JP2009258478A - Toner and method for producing the same, and image forming apparatus, image forming method, and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner and a method for producing the toner excellent in low temperature fixability, reducedin transfer residue when blade cleaning is used, and capable of forming an image with high picture quality and a high resolution, and to provide an image forming apparatus, an image forming method, and a process cartridge using the toner. <P>SOLUTION: The toner is produced by the producing method of the toner including an aqueous granulation step, a first solvent removal step, a temperature elevation step, a second solvent removal step, a filtration step, and a cleaning step. The concentration of a residual organic solvent in an emulsion or dispersion liquid after the first solvent removal step is specified to from 10 mass% to 33 mass% with respect to the toner in the emulsion or dispersion liquid; and the temperature elevation rate in the temperature elevation step is controlled to be within a range of 0.3°C/min to 1.5°C/min. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner used as a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, and the like, a method for producing the toner, an image forming apparatus using the toner, and an image forming method. And a process cartridge.

In recent years, the strong demand for higher image quality from the market has spurred the development of an electrophotographic image forming apparatus and toner suitable for it. As a toner corresponding to high image quality, it is essential that the toner has a uniform particle size. If the toner particle size is uniform and the particle size distribution is sharp, the development behavior of individual toners is uniform, and the fine dot reproducibility is remarkably improved.
However, a toner having a small particle size and a uniform particle size causes difficulty in cleaning. Particularly with blade cleaning, it is difficult to stably clean toner having a uniform and small particle diameter. Therefore, various methods for improving the blade cleaning property by improving the toner have been proposed. One of them is a method of changing the toner from a spherical shape to an irregular shape. By changing the shape of the toner, the powder flowability of the toner is lowered, and it is easy to dam by blade cleaning. However, if the degree of toner irregularity is too large, the behavior of the toner becomes unstable during development and the like, and there is a problem that the fine dot reproducibility deteriorates.

  Changing the shape of the toner in this way certainly improves the reliability of the toner with respect to blade cleaning, but on the other hand, a problem arises in terms of fixing. In other words, when the shape of the toner is changed, the toner filling density in the toner layer on the recording medium before fixing is reduced, the thermal conductivity in the toner layer is reduced during fixing, and the low-temperature fixability is deteriorated. Resulting in. In particular, when the pressure at the time of fixing is smaller than the conventional pressure, the thermal conductivity is further deteriorated and the low-temperature fixing property is hindered. In order to solve this problem, for example, Patent Document 1 proposes a toner made of a polyester resin having a Wadell practical sphericity of 0.90 to 1.00. However, since the toner is substantially spherical, the toner cleaning is performed. The sex issue has not been solved.

In addition to the suspension polymerization method, the polymerization toner method includes an emulsion polymerization method and a dissolution suspension method that are relatively easy to modify, but in the case of the emulsion polymerization method, complete removal of the styrene monomer, emulsifier and dispersion Removal of the agent is difficult. In particular, the problem with toners has become increasingly greater as environmental problems have recently been highlighted. Also, in the shape of the toner, due to the unevenness of the silica added as a fluidizing agent by making it uneven, the contamination of the photoreceptor by the toner is caused by the movement of the silica to the recess in use. Problems such as toner adhesion to the fixing roller occur.
On the other hand, in the case of the dissolution suspension method, there is a merit that a polyester resin that can be fixed at low temperature can be used. However, in order to achieve oil-less fixing, polymer control and production in order to widen the mold release width are required. Since the high molecular weight component is added in the step of dissolving or dispersing the resin and the colorant in the solvent, the liquid viscosity is increased, resulting in a problem in productivity. In the dissolution suspension method, the toner surface shape is made spherical and uneven to improve the cleaning property (see Patent Document 2). However, since it is an irregularly shaped toner with no regularity, charging stability is improved. In addition, the high molecular weight design for ensuring chipping and further basic durability and releasability has not been achieved, and a sufficiently satisfactory toner has not been obtained.

  In recent years, a method of obtaining resin particles for toner having a shape excellent in blade cleaning property and a wide fixing temperature range has been proposed (see Patent Document 3). However, even in this proposal, it is actually insufficient to achieve both blade cleaning properties and low-temperature fixing properties.

  Accordingly, a toner that is excellent in low-temperature fixability, has little untransferred toner when blade cleaning is used, and can form an image with high image quality and high resolution, and an image forming apparatus using the toner, At present, the image forming method and the process cartridge are not yet provided.

Japanese Patent Laid-Open No. 11-133665 JP 9-15903 A JP 2005-49858 A

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention is excellent in low-temperature fixability, has little transfer residual toner when blade cleaning is used, can form a high-quality image with high resolution, and a toner production method, and uses the toner. An object of the present invention is to provide an image forming apparatus, an image forming method, and a process cartridge.

Means for solving the problems are as follows. That is,
<1> A compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a binder resin, a colorant, a release agent, and ions contained in a layered inorganic mineral in an organic solvent An aqueous granulation step of emulsifying or dispersing an oil phase composed of a solution or dispersion obtained by dissolving or dispersing a modified layered inorganic mineral, at least a part of which is modified with organic ions, in an aqueous medium;
A first solvent removal step of removing a part of the organic solvent from the emulsification or dispersion obtained in the aqueous granulation step;
A temperature raising step in which the emulsification or dispersion removed in the first solvent removal step is heated to 40 ° C. to 60 ° C. and heated;
An aging step in which the heated emulsification or dispersion is heated at 40 ° C. to 60 ° C. and aged;
A second desolvation step for removing the organic solvent in the emulsification or dispersion that has undergone the aging step;
A filtration step of filtering the emulsification or dispersion that has undergone the second solvent removal step;
A toner produced by a method for producing a toner, comprising: a washing step of washing and drying the filtered particles,
The residual organic solvent concentration in the emulsification or dispersion after the first desolvation step is 10% by mass to 33% by mass with respect to the toner in the emulsification or dispersion,
The toner according to claim 1, wherein a temperature increase rate in the temperature increase step is 0.3 ° C./min to 1.5 ° C./min.
<2> The oil phase contains a kneaded composite containing a modified layered inorganic mineral and a binder resin, and the volume average particle size of the modified layered inorganic mineral in the kneaded composite is 0.1 μm to 0.55 μm. The toner according to <1>, wherein the modified layered inorganic mineral having a particle diameter of 1 μm or more in the kneaded composite is 15% by volume or less.
<3> The toner according to any one of <1> to <2>, wherein the shape factor SF-1 of the toner is 110 to 200, and the shape factor SF-2 of the toner is 110 to 300.
<4> The toner according to any one of <1> to <3>, wherein a content of the modified layered inorganic mineral in the toner is 0.1% by mass to 5% by mass.
<5> The toner according to any one of <1> to <4>, wherein the organic ions in the modified layered inorganic mineral are quaternary ammonium ions.
<6> The toner has a volume average particle diameter of 3 μm to 7 μm, and a ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.20 or less < The toner according to any one of <1> to <5>.
<7> BET specific surface area of the toner ^is the toner according the a 1.0m ² /g~6.0m 2 / g to any one of <1> to <6>.
<8> The toner according to any one of <1> to <7>, wherein a ratio of particles having a particle diameter of 2 μm or less is 1% by number to 10% by number.
<9> The toner according to any one of <1> to <8>, wherein the binder resin contains a polyester resin.
<10> The toner according to <9>, wherein the content of the polyester resin in the binder resin is 50% by mass to 100% by mass.
<11> The toner according to any one of <9> to <10>, wherein the mass average molecular weight of a tetrahydrofuran (THF) soluble portion of the polyester resin is 1,000 to 30,000.
<12> The toner according to any one of <9> to <11>, wherein the acid value of the polyester resin is 1.0 mgKOH / g to 50.0 mgKOH / g.
<13> The toner according to any one of <9> to <12>, wherein the polyester resin has a glass transition temperature of 35 ° C to 65 ° C.
<14> The toner according to any one of <1> to <13>, wherein the polymer having a site capable of reacting with the compound having an active hydrogen group has a mass average molecular weight of 3,000 to 20,000.
<15> The toner according to any one of <1> to <14>, wherein the toner has an acid value of 0.5 mgKOH / g to 40.0 mgKOH / g.
<16> The toner according to any one of <1> to <15>, wherein the glass transition temperature of the toner is 40 ° C to 70 ° C.
<17> A compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a binder resin, a colorant, a release agent, and an ion of a layered inorganic mineral in an organic solvent An aqueous granulation step of emulsifying or dispersing an oil phase composed of a solution or dispersion obtained by dissolving or dispersing a modified layered inorganic mineral, at least a part of which is modified with organic ions, in an aqueous medium;
A first solvent removal step of removing a part of the organic solvent from the emulsification or dispersion obtained in the aqueous granulation step;
A temperature raising step in which the emulsification or dispersion removed in the first solvent removal step is heated to 40 ° C. to 60 ° C. and heated;
An aging step in which the heated emulsification or dispersion is heated at 40 ° C. to 60 ° C. and aged;
A second desolvation step for removing the organic solvent in the emulsification or dispersion that has undergone the aging step;
A filtration step of filtering the emulsification or dispersion that has undergone the second solvent removal step;
A washing step of washing and drying the filtered particles, comprising:
The residual organic solvent concentration in the emulsification or dispersion after the first desolvation step is 10% by mass to 33% by mass with respect to the toner in the emulsification or dispersion,
A method for producing a toner, wherein a temperature raising rate in the temperature raising step is 0.3 ° C./min to 1.5 ° C./min.
<18> A two-component developer comprising the toner according to any one of <1> to <16> and a carrier.
<19> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, A transfer process for transferring a visible image to a recording medium, a fixing process for fixing the transferred image transferred to the recording medium, and a cleaning process for removing toner remaining on the surface of the electrostatic latent image carrier after the transfer using a blade. An image forming method including at least
An image forming method, wherein the toner is the toner according to any one of <1> to <16>.
<20> An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to make it visible Developing means for forming an image; transfer means for transferring the visible image to a recording medium; fixing means for fixing the transferred image transferred to the recording medium; and toner remaining on the surface of the electrostatic latent image carrier after transfer An image forming apparatus having at least a cleaning unit that removes the toner using a blade,
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <16>.
<21> An electrostatic latent image carrier, development means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image, and electrostatic latent image carrier after transfer A process cartridge having at least cleaning means for removing toner remaining on the body surface using a blade,
A process cartridge, wherein the toner is the toner according to any one of <1> to <16>.

