JP4313300B2 - Toner production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a small grain toner which has a small size distribution, and is excellent in various characteristics such as electrostatic chargeability and transferability and capable of obtaining high quality images with less scattering toner and generating fogging and also satisfying both low-temperature fixability and preservation stability, and provide a stable and efficient manufacturing method which can recycle organic solvents with waste solution processing less contaminating the environment, and an image forming method using this toner. <P>SOLUTION: This toner manufacturing method includes a step of dispersing a toner dissolved or dispersed solvent which is prepared by dissolving or dispersing a toner material in an organic solvent in a water based medium as a dispersant to form toner grains and removing this organic solvent from the dispersed grains. The toner material dissolved or dispersed solvent before forming the toner grains contains water of 10.0-200 mass% of the saturating dissolving amount of water in the organic solvent at 25&deg;C. It is preferable that the solution dissolving or dispersing the toner material contains 1.0 mass% or more of water in the organic solvent before forming the grains. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention relates to a toner suitably used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, an efficient manufacturing method thereof, a developer using the toner, a container containing toner, a process cartridge, an image The present invention relates to a forming apparatus and an image forming method.

  In image formation by electrophotography or the like, generally, an electrostatic image is formed on a photoreceptor (electrostatic image carrier), and the electrostatic image is developed with a developer to form a visible image (toner image). The visible image is transferred to a recording medium such as paper and fixed to form a fixed image (see Patent Document 1).

  As the developer, a one-component developer using a magnetic toner or a non-magnetic toner alone and a two-component developer composed of a toner and a carrier are known. The toner is a colored particle containing a colorant, a charge control agent and the like in a binder (binder resin). As a method for producing the toner, generally, a colorant, A pulverization method is used in which a charge control agent, an anti-offset agent and the like are melt-mixed and uniformly dispersed, and then pulverized and classified.

However, the pulverization method has a problem that the selection range of the material for forming the toner is narrow. That is, for example, a composition obtained by melt mixing must be sufficiently brittle, and when the composition is pulverized into particles, a toner having a wide particle size distribution is easily formed, and high resolution and high gradation properties are obtained. In order to obtain this image, for example, it is necessary to classify and remove fine powder having a particle diameter of 5 μm or less and coarse powder having a particle diameter of 20 μm or more, which causes a problem that the yield is significantly reduced. Regarding the average particle size of the toner, obtaining a toner having a small particle size, particularly 6 μm or less, is a very big problem in the pulverization method from the viewpoints of yield, productivity and cost.
The chargeability of the irregular toner produced by the pulverization method is such that the adhesion area to the developing roll in a one-component developer and the adhesion area to a carrier in a two-component developer are different for each toner particle. The adhesion force to the developing roll or the carrier is different, and the ease of development is also different. Toners with irregular particle sizes also differ in ease of development because the amount of charge per toner is different. Due to these differences, there is a problem that easily developed toner is selectively developed, and difficultly developed toner remains in the developing device, and developability changes with time. Similarly, in transfer to a recording medium, image quality deterioration such as toner scattering is likely to occur due to a mixture of toner that is easily transferred and toner that is difficult to transfer.
Further, when a toner is produced by internally adding a release agent such as wax, the release agent may be exposed on the surface of the toner in combination with a thermoplastic resin. In particular, in a combination of a resin imparted with elasticity by a high molecular weight component and slightly pulverized resin and a brittle wax such as polypropylene, the exposure of the wax is often observed on the toner surface. Such exposure of the release agent is advantageous for releasability at the time of fixing and cleaning of the toner remaining on the photoreceptor after transfer, but it is easily moved by the mechanical force of the fluidizing agent on the toner surface. Further, there is a problem that wax contamination of the developing roll, the photoconductor, the carrier, etc. is likely to occur, and the reliability of the image forming apparatus is lowered.

