JP2007279714A - Toner for developing electrostatic image, manufacturing method, image forming method and apparatus - Google Patents

Abstract

An object of the present invention is to solve problems such as low-temperature fixing property, hot offset property, charging property, cleaning property, resolution, and ease of manufacture in conventional toners.
A toner in which an oil phase containing at least a toner composition and / or a toner composition precursor is dispersed in an aqueous medium and granulated, and a release agent inside the toner particles uses a heating and cooling unit. A toner for developing an electrostatic charge image, wherein, in a heating test, the release agent dissolves on the outer surface of the toner particles at 65 ° C. to 90 ° C., and the colored particle toner and the release agent have a sea-island structure.
[Selection] Figure 2

Description

  The present invention relates to a toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, and an image forming method and apparatus using the toner. More particularly, the present invention relates to an electrophotographic toner, an electrophotographic developer, and an electrophotographic developing method and apparatus used for a copying machine, a laser printer, a plain paper fax machine, and the like using a direct or indirect electrophotographic developing system. Further, the present invention relates to an electrophotographic toner, an electrophotographic developer, and an electrophotographic developing method and apparatus used for a full color copying machine, a full color laser printer and a full color plain paper fax machine using a direct or indirect electrophotographic multicolor developing system. .

  In the electrophotographic method, a heating method using a heating roller is a method in which a toner image is transferred by passing the fixing sheet while pressing the surface of the heating roller having releasability to the toner and the toner image surface of the fixing sheet under pressure. Fixing is performed. In this method, the surface of the heat roller and the toner image on the fixing sheet are in contact with each other under pressure, so that the thermal efficiency when fusing the toner image on the fixing sheet is extremely good, and the fixing is performed quickly. Can do.

However, in this pressure bonding heating method, since the surface of the heat roller and the toner image are in contact with each other under a molten state and pressure, a part of the toner image adheres to the surface of the fixing roller and is transferred to the next sheet to be fixed. A so-called offset phenomenon occurs that re-transfers and soils the fixing sheet. Fixing and hot offset differ depending on the fixing method, but depending on the normal fixing speed, the problem relating to toner increases as the high-speed fixing device.
In high-speed fixing, a toner having a lower melt viscosity is generally used than in low-speed fixing, and the surface temperature of the heating roller is lowered to lower the fixing pressure, thereby preventing a high-temperature offset and a winding offset while preventing a toner image. It has become established. However, when such a low melt viscosity toner is used for low-speed fixing, an offset phenomenon tends to occur at a high temperature.
Thus, for fixing, a toner having a wide fixing temperature range that can be applied not only from a high-speed machine but also from low speed to high speed and excellent in offset resistance is desired.

  On the other hand, in order to obtain high image quality, the toner particle size has been reduced, and the resolution and sharpness of the image are increased. On the other hand, the fixability of the halftone portion formed with the small particle size toner is lowered. . This phenomenon is particularly remarkable in high-speed fixing. This is because the amount of toner in the halftone portion is small, and the toner transferred to the concave portion of the fixing sheet has a small amount of heat applied from the heating roller, and the fixing pressure is also reduced by the convex portion of the fixing sheet. It is because it becomes worse because of being suppressed. Since the toner transferred to the convex portion of the fixing sheet in the halftone portion has a thin toner layer thickness, the shearing force applied to each toner particle is larger than that of the solid black portion where the toner layer thickness is thick. Phenomenon is likely to occur, and a low-quality fixed image tends to be obtained.

  The toner used to achieve both the fixing performance and the hot offset resistance and to obtain a high-definition image quality is desired to have a small particle size distribution and a narrow particle size distribution. Further, in order to improve transferability, the toner shape is indefinite and spherical toner is desired. However, considering blade cleaning, the shape of the shape is more applicable to the machine than the true sphere. Toners are required not only for fixing performance, image performance, and cleaning performance, but also at high levels such as storability and charging performance. At the same time, various researches centering on binder resins have been conducted. It is coming.

Moreover, as a method for economically obtaining a dry toner having the above-mentioned performance, a kneading and pulverizing method, a polymerization method and the like have been actively implemented and put into practical use. In particular, in order to improve the clear image quality and fixing spade described above, and to further improve the cleaning properties, the toner particle size is small, narrow distribution, the shape is modified, and the binder resin is also selected considering the fixing performance. On the other hand, there is a situation where an inexpensive toner must be obtained in production while satisfying the performance. Patent Documents 1 and 2 disclose a dry toner comprising a toner binder obtained by subjecting an isocyanate group-containing prepolymer to an extension reaction and / or a crosslinking reaction, and a colorant. And the dry toner comprising particles formed by elongation reaction and / or crosslinking reaction with amines (B) in an aqueous medium of the isocyanate group-containing polyester prepolymer (A), and The manufacturing method is disclosed.

Patent Documents 1 and 2 relate to a toner production method by underwater granulation. When particles are formed in water, the pigment in the droplet-like oil phase aggregates at the interface of the aqueous phase, resulting in a decrease in volume resistance and uneven pigment. Causes problems with basic toner performance. In addition, in order to achieve oillessness, and simultaneously achieve small particle size and shape control and use on a machine, the effect cannot be exhibited unless there is a target shape and target characteristics. Each of the publications does not describe the means for changing the shape, so that the problem of blade cleaning remains. In particular, toner particles that have been granulated by underwater granulation tend to attract pigment from the toner to the particle surface, while lipophilic components in the aqueous phase also tend to adhere to the particle surface. In addition to polymer design with a large surface area, particle surface design is important in obtaining desired charging characteristics and fixing characteristics, but there is no means for achieving fixing performance.
Patent Document 3 discloses a chemical toner using an isocyanate-containing prepolymer, but the technical problems of fixing property and hot offset property are improved, but a charge control agent is fixed on the toner particle surface to ensure charging performance. Therefore, the inhibition of fixing is inevitable. In addition, for spindle shape control, atypical shape control is performed by applying shearing force to the particles, time for solvent removal, shearing force, etc., but particles made from an oil phase that originally contained a solvent are true. It tends to be a sphere and it is very difficult to make it atypical as a toner.

  As a recent trend, in particular, a high-quality image with high reproduction accuracy is required. This is a strong demand not only for monochrome images but also for full-color images. In particular, in a full-color image, there are many halftone portions, and by increasing the reproduction accuracy, it is possible to increase the number of colors that can be reproduced with less graininess. Therefore, a toner having a reduced particle size and / or a spherical shape has been developed.

  For example, Patent Documents 4 to 6 disclose a method for producing a toner containing at least a binder resin and a colorant, in which toner base particles are dispersed in water or an aqueous solvent containing a dispersant to form a dispersion system. The step of absorbing the softener into the toner base particles by introducing a mixed solution of the softener and the organic solvent that is soluble in water or an aqueous solvent and dissolves the softener into the dispersion, the softener A method for producing a toner having a step of removing toner from toner base particles is disclosed. Thus, the toner can be made spherical without being limited by the type of resin component contained in the toner and without impairing the particle size distribution of the toner base particles.

However, since the spherical toners disclosed in Patent Documents 4 to 6 tend to roll on the photoreceptor, the blade cleaning method often enters between the photoreceptor and the cleaning member, resulting in poor cleaning. In addition, there is a problem that there is a lot of dust around the toner dots during development and transfer.
In addition, the method of generating particles in an aqueous medium called chemical toner inevitably has a tendency to be spherical due to the interfacial tension of droplets generated in the dispersion process. Spherical toner has good fluidity even with a small particle size, and is advantageous for developing device design, such as hopper design and reduced torque for rotating the developing roll, but it is difficult to clean with some cleaning methods. There was a problem. That is, the surface of the photoreceptor after the toner image is transferred is cleaned by means such as a blade, a fur brush, or a magnetic brush. In particular, a blade cleaning method with a simple structure and good cleaning properties is generally used, but in this method, spherical toner rotates between the cleaning blade and the photoreceptor and enters the gap. It has a big problem that it is difficult to clean.

  In order to adapt the chemical toner to the blade cleaning method, several methods have been proposed so far. For example, in Patent Document 7, a resin solution composed of a polyester resin and an organic solvent is emulsified in an aqueous medium, and then the resin particles are formed by removing the organic solvent, and the resin particles are aggregated to form toner particles. Is characterized by a method for producing a toner for developing an electrostatic charge image, but there is no means for changing the shape of the toner, and the toner method tends to be spherical. Further, in Patent Document 8, it is a polymerized toner that is made into a particle state by suspension polymerization, and basically the fine primary particles having a particle diameter of 10 μm or less are aggregated to have a particle diameter of 5 to 25 μm. Although it is a polymerized toner composed of irregularly shaped aggregate particles, and the primary particles contain a pigment dispersed therein, it is a styrene acrylic material and has a limited improvement in fixability.

  The present invention has been made in view of the above circumstances, and the shape of the toner is irregularly shaped while maintaining the advantages of the chemical toner that the particle size distribution is narrow and the particle size can be reduced and the fluidity is excellent. To provide an image forming toner having high resolution, high image quality, low temperature fixability, a method for producing the same, a developer, an image forming apparatus, and a process cartridge without causing defective cleaning by a blade. Yes.

JP-A-11-149180 JP 2000-292981 A JP 2004-054204 A JP 2002-148863 A JP-A-5-313416 JP-A-2-148046 JP-A-2-511164 JP 2002-351139 A

  Accordingly, the object of the present invention is to provide an electrostatic charge that simultaneously solves the above-mentioned problems (low-temperature fixability performance, hot offset performance, charging performance, cleaning performance, high-resolution high-quality images, toner productivity) at a high level. Another object of the present invention is to provide a toner for developing an electrostatic image that can be fixed satisfactorily immediately after the power is turned on and that can be well fixed at a low power capacity. Another object of the present invention is to obtain a release property in a wide temperature range from a low speed to a high speed image forming apparatus, and is excellent in anti-offset property, blocking resistance and fluidity. Another object of the present invention is to provide an electrostatic image capable of producing a high-density and high-definition image without fogging from low speed to high-speed image forming apparatuses. For development Toner is to provide a this toner and two-component developer and a container and an image forming method which accommodates the toner or the two-component developer comprising a carrier device.