  According to the present invention, a toner and a toner that can solve the conventional problems, have excellent low-temperature fixability, have a small amount of residual toner when blade cleaning is used, and can form a high-quality and high-resolution image. Manufacturing method, an image forming apparatus using the toner, an image forming method, and a process cartridge can be provided.

(Toner and toner production method)
The toner of the present invention is a toner production process comprising an aqueous granulation step, a first solvent removal step, a temperature raising step, an aging step, a second solvent removal step, a filtration step, and a washing step. Manufactured by the method.
The toner production method of the present invention includes an aqueous granulation step, a first solvent removal step, a temperature raising step, an aging step, a second solvent removal step, a filtration step, and a washing step. In addition, other steps are included as necessary.
The aqueous granulation step is carried out in an organic solvent by using a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a binder resin, a colorant, a release agent, and a layered inorganic material. This is a step of emulsifying or dispersing an oil phase composed of a solution or dispersion obtained by dissolving or dispersing a modified layered inorganic mineral in which at least some of the ions of the mineral are modified with organic ions in an aqueous medium.
The first solvent removal step is a step of removing a part of the organic solvent from the emulsification or dispersion obtained in the aqueous granulation step.
The temperature raising step is a step of heating the emulsified or dispersed liquid desolvated in the first solvent removal step to 40 ° C. to 60 ° C. and heating.
The aging step is a step of heating and aging the heated emulsification or dispersion at 40 ° C to 60 ° C.
The second solvent removal step is a step of removing the organic solvent in the emulsification or dispersion that has undergone the aging step.
The filtration step is a step of filtering the emulsified or dispersed liquid that has undergone the second solvent removal step.
The washing step is a step of washing and drying the filtered particles.
Hereinafter, the toner of the present invention and the method for producing the toner will be described in detail.

In the present invention, the residual organic solvent concentration in the emulsification or dispersion after the first desolvation step is 10% by mass to 33% by mass with respect to the toner in the emulsification or dispersion. When the residual organic solvent concentration is less than 10% by mass, sufficient charging performance may not be obtained, and when it exceeds 33% by mass, toner particles may aggregate in the aging step.
The residual organic solvent concentration can be specifically measured by the following procedure when the organic solvent is, for example, ethyl acetate.
-Measurement equipment conditions-
・ Measurement device: GC-2010 (manufactured by Shimadzu Corporation, gas chromatograph)
・ Injection volume: 2.0μL
-Sample vaporization chamber-
・ Injection mode: Split ・ Vaporization chamber temperature: 180 ℃
・ Carrier gas: He
・ Pressure: 40.2kPa
・ Total flow rate: 56.0mL / min
・ Column flow rate: 1.04mL / min
・ Linear speed: 20.0cm / sec
・ Purge flow rate: 3.0mL / min
-Split ratio: 50.0
-Column-
・ Column name: ZB-50
・ Liquid film thickness 0.25μm
・ Length 30.0m
・ Inner diameter: 0.32mmID
・ Upper column temperature: 340 ℃
-Column oven-
・ Column temperature: 60 ℃
-Column oven temperature program-
60 ° C hold 6 min → Temperature rise rate 60 ° C / min → 230 ° C hold 5 min
-Detector-
・ Detector temperature: 250 ℃
・ Make-up gas: N ₂ / Air
・ Make-up flow rate: 30.0mL / min
・ H ₂ flow rate: 47.0mL / min
・ Air flow rate: 400mL / min
-Measurement method-
-Preparation of internal standard solution: 4 g of toluene was weighed into a volumetric flask and diluted to 500 mL with DMF.
-Preparation of measurement sample: After diluting 1.5 g of the measurement dispersion slurry to about 50 mL with DMF, 10 mL of the internal standard solution is collected and introduced with a whole pipette. After stirring the measurement sample with a stirrer at 400 rpm for 4 minutes, the sample is set on the autosampler of the measuring instrument GC and measured. After the measurement, the amount of ethyl acetate in the slurry was calculated from the ratio of toluene and ethyl acetate as the internal standard substance by the internal standard method, and the ethyl acetate concentration for the toner in the slurry was calculated from the value by the following formula.
Ethyl acetate concentration [%] with respect to toner in slurry = ethyl acetate amount in 100 g of slurry obtained by GC measurement / toner amount in 100 g of slurry [g]

  The temperature raising rate in the temperature raising step needs to be 0.3 ° C./min to 1.5 ° C./min. When the temperature increase rate is out of the above range, sufficient charging performance may not be obtained.

  In the toner of the present invention, the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is preferably 1.20 or less, more preferably 1.00 to 1.20. . Thereby, a high-resolution and high-quality toner can be obtained. Furthermore, in the case of a two-component developer, even if a long-term balance of the toner is performed, fluctuations in the particle size of the toner in the developer are reduced, and good and stable developability even with long-term stirring in the developing device. Is possible. When the Dv / Dn exceeds 1.20, the particle size variation of individual toners is large, the toner behavior varies during development, and the reproducibility of minute dots is impaired. High-quality images cannot be obtained.

The volume average particle diameter (Dv) of the toner of the present invention is preferably 3 μm to 7 μm. In general, it is said that the smaller the volume average particle diameter of the toner, the more advantageous it is to obtain a high-resolution and high-quality image. It is disadvantageous. Further, when the volume average particle diameter is smaller than the above range, 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 reduced. 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.
These phenomena are greatly related to the content of fine powder, and it is preferable that the number of particles having a particle size of 2 μm or less is 110% by number. If the number of particles having a particle size of 2 μm or less exceeds 10% by number, it may be a hindrance to adhesion to a carrier or high charge stability. Conversely, when the toner particle size is larger than the above range, it becomes difficult to obtain a high-resolution and high-quality image, and the toner particle size when the balance of the toner in the developer is performed. In many cases, fluctuations of It was also clarified that the same applies when the volume average particle diameter / number average particle diameter (Dv / Dn) is larger than 1.20.

  The volume average particle size and the particle size distribution of the toner can be measured by, for example, a car Coulter counter method. Examples of the measuring device for the volume average particle diameter and particle size distribution of the toner include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). In the present invention, measurement can be performed by using a Coulter Counter TA-II type, connected to an interface (manufactured by Nikka Giken Co., Ltd.) for outputting the number distribution and volume distribution, and a PC 9801 personal computer (manufactured by NEC Corporation). it can.

The toner of the present invention preferably has a BET specific surface area of 1.0m ² /g~6.0m ² / ^g, more preferably 2.0m ² /g~4.0m 2 / g. If the BET specific surface area is less than 1.0 m ² / g, the presence of coarse particles and inclusion of additives, and if it exceeds 6.0 m ² / g, the presence of fine particles and the floating of additives However, the surface roughness may easily affect the image quality.

The BET specific surface area is a specific surface area St per unit mass calculated from a specific surface area Sb (m ² / g) per unit mass measured by the BET method and a mass average particle diameter when the toner is assumed to be a true sphere. It is expressed as a ratio (Sb / St) to (m ² / g). The BET specific surface area is measured by a multi-point method of nitrogen adsorption method, and can be measured by, for example, a high-speed specific surface area / pore distribution measuring device NOVA1200 multi-point method manufactured by Yuasa Ionics Co., Ltd.
Specifically, it can be measured under the following conditions.
・ Adsorption gas: Nitrogen gas (99.995 or more)
-Refrigerant: Liquid nitrogen-Cell used: 9mm pellet short (large)
・ Pretreatment conditions: 12 hours at 30 ° C. (evacuation)
・ Measurement points: 3 points of relative pressure (P / PO) = 0.1-0.3

In the present invention, a toner having a small particle size and a uniform particle size causes difficulty in blade cleaning. Therefore, the toner shape factor SF-1 ranges from 110 to 200, and SF-2 ranges from 110 to 300. Preferably there is.
First, the relationship between toner shape and transferability will be described. When using a full-color copier that transfers images with multi-color development, the amount of toner on the photoconductor increases compared to the case of one-color black toner used in black-and-white copiers. It is difficult to improve transfer efficiency. In addition, when ordinary irregular toner is used, a shearing force or friction between the photosensitive member and the cleaning member, between the intermediate transfer member and the cleaning member, and / or between the photosensitive member and the intermediate transfer member. Due to the force, toner fusing or filming occurs on the surface of the photoreceptor or the intermediate transfer member, and transfer efficiency tends to deteriorate. When generating a full-color image, it is difficult to uniformly transfer four-color toner images. Furthermore, when an intermediate transfer member is used, problems are likely to occur in terms of color unevenness and color balance, and a high-quality full-color image is stabilized. Output is not easy.

  From the viewpoint of the balance between blade cleaning and transfer efficiency, the toner shape factor SF-1 is preferably 110 to 200, and more preferably 120 to 180. Blade cleanability and transferability are greatly related to the material of the blade and how to apply the blade, and transfer also varies depending on the process conditions, so that the design according to the process can be made within the above-described SF-1 range. However, when SF-1 falls below 110, cleaning with a blade becomes difficult. On the other hand, when SF-1 exceeds 200, the aforementioned transferability is deteriorated. This phenomenon is because the toner shape becomes irregular and the movement of toner during transfer (photosensitive member surface to transfer paper, photosensitive member surface to intermediate transfer belt, first intermediate transfer belt to second intermediate transfer belt, etc.) is smooth. Since the behavior varies among the toner particles, uniform and high transfer efficiency cannot be obtained. In addition, unstable charging and brittleness of particles begin to appear. Furthermore, it becomes a fine phenomenon in the developer, which causes a decrease in the durability of the developer.