In order to improve various problems in the pulverization method, a suspension polymerization method (see Patent Documents 2 to 3), an emulsion polymerization method (see Patent Document 4), and the like have been proposed.
However, the toner obtained by the suspension polymerization method has a problem that low-temperature fixability is insufficient and a large amount of energy required for fixing is required. This problem is particularly noticeable in full-color toner. In addition, since the viscosity difference between the release agent and the monomer is large and incompatible, it is extremely difficult to finely disperse the release agent, and as a result, no wax (release agent) is present in the resin. A large number of particles are generated, and the problem of unstable charging of toner due to uneven distribution among toner particles arises.
In addition, in the toner obtained by the emulsion polymerization method, a large amount of a dispersant such as a surfactant remains not only on the surface but also inside the particle even after a water washing step, thereby impairing the environmental stability of toner charging. In addition to this, the charge amount distribution is widened to cause image smearing. Further, there is a problem that the remaining surfactant or the like contaminates the photoconductor, the charging roller, the developing roller and the like and cannot exhibit the original charging performance.

  Therefore, a method has been proposed in which the binder resin contains a modified polyester resin capable of reacting with active hydrogen and the toner particles are granulated in an aqueous medium (see Patent Documents 5 to 6). According to this method, the problems in the suspension polymerization method and the emulsion polymerization method can be solved, and good low-temperature fixability and stable chargeability can be imparted. There is a problem that fine powder is generated when forming oil droplets composed of phases. If this fine powder remains, toner scattering and fogging (soil stains) are likely to occur, which makes it impossible to cope with a full-color copying machine or the like that particularly requires high image quality. Further, since the toner material to be dispersed in the aqueous medium is used after being dissolved or dispersed in an organic solvent, there is a concern about an environmental load due to waste liquid treatment.

  Therefore, small particle size and narrow particle size distribution, excellent characteristics such as chargeability, transferability, etc., less toner scattering and fogging, both low-temperature fixability and storage stability, and high-quality images. There is a strong demand for a production method in which the obtained toner is always stably and efficiently obtained, and the environmental load is small. However, at present, this method has not been provided.

US Pat. No. 2,297,691 JP-A-8-44111 JP-A-8-286416 Japanese Patent No. 2537503 Japanese Patent Laid-Open No. 11-133665 JP-A-11-133666

  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 various properties such as chargeability and transferability, has less toner scattering and fogging, achieves both low-temperature fixability and storage stability, and provides high image quality. Toner having a narrow distribution, a stable and efficient manufacturing method that can reuse an organic solvent, and has a low environmental impact due to waste liquid treatment, and a developer capable of improving image quality using the toner, An object is to provide a container containing toner, a process cartridge, an image forming apparatus, and an image forming method.

  As a result of intensive studies in view of the above problems, the present inventors have obtained the following knowledge. That is, in order to obtain a high-quality image with good developability over a long period of time, it is necessary to obtain a toner with a small amount of fine powder and a sharp particle size distribution, for example, it is necessary to remove fine particles generated in the manufacturing process. Unlike the methods for removing fine particles that reduce productivity and increase costs, such as yield loss and increased energy load represented by classification, dissolution of the toner material prepared by dissolving or dispersing the toner material in an organic solvent Or the dispersion liquid is dispersed as dispersed particles in an aqueous medium to granulate the toner, and the organic solvent is removed from the dispersed particles. By including 10.0 to 200% by mass of water in a saturated dissolution amount of the organic solvent in the organic solvent at a temperature, the affinity for the aqueous medium is imparted and dispersed in the aqueous medium. In this case, the occurrence of a phenomenon (dilution shock) in which the toner material aggregates and inhibits uniform dispersion is suppressed, and the amount of fine powder that causes toner scattering and fogging can be reduced. Excellent toner characteristics, less toner scattering and fogging, compatible with both low-temperature fixability and storage stability, high image quality, and a stable toner with a small particle size and narrow particle size distribution. I found out. Further, the organic solvent removed from the dispersed particles can be reused as the organic solvent used for dissolving or dispersing the toner material, reducing the amount of the organic solvent used as a waste liquid, and providing an environment for waste liquid treatment. As a result, the present invention has been completed.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> The toner material prepared by dissolving or dispersing the toner material in an organic solvent is dispersed as dispersed particles in an aqueous medium to granulate the toner, and the organic solvent is removed from the dispersed particles. Including removing,
In the toner production method, the toner material dissolved or dispersed before granulation contains 10.0 to 200% by mass of water in a saturated amount of water dissolved in the organic solvent at 25 ° C.
<2> The method for producing a toner according to <1>, wherein the dissolved or dispersed liquid of the toner material before granulation contains 1.0% by mass or more of water with respect to the organic solvent.
<3> The toner according to any one of <1> to <2>, wherein 60% by mass or more of the organic solvent in the dispersion of the toner material dissolves 40 g of water at 25 ° C. and 100 g. It is a manufacturing method.
<4> The method for producing a toner according to <3>, wherein 60% by mass or more of the organic solvent in the dispersion or dispersion of the toner material dissolves 2.94 g or less of water at 25 ° C. and 100 g. is there.
<5> The method for producing a toner according to any one of <3> to <4>, wherein 60% by mass or more of the organic solvent in the dispersion or dispersion of the toner material is ethyl acetate.
<6> The toner material includes at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound,
By granulating, by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound to produce an adhesive base material, particles containing at least the adhesive base material are obtained. The method for producing a toner according to any one of <1> to <5>, wherein the toner is produced.