The above problems are solved by the present invention described below.
(1) A toner in which an oil phase containing at least a toner composition and / or a toner composition precursor is dispersed in an aqueous medium and granulated, and the release agent inside the toner particles is heated using a heating and cooling unit. A toner for developing an electrostatic charge image, wherein in a test, the release agent melts on the outer surface of the toner particles at 65 ° C. to 90 ° C., and the colored particle toner and the release agent have a sea-island structure.
(2) An oil phase containing a modified layered inorganic mineral obtained by modifying at least part of the ions of the binder resin, colorant, release agent and layered inorganic mineral with organic ions in at least an organic solvent is dispersed in an aqueous medium and / or Or a toner obtained by emulsifying and granulating and removing the solvent from the resulting dispersion / or emulsion, wherein the release agent inside the toner particles is used in a heating test using a heating / cooling unit. A toner for developing an electrostatic charge image, wherein the release agent melts outside the toner particles at 65 ° C. to 90 ° C., and the color particle toner and the release agent have a sea-island structure.
(3) The volume average particle size of the toner of (1) is 3 to 6 μm, and the ratio Dv / Dn of the average particle size (Dv) to the number average particle size (Dn) of the toner is 1.00 to 1.00. The glass transition point (Tg) of the binder resin is 40 to 55 ° C, and the weight average molecular weight (Mw) of the binder resin is 3000 to 6500, according to claim 1 or 2, The toner for developing an electrostatic image according to the description.

(4) The toner for developing an electrostatic charge image according to any one of (1) to (3), wherein the releasing agent has a melting point of 65 ° C to 80 ° C.
(5) An oil phase in which a toner dissolves or disperses an isocyanate group-containing polyester-based prepolymer, a compound that extends or crosslinks with the prepolymer, a release agent, a modified layered inorganic mineral, and a toner component in an organic solvent, the solution Alternatively, a toner obtained by subjecting the dispersion to a crosslinking reaction and / or elongation reaction in an aqueous medium and removing the solvent from the obtained dispersion, wherein the release agent inside the toner particles is used as a heating / cooling unit. (1) to (4) above, wherein the release agent melts outside the toner particles at 65 ° C. to 90 ° C. in the heating test used, and the colored particle toner and the release agent have a sea-island structure. The toner for developing an electrostatic image according to any one of the above.

(6) The dispersion particle diameter of the release agent contained in the toner particles is such that 0.3 to 1.0 μm is within 70% by number or less (1) to (5), Toner for developing electrostatic images.
(7) The oil phase used in the toner, wherein the solution or dispersion has a Casson yield value at 25 ° C. of 1 to 10 Pa, and the solution or dispersion has a non-Newtonian index at 25 ° C. A toner obtained by removing a solvent from the obtained dispersion liquid having a tan θ of 0.75 to 0.95, wherein the toner has a shape factor SF-1 of 140 to 200. The toner for developing an electrostatic image according to any one of (1) to (6).
(8) The oil phase used in the production of the electrostatic image developing toner according to any one of the above (1) to (7) has a non-Newtonian index tanθ at 25 ° C. of the solution or dispersion of 0. The toner is obtained by removing the solvent from the obtained dispersion, and the shape factor SF-1 of the toner is 140 to 200. Toner manufacturing method.

(9) The oil phase used in the production of the toner has a Casson yield value at 25 ° C. of the solution or dispersion of 1 to 10 Pa, and the toner is removed by removing the solvent from the obtained dispersion. A method for producing a toner for developing an electrostatic charge image, wherein the toner has a shape factor SF-1 of 140 to 200.
(10) The method for producing a toner for developing an electrostatic charge image according to (8) or (9), wherein the toner is used for a two-component developer.
(11) An image forming method including a transfer step of transferring a toner image carried on a toner image carrier to a transfer material, and a cleaning step of cleaning toner remaining on the surface of the toner image carrier using a blade after the transfer. And a toner according to any one of the above (1) to (7).
(12) A toner container containing the electrostatic image toner according to any one of (1) to (7).
(13) An image forming apparatus using the toner for developing an electrostatic charge image according to any one of claims 1 to 7 for development.

  The toner of the present invention is granulated by dispersing and / or emulsifying in an aqueous medium an oil phase containing at least a binder resin, a colorant, a release agent and a modified layered inorganic mineral in an organic solvent. Alternatively, the toner obtained by removing the solvent from the emulsified liquid, wherein the toner particles include a wax as a release agent, a binder resin, a pigment, and a dispersion of a modified layered inorganic mineral. The toner particles are relatively dispersed in the vicinity of the surface of the toner particles, and the release agent melts to the outside of the toner particles at a temperature of 65 ° C. to 90 ° C. in a heating test using a heating / cooling unit. An electrostatic charge image developing toner characterized in that the agent has a sea-island structure.

  The dry toner of the present invention is excellent in releasability due to wax exudation and resin exudation during fixing, and low-temperature fixability, and the atypical toner shape is excellent in blade cleaning properties, and has low residual toner and high quality. Give an image. Further, since the modified layered inorganic mineral is dispersed in the toner, the toner particles add chargeability and further add cohesiveness of the oil phase at the time of emulsification, thereby assisting in deforming the toner particles.

Hereinafter, the present invention will be described in detail with reference to the drawings.
The toner of the present invention is obtained by dispersing and / or emulsifying in an aqueous medium an oil phase containing at least a binder resin, a colorant, a release agent and a modified layered inorganic mineral in an organic solvent, and granulating the resulting dispersion. / Or a toner obtained by removing the solvent from the emulsified liquid, wherein the toner particles are coated with a release agent on the outermost surface of the toner particles and organic resin fine particles on the outermost surface of the toner particles. The internal mold release agent is in a state where the mold release agent melts to the outside of the toner particles at 65 ° C. to 90 ° C. in a heating test using a heating / cooling unit, and the colored particles and the mold release agent have a sea-island structure. This is a toner for developing an electrostatic image. The toner of the present invention is a spindle-shaped or dimple-shaped toner having a volume average particle size in the range of 4.0 to 6.0 μm, and is a dry toner having a shape factor SF-1 of 140 to 200. FIG. 1 is a conceptual diagram illustrating the outer shape of a toner particle and the projected image shape of the toner of the present invention. FIG. 2 is a heating test in which the release agent inside the toner particle of the toner uses a heating / cooling unit. 3 is a conceptual diagram of toner particles showing that the release agent melts to the outside of the toner particles at 65 ° C. to 90 ° C., and the colored particle toner and the release agent have a sea-island structure.

(Toner structure, toner characteristics and toner quality)
The present inventors have intensively studied the toner fixing property, hot offset property, high image quality, heat resistant storage stability, charging property, and cleaning property, and proposed a particle structure having each function in the toner particle structure. The toner was invented. The toner is, for example, composed of particles formed by elongation reaction and / or crosslinking reaction with amines (B) in an aqueous medium of the dry toner (A) described in Patent Documents 1 and 2, and is produced in water. The inside of the toner particles is a low glass transition point and has a releasability in the vicinity of the toner particle surface layer mainly composed of a pigment component and a modified layered inorganic mineral dispersed with a low molecular weight unmodified polyester or modified polyester. By having a functioning releasable wax, the particle surface is coated with a release agent and organic fine particles to add the high charge necessary for toner development and transfer. The low-softening polymer with low thermal properties oozes out immediately and is used for fixing. In addition, the highly releasable wax dispersed in the interior near the surface layer exudes before the binder and ensures releasability with the roller. In addition, preservability, especially the low softening point binder prevents blocking by heat, so that organic fine particles form a thin layer on the toner particle surface, and a modified layered inorganic mineral of a chargeable functional material is dispersed in the particles. It is possible to achieve both storage stability (especially heat resistance).
The state representing the function of the particles is further clarified by dissolving and dispersing the pigment-binder-wax component by observing the heating / cooling state of the toner particles with a microscope cooling / heating unit (manufactured by Japan High-Tech Co., Ltd.).

(Heating / cooling unit observation method for microscope)
Optical microscope or various microscopes: Olympus magnification lens x 20x, 40x
Microscope heating / cooling unit: Toner heating rate 5 ° C / min
(Manufactured by Japan High-Tech Co., Ltd.)
Temperature range 40 ℃ → 120 ℃
Monitor: The above unit is equipped with a monitor and the toner particles are observed to soften.
Method: A microscope is provided with a heating / cooling unit so that the melting state of the toner can be observed on a monitor.
Subsequently, a toner sample is placed on the glass, a cover glass is placed on the glass, and heating is performed under a specified temperature rise condition to examine the softening of the toner.
Observation: Observe the temperature at which the sea-island structure when the wax is melted and the temperature at which the toner particles are melted.

(Modified layered inorganic mineral)
-Rheological additive-
Substances that can be dissolved or dispersed in an organic solvent and give an oil phase rheological effect when a modified layered inorganic mineral is dispersed in a binder pigment dispersion solution can be variously selected. It can be appropriately selected according to the purpose, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, montmorillonite or bentonite is preferable because the viscosity can be easily achieved and the addition amount is small.
Rheology additives, Bentone 3 and Bentone 38 Bentone 38V, sold by Leox, respectively, thixogel VP sold by United Catalyst, Clayton 34, Clayton 40 and Clayton XL Quartium 18 bentonite such as those sold by the company, those sold by Leox under the name Bentone 27, those sold by United Catalyst in Thixogel LG, Clayton AF, Clayton APA Southern Clay Stearalkonium bentonites such as those sold by Clayton HT, Quartium-18 / Benzalkonium bentonite such as those sold by Southern Clay under the name of Clayton HT.

  In the present invention, the shape of the toner can be easily deformed by using a layered inorganic mineral modified at least partly with organic ions in an aqueous medium and granulating it. The layered inorganic mineral is highly hydrophilic due to its layered structure. For this reason, if the layered inorganic mineral is used in a toner that is dispersed and granulated in an aqueous medium without modifying the layered inorganic mineral, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed. By modifying at least part of the layered inorganic mineral with an organic anion, it has moderate hydrophobicity, the oil phase containing the toner composition and / or toner composition precursor has a non-Newtonian viscosity, and the toner is deformed I can do it. At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner material with an organic anion is preferably 0.05 to 5% by weight.

The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.
Commercially available layered inorganic minerals partially modified with organic ions include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Quaternium 18 / benzalkonium bentonite, such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA.
In order to finely disperse the modified layered inorganic mineral on the surface of the toner particles, if finely dispersed in the binder resin used in the toner in advance, the modified layered inorganic mineral finely dispersed in the toner and finely dispersed during emulsification is fixed near the outermost surface of the toner particles. Turn into. This is presumably because the modified layered inorganic mineral is oriented to the water side during emulsification in the oil phase and to show affinity in hydrophilic water.
In order to finely disperse in the binder, fine dispersion can be achieved in the binder by dispersing by the pigment master batch method.