  In the case of the pulverized toner, the toner is indefinite shape (a shape that is not a specific and well-rounded shape) and the toner has a shape factor SF-1 exceeding 140. However, since the particle size distribution of the toner is generally broad, In order to make Dv / Dn 1.20 or less, this is an inefficient method. When a toner is obtained by a polymerization method, for example, in suspension polymerization and emulsion polymerization, it is difficult to make a polyester toner, and it cannot cope with further low-temperature fixing. In JP-A-11-149180 and JP-A-2000-292981, in 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, the dry toner includes A dry toner composed of particles formed by an extension reaction and / or a cross-linking reaction of the prepolymer (A) with an amine (B) in an aqueous medium has been proposed, and the toner shape of the present invention is obtained. As a result, both transferability and cleaning properties cannot be achieved.

  Therefore, in the present invention, in a method for producing a toner using a reaction between a prepolymer (A) and an amine (B), a modified layered inorganic mineral obtained by modifying at least part of ions of the layered inorganic mineral with organic ions is contained in the toner. And a kneading composite step of the modified layered inorganic mineral and the binder resin to obtain an appropriate dispersion state, and by dissolving or dispersing the kneaded composite, the toner has a shape factor SF-1 of 110 to 200, and the toner The toner having a shape factor SF-2 of 110 to 300 can be easily obtained, but such shape control is difficult in conventional suspension polymerization and emulsion polymerization.

Here, the shape factors SF-1 and SF-2, which are the circularity used in the present invention, are 300 random SEM images of the toner obtained by measurement with a FE-SEM (S-4200) manufactured by Hitachi, Ltd. The image information is introduced into an image analysis apparatus (LuzexAP) manufactured by Nireco Corporation via an interface and analyzed, and the values obtained from the following formulas are defined as SF-1 and SF-2. . The values of SF-1 and SF-2 are preferably values obtained by the above Luzex, but are not particularly limited to the FE-SEM device and the image analysis device as long as similar analysis results can be obtained.
SF-1 = (L2 / A) × (π / 4) × 100
SF-2 = (P2 / A) × (1 / 4π) × 100
In the above formula, L represents the absolute maximum length of the toner, A represents the projected area of the toner, and P represents the maximum peripheral length of the toner.
In the case of a true sphere, both SF-1 and SF-2 become 100, and the value becomes larger from 100 and becomes an indeterminate shape. SF-1 represents the shape of the entire toner (such as an ellipse or a sphere), and SF-2 is a shape factor indicating the degree of unevenness on the surface.

The acid value of the toner of the present invention is preferably 0.5 mgKOH / g to 40.0 mgKOH / g, and more preferably 5 mgKOH / g to 20 mgKOH / g. When the toner acid value exceeds 40.0 mgKOH / g, the extension or crosslinking reaction of the modified polyester becomes insufficient, and the high temperature offset resistance may be affected. In this case, the dispersion stabilizing effect of the base compound cannot be obtained, the elongation or crosslinking reaction of the modified polyester tends to proceed, and there may be a problem in production stability.
The acid value of the toner is determined by a method according to JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.

  The glass transition temperature of the toner of the present invention is preferably 40 ° C. to 70 ° C. in order to obtain low temperature fixability, heat resistant storage stability, and high durability. When the glass transition temperature is less than 40 ° C., blocking in the developing machine and filming to the photoreceptor are likely to occur, and when it exceeds 70 ° C., the low-temperature fixability tends to deteriorate.

  The toner of the present invention includes a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a binder resin, a colorant, a release agent, and a layered inorganic mineral in an organic solvent. A toner solution is prepared by emulsifying or dispersing an aqueous phase composed of a solution or dispersion obtained by dissolving or dispersing a toner material containing a modified layered inorganic mineral in which at least some of the ions of the resin are modified with organic ions in an aqueous medium. After the preparation, the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium are prepared. To produce an adhesive base material in the form of particles and remove the organic solvent.

-Adhesive substrate-
The adhesive substrate exhibits adhesiveness to a recording medium such as paper, and is formed by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. It comprises a polymer and a binder resin.

There is no restriction | limiting in particular as a mass mean molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 1,000 or more are preferable and 2,000-10,000,000 are more preferable. 3,000 to 1,000,000 are particularly preferred.
When the mass average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

The storage elastic modulus of the adhesive substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10,000 dyne / cm ² , Usually, it is 100 ° C or higher, and preferably 110 ° C to 200 ° C. When the (TG ′) is less than 100 ° C., the hot offset resistance may be deteriorated.
The viscosity of the adhesive substrate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature (Tη) at which a measurement frequency of 20 Hz is 1,000 poise is usually 180 ° C. or lower. Yes, 90 ° C to 160 ° C is preferable. When the (Tη) exceeds 180 ° C., the low-temperature fixability may be deteriorated.
Therefore, from the viewpoint of achieving both hot offset resistance and low-temperature fixability, the (TG ′) is preferably higher than the (Tη). That is, the difference (TG′−Tη) between (TG ′) and (Tη) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C. or higher. The larger the difference, the better.
Further, from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability, the (TG′−Tη) is preferably 0 ° C. to 100 ° C., more preferably 10 ° C. to 90 ° C., and further preferably 20 ° C. to 80 ° C. preferable.

Specific examples of the adhesive substrate are not particularly limited and may be appropriately selected depending on the intended purpose. Particularly preferred are polyester resins.
There is no restriction | limiting in particular as said polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester-type resin etc. are mentioned especially suitably.
The urea-modified polyester-based resin includes an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. In this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When the urea bond is less than 10, the hot offset resistance may be deteriorated.

  Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophoronediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol Polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate with isophorone diisocyanate and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene Mixture of oxide 2 mol adduct and terephthalic acid polycondensate, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A Polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and ureaated with hexamethylenediamine, a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate with urea and hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, (9) bisphenol A ethylene Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer urea-modified with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and isophthalic acid with toluene diisocyanate with urea methylenediamine, a 2-mole adduct of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) in which the amino group of B1 to B5 is blocked include, for example, a ketimine obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) or those blocked (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
When the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be lowered. When the mixing equivalent ratio exceeds 3/1, the molecular weight of the urea-modified polyester resin becomes low. The hot offset resistance may be deteriorated.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. However, it can be appropriately selected from known resins, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a heating medium for fixing. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond-forming group in the urea bond-forming group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And what made the said active hydrogen group containing polyester resin react with polyisocyanate (PIC), etc. are mentioned.

  There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol A mixture with (TO), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, and the like are preferable. Mixtures are particularly preferred.

As the trivalent or higher polyol (TO), those having 3 to 8 or higher valences are preferable. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the trivalent or higher polyphenols alkylene oxide adducts include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trivalent or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-100: 10 are preferable and 100: 0.01-100: 1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tricarboxylic or higher polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, sebacic acid, and the like. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TO) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
As said aromatic polycarboxylic acid, a C9-C20 thing is preferable, For example, trimellitic acid, pyromellitic acid, etc. are mentioned.

  As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-100: 10 are preferable and 100: 0.01-100: 1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5 mass%-40 mass% Is preferable, 1% by mass to 30% by mass is more preferable, and 2% by mass to 20% by mass is particularly preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate. These can be used alone or in combination of two or more.

As a mixing ratio when reacting the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin), the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and 4/1 to 1.2 / 1. Is more preferable, and 3/1 to 1.5 / 1 is particularly preferable.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5 mass%-40 mass % Is preferable, 1% by mass to 30% by mass is more preferable, and 2% by mass to 20% by mass is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

As an average number of the isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A), 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  The mass average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 3,000 to 20,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). preferable. When the mass average molecular weight (Mw) is less than 3,000, the heat resistant storage stability may be deteriorated, and when it exceeds 20,000, the low temperature fixability may be deteriorated.

The measurement of the molecular weight distribution by the gel permeation chromatography (GPC) can be performed, for example, as follows.
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml / min, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6% by mass is injected and measured. . 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 the calibration curve created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or the molecular weight made by Tosoh Corporation 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × It is preferable to use 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

--Binder resin--
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, although a polyester resin etc. are mentioned, Undenatured polyester resin (unmodified polyester resin) is especially preferable.
When the unmodified polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include those similar to the urea bond-forming group-containing polyester resin, that is, a polycondensate of a polyol (PO) and a polycarboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure that is compatible with each other. It is preferable in terms of hot offset resistance.

The mass average molecular weight (Mw) of the unmodified polyester resin is preferably 1,000 to 30,000, preferably 1,500 to 15, in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). 1,000 is more preferable. When the mass average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated. Therefore, the content of the component having the mass average molecular weight (Mw) of less than 1,000 as described above. Is required to be 8 to 28% by mass. On the other hand, when the mass average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may be deteriorated.
The glass transition temperature of the unmodified polyester resin is preferably 35 ° C to 65 ° C, more preferably 35 ° C to 50 ° C. When the glass transition temperature is less than 35 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 65 ° C., the low-temperature fixability may be insufficient.

The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g to 120 mgKOH / g, and still more preferably 20 mgKOH / g to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 mgKOH / g to 50.0 mgKOH / g, more preferably 1.0 mgKOH / g to 45.0 mgKOH / g, and 15.0 mgKOH / g to 45.0 mgKOH / g. g is more preferable. Generally, it becomes easy to be negatively charged by giving the toner an acid value.

Here, the acid value (AV) and the hydroxyl value (OHV) are specifically determined by the following procedure.
・ Measuring device: potentiometric automatic titrator DL-53 Titrator (Metler Toledo)
-Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
・ Analysis software: LabX Light Version1.00.000
-Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
・ Measurement temperature: 23 ℃
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
At maximum volume [mL] 10.0
At potential No
At slope No
After number EQPs Yes
n = 1
comb. Termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

-Method of measuring acid value-
The acid value can be measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate soluble component) is added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Furthermore, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, and specifically, the calculation is performed as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and obtain the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample mass (where N is a factor of N / 10 KOH)

-Method for measuring hydroxyl value-
The hydroxyl value can be measured under the following conditions based on the measurement method described in JIS K0070-1966.
Weigh accurately 0.5 g of sample into a 100 ml volumetric flask and add 5 ml of acetylating reagent correctly. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1-2 hours, the flask is removed from the bath, allowed to cool, water is added and shaken to decompose acetic anhydride. Next, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the hydroxyl value.

