight with respect to 100 parts by weight of the spherical toner base particles.

  Here, the amount of the external additive of the large particle size added to the irregular toner base particle is larger than the amount of the external additive of the small particle size particle, and the large particle size particle added to the spherical toner base particle The amount of the external additive is preferably smaller than the amount of the external additive of the small particle size because a child T that maintains the fluidity of the toner particles after the addition of the external additive can be formed.

  In order to remove toner remaining after transfer remaining on the photosensitive member or primary transfer medium (intermediate transfer member), a cleaning property improver is contained in the amorphous toner base particles or spherical toner base particles by a blade cleaning method. For example, as an external additive in the toner, or contained in or added to the developer. Examples of such cleaning improvers include fatty acid metal salts such as zinc stearate and calcium stearate, and polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. . The polymer fine particles preferably have a relatively narrow particle size distribution and a number average particle size of 1 nm to 100 nm.

  For mixing external additives, a general powder mixer is used. For example, examples of the mixer that can be used include a Roedige mixer, a Nauter mixer, a Henschel mixer (FM20B, manufactured by Mitsui Miike Kogyo Co., Ltd.), and the like.

The circularity of the irregular toner base particles is preferably 0.85 to 0.94, and the circularity of the spherical toner base particles is preferably 0.95 to 0.99. Furthermore, the spherical toner has a mixing ratio of 100 parts by weight of the total toner and 35 to 95 parts by weight, so that the dot reproducibility is excellent and the transferability is good. When the toner is high, the toner is uniformly developed and transferred, and the toner is less likely to clump together and adhere uniformly in the halftone portion and the solid portion.
This makes it possible to reproduce a uniform intermediate color with little color unevenness when the toners are stacked and color overlapped, and the color reproduction range can be further expanded. When the mixing ratio of the spherical toner is less than 35 parts by weight, the dot reproducibility and transferability are not good and high image quality cannot be obtained. On the other hand, if it exceeds 95 parts by weight, the cleaning property becomes unstable.

  The circularity of the toner base particles (amorphous toner base particles, spherical toner base particles) is a value obtained by optically detecting the particles and dividing by the perimeter of an equivalent circle having the same projected area. Specifically, the measurement is performed using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a 200 ml container, add 100 ml of water from which impure solids have been removed in advance, add 0.2 ml of a surfactant as a dispersant, and add about 0.2 g of a measurement sample. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, the dispersion concentration is set to 3,000 to 10,000 / μl, and the shape and distribution of the toner are measured.

  The toner of the present invention has a weight average particle diameter of 3.0 to 8.0 μm, and a ratio (D4 / Dn) of the weight average particle diameter (D4) to the number average particle diameter (Dn) is 1.00. It is preferable to use a toner using amorphous toner base particles and spherical toner base particles in the range of 1.40. The weight average particle diameter is preferably 3.0 to 7.0 μm and D4 / Dn 1.00 to 1.25. By using such a toner, a full color image has a wide reproduction range of intermediate colors and absorption. A vivid color image with a narrow area can be obtained. It is said that the smaller the toner particle diameter is, the more advantageous it is for obtaining a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning property.

  In addition, when the weight average particle diameter is smaller than this range, in the case of a two-component developer, the toner is fused to the surface of the magnetic carrier during a long period of stirring in the developing device, thereby reducing the charging ability of the magnetic carrier When used as a system developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur. In addition, these phenomena are greatly related to the content of fine powder. Particularly, when the particle diameter of the toner exceeds 3%, the adhesion to the magnetic carrier and the stability of charging at a high level are hindered. Become. On the contrary, when the weight average particle diameter of the toner is larger than this range, it is difficult to obtain a high-resolution and high-quality image. Further, in a color image, the reproducibility of intermediate colors is lowered, the graininess is increased, and the quality of the color image is lowered. On the other hand, if D4 / Dn exceeds 1.40, the charge amount distribution becomes wide and the resolving power decreases, which is not preferable.

The charge amount (Q / M) of toner or the like can be measured as follows.
The measurement is performed by the blow-off method. The outline is that a two-component developer consisting of a toner and a carrier is put in a cage made of a metal cylinder with a metal mesh on both sides of the cylinder, and the metal cylinder cage is set horizontally in the Faraday cage. A compressed gas is blown from the other end or both ends of the metal cylindrical cage to separate the toner and the carrier. The opening of the metal mesh is selected so that the toner passes and the carrier cannot pass. The charged toner passes through the mesh of the metal mesh and is blown out of the cage, but the carrier remains in the cage. The carrier in the cage retains a charge Q of the opposite polarity in the same amount as that of the charged toner removed, and charges the capacitor of capacitance C connected to the cage. The voltage V across the capacitor is measured, and the specific charge amount (charge amount) of the toner is obtained from the following equation.
・ Charge (Q) = Capacitance (C) x Voltage (V)
Using the developer amount (M), the specific charge amount (charge amount) of the toner per unit mass is represented by Q / M.
Faraday gauge configuration: A cage made of a metal cylinder containing a two-component developer is completely insulated with another grounded metal cylinder.
The measurement can be performed using a TB-200 model manufactured by Toshiba Chemical Corporation.

The particle size distribution and average particle size of the toner can be measured as follows. Specific examples of measurement are shown below.
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 100 μm
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether HLB 13.6) 5% electrolyte

Dispersion condition: 5 ml of the dispersion is put into a 100 ml beaker, and 10 mg of a measurement sample is added to the dispersion. And it disperse | distributes for 1 minute with an ultrasonic disperser, Then, 25 ml of electrolyte solution is added, and it disperses for another 1 minute with an ultrasonic disperser.
Measurement conditions: 70 ml of electrolyte solution is put into a 100 ml beaker. Then, a liquid in which the sample is dispersed is added. As a concentration condition for adding the dispersion liquid, an amount of the dispersion liquid that can measure 30,000 particles in 20 seconds is added. The particle size is measured for 20 seconds to determine the particle size distribution. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

  The particle diameter of the external additive (inorganic fine particles) is measured by a particle size distribution measuring apparatus using dynamic light scattering, for example, DLS-700 manufactured by Otsuka Electronics Co., Ltd. However, since it is difficult to dissociate secondary agglomeration of particles whose surface has been treated, for example, with silicone oil, the particle size is directly determined from a photograph obtained by a scanning electron microscope or a transmission electron microscope. In this case, at least 100 or more inorganic fine particles are observed, and the average value of the major axis is obtained.

In addition, the amorphous toner base particles that can be used in the toner of the present invention preferably have a shape factor SF-1 in the range of 150 to 190 and a shape factor SF-2 in the range of 150 to 190. The spherical toner base particles that can be used in the toner of the present invention preferably have a shape factor SF-1 in the range of 100 to 147 and a shape factor SF-2 in the range of 100 to 147.
FIGS. 1A and 1B are diagrams schematically illustrating the shape of the toner, and are diagrams for explaining the shape factor SF-1 and the shape factor SF-2.

The shape factor SF-1 indicates the ratio of the roundness of the toner shape and is represented by the following formula (1). This is a value obtained by dividing the square of the maximum length MXLNG of the shape formed by projecting the toner on a two-dimensional plane by the figure area AREA and multiplying by 100π / 4.
SF-1 = {(MXLNG) ² / AREA} × (100π / 4) (1)
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. When the value of SF-1 exceeds 190, the cleaning property is improved, but the spherical shape and the shape are greatly deviated, so that the charge amount distribution is widened, the ground cover is increased, and the image quality is deteriorated. If the value of SF-1 is 150 or less, the cleaning property does not contribute to improvement.

  The SF-1 of the amorphous toner base particles is 150 to 190, more preferably 155 to 180. The SF-1 of the spherical toner base particles is 100 to 147, more preferably 105 to 143.