The binder resin and the colorant can also be used as a master batch.
As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to modified and unmodified polyester resins, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; styrene-p- Chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-acrylic Acid butyl copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate Copolymer, styrene Acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrenic copolymers such as ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacryl Examples include acid resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, and aromatic petroleum resins, which can be used alone or in combination.

  The master batch can be obtained by mixing and kneading the resin for the master batch and the colorant under high shearing force and kneading. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Toner particle size distribution)
The smaller the volume average particle diameter Dv of the toner, the better the fine line reproducibility can be improved. However, since the cleaning property decreases as the particle size decreases, it is preferably at least 3 μm or more. In particular, if the toner particle size of 3 μm or less exceeds 20%, the toner having a small particle diameter that is difficult to be developed on the surface of the magnetic carrier or the developing roller increases. Insufficient friction increases the amount of reversely chargeable toner, resulting in background staining and image quality degradation.
The particle size distribution represented by the ratio (Dv / Dn) of the volume average particle size Dv to the number average particle size Dn is preferably in the range of 1.00 to 1.30. By sharpening the particle size distribution, the toner charge amount distribution becomes uniform and background fogging can be reduced. When Dv / Dn exceeds 1.30, the toner charge amount distribution becomes wide, and it becomes difficult to obtain a high-quality image. The particle size of the toner up to this point is 50, using a Coulter counter multisizer (manufactured by Coulter Co.) and selecting and using an aperture having a measurement hole size of 50 μm corresponding to the particle size of the toner to be measured. This was done by measuring the average particle size of 000 particles.

  The toner of the present invention has a spindle shape in response to a request to lower the low-temperature fixability and increase the hot offset property in order to obtain high-definition, high-quality images while minimizing power consumption. Each of the functions of high-definition image quality and fixing can be achieved simultaneously by forming an irregular shape such as a dimple shape or WAX in the vicinity of the toner particle surface. The amount of WAX present in the vicinity of the surface is 2 to 10 wt% with respect to all the components in the toner measured by total reflection infrared spectroscopy, and the volume average particle diameter (Dv) of the toner is 3.0 to The cleaning property is improved when the toner has a shape factor SF-1 of 6.0 to 200 μm and a shape factor SF-1 of the toner is 140 to 200. Particularly preferred is SF-1 of 140-160. When SF-1 exceeds 200, the particles are easily broken, leading to quality deterioration due to fine powder, and when SF-1 is 140 or less, the cleaning property is lowered.

(Shape factor (SF-1), test method thereof)
The toner shape factor SF-1 is defined by the following (Equation 1) and is used as a coefficient expressing the shape of the toner and the like together with (Equation 2) shown for reference. This is based on a statistical method of image analysis that can quantitatively analyze the area, length, shape, etc. of the captured image with high accuracy. For example, using a high-resolution scanning electron microscope S-2700 manufactured by Hitachi, Ltd. It is possible to randomly sample n (n = 100 to 300) projected images of toner particles enlarged to a magnification of 1000 times, calculate the images by introducing them to LUSEX III via an interface and applying statistical processing. it can.

(In the formulas (1) and (2), MXLG represents the length of the maximum particle size (major axis) of the projected image of the toner particles to be measured, and AREA represents the projected image area as shown in FIG. PERI represents the circumference of the projected image)

  As apparent from the equation (1), the shape factor SF-1 is obtained by multiplying the value obtained by squaring the maximum length of the toner particle diameter by the projected area of the toner particle by π / 4, and further multiplying by 100 times. As the toner particle shape is closer to a sphere, the value is closer to 100, and as the toner particle shape is elongated, the value is larger than 100. That is, the shape factor SF-1 represents the degree of roundness of the toner, increases the transfer efficiency in the transfer process, and reduces the amount of toner remaining on the photoreceptor.

In the present invention, the amount of wax in all components in the toner present near the surface depends on the average dispersion diameter of the finely divided wax, but usually 2 to 10% by weight is appropriate and 2% by weight is appropriate. If the ratio is less than 10% by weight, the desired hot offset property cannot be obtained, and if it exceeds 10% by weight, developability and transferability are deteriorated, and filming on the photoreceptor and the charge imparting member becomes remarkable. .
Here, “near the surface” means a range having a depth of about 0.3 μm from the outermost surface of the toner, and means a range that can be measured by ATR-IR at a wavelength of 2850 cm ⁻¹ .

(Measurement of WAX dispersion particle size by TEM)
In the present invention, the particle diameter in the maximum direction of the wax is defined as the wax dispersion diameter. Specifically, the toner is embedded in an epoxy resin, cut into an ultrathin section of about 100 nm, dyed with ruthenium tetroxide, and then observed with a transmission electron microscope (TEM) at a magnification of 10,000 to 50,000 times for photography. Then, this photograph was subjected to image evaluation to observe the dispersion state of the wax and measure the dispersion diameter.

In the present invention, the ratio of the wax exposed on the toner surface can be measured by FTATR-IR (total reflection infrared spectroscopy).
What is FTATR-IR (total reflection infrared spectroscopic analysis) method? ・ ATR crystal is brought into close contact with a sample, and infrared light is applied to detect a total reflection component;
-An amount of WAX of about 0.2 to 0.5 µm on the particle surface can be detected as the analysis depth;
・ Preparation of the amount of WAX in the toner in advance using FTIR;
・ Create a standard calibration curve by ATR method;
The amount of WAX is calculated from the relative calibration curve of the absorption wavelength of WAX and the absorption wavelength of resin;

  As the wax used in the toner of the present invention, a wax having a low melting point of 65 ° C. to 80 ° C. functions more effectively as the functional toner particles of the present invention as a release agent. When the wax in the toner is observed with a heating / cooling device (manufactured by Japan High-Tech Co., Ltd.), the wax begins to melt from around 65 ° C. When the wax that exudes from the toner particles and the pigment particles dissolve into the island is the sea, the sea-island structure is obtained . This state works between the fixing roller and the toner interface, thereby preventing high-temperature offset without applying a release material such as oil to the fixing roller, and the wax oozes out faster than conventional toner. On the other hand, since resin particles and modified layered inorganic minerals are immobilized on the outside of the particle, the protective substance (resin fine particles) outside the particle is a low-melting-point binder inside the particle and low softening against the summer temperature hazard (about 30-50 ° C) This is probably because the wax is protected.

The observation point where the wax is melted by the heating / cooling device and the wax and the resin dispersed particles have a sea-island structure is an optimum range in which 65 ° C. to 90 ° C. achieves low temperature fixing on the machine and satisfies the hot offset. If the temperature is lower than 65 ° C., the wax melts out too quickly, and the fixing property is decreased. If the temperature exceeds 95 ° C., the melt starts slowly and the hot offset function is deteriorated.
The melting point of the wax in the present invention was the maximum endothermic peak measured by a differential scanning calorimeter (DSC).

As a wax component that functions as a release agent that can be used in the present invention, a melting point of 65 ° C. to 80 ° C. is a temperature range in which hot offset property can be expressed by the heating and cooling device.
Specifically, specific examples of waxes and waxes include plant waxes such as candelilla wax (M.P 78 ° C., rice wax (M.P 80 ° C.), mineral waxes such as ozokerite (MP 72 ° C.), And paraffin wax (65 to 75 ° C.), microcrystalline wax, etc. In addition to these natural waxes, the melting point of synthetic hydrocarbon wax, ester wax, ketone wax, ether wax and the like is 65 ° C. to 8 ° C.
Examples include synthetic waxes having high releasability within the range of 0 ° C. A crystalline polymer material or the like can also be used. Of these, paraffin wax (65 to 78 ° C.) is more preferable.

  In order to make the wax exist in the vicinity of the toner particle surface, control is performed with a WAX dispersant. As the WAX dispersant, a monomer for a toner binder is used which is less compatible with water during emulsification of the toner and the polymerization reaction product is incompatible with WAX or poorly compatible with WAX. On the other hand, it can be controlled to be present in the vicinity of the particle surface from the inside of the toner particle by adding 20 to 100% and dispersing and polymerizing. If the dispersant is less than 20%, particles in which the wax is not contained in the toner particles are generated, and if it exceeds 100%, the wax dispersion becomes too small or the toner particles are likely to be present inside the toner particles, and the bleeding at the time of fixing is slow. The effect of wax will be reduced.

A monomer for a general binder for toner can be used for the binder resin which is not easily compatible.
Specifically, a styrene monomer [styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, Benzyl styrene, etc.], alkyl (C1-C18) ester of unsaturated carboxylic acid [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc.], vinyl ester Monomers (vinyl acetate, etc.), vinyl ether monomers (vinyl methyl ether, etc.), halogen-containing vinyl monomers (vinyl chloride, etc.), diene monomers (butadiene, isobutylene, etc.), (meth) acrylonitrile, cyanostyrene And unsaturated nitrile monomers and their combination thereof.
Of these, styrene monomers, unsaturated carboxylic acid alkyl esters, (meth) acrylonitrile and combinations thereof are preferable, and styrene and styrene, (meth) acrylic acid alkyl esters, and (meth) acrylonitrile are particularly preferable. It is.

It is presumed that the fixing to the paper in the roller fixing or the belt fixing starts at around 70 ° C. to 100 ° C. in the copying machine, printer, FAX, etc., in which the toner fixing effective temperature is recent energy saving. In order to allow the toner to melt, the toner must start to flow near this temperature, so that the toner must soften and start fixing at least at around 90 to 110 ° C.
However, in order to soften at 90 ° C., the glass transition must be 50 ° C. or lower, but the Tg (glass transition point) of such a polymer is also related to the molecular weight.
Usually, when the glass transition point is 50 ° C. or lower, the fixability is good, but the storage stability is not satisfied.