When the unmodified polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the unmodified polyester resin (PE) is 5/95. -20/80 is preferable and 10 / 90-25 / 75 is more preferable.
When the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Glossiness may deteriorate.
As content of the said unmodified polyester resin in the said binder resin, 50 mass%-100 mass% are preferable, for example, 70 mass%-95 mass% are more preferable, 80 mass%-90 mass% are still more preferable. When the content is less than 50% by mass, the low-temperature fixability and the glossiness of the image may be deteriorated.

-Modified layered inorganic mineral-
The modified layered inorganic mineral is preferably a layered inorganic mineral having a smectite-based basic crystal structure in which at least part of the ions of the layered inorganic mineral is modified with organic ions. Examples of the layered inorganic mineral modified with such organic ions include montmorillonite, bentonite, beidellite, nontronite, saponite, hectorite, and the like.
Examples of the organic ions include quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts, and the like, and quaternary alkyl ammonium salts are preferable. Examples of the quaternary alkyl ammonium include trimethyl stearyl ammonium, dimethyl stearyl benzyl ammonium, dimethyl octadecyl ammonium, oleyl bis (2-hydroxyethyl) methyl ammonium, and the like.

  There is no restriction | limiting in particular as said modified | denatured layered inorganic mineral, According to the objective, it can select suitably, A commercial item can be used. , BENTONE57, BENTONE SD1, BENTONE SD2, BENTONE SD3, etc .; CRAYTONE34, CRAYTONE40, CRAYTONE HT, CRAYTONE2000, CRAYTONE AF, CRAYTONE APA, H , Esben NZ70, esben W, esben N400, esben NX, esben NX80, esben NO1 S, S-BEN NEZ, S-BEN NO12, S-BEN WX, S-BEN NE, and the like; Kunimine Industries Co., Ltd. of Kunibisu 110, Kunibisu 120, Kunibisu 127, and the like.

  The kneaded composite of the modified layered inorganic mineral and the binder resin (ie, masterbatch) is prepared by mixing the binder resin and the modified layered inorganic mineral modified with an organic cation under high shear force, and kneading to mix the masterbatch. Obtainable. At this time, an organic solvent can be used in order to enhance the interaction between the modified layered inorganic mineral and the binder resin. There is also a so-called flushing method in which an aqueous paste containing the modified layered inorganic mineral and water is mixed and kneaded together with a resin and an organic solvent, and the modified layered inorganic mineral is transferred to the resin side to remove moisture and organic solvent components. Since the wet cake 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.

In the kneaded composite (that is, master batch) of the modified layered inorganic mineral and the binder resin, the volume average particle size of the modified layered inorganic mineral is 0.1 μm to 0.55 μm, and the volume average particle size is 1 μm or more. It is preferable that the ratio of the modified layered inorganic mineral satisfies 15% by volume or less. When the volume average particle diameter exceeds 0.55 μm, or the ratio of the particle diameter of 1 μm or more exceeds 15 deposition%, the effect on the toner shape and toner charging performance may be lowered.
The content of the modified layered inorganic mineral in the toner is preferably 0.1% by mass to 5% by mass. When the content is less than 0.1% by mass, the effect of the toner shape and the toner charging property may be deteriorated. When the content exceeds 5% by mass, the fixing performance may be deteriorated.

  The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. 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 Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon. These may be used individually by 1 type and may use 2 or more types together.

The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass.
When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion in the toner occurs, the coloring power decreases, The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, 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, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, a so-called flushing method is preferable in that a wet cake of a colorant can be used as it is, and there is no need to dry it.
The flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and the organic solvent component. For the mixing or kneading, for example, a high shear dispersion device such as a three roll mill is preferably used.

There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include carbonyl group-containing waxes, polyolefin waxes, and long-chain hydrocarbons. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, dialkyl ketones, and the like. Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Among these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferable.
Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40 to 160 degreeC is preferable, 50 to 120 degreeC is more preferable, and 60 to 90 degreeC is especially preferable. preferable.
If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and if it exceeds 160 ° C., a cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

  There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0 mass%-40 mass% are preferable, and 3 mass%-30 mass% are more preferable. . When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

The charge control agent is not particularly limited and may be appropriately selected from known materials according to the purpose. However, since a color tone may change when a colored material is used, a material that is colorless to nearly white is used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of phenol-based condensate (both manufactured by Orient Chemical Co., Ltd.); TP-302, TP-415 of quaternary ammonium salt molybdenum complex (both manufactured by Hodogaya Chemical Co., Ltd.) ); Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, LR-147 which is a boron complex (all manufactured by Nippon Carlit Co., Ltd.); quinacridone Azo pigments, sulfonate group, a carboxyl group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded together with the master batch and then dissolved or dispersed, or may be added together with the toner components when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of an additive, a dispersion method, and the like, and cannot be generally specified. On the other hand, 0.1 mass part-10 mass parts are preferable, and 0.2 mass part-5 mass parts are more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

-Resin fine particles-
The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate. Examples of the resin include vinyl resins. Among these, vinyl resins are particularly preferable.
These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins is preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). ", Sanyo Chemical Industries, Ltd.), divinylbenzene, 1,6-hexanediol acrylate, and the like.

  The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. As the specific surface area by BET method of the inorganic fine ^particles, 20m ² / ^g~500m 2 / g are preferred.
The content of the inorganic fine particles in the toner is preferably 0.01% by mass to 5.0% by mass, and more preferably 0.01% by mass to 5.0% by mass.

  There is no restriction | limiting in particular as another component, According to the objective, it can select suitably, For example, a fluidity improver, a cleaning property improver, a magnetic material, metal soap, etc. are mentioned.

The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 μm to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

  The toner includes at least one of a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a binder resin, a colorant, a release agent, and an ion of a layered inorganic mineral. A toner solution is prepared by dissolving the toner material containing a modified layered inorganic mineral whose part is modified with an organic ion in an organic solvent, and then the toner solution is dispersed in an aqueous medium to prepare a dispersion liquid. A toner obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in a medium to form an adhesive substrate in the form of particles and removing the organic solvent Are preferable.

-Toner solution-
The toner solution can be prepared by dissolving the toner material in the organic solvent.

-Organic solvent-
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, and methyl isobutyl ketone. Among these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular in the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40 mass parts-300 mass parts are preferable with respect to 100 mass parts of said toner materials, 60 mass parts-140 mass parts. A mass part is more preferable and 80 mass parts-120 mass parts are still more preferable.

-Dispersion-
The dispersion is prepared by dispersing the toner solution in an aqueous medium.
When the toner solution is dispersed in the aqueous medium, a dispersion (oil droplets) made of the toner solution is formed in the aqueous medium.

--- Aqueous medium--
The aqueous medium is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, solvents miscible with water, and mixtures thereof. Among these, Is particularly preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone. These may be used individually by 1 type and may use 2 or more types together.

The toner solution is preferably dispersed in the aqueous medium with stirring.
The dispersion method is not particularly limited and may be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction disperser. High pressure jet disperser, ultrasonic disperser, and the like. Among these, a high-speed shearing type disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 μm to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 The dispersion time is preferably from 0.1 to 5 minutes in the case of a batch system, and the dispersion temperature is 0 under pressure, preferably from 5,000 rpm to 30,000 rpm, more preferably from 5,000 rpm to 20,000 rpm. ° C to 150 ° C is preferable, and 40 ° C to 98 ° C is more preferable. The dispersion temperature is generally easier to disperse when the temperature is higher.

As an example of the method for producing the toner, a method for producing the toner by forming the adhesive base material in the form of particles will be described below.
In the method of granulating the toner by forming the adhesive base material in the form of particles, for example, preparation of an aqueous medium phase, preparation of the toner solution, preparation of the dispersion, addition of the aqueous medium, etc. Synthesis of a polymer (prepolymer) capable of reacting with an active hydrogen group-containing compound, synthesis of the active hydrogen group-containing compound, etc.).

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5 mass%-10 mass% are preferable.
The toner solution is prepared by mixing the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, the colorant, the release agent, and the ions of the layered inorganic mineral in the organic solvent. It can be carried out by dissolving or dispersing a toner material such as a modified layered inorganic mineral that is at least partially modified with organic ions, the charge control agent, and the unmodified polyester resin.
In the toner material, components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound are added when the resin fine particles are dispersed in the aqueous medium in the aqueous medium phase preparation. It may be added and mixed in the aqueous medium, or when the toner solution is added to the aqueous medium phase, it may be added to the aqueous medium phase together with the toner solution.

The dispersion can be prepared by emulsifying and dispersing the previously prepared toner solution in the previously prepared aqueous medium phase. In the emulsification / dispersion, when the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction, the adhesive base material is generated.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). The toner solution is emulsified and dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are subjected to an extension reaction or the like in the aqueous medium phase. (2) The toner solution is emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance, to form a dispersion, and in the aqueous medium phase (3) The toner solution may be added to and mixed with the aqueous medium, and then the active hydrogen group-containing solution may be formed. Compounds were added to form a dispersion, may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive base material by the emulsification or dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, and the reaction temperature is preferably 0 ° C to 150 ° C, more preferably 40 to 98 ° C. .

  In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, In an aqueous medium phase, a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, the release agent, the charge control agent, and the layered inorganic The toner solution prepared by dissolving or dispersing the toner material in the organic solvent such as a modified layered inorganic mineral in which at least a part of the ions of the mineral is modified with organic ions and the unmodified polyester resin is added and sheared. And a method of dispersing by force. The details of the dispersion method are as described above.

In the preparation of the dispersion, if necessary, a dispersant is used from the viewpoint of stabilizing the dispersion (oil droplets made of the toner solution) and sharpening the particle size distribution while obtaining a desired shape. Is preferred.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a sparingly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, anionic surfactants having a fluoroalkyl group, and those having a fluoroalkyl group are suitable. It is mentioned in. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Florad FC-93, FC-95, FC-98, FC -129 (manufactured by Sumitomo 3M Co., Ltd.); Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F-191, F-812, F- 833 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); 100, F150 (manufactured by Neos) and the like.