In the toner of the present invention, the unevenness of the toner surface is represented by a shape factor SF-2, and the value of SF-2 is preferably in the range of 100 to 190. Here, the shape factor SF-2 indicates the ratio of the unevenness of the toner shape, and is represented by the following formula (2). A value obtained by dividing the square of the perimeter PERI of the figure formed by projecting the toner onto the two-dimensional plane by the figure area AREA and multiplying by 100 / 4π.
SF-2 = {(PERI) ² / AREA} × (100 / 4π) (2)

  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. When the value of SF-2 exceeds 190, the cleaning property is improved, but the spherical shape and shape are greatly deviated, so that the charge amount distribution is widened, the ground cover is increased, and the image quality is lowered. If the value of SF-2 is 150 or less, the cleaning property does not contribute to improvement. The SF-2 of the amorphous toner base particles is 150 to 190, more preferably 155 to 180. The SF-2 of the spherical toner base particles that can be used in the toner of the present invention is 100 to 147, more preferably 105 to 143.

  The spherical toner base particles in the present invention are preferably obtained by a polymerization method. As spherical toner base particles by the polymerization method, for example, in the suspension polymerization method, a dispersion stabilizer, a colorant, a release agent, and, if necessary, a crosslinking agent, a charge control agent, etc., for a ball mill etc. Then, a polymerization initiator is added thereto to obtain a monomer phase, and the aqueous dispersion medium phase prepared by stirring with the monomer phase in advance is placed in a stirring tank and stirred with a homogenizer or the like. The obtained suspension is heated after nitrogen substitution to complete the polymerization reaction, whereby colored resin particles are obtained, and this is washed and dried to obtain spherical toner base particles having a high degree of circularity.

  In addition, at least one of a crosslinking reaction or an extension reaction in a toner solvent obtained by dispersing at least a polyester prepolymer having a functional group containing a nitrogen atom, a polyester, a colorant, and a release agent in an organic solvent. Polymerized toners obtained by two reactions can be mentioned. Furthermore, an emulsion polymerization method can be mentioned as a polymerization method, and this method can make a particle size suitable as a toner by agglomerating particles of submicron order while controlling.

  The following is a crosslinking reaction or elongation reaction in which at least a binder resin or a binder resin precursor and a release agent are dissolved or dispersed in an organic solvent or a polymerizable monomer to form particles in an aqueous medium. Constituent materials using a toner obtained by at least one reaction and a suitable production method will be described.

(polyester)
The polyester is obtained by a polycondensation reaction between a polyhydric alcohol compound and a polycarboxylic acid compound.
Examples of the polyhydric alcohol compound (PO) include dihydric alcohol (DIO) and trihydric or higher polyhydric alcohol (TO). (DIO) alone or a mixture of (DIO) and a small amount of (TO) preferable. Examples of the dihydric alcohol (DIO) include 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 above alicyclic diol; Alkylene oxide bisphenol (ethylene oxide, propylene oxide, butylene oxide, etc.), 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 polyhydric alcohol (TO) 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 polyvalent carboxylic acid (PC) include divalent carboxylic acid (DIC) and trivalent or higher polyvalent carboxylic acid (TC). (DIC) alone and (DIC) with a small amount of (TC) Mixtures are preferred.
Divalent carboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (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 polyvalent carboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polyhydric carboxylic acid (PC), you may make it react with polyhydric alcohol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).
The ratio of the polyhydric alcohol (PO) to the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. Is 1.5 / 1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  The polycondensation reaction of polyhydric alcohol (PO) and polycarboxylic acid (PC) is performed at 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, while reducing the pressure as necessary. The produced water is distilled off to obtain a polyester having a hydroxyl group. The hydroxyl value of the polyester is preferably 5 or more, and the acid value of the polyester is usually 1 to 30, preferably 5 to 20. By giving an acid value in a specific range, it tends to be negatively charged, and when fixing to a recording paper, the affinity between the recording paper and the toner is good and the low-temperature fixability is improved. However, when the acid value exceeds 30 (mgKOH / g), there is a tendency to deteriorate with respect to the stability of charging, particularly environmental fluctuation.

  The weight average molecular weight is 10,000 to 400,000, preferably 20,000 to 200,000. A weight average molecular weight of less than 10,000 is not preferable because offset resistance deteriorates. On the other hand, if it exceeds 400,000, the low-temperature fixability is deteriorated.

  In addition to the unmodified polyester obtained by the above polycondensation reaction, the polyester preferably contains a urea-modified polyester. The urea-modified polyester is obtained by reacting a terminal carboxyl group or hydroxyl group of the polyester obtained by the above polycondensation reaction with a polyvalent isocyanate compound (PIC) to obtain a polyester prepolymer (A) having an isocyanate group. It is obtained by cross-linking and / or extending the molecular chain by the reaction of the amine with amines.

  Examples of the polyvalent isocyanate compound (PIC) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate). Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanates; And those blocked with caprolactam; and combinations of two or more of these.

  The ratio of the polyvalent isocyanate compound (PIC) is usually 5/1 to 1/1, preferably as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a urea-modified polyester is used, the urea content in the ester is lowered and hot offset resistance is deteriorated.

  The content of the polyvalent isocyanate compound (PIC) component in the polyester prepolymer (A) having an isocyanate group is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. %. 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 polyester prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2 on average. Five. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  Next, as amines (B) to be reacted with the polyester prepolymer (A), a divalent amine compound (B1), a trivalent or higher polyvalent amine compound (B2), an amino alcohol (B3), an amino mercaptan (B4) ), Amino acid (B5), and amino acid block of B1 to B5 (B6).

  Examples of the divalent amine compound (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.

  Examples of the trivalent or higher polyvalent amine compound (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. Examples of the compound (B6) obtained by blocking the amino group of B1 to B5 include ketimine compounds and oxazolidine compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

 Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

   The ratio of amines (B) is equivalent to the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the polyester prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). 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 more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.

The urea-modified polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.
The urea-modified polyester is produced by a one-shot method or the like. Polyhydric alcohol (PO) and polyvalent carboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and water generated while reducing the pressure as necessary. Distill off to obtain a polyester having a hydroxyl group. Subsequently, at 40-140 degreeC, this is made to react with polyvalent isocyanate (PIC), and the polyester prepolymer (A) which has an isocyanate group is obtained. Further, this (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a urea-modified polyester.

When reacting the polyvalent isocyanate (PIC) and reacting the polyester prepolymer (A) and the amines (B), a solvent may be used as necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to isocyanates (PIC), such as tetrahydrofuran (such as tetrahydrofuran).
In addition, in the crosslinking reaction and / or extension reaction between the polyester prepolymer (A) and the amines (B), a reaction terminator may be used as necessary to adjust the molecular weight of the resulting urea-modified polyester. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

   The weight average molecular weight of the urea-modified polyester is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester or the like is not particularly limited when the above-mentioned unmodified polyester is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. When the urea-modified polyester is used alone, its number average molecular weight is usually 2000-15000, preferably 2000-10000, more preferably 2000-8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

By using the unmodified polyester and the urea-modified polyester in combination, the low-temperature fixability and the glossiness when used in a full-color image forming apparatus are improved. Therefore, it is preferable to use the urea-modified polyester alone. In addition, polyester modified by chemical bonds other than urea bonds may be included.
The unmodified polyester and the urea-modified polyester are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, it is preferable that the unmodified polyester and the urea-modified polyester have a similar composition.
The weight ratio of unmodified polyester to urea-modified polyester is usually 20/80 to 95/5, preferably 70/30 to 95/5, more preferably 75/25 to 95/5, and particularly preferably 80 /. 20-93 / 7. When the weight ratio of the urea-modified polyester is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The glass transition point (Tg) of the binder resin containing unmodified polyester and urea-modified polyester is usually 45 to 65 ° C, preferably 45 to 60 ° C. If it is less than 45 ° C., the heat resistance of the toner deteriorates, and if it exceeds 65 ° C., the low-temperature fixability becomes insufficient. In addition, since the urea-modified polyester is likely to be present on the surface of the obtained toner base particles, the heat-resistant storage stability tends to be good even when the glass transition point is low as compared with known polyester-based toners.