In the toner of the present invention, a Tg of the toner is designed with a very low temperature binder of 40 to 55 ° C., and a particle polymer having a glass transition at 50 to 110 ° C. is formed on the particle surface layer with respect to the toner particles of 0.3 to 2%. .5% present. As shown in FIG. 2, the particles uniformly coated on the toner particles become pseudo-capsule constituting particles that protect the heat against the low-softening binder. The reason for the effect on hot offset, low-temperature fixability, and heat-resistant storage is that the binder resin on the toner surface has a high molecular weight due to the urea bond obtained by reacting the prepolymer and amines, and part of the surface has a network structure. It has a three-dimensional structure that is relatively resistant to stress. In addition, the same surface thermal properties as conventional toner are used for the particle surface layer, while the inside uses a low-Tg polyester resin as a toner binder, which is advantageous for low-temperature fixability compared to uniformly kneaded pulverized toner. It becomes the particle structure of the target material component. The fine polymer particles coated on the surface layer must react quickly with the heat capacity of the heating roller at the time of fixing to allow the toner particle binder to ooze out of the surface layer. The balance between heat-resistant storage and toner exudation can be controlled by the amount of adhering fine particle polymer. The fine particle polymer remaining in the toner has a particle diameter of 10 to 200 nm and is attached in an amount of 0.3 to 2 wt%. When the particle diameter is 10 nm or less, it is difficult to obtain a fine particle polymer, and when it is 200 nm or more, it remains thick on the surface layer and the fixability is lowered. Regarding the Tg of the toner, 40 to 55 ° C. is effective as a range in which low temperature fixing is possible. Particle formation is difficult at 40 ° C or less, and the effect at low temperature fixing is lost at 55 ° C or more.

  The spherical toner formed by the wet polymerization method has poor cleaning properties, and even a toner having an average particle diameter of about 10 μm often causes poor cleaning in the blade cleaning method. This is because the toner surface is smooth and the toner on the photoconductor is likely to roll and sink into the gap between the cleaning blade and the photoconductor. Since the spherical toner has no irregularities on the surface, all of the attached external additive comes into contact with the photosensitive member. Up to now, a large amount of external additives such as silica has been added to the spherical toner, but the external additives such as silica are embedded in the photoreceptor, and the toner is fused from this as the starting point on the image. There is a problem that a streaky abnormal image is generated. On the other hand, the irregular toner has many irregularities and does not roll on the photoconductor before the cleaning blade, so that it can be easily cleaned with the cleaning blade. In this regard, by using a spindle-shaped toner, it is possible to obtain a toner that can be easily cleaned because the rotation axis that easily rolls on the photosensitive member is limited as compared with the spherical toner. In addition, in the case of a flat toner, even such rotation should be somewhat limited.

  In the electrostatic transfer system, the spherical toner on the photoreceptor has a smooth surface, good powder flowability, and low adhesion between toner particles or between toner particles and the photoreceptor. Therefore, the transfer rate is high because it is easily affected by the lines of electric force and is easily transferred faithfully along the lines of electric force. However, when the recording member moves away from the photosensitive member, a high electric field is generated between the photosensitive member and the recording member (burst phenomenon), and the toner on the recording member and the photosensitive member is disturbed, so that the dust on the recording member becomes dusty. appear. True toner that is easily affected by the lines of electric force often generates dust and lowers image quality.

However, the irregular toner and the flat toner have unevenness and are not easily affected by the electric lines of force of the toner, and are difficult to transfer along the lines of electric force, so the transfer rate is low. However, the adhesion between the toner particles is large, and the toner dots transferred to the recording member are not easily broken by an external force or the like, and the generation of dust due to the burst phenomenon is suppressed.
Since the spindle-shaped toner has a smooth surface and appropriate fluidity, the spindle-shaped toner is easily influenced by the electric force lines, and is easily transferred faithfully along the electric force lines, so that the transfer rate is increased. Further, in the spindle shape, since the rotation axis that is easy to roll is limited, the toner particles are not easily scattered from the toner dots on the recording member due to the burst phenomenon, so that a high-quality image can be obtained.

In the electrostatic development system, the spherical toner on the magnetic carrier or the developing roller is easily affected by the lines of electric force and is faithfully developed along the lines of electric force of the electrostatic latent image. When reproducing minute latent image dots, fine line reproducibility is improved because it is easy to obtain a dense and uniform toner arrangement. However, in the contact development method, the developed toner on the photoconductor is transferred by a magnetic brush or a developing roller. Since it is rubbed and moved, image quality deterioration such as dust is likely to occur.
The irregular toner on the magnetic carrier or the developing roller has poor powder fluidity, and the electric lines of force of the latent image do not act smoothly on individual toner particles. Therefore, when forming toner dots during development, Since it is not neatly arranged, faithful development is difficult and fine line reproducibility is low. Flat toner also has this tendency.

Since the spindle-shaped toner has a moderately adjusted powder fluidity, it is developed faithfully along the electric lines of force of the electrostatic latent image, so that the fine line reproducibility is high, and the developed on the photoreceptor. Since the toner hardly moves even when rubbed with a magnetic brush or a developing roller, a visible image with little deterioration in image quality such as dust can be obtained.

In the toner of the present invention, in order to obtain an irregularly shaped toner shape that exhibits a balanced function of charging, cleaning, fixing, and hot offset, the function is manifested by limiting the viscous flow of the emulsified toner oil phase. The viscous flow of the oil phase to be emulsified is obtained by dissolving or dispersing a binder resin, a prepolymer composed of a modified polyester resin, a compound that extends or crosslinks with the prepolymer, a colorant, and a release agent in at least an organic solvent. In an emulsified dispersion using only unmodified polyester as the liquid or dispersion or binder resin, the target toner shape is obtained by setting the Casson yield value at 25 ° C. to 1 to 25 Pa and tan θ to 0.75 to 0.95. Can be achieved.
If the Casson yield value is less than 1 Pa, it is difficult to obtain a target shape, and if it exceeds 25 Pa, shape controllability becomes difficult.

Further, the modified layered inorganic mineral is preferably contained in an amount of 0.05 to 5% in the solid content in the solution or dispersion. If it is less than 0.05%, the target Cassson yield value cannot be obtained.
Measurement method of yield value, tanθ:
The Casson yield value can be measured using a high shear viscometer or the like.
The measurement conditions are as follows.
Device: AR2000 (TA Instruments)
Shear stress 120 Pa / 5 min Geometry: 40 mm steel plate Geometry gap: 1 mm Analysis software: TA DATA ANALYSIS (TA Instruments)
Yield value (stress yield value Pa): From the Casson flow equation, the extrapolation point of s− = 0 of the shear rates s− = 1 and s− = 2. The range of shear rate on measurement is 0 → 300s-
tanθ: The oil phase flow curve is measured. Conditions are 25 ° C and GAP is 0.5mm
Measurement range shear rate: 0 → 1800 s− → 0 s−.
How to find tanθ: Find tanθ from the LOG-LOG graph of shear rate s- and shear stress.
Shear rate range is 0 → 2000s-

  The toner of the present invention needs to be provided with a substance that is immobilized on the surface of the toner to make the surface hydrophobic (hereinafter simply referred to as “immobilized substance”). The combined use of silica and titanium oxide as the immobilizing substance is most effective for charging and fixing properties. This is because the toner has a small particle size and inferior fluidity and the surface is covered with polymer fine particles, so that it easily binds to moisture in the air and has a large charge fluctuation. Conventionally, an inorganic substance that is a fluidizing agent is generally added to and mixed with the surface, but a substance that covers the surface lowers the fixability. However, by fixing silica and titanium oxide on the surface, charging property and fluidity can be secured, and fixing property is not greatly reduced. This is due to the hydrophobization of silica and titanium oxide, and it is presumed that the combined use of titanium oxide suppresses the increase in charge amount due to the small particle size toner. A desired charge amount cannot be obtained only with titanium oxide.

  When these toner surface protective substances are fixed to the toner surface, the toner surface protective substances are released from the toner surface and adhere to or damage the carrier, developing roller, photoconductor, contact charging means, etc. To prevent. For this purpose, an external force stronger than that of a general external additive mixing apparatus (conditions) must be applied.

In the present invention, the charge control agent can be immobilized as a step before using silica or titanium oxide as a protective substance for protecting the toner surface. This is because the triboelectric charging function can be positively imparted to the toner surface to stabilize the triboelectric charging.
In order to fix the protective substance on the toner surface, a mechanical or thermal treatment may be performed in the air. Moreover, you may perform an electrochemical or mechanical process in the solvent in the middle of manufacture of the wet polymerization method. For example, a method of mixing toner and a protective substance in a container using a rotating body is known. In this method, a toner having a protective substance adhered thereto can be obtained by mixing the rotating member rotating at a high speed in a container having no fixing member protruding from the inner wall of the container. In addition, the toner and the protective substance can be mixed in advance and sprayed together with a hot air current in a container such as an atomizer so that the toner surface is melted and then rapidly cooled to be fixed to the toner surface. Further, in the solvent, the protective substance can be fixed by adsorbing to the toner surface.
The amount of silica and titanium oxide fixed on the toner surface of the present invention is suitably 0.3 to 1.5% silica and 0.1 to 1.0% titanium oxide. When the total amount exceeds 1.5%, the fixing property is rapidly lowered.

The binder resin is not necessarily limited to an image in which modified polyester or unmodified polyester can be used advantageously.
The modified polyester refers to a state in which a bonding group other than an ester bond exists in the polyester resin, or resin components having different configurations are bonded to the polyester resin by a covalent bond, an ionic bond, or the like. For example, the polyester terminal is reacted with something other than an ester bond. Specifically, it refers to a product in which a functional group such as an isocyanate group that reacts with an acid group or a hydroxyl group is introduced at the terminal and further reacted with an active hydrogen compound to modify the terminal.
Specific examples of the modified polyester (i) include a reaction product of a polyester prepolymer (A) having an isocyanate group and amines (B). Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group further reacted with a polyisocyanate (3). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

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

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

The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

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

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

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

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates. In the present invention, the polyester (i) modified with a urea bond 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 (i) of the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the urea-modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. In this case, the peak molecular weight is 1,000 to 10,000, and if it is less than 1,000, the elongation reaction hardly occurs and the elasticity of the toner is small, and as a result, the hot offset resistance deteriorates. On the other hand, if it exceeds 10,000, the problem of production becomes high in terms of deterioration of fixability, particle formation and grinding. The number average molecular weight of the urea-modified polyester is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. In the case of urea-modified polyester (i) alone, the number average molecular weight is usually 20,000 or less, preferably 1,000 to 10,000, more preferably 2,000 to 8,000. If it exceeds 20,000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.