  Examples of the cationic surfactant include amine salt type surfactants, quaternary ammonium salt type cationic surfactants, and cationic surfactants having a fluoroalkyl group. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Examples of the cationic surfactant having a fluoroalkyl group include an aliphatic primary, secondary or tertiary amine acid having a fluoroalkyl group, and a perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt. Examples include aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (Asahi Glass Co., Ltd.); Florad FC-135 (Sumitomo 3M Co., Ltd.); Unidyne DS-202 (Daikin Industries Co., Ltd.), Megafuck F-150, F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products);

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers of compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, celluloses, and the like.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In preparing the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

The organic solvent is removed from the obtained dispersion (dispersion slurry) until the residual organic solvent concentration in the dispersion slurry is 10% by mass to 33% by mass with respect to the toner (first solvent removal step).
Next, the temperature of the reaction solution after the first solvent removal step was increased to 50 ° C. at a temperature increase rate of 1 ° C./min (temperature increase step) and aged at 50 ° C. for 2 hours (aging step). Next, the organic solvent is removed from the dispersion (second solvent removal step), filtered (filtering step), washed and dried (washing step), and then air-classified to produce a toner base.
The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed into a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, and the classification operation may be performed after obtaining a powder after drying.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board, etc. are mentioned. As an apparatus used in this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.), and a pulverization air pressure are lowered, a hybridization system (Nara Machinery Co., Ltd.) Manufactured by Seisakusho), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

  The coloration of the toner is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Can be obtained by appropriately selecting the type of the colorant, and is preferably a color toner.

(Developer)
The developer of the present invention contains at least the toner of the present invention and contains other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, the filming of the toner on the developing roller as the developer carrying member, and the thinning of the toner are performed. There is no fusion of toner to a layer thickness regulating member such as a blade for layering, and good and stable developability and images can be obtained even when the developing means is used for a long time (stirring). Further, in the case of the two-component developer using the toner, even if the toner balance is maintained over a long period of time, the toner particle diameter in the developer is small, and even if it is stirred for a long time in the developing means, it is good and stable. Developability is obtained.

-Career-
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state, and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used alone or in combination of two or more.

The particle diameter of the core material is preferably an average particle diameter (volume average particle diameter (D ₅₀ )) of 10 μm to 200 μm, and more preferably 40 μm to 100 μm. When the average particle diameter (volume average particle diameter (D ₅₀ )) is less than 10 μm, the distribution of carrier particles may increase the number of fine powders, lower the magnetization per particle, and cause carrier scattering. If the thickness exceeds 200 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and may be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyesters Resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride and Copolymers with vinyl fluoride, fluoroterpolymers (triple fluoride (multiple) copolymer) such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, etc. . These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin; Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.
Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Etc.
Commercially available products can be used as the modified silicone resin, such as KR206 (alkyd modified), KR5208 (acrylic modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Dow Corning Silicone Co., Ltd., and the like.
In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

  The amount of the resin layer in the carrier is preferably 0.01% by mass to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. 98 mass% is preferable and 93 mass%-97 mass% are more preferable.
In general, the mixing ratio of the toner and the carrier of the two-component developer is preferably 1 part by mass to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

<Toner container>
The toner-containing container used in the present invention contains the toner or developer of the present invention in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body and a cap containing a toner etc. are mentioned suitably.
The size, shape, structure, material and the like of the container body containing toner are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. A spiral irregularity is formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred.
The material of the toner-containing container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferably used. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The container containing toner is easy to store and transport, has excellent handling properties, and can be attached to a process cartridge, an image forming apparatus, etc., which will be described later, detachably and can be suitably used for replenishing toner.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a toner to produce a visible image. It comprises at least developing means to be formed and cleaning means, and further comprises other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge can be detachably provided in various electrophotographic image forming apparatuses, and is preferably provided detachably in the image forming apparatus of the present invention described later.

Here, for example, as shown in FIG. 1, the process cartridge includes an electrostatic latent image carrier 101, and includes a charging unit 102, a developing unit 104, a transfer unit 108, and a cleaning unit 107, and further, if necessary. And other means. In FIG. 1, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.
Next, the image forming process using the process cartridge shown in FIG. 1 will be described. The electrostatic latent image carrier 101 is charged by the charging unit 102 while being rotated in the direction of the arrow, and exposure 103 by the exposure unit (not shown). An electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed by the developing unit 104, and the obtained visible image is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by the cleaning unit 107, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, a fixing step, and a cleaning step, and further other steps appropriately selected as necessary, for example, static elimination. Includes processes, recycling processes, control processes, etc.
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, a fixing unit, and a cleaning unit, and further if necessary. And other means appropriately selected, for example, static elimination means, recycling means, control means, and the like.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The material, shape, structure, size, etc. of the electrostatic latent image carrier (hereinafter, sometimes referred to as “electrophotographic photoreceptor”, “photoreceptor”, “image carrier”) are particularly limited. However, it can be appropriately selected from known ones, and the shape thereof is preferably a drum shape. Examples of the material thereof include inorganic photoconductors such as amorphous silicon and selenium, polysilane, and phthalopolymethine. Organic photoreceptors, and the like. Among these, amorphous silicon or the like is preferable in terms of long life.

  The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back surface side of the electrostatic latent image carrier may be adopted.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, the toner or developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention A developer having at least a developer, preferably having at least a developer capable of contacting or non-contacting the toner or the developer with the electrostatic latent image is provided. Etc. are more preferable.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means, the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like. Among these, a blade cleaner is particularly preferable. The cleaning blade always abuts on the photoconductor during image formation and wears as the photoconductor rotates. When the cleaning blade is worn, the function of removing the residual toner on the surface of the photoreceptor is lowered, and the copy image quality is deteriorated. Even if the toner is not worn, the transferability is improved when the toner is close to a true sphere and the fluidity is improved as compared with the pulverized toner. However, in cleaning, it is easy to cause defective cleaning through the installed blade. Is done. By using the toner of the present invention with respect to this problem, it can be satisfactorily cleaned.

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode of carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier, a charging roller 20 as the charging unit, an exposure device 30 as the exposure unit, and a developing unit. A developing device 40, an intermediate transfer member 50, a cleaning device 60 as the cleaning unit having a cleaning blade, and a static elimination lamp 70 as the static elimination unit.

  The intermediate transfer member 50 is an endless belt, and is designed so as to be movable in the direction of the arrow in the figure by three rollers 51 that are arranged on the inner side and stretch the belt. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. An intermediate transfer member cleaning blade 90 is disposed in the vicinity of the intermediate transfer member 50, and a transfer bias for transferring a visible image (toner image) to the recording medium 95 (secondary transfer) is applied. Possible transfer rollers 80 as the transfer means are arranged to face each other. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the visible image on the intermediate transfer member 50 is connected to the electrostatic latent image carrier 10 in the rotation direction of the intermediate transfer member 50. The contact portion between the intermediate transfer member 50 and the contact portion between the intermediate transfer member 50 and the recording medium 95 is disposed.

  The developing device 40 includes a developing belt 41 as a developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. Yes. The black developing unit 45K includes a developer accommodating portion 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. Further, the developing belt 41 is an endless belt, is rotatably stretched by a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 10.

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 4 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 4. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. .

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image bearing member 10 is uniformly charged, and the electrostatic latent image bearing member is exposed (L in FIG. 5) for each color image corresponding to each color image information. An exposure device that forms an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and each color toner (black toner, yellow toner, magenta toner, and cyan toner) Develop with A developing device 61 for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a static eliminator 64 are provided. Each single color image (black image, yellow image, magenta image, and cyan image) can be formed based on the color image information. The black image, the yellow image, the magenta image, and the cyan image formed in this manner are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15 and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 145, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming apparatus and the image forming method of the present invention, the toner of the present invention is excellent in low-temperature fixability, has little residual toner when blade cleaning is used, and can form an image with high image quality and high resolution. Since it is used, a high-quality image can be formed efficiently.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Production Example 1)
-Preparation of resin fine particle dispersion 1-
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 83 parts by mass of styrene Part, 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, and 1 part by weight of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Furthermore, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and the vinyl resin (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt An aqueous dispersion [resin fine particle dispersion 1] was prepared.
The volume average particle diameter of the obtained [resin fine particle dispersion 1] measured with a particle size distribution meter (LA-920, manufactured by Horiba Seisakusho) was 105 nm. A portion of the obtained [resin fine particle dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 59 ° C., and the mass average molecular weight was 150,000.

(Production Example 2)
-Synthesis of low molecular weight polyester 1 (binder resin)-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 229 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 529 parts by mass of bisphenol A propion oxide 3 mol adduct, 208 parts by mass of terephthalic acid, 46 of isophthalic acid Part by mass and 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 5 hours under normal pressure. Next, after the reaction solution was reacted for 5 hours under reduced pressure of 10 to 15 mmHg, 44 parts by mass of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. Low molecular weight polyester 1] was synthesized.
The obtained [low molecular weight polyester 1] had a mass average molecular weight of 5,200, a glass transition temperature (Tg) of 45 ° C., and an acid value of 20 mgKOH / g.

(Production Example 3)
-Synthesis of prepolymer 1 (polymer having a site capable of reacting with a compound having an active hydrogen group)-
795 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 200 parts by mass of isophthalic acid, 65 parts by mass of terephthalic acid, and 2 parts by mass of dibutyltin oxide are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. Then, a condensation reaction was carried out at 210 ° C. for 8 hours under nitrogen flow. Next, the reaction was continued for 5 hours while dehydrating under reduced pressure of 10 to 15 mmHg, then cooled to 80 ° C., and reacted with 170 parts by mass of isophorone diisocyanate in ethyl acetate to obtain [Prepolymer 1]. . The obtained [Prepolymer 1] had a mass average molecular weight of 5,000.