(Coloring agent)
As the colorant, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher , Yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sayred, Parachlor Ortonito Aniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, 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, Thio Indigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red 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, chromium oxide, pyridian, emerald green, pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Lid Russian nin green, anthraquinone green, titanium oxide, zinc white, litbon 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 can also be used as a master batch combined with a resin. As a binder resin to be kneaded with the production of the master batch or the master batch, a polymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene or the like, or a copolymer of these and a vinyl compound, Polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be mentioned, and these can be used alone or in combination.

(Release agent)
The toner base particles used in the toner of the present invention contain a wax as a release agent in order to give the developer releasability. Such a wax as a release agent has a melting point of 40 to 120 ° C., particularly preferably 50 to 110 ° C. When the melting point of the wax is excessive, the fixing property at a low temperature may be insufficient. On the other hand, when the melting point is excessively low, the offset resistance and durability may be decreased. The melting point of the wax can be determined by a differential scanning calorimeter (DSC). That is, the melting peak value when a sample (wax) of several mg is ripened at a constant temperature increase rate, for example, (10 ° C./min) is defined as the melting point. The content of the wax in the toner containing the wax is preferably 1.0 to 15.0% by weight, and more preferably 2.5 to 12.5% by weight.

  Examples of the wax that is a release agent that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketone, fatty acid metal salt wax, and fatty acid ester. And waxes, partially saponified fatty acid ester waxes, silicone varnishes, higher alcohols and carnauba waxes. Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used. Particularly, a polyolefin having a softening point of 70 to 150 ° C. by the ring and ball method is preferable, and a polyolefin having a softening point of 120 to 150 ° C. is more preferable.

(Charge control agent)
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, Bontron 03 of a nigrosine dye, Bontron P-51 of a quaternary ammonium salt, Bontron S-34 of a metal-containing azo dye, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex , Phenolic condensate E-89 (above, Orient Chemical Industries, Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy Charge PSY VP2038, 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) Manufactured), copper phthalocyanine, perylene, quinacridone, azo series Fee, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as quaternary ammonium salts. Of these, substances that control the negative polarity of the toner are particularly preferably used.

  The amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not limited to a specific one. Preferably, it is 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 charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is lowered, and the image density is lowered. Invite. The charge control agent and the release agent may be melt-kneaded together with the master batch and the binder resin, or may be added when dissolved and dispersed in an organic solvent.

  Next, a toner manufacturing method will be described. Here, although a preferable manufacturing method is shown, the present invention is not limited to this.

[Toner Production Method]
(1) A toner material solution is prepared by dispersing a colorant, unmodified polyester, a polyester prepolymer having an isocyanate group, and a release agent in an organic solvent.
The organic solvent is preferably volatile with a boiling point of less than 10 ° C. from the viewpoint of easy removal after toner base particle formation. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, Methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. The usage-amount of an organic solvent is 0-300 weight part normally with respect to 100 weight part of polyester prepolymers, Preferably it is 0-100 weight part, More preferably, it is 25-70 weight part.

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

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

Preferred anionic surfactants having a fluoroalkyl group include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C _6- C ₁₁ ) oxy] -1-alkyl (C ₃ -C ₄ ) sodium sulfonate, 3- [ω-fluoroalkanoyl (C ₆ -C ₈ ) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl _(C 11 ~C ₂₀₎ carboxylic acids and metal salts thereof, perfluoroalkyl carboxylic acids _(C 7 _{~C 13)} and metal salts thereof, perfluoroalkyl _(C 4 _{~C 12)} sulfonic acids and metal salts thereof, perfluorooctane Sulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctane sulfonamide, perfluoroalkyl _(C 6 _{~C 10:} Number 6-10) sulfonamide propyl trimethyl ammonium salts atoms, perfluoroalkyl _{(C 6 ~C} 10) -N- ethylsulfonyl glycine salts, mono and perfluoroalkyl _(C 6 _{~C 16)} ethyl phosphates.
As a trade name, Surflon S-111, S-112, S-113 (above, Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (above, made by Sumitomo 3M), Unidyne DS-101, DS-102 (above, Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (above, Dainippon Ink Co., Ltd.) ), Ectop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, manufactured by Tochem Products), aftergent F-100, F150 (above, Neos) Manufactured).

In addition, examples of the cationic surfactant include aliphatic quaternary compounds such as aliphatic primary, secondary or secondary amine acids having fluoroalkyl groups, and perfluoroalkyl (C ₆ -C ₁₀ ) sulfonamidopropyltrimethylammonium salts. Ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 ( Daikin-E Industries Co., Ltd.), Mega-Fac F-150, F-824 (above, Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), etc. Can be mentioned.

As the resin fine particles, the aforementioned substances can be used. In addition, inorganic compound dispersants such as tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite can also be used.
As a dispersant that can be used in combination with the above resin fine particles and inorganic compound dispersant, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxypropyl , 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Luric acid esters, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and a carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl Nitrogen compounds such as imidazole and ethyleneimine, or homopolymers or copolymers such as those having a heterocyclic ring thereof, polyoxyethylene, poly Xoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable in order to make the particle size of the dispersion 2 to 20 μm. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C.

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

(4) After completion of the reaction, the organic solvent is removed from the emulsified dispersion (reactant), washed and dried to obtain toner base particles.
In order to remove the organic solvent, the temperature of the entire system is gradually raised in a laminar stirring state, and after giving strong stirring in a certain temperature range, the solvent base is removed to produce spindle-shaped toner base particles. . Further, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is dissolved from the toner base particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. Remove. It can also be removed by operations such as enzymatic degradation.
Either before or after the washing and solvent-removing steps, a step can be provided in which the emulsified dispersion is allowed to stand at a certain temperature for a certain period of time and the produced toner particles are aged. Thereby, toner particles having a desired particle diameter can be produced. The temperature of the aging step is preferably 25 to 50 ° C., and the time is preferably 10 minutes to 23 hours.

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

  The toner of the present invention can be mixed with a magnetic carrier and used as a two-component developer. In this case, the carrier to toner content ratio in the developer is preferably 1 to 10 parts by weight of toner with respect to 100 parts by weight of carrier. 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 100 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 styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride and non- Monomers including a fluoro terpolymers such, 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.
As a method for forming the resin layer, the resin may be applied to the surface of the carrier core particle by means of a spraying method, a dipping method, or the like, as in the past. Examples include tilting pan by rolling, drum, fluidized bed, movable spray, fluidized bed by aeration (spray drying, vibration, draft pipe, movable draft pipe), spouted bed (jet fluidized bed), rolling fluidized bed (with slits) The carrier core material is coated with resin by a rotating disk) or by stirring and mixing (stirring blade, high-speed shearing, vertical stirring blade, eccentric stirring blade).

   Furthermore, the coated carrier used in the present invention may be one in which a conductive material is dispersed in the coating layer in order to adjust carrier resistance. Specific examples of the conductive material in this case include the following. These conductive materials 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.

(A) White conductive material ETC-52 (TiO ₂ series) Titanium Industry Co., Ltd. KV400 (TiO ₂ series) Titanium Industry Co., Ltd. ECR-72 (TiO ₂ series) Titanium Industry Co., Ltd. ECTR-82 (TiO ₂ series) Titanium 500 W (TiO ₂ system) manufactured by Kogyo Co., Ltd. 300 W (TiO ₂ system) manufactured by Ishihara Sangyo Co., Ltd. S-1 (TiO ₂ system) manufactured by Ishihara Sangyo Co., Ltd. W-1 (SnO ₂ system) 23 K (ZnO) manufactured by Mitsubishi Metal Corporation ) Conductive zinc white no. 1 (ZnO) Honjo Chemical Co., Ltd., conductive zinc white 2 (ZnO) Honjo Chemical Co., Ltd. W-10 (TiO_ system) Mitsubishi Metals Co., Ltd. Dentor WK-100 (conductive fiber) Otsuka Chemical Co., Ltd. Dentor WK-200 (conductive fiber) Otsuka Chemical Co., Ltd. Dentor WK-300 (conductive fiber) manufactured by Otsuka Chemical Co. MEC300 (SnO ₂ system) Teikoku Kako Co. MEC500 (SnO ₂ system) Teikoku Kako Co.