The toner of the present invention can contain not only the polyester (i) modified with a urea bond, but also the polyester (ii) not modified with the polyester (i) as a toner binder component. By using polyester (ii) in combination, the low-temperature fixability and the glossiness when used in a full-color apparatus are improved, which is preferable to single use. Examples of polyester (ii) include polycondensates of polyol (1) and polycarboxylic acid (2) similar to the polyester component of polyester (i), and preferred ones are also the same as polyester (i). The polyester (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. It is preferable that polyester (i) and polyester (ii) are at least partially compatible in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component of polyester (i) and polyester (ii) preferably have similar compositions. When the polyester (ii) is contained, the weight ratio of the polyester (i) and the polyester (ii) is as follows:
Usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, and particularly preferably 7/93 to 20/80. When the weight ratio of the polyester (i) is less than 5 wt%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The peak molecular weight of the polyester (ii) is usually 1,000 to 10,000, preferably 2,000 to 8,000, and more preferably 2,000 to 5,000. If it is less than 1,000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of the polyester (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of polyester (ii) is 1-5, preferably 2-4.

  In the toner of the present invention, the glass transition point (Tg) of the toner binder is 40 to 55 ° C. When the glass transition point is less than 40 ° C., the heat-resistant storage stability of the toner is deteriorated. Due to the coexistence of the urea-modified polyester resin, the dry toner of the present invention has heat resistance even when the glass transition point is low by effectively arranging the material function in the toner particle structure as compared with the known polyester toner. It shows a tendency of good storage stability and hot offset property.

The primary particle size of the hydrophobic silica and hydrophobic titanium oxide used in the toner of the present invention is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.

In addition, as the colorant of the toner of the present invention, 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, Lead Red, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faisa Red, Lachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin 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, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y , Alizarin lake, thioindigo red B, thioindigo maroon, oil red, quinacridone , Pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, Indanthrene blue (RS, BC), indigo, ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, 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, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15 wt%, preferably 3 to 10 wt%, based on the toner.

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

The method for producing the toner of the present invention will be described below.
As the aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (methanol, isopropyl alcohol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (eg, methyl cellosolve), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.

In the present invention, a urea-modified polyester (UMPE) can be obtained by reacting a polyester prepolymer (A) having an isocyanate group with an amine (B) in an aqueous medium. As a method for stably forming a dispersion composed of a modified polyester such as urea-modified polyester or a prepolymer (A) in an aqueous medium, the dispersion is made of a modified polyester or prepolymer (A) such as a urea-modified polyester in an aqueous medium. Examples thereof include a method in which the composition of the toner raw material is added and dispersed by shearing force. Prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials), a colorant masterbatch, a release agent, a charge control agent, an unmodified polyester resin, etc. are dispersed in an aqueous medium. It is preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.
In the present invention, an oil phase for emulsification can be prepared using only the unmodified polyester binder in the binder resin. From emulsified dispersion using modified layered inorganic mineral, it can be developed into toner.

The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is usually 1,000 to 30,000 rpm, preferably 5,000 to 20,000 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 4
0-98 ° C. Higher temperatures are preferred in that the dispersion of the urea-modified polyester or prepolymer (A) has a low viscosity and is easy to disperse.

The amount of the aqueous medium used is usually 50 to 2,000 parts by weight, preferably 100 to 1,000 parts by weight, based on 100 parts of the toner composition containing a polyester such as urea-modified polyester or prepolymer (A). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2,000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.
Various surfactants are used for dispersing the toner composition in the oil phase and emulsifying the oil phase in the aqueous phase. Such a dispersant includes a surfactant, an inorganic fine particle dispersant, a polymer fine particle dispersant and the like.

  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. It is.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be increased in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

Examples of cationic surfactants include aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, benza Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-20
2 (Daikin Kogyo Co., Ltd.), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), etc. Can be mentioned.

Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant that is hardly soluble in water.
Moreover, the same effect as the inorganic dispersant was confirmed for the fine particle polymer. For example, MMA polymer fine particles 1 μm and 3 μm, styrene fine particles 0.5 μm and 2 μm, styrene-acrylonitrile fine particle polymer 1 μm, (PB-200H (Kao) SGP (Soken), Technopolymer SB (Sekisui Plastics), SGP-3G (Soken) and Micropearl (Sekisui Fine Chemical).

  Further, as a dispersant that can be used in combination with the above inorganic dispersant and fine particle polymer, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, acrylic acid 3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate , N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of compounds containing vinyl alcohol and a carboxyl group For example, pinyl acetate, pinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine Homopolymers or copolymers such as those having a nitrogen atom or its heterocyclic ring, polyoxyethylene, polyoxypropylene Polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl Polyoxyethylenes such as phenyl esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  In order to remove the organic solvent from the obtained emulsified dispersion (reactant), the entire system is gradually heated in a laminar stirring state, and after strong stirring in a certain temperature range, desolvation is performed. Spindle-shaped toner particles or dimple-shaped toner can be produced. In addition, when an acid such as calcium phosphate salt or an alkali-soluble one is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as washing with water after dissolving the calcium phosphate salt with an acid such as hydrochloric acid. To do. It can also be removed by operations such as enzymatic degradation. When a dispersant is used, the dispersant can remain on the toner particle surface. When a solvent is used, the solvent (solvent) is removed from the obtained reaction product under normal pressure or reduced pressure after the extension and / or crosslinking reaction of the modified polyester (prepolymer) with an amine.

Furthermore, in order to reduce the viscosity of the dispersion medium containing the toner composition, a solvent in which a polyester such as urea-modified polyester or prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate and the like. These are water-insoluble, or 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 preferred. The usage-amount of the solvent with respect to 100 parts of prepolymers (A) is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln. This is presumably because ethyl acetate or the like contained in the granulation lowered the viscosity of the emulsion and changed from a spherical shape to a spindle shape by a stronger stirring force. As described above, the volume average particle diameter Dv, the number average particle diameter Dn, the ratio Dv / Dn, the spindle shape ratio, and the like of the toner adjust the water phase viscosity, oil phase viscosity, resin fine particle characteristics, addition amount, and the like. You can control it.

The toner of the present invention can be used as a two-component developer. In this case, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is preferably 1 to 10 parts by weight of the toner with respect to 100 parts by weight of the 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 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and 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 fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner or non-magnetic toner that does not use a carrier.

When the volume average particle diameter is smaller than the range in the present invention, in the case of a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is lowered, or the one-component developer When it is used, 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. In particular, if the particle size of 3 μm or less exceeds 10%, it becomes an obstacle to adhesion to a carrier or high level charging stability.

Conversely, when the toner particle size is larger than the range specified in the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and the balance of the toner in the developer is performed. In many cases, the variation in the particle diameter of the toner becomes large. It was also clarified that the same was true when the weight average particle diameter / number average particle diameter was larger than 1.20.
The average particle size and particle size distribution of the toner can be measured by a Coulter counter method, and examples of the toner particle size distribution measuring device include Coulter Counter TA-II and Coulter Multisizer IIe (both manufactured by Coulter). . In the present invention, measurement was performed by using a Coulter Counter TA-II type and connecting an interface (Nichiken Giken) that outputs number distribution and volume distribution and a PC9801 personal computer (manufactured by NEC).

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

  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 of 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 volume-based volume average particle diameter (Dv) obtained from the volume distribution according to the present invention and the number average particle diameter (Dn) obtained from the number distribution and the ratio Dv / Dn were obtained.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of carrier. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resin such as vinyl chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexa Fluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro such as terpolymers of emission and non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.
As described above, the surface presence state of the WAX particles dispersed in the toner particles is observed by observing the section of the toner particles with a transmission electron microscope (TEM). As far as observed with this TEM, WAX particles having a diameter of 0.2 to 1.0 μm are dispersed in the toner near the center of the surface. The vicinity of the surface was further quantitatively defined. In addition to ATR-IR (total reflection infrared spectroscopy), when measuring the relative intensity of WAX, measuring the wavelength of 2850 cm ^-1 can measure the CH vibration of WAX, and the depth to be measured is this wavelength. In this case, the thickness is about 0.3 μm, but the absorption wavelength accuracy is 0.2 to 1.2 μm.
Conventionally, the amount of WAX has been quantified by X-ray irradiation analysis such as ESCA. However, since the analysis depth is 2 μm or more, the input amount of WAX is almost the measured value.

Next, a WAX dispersant is used as a method for dispersing WAX near the surface. In this method, the dispersion state can be controlled by the amount of the WAX dispersant.
The dispersant used in the present invention is typically a graft polymer (C), for example, and has a structure in which at least a part of the polyolefin resin (A) is grafted with a vinyl resin (B).
In the toner of the present invention, at least a part of the release agent is encapsulated in the graft polymer (C). The inclusion in this case means that “the polyolefin resin (A) portion of the graft polymer (C) and the release agent have good compatibility, so that the polyolefin resin (A) portion of the graft polymer (C) is selectively used. It means that the release agent is taken in or adhered.

A toner composition is dissolved or dispersed in an organic solvent, the dissolved product or dispersion is dispersed in an aqueous medium in the presence of an inorganic dispersant or fine particle polymer, and the resulting dissolved product or dispersion is subjected to a polyaddition reaction. In a dry toner manufacturing method in which a toner composition comprising a polyester resin is dispersed in an aqueous medium to form toner particles obtained by removing the solvent of the obtained emulsified dispersion, the toner binder is modified. The polyester and the release agent having a highly polar bond part cause negative adsorption at the interface and selectively migrate to the vicinity of the toner surface, or the release agent having a bond part with few polar groups gathers at the center of the toner particle. The graft polymer (C) in which at least a part of the polyolefin resin (A) is modified with the vinyl resin (B) is released from the mold. Between the toner binder and the toner binder, preventing the release agent from being exposed to the surface of the toner, and in the vicinity of the surface of the toner particles stably in order to exhibit the release effect quickly when passing through the fixing device. In addition, there is an effect of obtaining a toner that can be dispersed with an appropriate dispersion diameter.
In the case of the toner of the present invention, even when the release agent is present in the vicinity of the surface of the toner particles, unlike the case of the conventional toner particles, various problems seen when existing on the surface of the conventional toner particles are unlikely to occur. Therefore, the dispersion diameter of the release agent can be made relatively large. As a result, it is possible to easily exude the release agent from the toner surface and enhance the release effect.

In addition, the larger the dispersion diameter in the resin of the graft polymer (C), the easier it is to take in or adhere to the release agent, and it is easier for the release agent to ooze out from the toner surface or to be easily removed. However, when the dispersion diameter of the graft polymer (C) in the resin becomes too large, the dispersion diameter of the release agent contained therein tends to increase.
The amount of the release agent contained in the graft polymer (C) is 33 to 1,000 parts by weight, preferably 50 to 300 parts by weight with respect to 100 parts by weight of the graft polymer (C). Of the total wax contained in the toner, 80% by weight or more, preferably 90% by weight or more is preferably contained in the graft polymer (C).