(Production Example 4)
-Preparation of master batch 1-
1,200 parts by weight of water, 174 parts by weight of ELEMENTIS BENTONE57 (organic modified bentonite, quaternary ammonium cation modified product), and 1,570 parts by weight of the above [low molecular weight polyester 1], Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) And mixed. The mixture was kneaded with a two-roller at 150 ° C. for 30 minutes, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare [Masterbatch-1].
With respect to the obtained master batch, the dispersion particle size of the modified layered inorganic mineral measured as follows was 0.4 μm, and the proportion of the modified layered inorganic mineral having a particle size of 1 μm or more was 2% by volume.
<Dispersed particle size (volume average particle size) of modified layered inorganic mineral and ratio of modified layered inorganic mineral having a particle size of 1 μm or more>
-Preparation of measurement sample-
The amount of organic cation-modified layered inorganic mineral in the masterbatch / the amount of binder resin used in the masterbatch = 1/10 in a ratio of dispersing the masterbatch and the binder resin (BYK Chemie, Disperbyk-167) Was added into ethyl acetate in which 5% by mass was dissolved. At this time, the total amount of the master batch amount and the binder resin amount was adjusted to 5% by mass. The prepared sample was stirred for 12 hours.
-Measurement of dispersed particle size and particle size distribution-
The prepared sample was measured using a laser Doppler particle size distribution analyzer (nanotrac UPA-150EX, manufactured by Nikkiso Co., Ltd.). The measuring method is as follows.
(1) Measuring conditions of measuring instrument Distribution display: Volume Number of channels: 52
Measurement time: 15 sec
Particle refractive index: 1.54
Temperature: 25 ° C
Particle shape: non-spherical viscosity (cP): 0.441
Solvent refractive index: 1.37
Solvent name: ethyl acetate (2) The sample diluent to be measured was added using a dropper or a syringe so as to enter (1 to 100) while looking at the sample loading of the measuring instrument.

(Preparation Example 1)
-Preparation of Toner Material Oily Dispersion 1-
In a beaker, 23.4 parts by mass of [Prepolymer 1], 123.6 parts by mass of [Low molecular polyester 1], 20 parts by mass of [Masterbatch 1], and 80 parts by mass of ethyl acetate were stirred and dissolved.
Separately, 15 parts by mass of carnauba wax as a release agent, 20 parts by mass of carbon black, and 120 parts by mass of ethyl acetate were placed in a bead mill and dispersed for 30 minutes.
The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 2.9 parts by mass of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to prepare [Oil Material Dispersion Liquid 1].

(Preparation Example 2)
-Preparation of Toner Material Oily Dispersion 2-
In a beaker, 23.4 parts by mass of [Prepolymer 1], 141.6 parts by mass of [Low molecular polyester 1] and 80 parts by mass of ethyl acetate were stirred and dissolved. Separately, 15 parts by mass of carnauba wax as a release agent, 20 parts by mass of carbon black, and 120 parts by mass of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 2.9 parts by mass of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at 12,000 rpm using a TK homomixer to prepare [Toner material oily dispersion 2].

(Preparation Example 3)
-Preparation of Toner Material Oily Dispersion 3-
In a beaker, 23.4 parts by weight of [Prepolymer 1], 141.6 parts by weight of [low molecular weight polyester 1], organosilica sol (MEK-ST, solid content concentration 30% by weight, average primary particle size 15 nm, Nissan Chemical Industries) 7 parts by mass) and 64 parts by mass of ethyl acetate were added and dissolved by stirring. Separately, 15 parts by mass of carnauba wax as a release agent, 20 parts by mass of carbon black, and 120 parts by mass of ethyl acetate were placed in a bead mill and dispersed for 30 minutes. The two liquids were mixed and stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer, and then dispersed in a bead mill for 10 minutes. 2.9 parts by mass of isophorone diamine was added to the dispersion, and the mixture was stirred for 5 minutes at a rotational speed of 12,000 rpm using a TK homomixer to prepare [Oil Material Dispersion 3].

(Example 1)
-Production of Toner 1-
In a beaker, 529.5 parts by mass of ion-exchanged water, 70 parts by mass of [resin fine particle dispersion 1], and 0.5 parts by mass of sodium dodecylbenzenesulfonate were stirred at 10,000 rpm with a TK homomixer. To this aqueous dispersion, 405.1 parts by mass of [Toner Material Oily Dispersion 1] was added and reacted while stirring for 5 minutes to obtain a dispersion slurry. Subsequently, the obtained dispersion slurry is transferred to a flask equipped with a cooling pipe, and ethyl acetate is removed from the dispersion slurry until the concentration of ethyl acetate per 1 kg of toner in the dispersion slurry is 23% by mass. (First solvent removal step). The ethyl acetate concentration in the dispersed slurry was measured as follows.
Next, the temperature of the reaction solution after the first solvent removal step was increased to 50 ° C. at a temperature increase rate of 1 ° C./min (temperature increase step) and aged at 50 ° C. for 2 hours (aging step). Next, the organic solvent was removed from the dispersion (second solvent removal step), filtered (filtering step), washed and dried (washing step), and then air-classified to prepare a toner base.
100 parts by mass of the obtained toner base and 0.25 parts by mass of charge control agent (Orient Chemical Co., Ltd., Bontron E-84) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine type blades Was set to 50 m / sec and mixed. In this case, the mixing operation was performed for 2 minutes, 5 cycles of 1 minute pause, and the total treatment time was 10 minutes. Further, 0.5 part by mass of hydrophobic silica (H2000, manufactured by Clariant Japan) was added and mixed. In this case, in the mixing operation, the peripheral speed was 15 m / sec, and the suspension for 1 minute for 30 seconds was carried out for 5 cycles to produce [Toner 1].

<Ethyl acetate concentration in dispersed slurry>
Specifically, the ethyl acetate concentration in the dispersed slurry was measured by the following procedure.
-Measurement equipment conditions-
・ Measurement device: GC-2010 (manufactured by Shimadzu Corporation, gas chromatograph)
・ Injection volume: 2.0μL
-Sample vaporization chamber-
・ Injection mode: Split ・ Vaporization chamber temperature: 180 ℃
・ Carrier gas: He
・ Pressure: 40.2kPa
・ Total flow rate: 56.0mL / min
・ Column flow rate: 1.04mL / min
・ Linear speed: 20.0cm / sec
・ Purge flow rate: 3.0mL / min
-Split ratio: 50.0
-Column-
・ Column name: ZB-50
・ Liquid film thickness 0.25μm
・ Length 30.0m
・ Inner diameter: 0.32mmID
・ Upper column temperature: 340 ℃
-Column oven-
・ Column temperature: 60 ℃
-Column oven temperature program-
60 ° C hold 6 min → Temperature rise rate 60 ° C / min → 230 ° C hold 5 min
-Detector-
・ Detector temperature: 250 ℃
・ Make-up gas: N ₂ / Air
・ Make-up flow rate: 30.0mL / min
・ H ₂ flow rate: 47.0mL / min
・ Air flow rate: 400mL / min
-Measurement method-
-Preparation of internal standard solution: 4 g of toluene was weighed into a volumetric flask and diluted to 500 mL with DMF.
-Preparation of measurement sample: After diluting 1.5 g of the measurement dispersion slurry to about 50 mL with DMF, 10 mL of the internal standard solution is collected and introduced with a whole pipette. After stirring the measurement sample with a stirrer at 400 rpm for 4 minutes, the sample is set on the autosampler of the measuring instrument GC and measured. After the measurement, the amount of ethyl acetate in the slurry was calculated from the ratio of toluene and ethyl acetate as the internal standard substance by the internal standard method, and the ethyl acetate concentration for the toner in the slurry was calculated from the value by the following formula.
Ethyl acetate concentration [%] with respect to toner in slurry = ethyl acetate amount in 100 g of slurry obtained by GC measurement / toner amount in 100 g of slurry [g]

(Example 2)
-Production of Toner 2-
In Example 1, Toner 2 was produced in the same manner as Example 1 except that the concentration of ethyl acetate per 1 kg of toner in the dispersion slurry in the first solvent removal step was 10% by mass.

(Example 3)
-Production of Toner 3-
In Example 1, Toner 3 was produced in the same manner as in Example 1 except that the concentration of ethyl acetate per kg of toner in the dispersed slurry in the first solvent removal step was 33% by mass.

Example 4
-Production of Toner 4-
In Example 1, Toner 4 was produced in the same manner as in Example 1 except that the temperature raising rate in the temperature raising step was 0.3 ° C./min.

(Example 5)
-Production of Toner 5-
In Example 1, Toner 5 was produced in the same manner as Example 1 except that the temperature raising rate in the temperature raising step was 1.5 ° C./min.

(Example 6)
-Production of Toner 6-
In Example 1, except that the concentration of ethyl acetate per 1 kg of toner in the dispersion slurry in the first solvent removal step was 33% by mass and the temperature increase rate in the temperature increase step was 1.5 ° C./min. In the same manner as in Example 1, a toner 6 was produced.

(Example 7)
-Production of Toner 7-
Example 1 in Example 1, except that the concentration of ethyl acetate per 1 kg of toner in the dispersion slurry in the first solvent removal step was 33% by mass and the temperature increase rate in the temperature increase step was 0.3 ° C./min. In the same manner as in Example 1, toner 7 was produced.

(Example 8)
-Production of Toner 8-
In Example 1, except that the concentration of ethyl acetate per 1 kg of toner in the dispersion slurry in the first solvent removal step was 10% by mass, and the temperature increase rate in the temperature increase step was 1.5 ° C./min. In the same manner as in Example 1, toner 8 was produced.

Example 9
-Production of Toner 9-
In Example 1, except that the concentration of ethyl acetate per 1 kg of toner in the dispersion slurry in the first solvent removal step was 10 mass%, and the temperature increase rate in the temperature increase step was 0.3 ° C./min. In the same manner as in Example 1, a toner 9 was produced.

(Comparative Example 1)
-Production of Toner 10-
In Example 1, Toner 10 was prepared in the same manner as Example 1 except that 405.1 parts by mass of [Toner material oily dispersion 1] was changed to 405.1 parts by mass of [Toner material oily dispersion 2] 405.1 parts. did.