(B) Carbon Black Pearls 2000, VULCANXC-72 (above, manufactured by Cabot), Ketjen black EC / DJ500, Ketjen black EC / DJ600 (above, made by Lion Akzo), Denka black granular, Denka black powder (above, CONDUCTEX 975, CONDUCTEX SC (above, Columbia Carbon Co., Ltd.)

  Further, a coupling agent may be added to the coating layer. The addition of this coupling agent improves the adhesion between the carrier core material and the coating layer, and the layer does not peel off even when the developing part is stirred. In addition, the charge amount can be adjusted. For example, the charge amount is hardly generated under the influence of moisture under high temperature and high humidity conditions, but a good charge amount can be secured by adding a coupling agent.

   Examples of silane coupling agents include trade names: SH6020 (γ- (2-aminoethyl) aminopropyltrimethoxysilane), SZ6023 (γ- (2-aminoethyl) aminopropylmethyldimethoxysilane), SH6026 (aminosilane). , SZ6030 (γ-methacryloxypropyltrimethoxysilane), SZ6032 (N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride), SZ6050 (aminosilane), SZ6040 (γ-glycol) Sidoxypropyltrimethoxysilane), SH6062 (γ-mercaptopropyltrimethoxysilane), SZ6070 (methyltrimethoxysilane), SZ6072 (methyltriethoxysilane), SZ6075 (vinyltriacetoxysilane), S 6076 (γ-chloropropyltrimethoxysilane), SZ6079 (hexamethyldisilazane), SZ6083 (γ-anilinopropyltrimethoxysilane) and the like are manufactured by Toray Dow Corning Silicone, KA1003 (vinylchlorosilane), KBC1003 (Vinyltris (βmethoxyethoxy) silane), KBM1003 (vinyltrimethoxysilane), KBE1003 (vinyltriethoxysilane), KBM503 (γ-methacryloxypropyltrimethoxysilane), KBM303 (β- (3,4 epoxy cyclohexyl) ethyl Trimethoxysilane), KBM403 (γ-glycidoxypropyltrimethoxysilane), KBM402 (γ-glycidoxypropylmethylethoxysilane), KBM603 (N-β (aminoethyl) γ-aminopropyltrimethoxysilane), KBM602 (N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane), KBM903 (γ-aminopropyltriethoxysilane), KBM803 (γ-mercaptopropyltrimethoxysilane), KBM573 (N-phenyl-γ-aminopropyltrimethoxysilane), KBM703 (γ-chloropropyltrimethoxysilane), etc. manufactured by Shin-Etsu Chemical Co., Ltd., aluminum-based coupling agents, and titanium-based coupling agents may be used. .

  Moreover, the same material as the material which coat | covers a carrier core material can be used for a magnetic body dispersion type carrier particle. Examples of the magnetic fine powder include any material exhibiting magnetic sensitivity. For example, metals such as iron, nickel and cobalt, metal oxides, alloys and the like. Often used materials include triiron tetroxide, iron sesquioxide, cobalt-added iron oxide, ferrite, and nickel fine powder. In some cases, the magnetic fine powder may be a colored magnetic substance. The toner of the present invention may be used as a one-component magnetic toner by containing a magnetic material without using a carrier, or may be used as a one-component non-magnetic toner without containing a magnetic material. it can.

An image forming apparatus using the toner of the present invention as a developer will be described.
As shown in FIG. 2, it is wound around three support rollers 14 to 16 so that it can be rotated and conveyed clockwise in the figure. In this example, an intermediate transfer body cleaning device 17 (not shown) that removes residual toner remaining on the intermediate transfer body 10 after image transfer can be provided on the left of the second support roller 15 among the three. Further, four images of yellow, cyan, magenta, and black are arranged on the intermediate transfer member 10 stretched between the first support roller 14 and the second support roller 15 among the three along the conveyance direction. The tandem image forming apparatus 20 can be configured by arranging the forming units 18 side by side.

  An exposure apparatus 21 can be further provided on the tandem image forming apparatus 20 as shown in FIG. On the other hand, a secondary transfer device 22 can be provided on the side opposite to the tandem image forming apparatus 20 with the intermediate transfer body 10 interposed therebetween. In the illustrated example, the secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23 (one roller also serves as a transfer roller). The image on the intermediate transfer body 10 is transferred by the transfer roller 23 via the sheet. A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt (not shown) which is an endless belt.

  The secondary transfer device 22 described above is also provided with a sheet transport function for transporting the image-transferred sheet to the fixing device 25. In the illustrated example, a sheet for reversing the sheet so as to record an image on both sides of a sheet (not shown) is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming device 20 described above. A reversing device 28 is provided.

  When copying using this color electrophotographic apparatus, an original is set on the original table 30 of the automatic original conveying apparatus 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. At that time, the scanner 300 is immediately driven to travel the first traveling body 33 and the second traveling body 34. Then, the first traveling body 33 emits light from the light source and further reflects the reflected light from the document surface toward the second traveling body 34, and is reflected by the mirror of the second traveling body 34 and passes through the imaging lens 35. It puts in the reading sensor 36 and reads the contents of the document. When a start switch (not shown) is pressed, one of the support rollers 14 to 16 is rotationally driven by a drive motor (not shown), the other two support rollers are driven to rotate, and the intermediate transfer body 10 is rotated and conveyed. At the same time, the individual image forming means 18 rotates the photoconductor 40 to form black, yellow, magenta, and cyan monochrome images on each photoconductor 40. Then, along with the conveyance of the intermediate transfer member 10, the single color images are sequentially transferred to form a composite color image on the intermediate transfer member 10.

  On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, and the sheet is fed out from one of the paper feed cassettes 44 provided in multiple stages in the paper bank 43, and the separation roller 45. Then, the sheets are separated one by one into the paper feed path 46, transported by the transport roller 47, guided to the paper feed path 48 in the copying machine main body 100, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 50 (not shown) is rotated to feed out the sheets on the manual feed tray (not shown), separated one by one by a separation roller (not shown), and put into the manual feed path 53 (not shown). Similarly, it abuts against the registration roller 49 and stops. Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer member 10, the sheet is fed between the intermediate transfer member 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet.

  The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image, and then the switching claw 55 (not shown). The sheet is switched and discharged by the discharge roller, and stacked on the discharge tray 57. Alternatively, it is switched by a switching claw (not shown) and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller. .

  On the other hand, the intermediate transfer body 10 after the image transfer is removed by the intermediate transfer body cleaning device 17 to remove residual toner remaining on the intermediate transfer body 10 after the image transfer, so that the tandem image forming apparatus 20 can prepare for another image formation. Here, the registration roller 49 is generally used while being grounded, but it is also possible to apply a bias for removing paper dust from the sheet.

  In the present invention, it is preferable to use the image forming apparatus as described above as the image forming method, but it is preferable to carry out the image forming method using such an image forming apparatus. Such an image forming method of the present invention includes a charging step for uniformly charging an electrostatic latent image carrier, an image exposure step for forming a latent image on the uniformly charged electrostatic latent image carrier, A developing step of developing the latent image formed using the developer, a step of transferring the developed image, and a cleaning step of removing the residual developer of the electrostatic latent image carrier after the transfer. . In such an image forming method of the present invention, the above-described one-component developer or the two-component developer composed of the above-described carrier and the toner of the present invention is used as the developer in the above-described development step. In the image forming method of the present invention, the cleaning step is preferably a blade cleaning method.

The process cartridge of the present invention integrally supports an image carrier that carries an electrostatic latent image and at least a developing device that is disposed to face the image carrier that carries an electrostatic latent image, thereby forming an image. It is a process cartridge that can be attached to and detached from the device body.
This process cartridge preferably has the above-described toner or developer.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, it cannot be overemphasized that this invention is restrained by description of these Examples, and is not interpreted. In addition, unless otherwise indicated,% and a part represent weight% and a weight part.