<7> A toner produced by the method for producing a toner according to any one of <1> to <6>.
<8> A toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound is dissolved or dispersed in an organic solvent to prepare a solution or dispersion of the toner material. After the dispersion is dispersed as dispersed particles in an aqueous medium to prepare an oil-in-water dispersion, the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium To produce particles containing at least an adhesive substrate, and obtained by removing the organic solvent from the dispersed particles,
The toner is characterized in that the toner material dissolved or dispersed before granulation contains 10.0 to 200% by mass of water in a saturated amount of water in the organic solvent at 25 ° C.
<9> The toner according to any one of <7> to <8>, wherein the adhesive base material includes a polyester resin.
<10> The toner according to <9>, wherein the molecular weight distribution of a tetrahydrofuran (THF) soluble portion of the polyester resin is 1,000 to 30,000 in terms of weight average molecular weight (Mw).
<11> The toner according to any one of <9> to <10>, wherein the acid value of the polyester resin is 1.0 to 50.0 (KOHmg / g).
<12> The toner according to any one of <9> to <11>, wherein the polyester resin has a glass transition temperature (Tg) of 35 to 70 ° C.
<13> The toner according to any one of <7> to <12>, wherein the toner has a volume average particle diameter of 3 to 7 μm.
<14> The toner according to any one of <7> to <13>, wherein the toner has a volume average particle diameter (Dv) / number average particle diameter (Dn) of 1.05 to 1.25.
<15> The toner according to <7> to <14>, wherein the toner has an average circularity of 0.92 to 0.99.
<16> The toner according to any one of <7> to <15>, wherein the glass transition temperature (Tg) of the toner is 40 to 70 ° C.
<17> The toner according to any one of <7> to <16>, wherein the toner has an acid value of 4.0 to 40.0 (KOH mg / g).

<18> A developer comprising the toner according to any one of <7> to <16>.
<19> A toner-containing container filled with the toner according to any one of <7> to <16>.
<20> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <7> to <16> to be a visible image And a developing means for forming a process cartridge.
<21> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image according to <7> to <16> Developing means for developing a visible image by developing using any of the toners, Transfer means for transferring the visible image to a recording medium, Fixing means for fixing the transferred image transferred to the recording medium, An image forming apparatus having at least
<22> The image forming apparatus according to <21>, wherein the electrostatic latent image carrier has a layer made of amorphous silicon.
<23> The image forming apparatus according to any one of <21> to <22>, wherein the developing unit forms a visible image by applying an alternating electric field.
<24> The fixing unit includes at least a heating member, a film in contact with the heating member, and a pressure member disposed in pressure contact with the heating member via the film, and the film and the pressure member The image forming apparatus according to any one of <21> to <23>, wherein a recording medium on which a transfer image is formed is passed between the images and the transfer image is fixed.
<25> Cleaning means for cleaning the surface of the electrostatic latent image carrier, wherein the cleaning means includes a first cleaning blade and a second cleaning blade in order from the upstream side in the rotation direction of the electrostatic latent image carrier. The image forming apparatus according to any one of <21> to <24>, wherein the second cleaning blade is a polishing blade having a two-layer structure including a blade base layer and an abrasive particle-containing layer. is there.
<26> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <7> to <17> An image comprising at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium It is a forming method.