(Process cartridge)
In the present invention, the process cartridge includes a latent image carrier (for example, a photoreceptor) and a developing unit, and further includes at least one unit selected from components such as a charging unit, a cleaning unit, and a transfer unit. A plurality of means that may be configured is integrally coupled as a process cartridge, and the process cartridge is configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.
FIG. 3 shows a conceptual diagram of an example of a process cartridge having the toner of the present invention.
The process cartridge in this example has a proximity non-contact roller type charging unit, a developing unit, and a cleaning unit around a drum-shaped photoconductor as a latent image carrier. In the developing unit, the developer storage unit and the toner storage unit are connected by a toner replenishment path. The developer storage unit magnetically pumps up the developer composed of toner and a magnetic carrier, and developer agitation unit. A magnetic roller that is stirred and charged in cooperation with the developer, a developer roller that supplies the developer sleeve, a developer supply restricting means for restricting the amount of developer supplied to the developer sleeve, and a developer storage case. The toner storage unit has a toner stirring means. The cleaning unit has a collected toner storage tank for storing the toner scraped off from the developing surface by the cleaning blade.

  The present invention improves the low-temperature fixability, hot offset performance, charging performance, cleaning performance, high resolution, ease of production, etc. of the toner, and ensures releasability in a wide temperature range from low speed to high speed image formation. Images can be formed.

Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited thereto. (Synthesis of organic fine particle emulsion)
Production Example 1 <Fine Particle Dispersion 1>
In a reaction vessel equipped with a stirring bar and a thermometer, 780 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 90 parts of styrene, 90 parts of methacrylic acid, When 120 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to obtain an aqueous dispersion (fine particle dispersion 1) of a vinyl-based cross-linked resin (styrene-methacrylic acid-butyl acrylate copolymer). . The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 50 nm.

Production Example 2 <Modified Layered Inorganic Mineral Dispersion 1>
Binder resin: polyester resin (polyester resin composed of sphenol acid derivative bisphenol A propylene oxide adduct manufactured by Sanyo Chemical) (acid value 10, Tg 52 ° C.) 2 parts set at a roll surface temperature of 110 ° C. and 2 mm roll nip Kneading is carried out for 15 minutes with a roll, and then modified montmorillonite (Clayton HY Wilber Ellis): 10 parts are put into the kneaded polyester resin, kneading is continued for 30 minutes and cooling to room temperature. This was pulverized to a size of 2 mmφ with a pulverizer to obtain [modified layered inorganic mineral dispersion 1].

Production Example 3 <Modified Layered Inorganic Mineral Dispersion 2>
Binder resin: Polyester resin (polyester resin composed of succinic acid derivative, bisphenol A propylene oxide adduct manufactured by Sanyo Kasei) 2 parts set with 85 parts of roll surface temperature of 110 ° C. and 2 mm roll roll, acid value of 10, Tg 52 ° C. Kneading is carried out for 15 minutes with a roll, and then modified montmorillonite (Clayton APA Wilber Ellis): 15 parts are put into the kneaded polyester resin, kneading is continued for 30 minutes and cooling to room temperature. This was pulverized to a size of 2 mmφ with a pulverizer to obtain [Modified Layered Inorganic Mineral Dispersion 2].

(Preparation of aqueous phase)
Production Example 4 <Aqueous Phase 1>
990 parts of water, 80 parts of [fine particle dispersion 1], 40 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7): 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].
Production Example 5 <Aqueous Phase 2>
990 parts of water, 80 parts of [fine particle dispersion 2], 40 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate were mixed and stirred. A liquid was obtained. This is designated as [Aqueous Phase 2].

<Fine particle dispersion 2>
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium acetate of ethylene methacrylate oxycide adduct sulfate (ELEMIRARS RS-30, manufactured by Sanyo Chemical Industries), 90 parts of styrene, 100 parts of methacrylic acid Then, 110 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, whereby a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours. An aqueous dispersion [fine particle dispersion 2] was obtained. The volume average particle diameter of [fine particle dispersion 2] measured by LA-920 was 20 nm.

Production Example 6 <Aqueous Phase 3>
990 parts of water, 80 parts of [fine particle dispersion 3], 40 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7): manufactured by Sanyo Chemical Industries, Ltd. and 90 parts of ethyl acetate were mixed and stirred. A liquid was obtained. This is designated as [Aqueous Phase 3].
(Synthesis of low molecular weight polyester)
Production Example 7 <Low molecular polyester 1>
In a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube, 220 parts of bisphenol A ethylene oxide 2-mole adduct, 561 parts of bisphenol A propylene oxide 3-mole adduct, 218 parts of isophthalic acid, 48 parts of adipic acid and dibutyl Add 2 parts of tin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg, then add 45 parts of trimellitic anhydride to the reaction vessel, and add 2 parts at 180 ° C. under normal pressure. The reaction was performed for a while to obtain [Low molecular weight polyester 1]. [Low molecular weight polyester 1] had a weight average molecular weight (MW) of 4500 and an acid value of 28.

<Fine particle dispersion 3>
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), 90 parts of styrene, 100 parts of methacrylic acid, When 110 parts of butyl acrylate, 1.6 HDD <20 parts of hexanediol acrylate> and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to obtain an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 3] was obtained. The volume average particle size of [fine particle dispersion 3] measured with LA-920 was 100 nm.

(Prepolymer synthesis)
Production Example 8 <Prepolymer 1>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction pipe, 712 parts of bisphenol A ethylene oxide 2-mole adduct, 84 parts of bisphenol A propylene oxide 2-mole adduct, 292 parts of terephthalic acid, 32 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 10,500, a Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 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% of 1.48%.

(Synthesis of ketimine)
Production Example 9 <Ketimine 1>
In a reaction vessel equipped with a stirrer and a thermometer, 60 parts of isophoronediamine and 140 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 408.
(Synthesis of master batch)
Production Example 10 <Masterbatch 1>
Carbon black (Mitsubishi Chemical Corporation # 44): 40 parts, Binder resin: Polyester resin (Sanyo Kasei polyester acid value 10, Mw 7000, Tg 52 ° C.): 60 parts, water: 20 parts are mixed in a Henschel mixer and pigment A mixture with water soaked into the aggregate was obtained. This was kneaded for 60 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 1].

(Create oil phase)
Production Example 11 <Pigment, Wax Dispersion 1>
In a container equipped with a stir bar and a thermometer, 378 parts of [Low molecular polyester 1], 110 parts of paraffin wax (Nippon Seiki HNP-9, M.P 75 ° C., 947 parts of ethyl acetate, and heated to 80 ° C. with stirring) Warm and hold at 80 ° C. for 5 hours, then cool to 30 ° C. in 1 hour, then charge 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate into the container and mix for 1 hour [Raw material solution 1] Got.
[Raw material solution 1] 1324 parts, 110 parts of the modified layered inorganic mineral 1 are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), the liquid feeding speed is 1 kg / hr, the disk peripheral speed is 6 m / second, 0 Filled with 80% by volume of 5 mm zirconia beads, dispersion of the modified layered inorganic mineral, carbon black, and WAX was performed under conditions of 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 1] was added, followed by one pass 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%.

Example 1
[Pigment / WAX Dispersion 1] 618 parts, [Prepolymer 1] 115 parts, [Ketimine Compound 1] 6.6 parts in a container, and TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute After mixing, 1200 parts of [Aqueous phase 1] was added to the container, and mixed with a TK homomixer at 13,000 rpm for 20 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 4 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 (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of 10% sodium hydroxide aqueous solution was added to the filter cake of (1), ultrasonic vibration was applied and mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. . This ultrasonic alkali cleaning was performed again (two ultrasonic alkali cleanings).
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (10 minutes at 12,000 rpm) and then filter twice to obtain [Filter cake 1]. It was.
[Filter cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, sieved with a mesh of 75 μm, and then 100 parts of toner particles with 0.5 parts of hydrophobic silica and 0.5% of hydrophobic titanium oxide. Parts were mixed with a Henschel mixer to obtain toner (1). The volume average particle size was 5.85 μm, and the number average particle size was 4.33 μm (measured with Multisizer II).

Example 2
The modified layered inorganic mineral dispersion 1 of Production Example 2 was changed to the modified layered inorganic mineral dispersion 2 of Production Example 3, the input amount was changed from 110 parts to 220 parts, and the aqueous phase 1 was changed to the aqueous phase 2. Otherwise, the same procedure as in Example 1 was carried out to obtain (Toner 2) having a volume average particle size of 5.65, a number average particle size of 5.09 μm and DV / Dn of 1.11.
(Synthesis of low molecular weight polyester)
Production Example 12 <Low Molecular Polyester 2>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 262 parts of bisphenol A ethylene oxide 2 mol adduct, 202 parts of bisphenol A propylene oxide 2 mol adduct, 236 parts of bisphenol A propylene oxide 3 mol adduct, 266 parts of terephthalic acid, 48 parts of maleic acid and 2 parts of dibutyltin oxide were added, reacted at normal pressure 230 ° C. for 8 hours, further reacted at a reduced pressure of 10-15 mmHg for 5 hours, and then at 180 ° C. at normal pressure for 2 hours. The reaction yielded [low molecular weight polyester 2]. [Low molecular weight polyester 2] had a weight average molecular weight of 3900, Tg of 58 ° C, and an acid value of 16.5.

(Create oil phase)
Production Example 13 <Pigment / Wax Dispersion 3>
288 parts of [Low molecular polyester 2], paraffin wax HNP-3 (Nihon Seiki M.P66, 220 parts, ethyl acetate 947 parts) are charged into a container equipped with a stirring bar and a thermometer, and the temperature is raised to 80 ° C. with stirring. The mixture was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour, and then 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were placed in the container and mixed for 1 hour. ] Was obtained.
[Raw material solution 2] 1224 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed is 1 kg / hr, disk peripheral speed is 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Subsequently, 1224 parts of a 65% ethyl acetate solution of [low molecular weight polyester 2] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 3].

Example 3
[Toner 3] having a volume average particle diameter Dv of 4.95 μm, a number average particle diameter of Dn of 4.19 μm, and Dv / Dn of 1.18, except that [Pigment / WAX Dispersion 3] in Example 2 is used. ] Was obtained.
Example 4
[Toner with volume average particle diameter Dv 5.60 μm, number average particle diameter Dn 4.96 μm, and Dv / Dn 1.13 in the same manner as in Example 2 except that 115 parts → 50 parts of prepolymer 1 in Example 2 were used. 4] was obtained.