Example 1
(1) First toner Binder resin Partially crosslinked polyester resin 100 parts (condensation polymer of bisphenol A ethylene oxide addition alcohol, bisphenol A propylene oxide addition alcohol, terephthalic acid, trimellitic acid: MW 15000, glass transition temperature 61 ℃)
Release agent: Carnauba wax 5 parts Charge control agent: Azo complex dye 2 parts Colorant: Carbon black (# 44, manufactured by Mitsubishi Chemical Corporation) 13 parts

The mixture having the above composition is kneaded for 30 minutes with a two-roll kneader heated to 110 ° C., and then pulverized and classified with a mechanical pulverizer / airflow classifier to adjust toner base particles having an average particle size of 7.0 μm. A was obtained. The toner base particles A have a circularity of 0.92, SF-1 = 165, and SF-2 = 156.
To 100 parts of toner base particle A, 1.2 parts of silica fine powder (dimethylsiloxane treatment) with an average particle diameter of 120 nm and 0.7 parts of silica fine powder with an average particle diameter of 15 nm (dimethylsiloxane) are Henschel mixer. The first toner (black toner A) was prepared by mixing at a peripheral speed of 20 m / sec.

(2) Second toner A toner base particle B was obtained by treating the toner base particle A with a hybridizer manufactured by Nara Machine for 40 minutes at 12,000 rpm. The toner base particles B have a circularity of 0.97, SF-1 = 131, and SF-2 = 121.
To 100 parts of toner base particle B, 0.3 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm and 0.9 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 15 nm were added to a Henschel mixer. The second toner (black toner B) was prepared by mixing at a peripheral speed of 20 m / sec.
(3) Preparation of Toner of the Present Invention Mixing is carried out for 2 minutes at 20 m / sec with a Henschel mixer at a ratio of 30 parts for the first toner and 70 parts for the second toner. After mixing, it was passed through a 63 μm sieve to prepare Black Toner C.

(4) Preparation of carrier On the other hand, the carrier prepared the coating liquid by the following prescription.
300 parts of silicone resin (SR2411: solid content 20%, manufactured by Torre Dow Corning)
Aminosilane 3.5 parts (SH6020: manufactured by Toray Dow Corning Silicone)
1200 parts of toluene

  1503.5 g of the above coating solution was placed in a rotating disk type fluidized bed coating apparatus together with 5 kg of a ferrite core material / carrier having an average particle diameter of 50 μm to coat the carrier. Thereafter, this coating was taken out from the apparatus, heated at 250 ° C. for 2 hours, and the film was aged to prepare a carrier.

(5) Preparation of a two-component developer Using the toner C and carrier described above, a two-component developer is prepared by measuring the toner and carrier so that the total amount of toner and carrier is 1000 g. did.

(6) Evaluation Using imagi Neo 451 (Ricoh Co., Ltd.), the above-mentioned two-component developer was set in this machine and an initial image was produced. As a result, a good image was obtained. Thereafter, 100,000 continuous sheets of A4 paper were fed in the horizontal direction. The evaluation results are shown in Table 1.

Example 2
In Example 1, the two-component developer is the same as Example 1 except that the mixing ratio of the first toner and the second toner is changed to 5 parts of the first toner and 95 parts of the second toner. It was created. The evaluation results are shown in Table 1.

Example 3
In Example 1, the two-component developer is the same as Example 1 except that the mixing ratio of the first toner and the second toner is changed to 65 parts of the first toner and 35 parts of the second toner. It was created. The evaluation results are shown in Table 1.

Example 4
In Example 1, the toner base particles A were treated at 12,000 rpm for 15 minutes using a hybridizer manufactured by Nara Machinery. The toner base particles have a circularity of 0.95, SF-1 = 140, and SF-2 = 132. Except for this, a two-component developer was prepared in the same manner as in Example 1 and tested in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 5
In Example 1, 1.1 parts of silica fine powder having an average particle diameter of 120 nm (dimethylsiloxane treatment) as an external additive and 100 parts of silica fine powder having an average particle diameter of 25 nm (dimethylsiloxane) are added to 100 parts of toner base particle A. 8 parts were mixed with a Henschel mixer at a peripheral speed of 20 m / sec to prepare a new first toner.
On the other hand, 0.3 part of silica fine powder (dimethylsiloxane treatment) with an average particle diameter of 120 nm and 0.6 part of silica fine powder with an average particle diameter of 25 nm (dimethylsiloxane) are added to 100 parts of the toner base particle B. A new second toner was prepared by mixing at a peripheral speed of 20 m / sec with a mixer.
A two-component developer was prepared in the same manner as in Example 1 except that these new first toner and new second toner were used, and tested in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 6
In Example 1, 1.1 parts of silica fine powder having an average particle diameter of 120 nm (dimethylsiloxane treatment) as an external additive and 100 parts of silica fine powder having an average particle diameter of 5 nm (dimethylsiloxane) are added to 100 parts of toner base particle A. .5 parts were mixed with a Henschel mixer at a peripheral speed of 20 m / sec to prepare a new first toner.
On the other hand, with respect to 100 parts of toner base particles B, 0.3 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm and 0.4 part of silica fine powder (dimethylsiloxane) having an average particle diameter of 5 nm were added to Henschel. A new second toner was prepared by mixing at a peripheral speed of 20 m / sec with a mixer.
A two-component developer was prepared in the same manner as in Example 1 except that these new first toner and new second toner were used, and tested in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 7
In Example 1, 4.0 parts of silica fine powder having an average particle size of 120 nm (dimethylsiloxane treatment) as an external additive with respect to 100 parts of toner base particles A and silica fine powder having a mean particle size of 15 nm (dimethylsiloxane) 1 3 parts were mixed with a Henschel mixer at a peripheral speed of 20 m / sec to prepare a new first toner.
On the other hand, with respect to 100 parts of toner base B, 0.7 parts of silica fine powder (dimethylsiloxane treatment) with an average particle diameter of 120 nm and 1.3 parts of silica fine powder with an average particle diameter of 15 nm (dimethylsiloxane) are obtained using a Henschel mixer. A new second toner was prepared by mixing at a peripheral speed of 20 m / sec.
A two-component developer was prepared in the same manner as in Example 1 except that these new first toner and new second toner were used, and tested in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 8
In Example 1, 0.8 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm as an external additive and 100 parts of silica fine powder (dimethylsiloxane basis) having an average particle diameter of 15 nm were added to 100 parts of the toner base particles A. 2 parts were mixed with a Henschel mixer at a peripheral speed of 20 m / sec to prepare a new first toner.
On the other hand, 0.1 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm and 0.7 part of silica fine powder (dimethylsiloxane) having an average particle diameter of 15 nm are added to 100 parts of toner base particle B. Then, a new second toner was prepared by mixing with a Henschel mixer at a peripheral speed of 20 m / sec.
A two-component developer was prepared in the same manner as in Example 1 except that these new first toner and new second toner were used, and tested in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 9
(1) First Toner In Example 1, toner base particles A having an average particle diameter of 7.0 μm to 4.1 μm were obtained. The toner base particles A have a circularity of 0.92, SF-1 = 161, and SF-2 = 154. With respect to 100 parts of the toner base particles A, 1.9 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm and 1.1 parts of silica fine powder (dimethylsiloxane) having an average particle diameter of 15 nm are obtained. A new first toner was prepared by mixing with a Henschel mixer at a peripheral speed of 20 m / sec.

(2) Second Toner Toner base particle B was obtained by using a hybridizer manufactured by Nara Machine on 4.1 μm toner base particle A and treating it at 12,000 rpm for 40 minutes. The toner base particles B have a circularity of 0.97, SF-1 = 138, and SF-2 = 129. For 100 parts of the toner base particles B, 0.7 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm and 1.3 parts of silica fine powder (dimethylsiloxane) having an average particle diameter of 15 nm are added to Henschel. A new second toner was prepared by mixing at a peripheral speed of 20 m / sec with a mixer.