(Comparative Example 2)
-Production of Toner 11-
In Example 1, Toner 11 was produced in the same manner as in Example 1 except that the ethyl acetate concentration per kg of toner in the dispersion slurry in the first solvent removal step was 8% by mass.

(Comparative Example 3)
-Production of Toner 12-
In Example 1, except that the ethyl acetate concentration per 1 kg of toner in the dispersion slurry in the first solvent removal step was 8 mass%, and the temperature increase rate in the temperature increase step was 1.5 ° C./min. In the same manner as in Example 1, a toner 12 was produced.

(Comparative Example 4)
-Production of Toner 13-
In Example 1, Toner 13 was produced in the same manner as in Example 1 except that the concentration of ethyl acetate per 1 kg of toner in the dispersed slurry in the first solvent removal step was 35% by mass.

(Comparative Example 5)
-Production of Toner 14-
In Example 1, a toner 14 was produced in the same manner as in Example 1 except that the temperature raising rate in the temperature raising step was set to 0.2 ° C./min.

(Comparative Example 6)
-Production of Toner 15-
Example 1 in Example 1, except that the concentration of ethyl acetate per 1 kg of toner in the dispersion slurry in the first desolvation step was 35% by mass and the temperature increase rate in the temperature increase step was 0.2 ° C./min. In the same manner as in Example 1, a toner 15 was produced.

(Comparative Example 7)
-Production of Toner 16-
In Example 1, Toner 16 was produced in the same manner as Example 1 except that the temperature increase rate in the temperature increase step was 1.7 ° C./min.

(Comparative Example 8)
-Production of Toner 17-
Example 1 in Example 1, except that the concentration of ethyl acetate per 1 kg of toner in the dispersion slurry in the first solvent removal step was 10 mass% and the temperature increase rate in the temperature increase step was 1.7 ° C./min. In the same manner as in Example 1, a toner 17 was produced.

(Comparative Example 9)
-Production of Toner 18-
Example 1 in Example 1, except that the concentration of ethyl acetate per 1 kg of toner in the dispersion slurry in the first desolvation step was 33% by mass and the temperature increase rate in the temperature increase step was 1.7 ° C./min. In the same manner as in Example 1, a toner 18 was produced.

(Comparative Example 10)
-Production of Toner 19-
Toner 19 was produced in the same manner as in Example 1 except that 405.1 parts by weight of [Toner Material Oily Dispersion 1] was changed to 405.1 parts by weight of [Toner Material Oily Dispersion 3] in Example 1. did.

  Next, various properties of the toners 1 to 19 produced in Examples 1 to 9 and Comparative Examples 1 to 10 were measured as follows. The results are shown in Table 1.

<BET specific surface area of toner>
The BET specific surface area of the toner is the specific surface area per unit mass calculated from the specific surface area Sb (m ² / g) per unit mass measured by the BET method and the mass average particle diameter when the toner is assumed to be a true sphere. It is expressed as a ratio (Sb / St) to St (m ² / g). The BET specific surface area was measured by a multi-point method of nitrogen adsorption method, and was measured by a high-speed specific surface area / pore distribution measuring device NOVA1200 multi-point method manufactured by Yuasa Ionics Co., Ltd.
Specifically, the measurement was performed under the following conditions.
・ Adsorption gas: Nitrogen gas (99.995 or more)
-Refrigerant: Liquid nitrogen-Cell used: 9mm pellet short (large)
・ Pretreatment conditions: 12 hours at 30 ° C. (evacuation)
・ Measurement points: 3 points of relative pressure (P / PO) = 0.1-0.3

<Measurement of toner volume average particle size and particle size distribution>
First, 0.1 to 5 ml of a surfactant (alkylbenzene sulfonate) was added as a dispersant to 100 to 150 ml of the aqueous electrolytic solution. Here, ISOTON-II (manufactured by Coulter, Inc.) in which a 1% by mass NaCl aqueous solution was prepared using first grade sodium chloride as an electrolytic solution was used. Next, 2 to 20 mg of a measurement sample is 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 volume and the number of toners are measured with the measuring device using a 100 μm aperture as an aperture. The number distribution was calculated.
As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

<Toner Shape Factors SF-1 and SF-2>
The toner shape factors SF-1 and SF-2 are obtained by randomly sampling 300 SEM images of the toner obtained by measurement with Hitachi FE-SEM (S-4200) and using the image information as an interface. And introduced into an image analysis apparatus (Luzex AP) manufactured by Nireco Corp., and analyzed, and values obtained from the following mathematical expressions were defined as SF-1 and SF-2.
SF-1 = (L ² / A) × (π / 4) × 100
SF-2 = (P ² / A) × (1 / 4π) × 100
In the above formula, L represents the absolute maximum length of the toner, A represents the projected area of the toner, and P represents the maximum peripheral length of the toner.

<Measurement of acid value of toner>
The acid value of the toner was measured by the method specified in JIS K0070. However, when the sample did not dissolve, dioxane or tetrahydrofuran was used as the solvent.
The acid value is specifically determined by the following procedure.
・ Measuring device: potentiometric automatic titrator DL-53 Titrator (Metler Toledo)
-Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
・ Analysis software: LabX Light Version 1.00.000
-Calibration of apparatus: A mixed solvent of 120 ml of toluene and 30 ml of ethanol was used.
・ Measurement temperature: 23 ℃
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
At maximum volume [mL] 10.0
At potential No
At slope No
After number EQPs Yes
n = 1
comb. Termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

-Method of measuring acid value-
Measurement was performed under the following conditions in accordance with the measurement method described in JIS K0070-1992.
First, 0.5 g of each toner (0.3 g for ethyl acetate soluble component) was added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for 10 hours. Next, 30 ml of ethanol was added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, and specifically, the calculation is performed as follows.
Titration was carried out with N / 10 caustic potash-alcohol solution standardized in advance, and the acid value was determined from the consumption of alcohol potash solution by the following calculation.
Acid value = KOH (ml number) × N × 56.1 / sample weight N represents a factor of N / 10 KOH.

<Measurement of Glass Transition Temperature (Tg) of Toner>
The glass transition temperature of the toner was measured with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation at a temperature increase rate of 10 ° C./min.
As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, 10 mg of a sample was placed in an aluminum sample container, placed on a holder unit, and set in an electric furnace. Next, after heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is allowed to stand at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. DSC measurement was performed by heating at a rate of 10 ° C./min. Tg was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

  Next, various properties of the toners of Examples 1 to 9 and Comparative Examples 1 to 10 were evaluated as follows. The results are shown in Tables 2 and 3.

<Image density>
Using a digital full-color copier (Imagio Color 2800, manufactured by Ricoh Co., Ltd .; using blade cleaning), 150,000 sheets of 50% image area image charts were output in a single color mode, and then a solid image was obtained from 6000 paper manufactured by Ricoh Co., Ltd. After the image was output, the image density was measured by XRite (manufactured by X-Rite), and this was performed for four colors alone to obtain an average, and evaluated according to the following criteria.
〔Evaluation criteria〕
×: Image density is less than 1.2 Δ: Image density is 1.2 or more and less than 1.4 ○: Image density is 1.4 or more and less than 1.8 ◎: Image density is 1.8 or more and less than 2.2

<Image graininess and sharpness>
Using a digital full-color copying machine (manufactured by Ricoh Co., Ltd., imgio Color 2800; using blade cleaning), a photographic image was output in a single color, and the degree of graininess and sharpness was visually evaluated and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Same as offset printing ○: Slightly worse than offset printing △: Slightly worse than offset printing ×: About conventional electrophotographic image (very bad)

<Soil dirt>
Using a digital full-color copier (made by Ricoh Co., Ltd., imagio Color 2800; using blade cleaning), after running 30,000 image charts with 50% image area in monochrome mode, the blank image was stopped during development. The developer on the photoconductor after development was transferred to a tape, and the difference from the image density of the untransferred tape was measured with a 938 spectrocytometer (manufactured by X-Rite). The smaller the image density difference was, the less the background stains were, and the better ones were ranked in the order of “◎”, “◯”, “Δ”, “×”.

<Toner scattering>
Using a digital full-color copying machine (manufactured by Ricoh Co., Ltd., imgio Color 2800; using blade cleaning), the degree of toner contamination in the machine was confirmed after continuous printing of 50,000 sheets. A problem-free level was indicated by “◯”, a toner was observed, but a problem-free level was indicated by “Δ”, and a markedly contaminated and problematic problem was indicated by “X”.

<Cleanability>
Transfer residual toner on the photoconductor after blade cleaning to white paper with Scotch tape (manufactured by Sumitomo 3M Limited), measure it with a Macbeth reflection densitometer RD514, O (good), the thing exceeding it was evaluated as x (defect).

<Evaluation of charge amount>
(1) Charge for 15 seconds stirring Charge 10 g of each toner and 100 g of ferrite carrier into a stainless steel pot up to 30% of the internal volume in an environment with a temperature of 28 ° C. and a humidity of 80% RH, and stir for 15 seconds at a stirring speed of 100 rpm. The charge amount (μC / g) of the developer was measured with [Toshiba Chemical Co., Ltd., TB-200].
The charge amount of the toner was measured by the blow-off method.
(2) Charge amount for 5 minutes stirring Charge amount when stirring for 5 minutes as in (1) (3) Charge amount when stirring for 10 minutes Charge amount when stirring for 10 minutes as in (1)

<Charging stability>
(1) Charging stability in a high temperature and high humidity environment Under an environment of a temperature of 40 ° C. and a humidity of 90% RH, a digital full color copier (image color 2800; manufactured by Ricoh Co., Ltd .; blade) The cleaning stability was evaluated by sampling a part of the developer for every 1,000 sheets and measuring the charge amount by the blow-off method during the running output of 100,000 sheets.
When the change in the charge amount was 5 μc / g or less, it was evaluated as ◯, when it was 10 μc / g or less, Δ when it exceeded 10 μc / g.
(2) Charging stability in a low-temperature and low-humidity environment A digital full-color copier (image Color 2800, manufactured by Ricoh Co., Ltd.) produces an image chart with a 7% image area in a monochrome mode under an environment of a temperature of 10 ° C. and a humidity of 15% RH. During 100,000 sheet running output, a part of the developer was sampled every 1,000 sheets, and the charge amount was measured by the blow-off method to evaluate the charging stability.
When the change in the charge amount was 5 μc / g or less, it was evaluated as ◯, when it was 10 μc / g or less, Δ when it exceeded 10 μc / g.
The charge amount measurement by the blow-off method (1) and (2) was performed as follows.
In a test room with a temperature of 20 ° C. and a humidity of 50% RH, 10 g of each toner and 100 g of ferrite carrier are placed in a stainless steel pot up to 30% of the internal volume, and stirred for 10 minutes at a stirring speed of 100 rpm. / G) was measured by [Toshiba Chemical Co., Ltd., TB-200].