(Synthesis of master batch)
Production Example 14 <Masterbatch 2>
Cyan pigment ECB-301 (manufactured by Dainichi Seika Co., Ltd.): 40 parts, binder resin: polyester resin (polyester manufactured by Sanyo Kasei, acid value 10, Mw 7000, Tg 52 ° C.): 60 parts, water: 20 parts are mixed in a Henschel mixer. Thus, a mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 60 minutes with two rolls set at a roll surface temperature of 130 ° C., and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 3].

Production Example 15 <Masterbatch 3>
Magenta pigment PR-F6B (manufactured by Clariant): 40 parts, binder resin: polyester resin (polyester manufactured by Sanyo Kasei, acid value 10, Mw 7000, Tg 52 ° C.): 60 parts, water: 20 parts are mixed in a Henschel mixer, A mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 60 minutes with two rolls set at a roll surface temperature of 130 ° C., and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 3].

Production Example 16 <Masterbatch 4>
Yellow pigment PY-HG (manufactured by Clariant): 40 parts, binder resin: polyester resin (Sanyo Kasei polyester acid value 10, Mw 7000, Tg 52 ° C.): 60 parts, water: 20 parts are mixed in a Henschel mixer, A mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 60 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 4].

(Create oil phase)
Production Example 17 <WAX / Pigment Dispersion 4>
In a container equipped with a stirrer and a thermometer, 278 parts of [Low molecular weight polyester 2], 110 parts of paraffin wax 145 ° N Nippon Oil Co., Ltd. and 947 parts of ethyl acetate were charged. After maintaining for 5 hours, it was cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 2] and 500 parts of ethyl acetate were charged in the container, and mixed for 1 hour to obtain [Raw material solution 3].
[Raw Material Solution 3] 1324 parts were transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed 1 kg / hr, disk peripheral speed 6 m / sec, 0.5 mm zirconia beads 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [low molecular weight polyester 2] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 4].

Example 5
Instead of [Pigment / WAX Dispersion 1] in Example 1, [Pigment / WAX Dispersion 4] is used, [Pigment / WAX Dispersion 4] is 618 parts, Modified Layered Inorganic Mineral Dispersion 2 is 220 parts, [ 115 parts of Prepolymer 1 and 6.6 parts of [Ketimine Compound 1] are put in a container and mixed with a TK homomixer (manufactured by Special Machine) for 1 minute at 5,000 rpm, and then [Water Phase 3] 1200 in the container. Part was added and mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsified slurry 5].
Next, this mixed liquid was transferred to a colben with a thermometer equipped with a vertical stirring rod capable of a peripheral speed of 5 m / s or more, and Serogen BS (Daiichi Kogyo Seiyaku Co., Ltd.) was used as a thickener in the emulsified slurry. 40 parts was added and the emulsion was set at 30 ° C. and stirred rapidly for 2 hours at a peripheral speed of 6 m / s to obtain spindle-shaped base toner particles.If the spindle shape is insufficient, the stirring time is extended. The solvent was removed at 50 ° C. or lower for 1.0 hour, filtered, washed and dried, followed by air classification to obtain spindle-shaped base particles, and then 0.5 parts of hydrophobic silica on 100 parts of toner particles. And 0.5 part of hydrophobized titanium oxide were mixed with a Henschel mixer to obtain toner (5).
The volume-average particle size was 5.32 μm, the number-average particle size was 4.25 μm, and Dv / Dn 1.25 (measured with Multisizer II).

Example 6 <M Toner>
An emulsified slurry 6 was produced in the same manner as in Example 5 except that the master batch in Example 5 was replaced with → masterbatch 3. Otherwise, in the same manner as in Example 5, a (toner 6) having a volume average particle size of 5.95, a number average particle size of 5.04 μm and DV / Dn of 1.18 was obtained.
Example 7 <Y Toner>
An emulsified slurry 7 was produced in the same manner as in Example 5 except that the master batch in Example 6 was replaced with → master batch 4. Otherwise, in the same manner as in Example 5, (Toner 7) having a volume average particle size of 4.85, a number average particle size of 4.61 μm, and DV / Dn 1.05 was obtained.
Example 8 <BK Dissolved Suspension Toner>
A toner 8 was produced in the same manner as in Example 1, except that [Prepolymer 1] and 115 parts and [Ketimine Compound 1] 6.6 parts were used from the material of Example 1. [Toner 8] having a volume average particle diameter Dv of 3.65 μm, a number average particle diameter Dn of 3.11 μm and Dv / Dn of 1.17 was obtained.

Example 9 <BK Dissolving Suspension Toner>
A toner 8 was produced in the same manner as in Example 1, except that [Prepolymer 1] and 115 parts and [Ketimine Compound 1] 6.6 parts were used from the material of Example 5. [Toner 9] having a volume average particle diameter Dv of 5.30 μm, a number average particle diameter of Dn of 4.77 μm, and Dv / Dn of 1.11 was obtained.
Example 10 <Evaluation of Toner Process>
As the toner, a black toner was used in Example 4, a cyan toner was used in Example 5, a magenta toner was used in Example 6, and a yellow toner was used in Example 7.
On the other hand, as a carrier, a copolymer of 2-hydroxyethyl metal acrylate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene is a resin having an average particle diameter of 75/25 by weight. A coated carrier obtained by coating 0.75 wt% (based on the core material) on a 50 μ ferrite core material was used.
A developer was prepared by weighing so that the toner concentration was 5% and the total amount of the toner and the carrier was 1000 g.

This developer was set with a black developer in the developing section of the apparatus, a yellow developer in the developing section, a magenta developer in the developing section, and a cyan developer in the developing section. A scorotron charger was arranged in the charging process, a blade cleaning unit made of urethane was arranged in the cleaning process, and a roller fixing unit was arranged in the fixing process.
Then, after the power is turned on, only the first image forming unit develops the solid image until the roller temperature of the fixing unit reaches a constant temperature. At that time, the toner is transferred without transferring the transfer paper (without passing the paper), and the solid image is transferred onto the conveyance belt. The toner image on the belt is passed through the second, third, and fourth image forming portions. Thereafter, the transport belt is added with an operation for performing a process of cleaning in the cleaning unit. A continuous test was performed at a speed of copying 28 sheets per minute after the temperature of the fixing portion reached a constant temperature, and the cleaning performance after 100,000 sheets was good.

Comparative Example (Preparation of aqueous dispersion of wax particles)
Production Example 18
1000 ml of distilled water degassed into a 4-head Kolben with a stirring device, temperature sensor, nitrogen inlet tube and cooling tube, 28.5 g of New Coal 565C (manufactured by Nippon Emulsifier Co., Ltd.), 1 (manufactured by Noda Wax Co., Ltd.) 185.5 g was added and the temperature was raised while stirring under a nitrogen stream. When the internal temperature was 85 ° C., a 5N aqueous sodium hydroxide solution was added and the temperature was raised to 75 ° C. as it was, followed by continuing heating and stirring as it was for 1 hour and cooling to room temperature to obtain [Wax Particle Aqueous Dispersion 1].

(Preparation of aqueous colorant dispersion)
After adding 100 g of carbon black (trade name: Mogal L, manufactured by Cabot Corporation) and 25 g of sodium dodecyl sulfate to 540 ml of distilled water and sufficiently stirring, a pressure disperser (MINI-LAB: manufactured by Lani Corporation) was used. Dispersion was performed to obtain [Colorant Dispersion Liquid I].
(Synthesis of aqueous binder fine particle dispersion)
Production Example 19
A 1 L 4-head Kolben equipped with a stirrer, cooling tube, temperature sensor and nitrogen inlet tube is 480 ml of distilled water, 0.6 g of sodium dodecyl sulfate, 106.4 g of styrene, 43.2 g of n-butyl acrylate, 10.4 g of methacrylic acid. The mixture was heated to 70 ° C. under a nitrogen stream while stirring. Here, an initiator aqueous solution in which 2.1 g of potassium persulfate was dissolved in 120 ml of distilled water was added, and the mixture was stirred at 70 ° C. for 3 hours under a nitrogen stream to complete the polymerization, and then cooled to room temperature. A fine particle dispersion 1] was obtained.
A 5 L 4-head Kolben equipped with a stirrer, a condenser, a temperature sensor, and a nitrogen inlet tube was subjected to 2400 ml of distilled water, 2.8 g of sodium dodecyl sulfate, 620 g of styrene, 128 g of n-butyl acrylate, 52 g of methacrylic acid, and tert-dodecyl mercaptan 27 The temperature was raised to 70 ° C. under a nitrogen stream while adding 4 g and stirring. Here, an initiator aqueous solution in which 11.2 g of potassium persulfate was dissolved in 600 ml of distilled water was added, and the mixture was stirred at 70 ° C. for 3 hours in a nitrogen stream to complete the polymerization, and then cooled to room temperature. A fine particle dispersion 2] was obtained.

Comparative Example 1
(Toner synthesis)
In a 1 L separable flask equipped with a stirrer, a condenser, and a temperature sensor, 47.6 g of [High molecular weight binder fine particle dispersion 1], 190.5 g of [Low molecular weight binder fine particle dispersion 2], [Wax particle aqueous dispersion 1] 7.7 g, [Colorant Dispersion I] 26.7 g and 252.5 ml of distilled water were added and mixed and stirred, and then adjusted to pH = 9.5 using a 5N aqueous sodium hydroxide solution. Further, with stirring, a surfactant in which 50 g of sodium chloride was dissolved in 600 ml of distilled water, 77 ml of isopropanol, and Fluorard FC-170C (manufactured by Sumitomo 3M: Fluoro-based nonionic surfactant) 10 mg in 10 ml of distilled water. Aqueous solutions were sequentially added, the internal temperature was raised to 85 ° C., the reaction was performed for 6 hours, and then cooled to room temperature. The reaction solution was adjusted to pH = 13 using 5N aqueous sodium hydroxide solution, filtered, resuspended in distilled water, filtered and resuspended repeatedly, washed, dried and [Toner Comparison 1] having an average particle diameter Dv of 6.52 μm, a number average particle diameter Dn of 5.31 μm, and Dv / Dn of 1.23 was obtained.