(3) Preparation and Evaluation of Toner of the Present Invention Mixing is performed for 2 minutes at 20 m / sec with a Henschel mixer at a ratio of 30 parts of the new first toner and 70 parts of the new second toner. After that, a two-component developer was prepared in the same manner as in Example 1 except that the toner was prepared by passing through a 63 μm sieve and tested in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 10
In Example 1, a toner and a carrier were prepared in the same manner as in Example 1 except that the charge control agent of the toner was changed from an azo metal complex dye to a salicylic acid metal derivative (E-84: manufactured by Orient Chemical Co., Ltd.). When tested in the same manner as in Example 1, the evaluation results shown in Table 1 were obtained.

Example 11
In Example 1, a toner and a carrier were prepared in the same manner as in Example 1 except that the charge control agent of the toner was changed from an azo metal complex dye to a fluorine-containing quaternary ammonium salt (copy charge NXVP434: manufactured by Hoechst). When tested in the same manner as in Example 1, the evaluation results shown in Table 1 were obtained.

Example 12
In Example 1, 100 parts of toner base particle A, 3.2 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm as an external additive, and silica fine powder (dimethylsiloxane texture) 1 having an average particle diameter of 15 nm are used. .2 parts and 0.5 parts of titanium fine powder having a particle size of about 15 nm whose surface was treated with isobutyltrimethoxysilane were mixed at a peripheral speed of 20 m / sec with a Henschel mixer to obtain a new first toner. Created.
On the other hand, with respect to 100 parts of toner base particle B, 0.7 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm, 1.1 parts of silica fine powder having an average particle diameter of 15 nm (dimethylsiloxane), A new second toner was prepared by mixing 0.5 parts of titanium fine powder having a particle diameter of about 15 nm, the surface of which was treated with isobutyltrimethoxysilane, at a peripheral speed of 20 m / sec using a Henschel mixer.
A two-component developer was prepared in the same manner as in Example 1 except that these new first toner and new second toner were used, and tested in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 13
An example of color toner will be described.
(1) Production of masterbatch pigment Production example 1 of yellow toner masterbatch
Binder resin: 50 parts of polyester resin A (polyester resin synthesized from ethylene oxide adduct of bisphenol A, terephthalic acid, fumaric acid, softening point: 95 ° C.)
Colorant 50 parts (Imidazolone yellow pigment: CI Pigment Yellow 180)
30 parts of water After mixing the said raw material with a Henschel mixer, it knead | mixed for 30 minutes with the two rolls which set roll surface temperature to 110 degreeC, and obtained the masterbatch pigment A.

2. Production example 2 of magenta toner master batch
Binder resin: 50 parts of polyester resin A (polyester resin synthesized from ethylene oxide adduct of bisphenol A, terephthalic acid, fumaric acid, softening point: 95 ° C.)
50 parts of colorant (quinacridone magenta pigment: CI Pigment Red 122)
30 parts of water The above raw materials were mixed with a Henschel mixer, and then kneaded for 30 minutes with two rolls set at a roll surface temperature of 110 ° C. to obtain a master batch pigment B.

3. Cyan toner master batch production example 3
Binder resin: 50 parts of polyester resin A (polyester resin synthesized from ethylene oxide adduct of bisphenol A, terephthalic acid, fumaric acid, softening point: 95 ° C.)
50 parts of colorant (copper phthalocyanine cyan pigment: CI Pigment Blue 15: 3)
30 parts of water After mixing the above-mentioned raw materials using a Henschel mixer, 30 kneading was performed with two rolls set at a roll surface temperature of 110 ° C., and master batch pigment C was obtained.

4). Black toner masterbatch production example 4
Binder resin: 50 parts of polyester resin A (polyester resin synthesized from ethylene oxide adduct of bisphenol A, terephthalic acid, fumaric acid, softening point: 95 ° C.)
Colorant 50 parts (carbon black pigment: CI Pigment Bullack 1)
30 parts of water After mixing the said raw material with a Henschel mixer, it knead | mixed for 30 minutes with the 2 roll which set roll surface temperature to 110 degreeC, and obtained the masterbatch pigment D.

(2) Preparation of amorphous toner base particles Yellow toner, magenta toner, cyan toner and black toner were prepared for each master batch pigment A, B, C and D according to the following formulation.
Binder resin: 100 parts of polyester resin A (polyester resin synthesized from ethylene oxide adduct of bisphenol A, terephthalic acid, fumaric acid, Mw / Mn = 1.1, softening point: 95 ° C.)
Colorant: Masterbatch pigment (each A to D) 15 parts Release agent (carnauba wax: melting point 92 ° C.) 5 parts Charge control agent (salicylic acid derivative zinc salt) 2.5 parts

  The raw materials were mixed with a Henschel mixer and then melt-kneaded for 30 minutes using a three-roll kneader set at 110 ° C. The kneaded product is cooled with water, coarsely pulverized with a cutter mill, pulverized with a fine pulverizer using a jet stream, and then used with an air classifier to prepare a yellow toner base particle D, a magenta toner base particle E, and a cyan with a particle size of 6.3 μm. Toner base particles F and black toner base particles G were prepared.

(3) Preparation of irregular toner The circularity of the yellow toner base particles D is 0.92, SF-1 = 158, and SF-2 = 150.
With respect to 100 parts of yellow toner base particles D, 1.5 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm, 0.9 parts of silica fine powder (dimethylsiloxane) having an average particle diameter of 15 nm, surface A yellow toner D was prepared by mixing 0.4 parts of titanium fine powder having a particle diameter of about 15 nm treated with isobutyltrimethoxysilane at a peripheral speed of 20 m / sec using a Henschel mixer.

The circularity of the magenta toner base particle E is 0.92, SF-1 = 161, and SF-2 = 151.
With respect to 100 parts of magenta toner base particles E, 1.5 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm, 0.9 parts of silica fine powder (dimethylsiloxane) having an average particle diameter of 15 nm, surface A magenta toner E was prepared by mixing 0.4 parts of titanium fine powder having a particle diameter of about 15 nm treated with isobutyltrimethoxysilane at a peripheral speed of 20 m / sec using a Henschel mixer.

The circularity of the cyan toner base particles F is 0.93, SF-1 = 160, and SF-2 = 151.
With respect to 100 parts of the sheer toner base particles F, 1.5 parts of silica fine powder (dimethylsiloxane treatment) with an average particle diameter of 120 nm, 0.9 parts of silica fine powder with an average particle diameter of 15 nm (dimethylsiloxane), Cyan toner F was prepared by mixing 0.4 parts of titanium fine powder having a particle diameter of about 15 nm treated with isobutyltrimethoxysilane at a peripheral speed of 20 m / sec using a Henschel mixer.

The circularity of the black toner base particles G is 0.94, SF-1 = 159, and SF-2 = 150.
With respect to 100 parts of black toner base particles G, 1.5 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm, 0.9 parts of silica fine powder (dimethylsiloxane) having an average particle diameter of 15 nm, surface A black toner G was prepared by mixing 0.4 parts of titanium fine powder having a particle diameter of about 15 nm treated with isobutyltrimethoxysilane at a peripheral speed of 20 m / sec using a Henschel mixer.

(4) Preparation of Spherical Toner 12,000 by using a hybridizer manufactured by Nara Machinery Co., Ltd. on each of the toner base particles of yellow toner base particles D, magenta toner base particles E, cyan toner base particles F and black toner base particles G. By processing for 40 minutes by rotation, yellow toner base particles H, magenta toner base particles I, cyan toner base particles J and black toner base particles K were prepared.

The circularity of the yellow toner base particles H is 0.95, SF-1 = 135, and SF-2 = 121.
For 100 parts of yellow toner base particles H, 0.6 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm, 0.7 parts of silica fine powder (dimethylsiloxane) having an average particle diameter of 15 nm, surface A yellow toner H was prepared by mixing 0.5 parts of titanium fine powder having a particle diameter of about 15 nm treated with isobutyltrimethoxysilane at a peripheral speed of 20 m / sec using a Henschel mixer.