<Fixability evaluation>
Using a device obtained by modifying the fixing unit MF2200 manufactured by Ricoh Co., Ltd., which uses a Teflon (registered trademark) roller as a fixing roller, type 6200 paper manufactured by Ricoh Co., Ltd. was set on this and a copy test was performed. The low temperature fixability (fixing lower limit temperature) and the hot offset property (hot offset temperature resistance) were determined according to the following criteria by changing the fixing temperature. The fixing minimum temperature of the conventional low-temperature fixing toner is about 140 ° C. to 150 ° C. The evaluation conditions for low-temperature fixing were a paper feed linear velocity of 120 to 150 mm / sec, a surface pressure of 1.2 kgf / cm ² , and a nip width of 3 mm. The evaluation conditions for the high temperature offset were a paper feed linear velocity of 50 mm / sec, a surface pressure of 2.0 kgf / cm ² , and a nip width of 4.5 mm.
[Low-temperature fixability (5-level evaluation)]
◎: Less than 140 ° C. ○: 140 ° C. or more and less than 150 ° C. □: 150 ° C. or more and less than 160 ° C. Δ: 160 ° C. or more and less than 170 ° C. ×: 170 ° C. or more
◎: 201 ° C or higher ○: 200 ° C or higher and 191 ° C or lower □: 190 ° C or higher and 181 ° C or lower Δ: 180 ° C or higher and 171 ° C or lower ×: 170 ° C or lower

<Heat resistant storage stability>
After each toner was stored at 50 ° C. for 8 hours, it was sieved with a 42 mesh sieve for 2 minutes, and the residual rate on the wire mesh was regarded as heat resistant storage stability. A toner having better heat-resistant storage stability has a lower residual ratio. The following four levels were evaluated.
〔Evaluation criteria〕
×: 30% or more △: 20% or more and less than 30% ○: 10% or more and less than 20% ◎: Less than 10%

The toner of the present invention is excellent in low-temperature fixability, has little residual toner when blade cleaning is used, and can form an image with high image quality and high resolution. It is preferably used for a method and a process cartridge.
The image forming apparatus, the image forming method, and the process cartridge according to the present invention use the toner according to the present invention, and there is no change in color tone over a long period of time. Because it can form high-quality images, it is widely used in laser printers, direct digital plate-making machines, full-color copiers using direct or indirect electrophotographic multicolor image development systems, full-color laser printers, full-color plain paper fax machines, etc. Can be used.

FIG. 1 is a schematic view showing an example of the process cartridge of the present invention. FIG. 2 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 3 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 4 is a schematic explanatory view showing an example of carrying out the image forming method of the present invention by the image forming apparatus (tandem color image forming apparatus) of the present invention. FIG. 5 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.

Explanation of symbols

10 Electrostatic latent image carrier (photosensitive drum)
10K Electrostatic latent image carrier for black 10Y Electrostatic latent image carrier for yellow 10M Electrostatic latent image carrier for magenta 10C Electrostatic latent image carrier for cyan 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device DESCRIPTION OF SYMBOLS 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling body 34 Second Traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Development roller La 44Y Development roller 44M Development roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 switching claw 56 discharge roller 57 discharge tray 58 corona charger 60 cleaning device 61 developing device 62 transfer charger 63 photoconductor cleaning device 64 discharger 70 discharge lamp 80 transfer roller 90 cleaning device 95 transfer paper 100 image forming device 101 photoconductor DESCRIPTION OF SYMBOLS 102 Charging means 103 Exposure 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem type developer 121 Heating roller 122 Fixing roller 123 Fixing belt 124 Addition Roller 125 Heating source 126 Cleaning roller 127 Temperature sensor 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copier main body 160 Charging device 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Claims (21)

In an organic solvent, at least one of a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a binder resin, a colorant, a release agent, and an ion of a layered inorganic mineral. An aqueous granulation step of emulsifying or dispersing an oil phase composed of a solution or dispersion obtained by dissolving or dispersing a modified layered inorganic mineral whose part is modified with organic ions in an aqueous medium;
A first solvent removal step of removing a part of the organic solvent from the emulsification or dispersion obtained in the aqueous granulation step;
A temperature raising step in which the emulsification or dispersion removed in the first solvent removal step is heated to 40 ° C. to 60 ° C. and heated;
An aging step in which the heated emulsification or dispersion is heated at 40 ° C. to 60 ° C. and aged;
A second desolvation step for removing the organic solvent in the emulsification or dispersion that has undergone the aging step;
A filtration step of filtering the emulsification or dispersion that has undergone the second solvent removal step;
A toner produced by a method for producing a toner, comprising: a washing step of washing and drying the filtered particles,
The residual organic solvent concentration in the emulsification or dispersion after the first desolvation step is 10% by mass to 33% by mass with respect to the toner in the emulsification or dispersion,
The toner according to claim 1, wherein a temperature increase rate in the temperature increase step is 0.3 ° C./min to 1.5 ° C./min.   The oil phase contains a kneaded composite containing a modified layered inorganic mineral and a binder resin, and the volume average particle size of the modified layered inorganic mineral in the kneaded composite is 0.1 μm to 0.55 μm. The toner according to claim 1, wherein a modified layered inorganic mineral having a particle diameter of 1 μm or more in the composite is 15% by volume or less.   The toner according to claim 1, wherein the shape factor SF-1 of the toner is 110 to 200, and the shape factor SF-2 of the toner is 110 to 300.   The toner according to any one of claims 1 to 3, wherein the content of the modified layered inorganic mineral in the toner is 0.1 mass% to 5 mass%.   The toner according to claim 1, wherein the organic ion in the modified layered inorganic mineral is a quaternary ammonium ion.   The volume average particle diameter of the toner is 3 μm to 7 μm, and the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.20 or less. The toner according to any one of the above. BET specific surface area of the toner is ^the toner according to any one of claims 1 to 6, which is 1.0m ² /g~6.0m 2 / g.   The toner according to claim 1, wherein a ratio of particles having a particle diameter of 2 μm or less is 1% by number to 10% by number.   The toner according to claim 1, wherein the binder resin contains a polyester resin.   The toner according to claim 9, wherein the content of the polyester resin in the binder resin is 50% by mass to 100% by mass.   The toner according to claim 9, wherein the weight average molecular weight of the tetrahydrofuran (THF) soluble part of the polyester resin is 1,000 to 30,000.   The toner according to claim 9, wherein the acid value of the polyester resin is 1.0 mgKOH / g to 50.0 mgKOH / g.   The toner according to claim 9, wherein the polyester resin has a glass transition temperature of 35 ° C. to 65 ° C.   The toner according to any one of claims 1 to 13, wherein the polymer having a site capable of reacting with the compound having an active hydrogen group has a mass average molecular weight of 3,000 to 20,000.   The toner according to claim 1, wherein the toner has an acid value of 0.5 mgKOH / g to 40.0 mgKOH / g.   The toner according to claim 1, wherein the toner has a glass transition temperature of 40 ° C. to 70 ° C. In an organic solvent, at least one of a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, a binder resin, a colorant, a release agent, and an ion of a layered inorganic mineral. An aqueous granulation step of emulsifying or dispersing an oil phase composed of a solution or dispersion obtained by dissolving or dispersing a modified layered inorganic mineral whose part is modified with organic ions in an aqueous medium;
A first solvent removal step of removing a part of the organic solvent from the emulsification or dispersion obtained in the aqueous granulation step;
A temperature raising step in which the emulsification or dispersion removed in the first solvent removal step is heated to 40 ° C. to 60 ° C. and heated;
An aging step in which the heated emulsification or dispersion is heated at 40 ° C. to 60 ° C. and aged;
A second desolvation step for removing the organic solvent in the emulsification or dispersion that has undergone the aging step;
A filtration step of filtering the emulsification or dispersion that has undergone the second solvent removal step;
A washing step of washing and drying the filtered particles, comprising:
The residual organic solvent concentration in the emulsification or dispersion after the first desolvation step is 10% by mass to 33% by mass with respect to the toner in the emulsification or dispersion,
A method for producing a toner, wherein a temperature raising rate in the temperature raising step is 0.3 ° C./min to 1.5 ° C./min.   A two-component developer comprising the toner according to any one of claims 1 to 16 and a carrier. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of developing the electrostatic latent image with toner to form a visible image, and the visible image At least a transfer process for transferring the toner image to the recording medium, a fixing process for fixing the transferred image transferred to the recording medium, and a cleaning process for removing the toner remaining on the surface of the electrostatic latent image carrier after the transfer using a blade. An image forming method comprising:
The image forming method according to claim 1, wherein the toner is the toner according to claim 1. An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image with toner to form a visible image A developing means for transferring the visible image to a recording medium, a fixing means for fixing the transferred image transferred to the recording medium, and a blade for removing toner remaining on the surface of the electrostatic latent image carrier after the transfer. An image forming apparatus having at least a cleaning unit to be removed using
The image forming apparatus according to claim 1, wherein the toner is the toner according to claim 1. An electrostatic latent image carrier, development means for developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a visible image, and a surface of the electrostatic latent image carrier after transfer. A process cartridge having at least cleaning means for removing residual toner using a blade,
The process cartridge according to claim 1, wherein the toner is the toner according to claim 1.

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