Comparative Example 2
A toner was prepared using the materials and methods of Example 1 except that the modified layered inorganic mineral used in Example 1 was not added.
[Toner Comparison 2] having a volume average particle diameter Dv of 5.60 μm, a number average particle diameter of Dn of 4.14 μm, and Dv / Dn of 1.35 was obtained.
Comparative Example 3
A toner was prepared using the material and method of Example 3 except that ethylene wax (MP110 ° C., manufactured by Sanyo Chemical Industries) was used instead of the paraffin wax used in Example 3.
[Toner Comparison 3] having a volume average particle diameter Dv of 5.65 μm, a number average particle diameter of Dn 4.51 μm, and Dv / Dn1.25 was obtained.

To 100 parts of each toner obtained as described above, 0.7 part of hydrophobic silica and 0.3 part of hydrophobic titanium oxide were mixed with a Henschel mixer. Table 1 shows the obtained toner physical property values.
It was shown to.
A developer composed of 5% by weight of a toner subjected to external additive treatment and 95% by weight of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin was prepared and tested based on each test method. It is shown in Table 1.

(Evaluation item)
(A) APA addition amount part The amount of addition of Kraton APA (manufactured by Southern Clay Co., Ltd.) as a layered inorganic mineral product is shown in parts.
(B) S.M. C.
Represents solid content concentration%.
(C) Charge amount 6 g of developer is weighed, charged into a metal cylinder that can be sealed, and blown to obtain the charge amount. The toner concentration is adjusted to 4.5 to 5.5 wt%.
(D) Fixability Using a Ricoh imagio Neo 450, a single toner test was conducted on a plain paper and a cardboard transfer paper (Ricoh type 6200 and NBS Ricoh copy printing paper <135>) with a solid image of 1.0. Adjust so that the toner of ± 0.1 mg / cm ² is developed, and adjust the temperature of the fixing belt to be variable so that the temperature at which offset does not occur on plain paper and the lower limit of fixing temperature on thick paper It was measured. The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.
10.6 g of toner was collected in a 50 ml sample bottle, tapped for 35 seconds, stored in a constant temperature bath at 50 ° C. for 24 hours, and measured with a needle penetration meter. The following judgment is made based on the value of the needle entry degree when N = 3.
Judgment: 10mm or less ×
More than 10mm and less than 15mm △
15mm or more ○

(E) Flow tester As a flow tester, for example, there is an elevated flow tester CFT500D manufactured by Shimadzu Corporation. The flow curve obtained by the temperature raising method of the flow tester is the data shown in the figure, and each temperature can be read therefrom. In the figure, Ts is the softening temperature, Tfb is the outflow start temperature, and the melting temperature in the 1/2 method is the T1 / 2 temperature.
"Measurement condition"
Load: 10 kg / cm ² , heating rate: 3.0 ° C./min,
Die diameter: 0.5 mm, die length: 1.0 mm, starting temperature 50 ° C.,
Achieving temperature 250.0 ° C, preheating time 200s,
<Sample preparation conditions>
A sample weight of 1.00 g is molded to a diameter of 10.0 mm using a flow tester molding machine.

The temperature raising method is a method of testing while raising the temperature at a constant rate as the test time elapses. In this test, it is possible to continuously measure the process from the solid region to the transition region, the rubbery elastic region, and the flow region.
With this device, the shear rate and clay at each temperature in the flow zone can be measured. Moreover, the softening temperature Ts when moving from the solid region to the transition region, and the outflow start temperature Tfb from which the sample flows can be measured.
The flow curve in the temperature raising method shows the behavior as shown in FIG.

(F) Tg Measurement Method The melting point (° C.) of the release agent and the glass transition point (Tg) of the resin in the present invention are measured by differential scanning calorimetry (DSC). The melting point (° C.) of the wax is determined by the peak top showing the maximum endotherm of the DSC curve. Moreover, the measurement was performed under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.
Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C

The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method specifies a range of ± 5 ° C around the point showing the maximum peak of the DrDSC curve which is the DSC differential curve of the second temperature rise, and obtains the peak temperature using the peak analysis function of the analysis software. Next, the maximum endothermic temperature of the DSC curve is obtained by using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the melting point.
The Tg of the resin is measured by the following method.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, the sample was cooled to room temperature and left for 10 min, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at min. Tg was analyzed using (TA-60, version 1.52). Using an analysis system, calculation was performed from the contact point between the tangent line of the endothermic curve near the Tg and the base line.

(G) Low molecular weight pes
It is a low molecular weight polyester.
(H) 10.6 g of heat-resistant storage toner is collected in a 50 ml sample bottle, tapped for 35 seconds, stored in a constant temperature bath at 50 ° C. for 24 hours, and measured with a needle penetration meter. The following determination is made based on the value of the needle approach degree when N = 3.
Judgment: 10mm or less ×
More than 10mm and less than 15mm △
15mm or more ○

(I) Image Density A solid toner test is output to a plain paper and a cardboard transfer paper (Ricoh Type 6200 and NBS Ricoh Copied Printing Paper <135>) using a Ricoh imageio Neo 450. After outputting a solid image, the image density was measured by X-Rite (manufactured by X-Rite). This was measured at five points for each color alone, and the average was obtained for each color.
(J) Background stain The blank image is stopped during development, the developer on the photoconductor after development is transferred to tape, and the difference from the image density of the untransferred tape is measured by 938 Spectrodensitometer (manufactured by X-Rite) )
Judgment: Acceptance criteria is 0.05 or less

(K) Cleaning property The transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.), measured with a Macbeth reflection densitometer RD514, and the difference from the blank is Those with 0.01 or less were evaluated as ◯ (good), and those exceeding it were evaluated as x (defect).
(L) Dot reproducibility Evaluation using a Ricoh imago Neo Neo 450 (optical system laser 600 dpi) and a 600 dpi image by an optical microscope (× 20) in the following three stages.
○: Excellent △: Inferior ×: Very inferior

(M) Molecular weight distribution test method MW distribution measurement Here, the measurement method by GPC will be described. That is, the column was stabilized in a heat chamber at 40 ° C., THF was flowed through the column at this temperature as a solvent at a flow rate of 1 ml / min, and the sample was prepared in a THF sample solution of 0.05 to 0.6% by weight. Is measured by injecting 50 to 200 μl. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Alternatively, the molecular weights of Toyo Soda Kogyo Co., Ltd. are 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9. It is appropriate to use x10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.
The weight average molecular weight (MW), number average molecular weight (MN), and MW / MN are automatically calculated from the obtained values.

It is explanatory drawing of the shape of this invention toner. It is explanatory drawing of the sea island structure of a colored particle. It is explanatory drawing of an example of a process cartridge. It is a graph which shows the flow curve by a flow curve (temperature raising method).

Claims (13)

  In a toner in which an oil phase containing at least a toner composition and / or a toner composition precursor is dispersed in an aqueous medium and granulated, and a release agent inside the toner particles is used in a heating test using a heating and cooling unit. A toner for developing an electrostatic charge image, wherein the release agent dissolves on the outer surface of the toner particles at 65 ° C. to 90 ° C., and the colored particle toner and the release agent have a sea-island structure.   Disperse and / or emulsify in an aqueous medium an oil phase containing a modified layered inorganic mineral in which at least some of the ions of the binder resin, colorant, release agent and layered inorganic mineral are modified with organic ions in an organic solvent. The toner obtained by removing the solvent from the obtained dispersion / emulsion, and the release agent inside the toner particles is 65 ° C. to 65 ° C. in a heating test using a heating / cooling unit. A toner for developing an electrostatic charge image, wherein the release agent melts outside the toner particles at 90 ° C., and the color particle toner and the release agent have a sea-island structure.   The volume average particle diameter of the toner is 3 to 6 μm, the ratio Dv / Dn of the average particle diameter (Dv) to the number average particle diameter (Dn) of the toner is 1.00 to 1.30, and the binder The glass transition point (Tg) of the resin is 40 to 55 ° C, and the weight average molecular weight (Mw) of the binder resin is 3000 to 6500, for electrostatic image development according to claim 1 or 2 toner.   The electrostatic charge image developing toner according to claim 1, wherein the releasing agent has a melting point of 65 ° C. to 80 ° C.   The toner contains an isocyanate group-containing polyester prepolymer in an organic solvent, a compound that extends or crosslinks with the prepolymer, a release agent, and an oil phase in which the toner component is dissolved or dispersed, and the dissolved or dispersed material in an aqueous medium. In the toner obtained by carrying out a crosslinking reaction and / or an extension reaction in Step 3 and removing the solvent from the obtained dispersion, the release agent inside the toner particles is 65 ° C. in a heating test using a heating / cooling unit. The electrostatic charge image developing device according to any one of claims 1 to 4, wherein the release agent melts outside the toner particles at ~ 90 ° C and the color particle toner and the release agent have a sea-island structure. toner.   6. The electrostatic charge image developing device according to claim 1, wherein a dispersion particle size of the release agent contained in the toner particles is within a range of 70% by number within a range from 0.3 to 1.0 μm. toner.   The oil phase used in the toner, wherein the solution or dispersion has a Casson yield value at 25 ° C. of 1 to 10 Pa, and the solution or dispersion has a non-Newtonian index tan θ of 0 at 25 ° C. A toner obtained by removing a solvent from the obtained dispersion, wherein the toner has a shape factor SF-1 of 140 to 200. The toner for developing an electrostatic charge image according to any one of 1 to 6.   The oil phase used for producing the toner for developing an electrostatic charge image according to any one of claims 1 to 7 has a non-Newtonian index tanθ at 25 ° C of the solution or dispersion of 0.75 to 0.95. A toner is obtained by removing the solvent from the obtained dispersion, and the toner has a shape factor SF-1 of 140 to 200.   The oil phase used in the production of the toner has a Casson yield value of 1 to 10 Pa at 25 ° C. of the solution or dispersion, and a toner is obtained by removing the solvent from the obtained dispersion. A method for producing a toner for developing an electrostatic charge image, wherein the toner has a shape factor SF-1 of 140 to 200.   10. The method for producing a toner for developing an electrostatic charge image according to claim 8, wherein the toner is used for a two-component developer.   An image forming method comprising: a transfer step of transferring a toner image carried on a toner image carrier to a transfer material; and a cleaning step of cleaning toner remaining on the surface of the toner image carrier using a blade after the transfer. Item 8. A method for forming an image, comprising using the toner according to any one of Items 1 to 7.   A toner container containing the electrostatic image developing toner according to claim 1.   An image forming apparatus using the electrostatic image developing toner according to claim 1 for development.