The magenta base particle I has a circularity of 0.95, SF-1 = 136, and SF-2 = 122.
100 parts of magenta toner base particles I, 0.6 parts of silica fine powder having an average particle diameter of 120 nm (dimethylsiloxane treatment), 0.7 parts of silica fine powder having an average particle diameter of 15 nm (dimethylsiloxane), Magenta toner I was prepared by mixing 0.5 parts of titanium fine powder having a particle size of about 15 nm treated with isobutyltrimethoxysilane at a peripheral speed of 20 m / sec using a Henschel mixer.

The circularity of the cyan toner base particles J is 0.95, SF-1 = 134, and SF-2 = 119.
0.6 parts of silica fine powder (dimethylsiloxane treatment) with an average particle diameter of 120 nm, 0.7 parts of silica fine powder (dimethylsiloxane) with an average particle diameter of 15 nm, and 100 parts of cyan toner base particles J Cyan toner J was prepared by mixing 0.5 parts of titanium fine powder having a particle diameter of about 15 nm treated with isobutyltrimethoxysilane at a peripheral speed of 20 m / sec using a Henschel mixer.

The black toner base particles K have a circularity of 0.96, SF-1 = 133, and SF-2 = 118.
With respect to 100 parts of black toner base particles K, 0.6 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm, 0.7 parts of silica fine powder (dimethylsiloxane) having an average particle diameter of 15 nm, surface A black toner K was prepared by mixing 0.5 parts of a fine titanium powder having a particle diameter of about 15 nm treated with isobutyltrimethoxysilane at a peripheral speed of 20 m / sec using a Henschel mixer.

  30 parts of the yellow toner D and 70 parts of the yellow toner H were mixed with a Henschel mixer at 20 m / sec for 2 minutes. After mixing, yellow toner L was prepared by passing through a 63 μm sieve.

  30 parts of the magenta toner E and 70 parts of magenta toner I were mixed at 20 m / sec with a Henschel mixer for 2 minutes. After mixing, a magenta toner M was prepared by passing through a 63 μm sieve.

  30 parts of the cyan toner F and 70 parts of the cyan toner J were mixed with a Henschel mixer at 20 m / sec for 2 minutes. After mixing, a cyan toner N was prepared by passing through a 63 μm sieve.

  The black toner G is 30 parts and the black toner K is 70 parts, and mixing is performed at 20 m / sec for 2 minutes using a Henschel mixer. After mixing, a black toner O was prepared by passing through a 63 μm sieve.

On the other hand, the carrier prepared the coating liquid by the following prescription.
300 parts of silicone resin (SR2411, solid content 20%, manufactured by Tore Dow Corning)
Silane coupling agent 10 parts (γ- (2-aminoethyl) aminopropyltotimethoxysilane)
Toluene 1200 parts The above coating liquid 1510 g was put into a rotating disk type fluidized bed coating apparatus together with 5 kg of ferrite core material / carrier having an average particle diameter of 50 μm to coat the carrier. Thereafter, the coating was taken out from the apparatus and heated at 250 ° C. for 2 hours to age the film. Using yellow toner L, magenta toner M, cyan toner N, and black toner O of each color, the toner toner and carrier are weighed so that the total amount of toner and carrier is 1000 g. Thus, yellow, magenta, cyan and black developers were prepared.

  Thereafter, each color developer was set in an imagio Neo C285 (attached with a blade cleaning device / Ricoh copier) machine and an initial image was obtained. As a result, a good image was obtained. Thereafter, 100,000 sheets of A4 paper were continuously fed by horizontal feeding. The results are shown in Table 1.

Example 14
(Example of toner by cross-linking and / or elongation reaction)
1. Production Example of Black Toner Base Particles -Synthesis of Organic Fine Particle Emulsion-
In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30; manufactured by Sanyo Chemical Industries), 166 parts of methacrylic acid, butyl acrylate When 110 parts and 1 part of ammonium persulfate were charged and stirred at 3800 rpm for 30 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 4 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours to obtain an aqueous dispersion of a vinyl resin (methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer). A liquid [fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by a laser diffraction particle size distribution analyzer (LA-920; manufactured by Shimadzu Corporation) 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-
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of a 48.3% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7; manufactured by Sanyo Kasei Kogyo Co., Ltd.) and 90 parts of ethyl acetate were mixed and stirred. A liquid was obtained. This is designated as [Aqueous Phase 1].

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

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

~ Synthesis of ketimine ~
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 mgKOH / g.

~ Master batch synthesis ~
Add 1200 parts of water, 540 parts of carbon black (Printex35; manufactured by Dexa) (DBP oil absorption = 42 ml / 100 mg, pH = 9.5), 1200 parts of polyester resin, and mix with a Henschel mixer (manufactured by Mitsui Mining). The mixture was kneaded at 130 ° C. for 1 hour using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

~ Preparation of oil phase ~
In a container equipped with a stir bar and a thermometer, 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 placed in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw Material Solution 1] 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 (WAX) were dispersed under the conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by two passes with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%.

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

~ Washing, drying ~
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (rotation speed 12,000 rpm for 10 minutes), and then filter twice to perform [filter cake 1]. Obtained.

  [Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating dryer. 100 parts of the base toner particles were mixed with a mixer at a ratio of 0.6 part of zinc salicylate (E-84; manufactured by Orient Chemical Co., Ltd.). Then, black toner base particles were prepared by sieving with a mesh of 75 μm. The toner base particles have a weight average particle diameter (D4) of 6.1 μm, a number average particle diameter (Dn) of 5.5 μm, D4 / Dn = 1.11, an average circularity of 0.97, and a shape factor SF-1 = 135. The shape factor SF-2 = 118.

2. Production Example of Yellow Toner Base Particles In the synthesis of the masterbatch, C.I. I. Yellow toner base particles were prepared in the same manner as in the black toner base particle production example, except that CI Pigment Yellow 180 (PV Fast Yellow HG; manufactured by Clariant) was used.
The toner base particles have a weight average particle diameter (D4) of 6.0 μm, a number average particle diameter (Dn) of 5.4 μm, D4 / Dn = 1.11, an average circularity of 0.97, and a shape factor SF-1 = 132. The shape factor SF-2 = 115.

3. Production Example of Magenta Toner Base Particles In the synthesis of the masterbatch, C.I. I. Magenta toner base particles were prepared in the same manner as in the black toner base particle production example, except that CI Pigment Red 122 (Hostaperm Pink E; manufactured by Clariant) was used.
The toner base particles have a weight average particle diameter (D4) of 6.5 μm, a number average particle diameter (Dn) of 5.6 μm, D4 / Dn = 1.16, an average circularity of 0.96, and a shape factor SF-1 = 137. The shape factor SF-2 = 117.

4). Example of Cyan Toner Base Particles In the master batch synthesis, C.I. I. Cyan toner base particles were prepared in the same manner as in the black toner base particle production example except that CI Pigment Blue 15: 3 (Lionol Blue FG-7351; manufactured by Toyo Ink Co., Ltd.) was used.
The toner base particles have a weight average particle diameter (D4) of 6.2 μm, a number average particle diameter (Dn) of 5.5 μm, D4 / Dn = 1.13, an average circularity of 0.97, and a shape factor SF-1 = 134. The shape factor SF-2 = 115.

~ External additive treatment ~
For each 100 parts of black toner base particles, yellow toner base particles, magenta toner base particles, and cyan toner base particles, 5 parts of zinc salicylate-based metal complex (E-84, manufactured by Orient Chemical Industry Co., Ltd.) was surrounded by a Henschel mixer. Mixing was performed at a speed of 20 m / sec. Thereafter, black toner particles, yellow toner base particles, magenta base particles and cyan base particles were mixed with external additives in the same prescription amounts as in Example 13 to obtain toner of each color. Then, the toners of each color were obtained in the same mixing ratio as in Example 13 using the spherical yellow, magenta, cyan and black toners mixed with the toners H, I, J and K of Example 13. This toner was used and tested as in Example 13. The results are shown in Table 1.

Example 15
(Example of toner by suspension polymerization)
40 parts of styrene monomer, 20 parts of carbon black (MA100, manufactured by Mitsubishi Kasei Co., Ltd.) and 0.5 part of 2,2'-azobisisobutyronitrile as a polymerization initiator are added, and a three-one motor driven stirring blade, cooler, gas The flask was placed in a 500 ml four-necked separable flask equipped with an inlet tube and a thermometer, and stirred for 30 minutes at room temperature under a nitrogen stream, and the inside of the flask was replaced with nitrogen. Thereafter, the mixture was stirred at 60 rpm in a 70 ° C. hot water bath for 6 hours to obtain graft carbon black.

The following mixture was dispersed on a ball mill for 10 hours.
Styrene monomer 50.0 parts n-Butyl methacrylate 14.5 parts 1,3-butanediol dimethacrylate 0.5 parts t-butylacrylamide sulfonic acid 3.0 parts Low molecular weight polyethylene 2.0 parts (Mitsui Petrochemical Co., Ltd.) Mitsui High Wax 210P)
Graft carbon black 30.0 parts

  After dissolving 1 part each of 2,2′-azobisisobutyronitrile and sodium nitrite in this dispersion, it was added to 250 parts of a 2% aqueous solution of polyvinyl alcohol, and TK homomixer (manufactured by Tokushu Kika Co., Ltd.) Was stirred at 6000 rpm for 10 minutes to obtain a suspension.

The suspension was put into a 500 ml four-necked separable flask equipped with a three-one motor-driven stirring blade, a cooler, a gas inlet tube, and a thermometer, and stirred at room temperature for 30 minutes under a nitrogen stream to obtain oxygen in the flask. Was replaced with nitrogen. Thereafter, the mixture was stirred in a hot water bath at 70 ° C. for 8 hours at 90 rpm to complete the polymerization, thereby producing suspended polymer particles.
100 parts of these particles are redispersed in a mixed solution of water / methanol = 1/1 (weight ratio) to a solid content of 30%, and 3 parts of ditertiary butylsalicylic acid zinc salt is added as a charge control agent, followed by filtration after stirring. The toner base particles having an average particle diameter of 6.1 μm were obtained by drying. The toner base particles have a circularity of 0.97, SF-1 = 136, and SF-2 = 119.
To 100 parts of the toner base particles, 0.3 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm and 0.9 part of silica fine powder (dimethylsiloxane basis) having an average particle diameter of 15 nm were added to Henschel. Black toner was prepared by mixing at a peripheral speed of 20 m / sec with a mixer.

  60 parts of the black toner and 40 parts of the black toner A prepared in Example 1 were mixed at 20 m / sec for 2 minutes using a Henschel mixer. After mixing, a black toner was prepared by passing through a 63 μm sieve, and the test was performed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1
In Example 1, the external additive of toner A was changed as follows. For 100 parts of toner base particle A, 0.7 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm and 0.9 part of silica fine powder (dimethylsiloxane) having an average particle diameter of 15 nm are added to Henschel. A toner was prepared by mixing with a mixer at a peripheral speed of 20 m / sec. Further, the external additive of toner B was changed as follows. To 100 parts of toner base particle B, 1.5 parts of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 120 nm and 0.9 part of silica fine powder (dimethylsiloxane treatment) having an average particle diameter of 15 nm are added to Henschel. A toner was prepared by mixing with a mixer at a peripheral speed of 20 m / sec.
When this toner was used in the same manner as in Example 1, a good image was obtained in the initial image output. Thereafter, 100,000 sheets of A4 size paper were continuously fed by the horizontal feed. A large amount of the external additive is released from the spherical toner, and the amount of the developer drawn up to the developing sleeve is small, so that the image density becomes extremely low. The results are shown in Table 1.

FIG. 4 is a diagram for explaining the shape of toner base particles in the toner of the present invention. 1 is a diagram illustrating a configuration example of an image forming apparatus using a toner of the present invention.

Explanation of symbols

100 Copying machine main body (image forming device main body)
200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)
DESCRIPTION OF SYMBOLS 10 Intermediate transfer body 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer body cleaning apparatus 18 Image forming means 20 Image forming apparatus (tandem type image forming apparatus)
21 exposure means 22 secondary transfer device 23 roller 24 secondary transfer belt 25 fixing device 26 fixing belt 27 pressure roller 28 sheet reversing device 30 document table 32 contact glass 33 first traveling body 34 second traveling body 35 imaging lens 36 Reading sensor 40 Photoconductor 42 Paper feed roller 43 Paper bank 44 Paper feed cassette 45 Separating roller 46 Paper feed path 47 Transport roller 48 Paper feed path 49 Registration roller 50 Paper feed roller 51 Manual feed tray 52 Separating roller 53 Paper feed path 55 Switching claw 56 discharge roller 57 discharge tray 60 charging device 61 developing device 62 primary transfer device 63 photoconductor cleaning device 64 static eliminating device

Claims (12)

A toner containing at least a binder resin, a colorant, a release agent and an external additive,
First toner particles obtained by adding large particle size particles and small particle size particle external additives to amorphous toner base particles, and external addition of the large particle size particles and small particle size particles to spherical toner base particles Containing second toner particles to which an agent has been added;
The addition amount of the large particle size external additive in the first toner particles is larger than the addition amount of the large particle size external additive in the second toner particles.
Toner characterized by the above. The toner according to claim 1, wherein the circularity of the irregular toner base particles and the spherical toner base particles satisfy the following expressions, respectively.
0.85 ≦ circularity of irregular toner base particles ≦ 0.94,
0.95 ≦ Circularity of spherical toner base particles ≦ 0.99   3. The toner according to claim 1, wherein the external additive of the large particle size added to the irregular toner base particle and the spherical toner base particle is 30 to 300 nm, and the external additive of the small particle size Is 5 to 25 nm, and the amount of the external additive added to the irregular toner base particles is larger than the amount of the external additive added to the spherical toner base particles. The amount of the external additive for the large particle size particles is smaller than the amount of the external additive for the small particle size particles.   4. The toner according to claim 1, wherein the amorphous toner base particles and the spherical toner base particles have a weight average particle diameter of 4.0 to 9.5 μm, a weight average particle diameter (D4) and a number of the toner base particles. A toner having a ratio (D4 / Dn) to an average particle diameter (Dn) in the range of 1.00 to 1.40.   5. The toner according to claim 1, wherein the irregular toner base particles have a shape factor SF-1 in the range of 150 to 190, a shape factor SF-2 in the range of 150 to 190, and A toner having a spherical toner base particle having a shape factor SF-1 in the range of 100 to 147 and a shape factor SF-2 in the range of 100 to 147.   6. The toner according to claim 1, wherein the spherical toner base particles are obtained by a polymerization method.   7. The toner according to claim 1, wherein the first toner particles obtained by adding an external additive to the irregular toner base particles are 5 to 65 parts by weight, and the second toner particles are 95 to 65 parts by weight. 35 parts by weight of toner (provided that the total amount of the first toner particles and the second toner particles is 100 parts by weight).   A developer for developing an electrostatic latent image on an image carrier, comprising the toner according to claim 1 and a magnetic carrier coated with a resin.   A developing device arranged to face an image carrier that carries an electrostatic latent image, wherein the toner according to claim 7 or the developer according to claim 8 is used.   The image forming method includes at least a step of developing the electrostatic latent image on the image carrier with a developer, and a step of cleaning the residual toner on the image carrier with a cleaning blade. An image forming method, wherein the toner according to claim 7 or the developer according to claim 8 is used, and the cleaning step is performed by blade cleaning. In a process cartridge that integrally supports an image carrier that carries an electrostatic latent image and at least a developing device that is disposed to face the image carrier, and is detachable from the image forming apparatus main body,
A process cartridge using the developing device according to claim 9. In an image forming apparatus comprising at least an image carrier that carries an electrostatic latent image, and a developing device that is disposed to face the image carrier.
An image forming apparatus using the developing device according to claim 9.

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