  The method for producing a toner of the present invention includes granulating the toner by dispersing a dispersion or dispersion of the toner material prepared by dissolving or dispersing the toner material in an organic solvent as dispersed particles in an aqueous medium, The dissolved or dispersed liquid of the toner material before granulation is characterized by containing 10.0 to 200% by mass of water based on the saturated dissolution amount of water in the organic solvent at 25 ° C. In the toner manufacturing method, the toner material dissolved or dispersed liquid prepared by dissolving or dispersing the toner material in the organic solvent is dispersed as dispersed particles in an aqueous medium, and the toner is granulated. . At this time, the dissolved or dispersed liquid of the toner material before granulation contains 10.0 to 200% by mass of water of the saturated dissolution amount of water in the organic solvent at 25 ° C. As a result, when the toner material is dissolved or the dispersion liquid is dispersed in the aqueous medium, occurrence of a phenomenon (dilution shock) in which the toner material is aggregated to prevent uniform dispersion is suppressed, and toner scattering and fogging are suppressed. Can reduce the amount of fine powder that causes toner, is excellent in various characteristics such as chargeability and transferability, has little toner scattering and fogging, has both low-temperature fixability and storage stability, and has high image quality. The toner having a small particle size and a narrow particle size distribution is produced stably and efficiently. In the method for producing the toner, when the organic solvent is removed from the dispersed particles, the removed organic solvent can be reused as the organic solvent used for dissolving or dispersing the toner material. The amount of the organic solvent that becomes the waste liquid is reduced, and the burden on the environment due to the waste liquid treatment is also reduced.

The toner material includes at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the granulation includes the active hydrogen group-containing compound and the active hydrogen group-containing compound. And a polymer capable of reacting with each other to produce particles having at least the adhesive substrate while producing an adhesive substrate. A toner that is excellent in various properties such as moldability and fixability, in particular, low-temperature fixability and can obtain high image quality is efficiently produced.
In addition, an aspect in which 60% by mass or more of the organic solvent in the dispersion or dispersion of the toner material dissolves 40 g or less of water at 25 ° C. and 100 g, 2.94 g of water dissolves at 25 ° C. and 100 g. And an embodiment in which the constituent component is ethyl acetate.

  The toner of the present invention is produced by the toner production method of the present invention. For this reason, the toner has a small particle size and a narrow particle size distribution, is excellent in various properties such as chargeability and transferability, has little toner scattering and fogging, has both low-temperature fixability and storage stability, and has high Image quality can be obtained. Further, when the toner contains particles containing at least an adhesive substrate obtained by reacting the active hydrogen group-containing compound with a polymer capable of reacting with the active hydrogen group-containing compound, anti-aggregation property, charging property, fluidity, releasability Excellent properties such as fixing properties. When image formation is performed using the toner, high image quality can be obtained under low-temperature fixing conditions.

  The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, a high-quality image with high image density and high sharpness is formed.

  The toner container of the present invention is filled with the toner of the present invention. For this reason, when an image is formed by electrophotography using the toner of the present invention filled in the toner-containing container, a high-quality image with high image density and high sharpness is formed.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge is detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that a high quality image with high image density and high sharpness can be formed.

  The image forming apparatus of the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of the present invention. The image forming apparatus includes at least a developing unit that forms a visible image by developing with toner, a transfer unit that transfers the visible image to a recording medium, and a fixing unit that fixes the transferred image transferred to the recording medium. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops the electrostatic latent image using the toner of the present invention to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, a high-quality image with high image density and high sharpness is formed.

  The image forming method of the present invention comprises an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image with the toner of the present invention to make visible. It includes at least a developing step for forming an image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. In the image forming apparatus, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, a high-quality image with high image density and high sharpness is formed.

  According to the present invention, it is possible to solve various problems in the past, excellent in various characteristics such as chargeability and transferability, less toner scattering and fogging, achieving both low temperature fixability and storage stability, and high A toner having a small particle size and a narrow particle size distribution capable of obtaining image quality, a stable and efficient manufacturing method that can reuse an organic solvent, and has a low environmental impact due to waste liquid treatment, and using the toner, It is possible to provide a developer, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method capable of improving image quality.

(Toner and toner production method)
The method for producing a toner of the present invention comprises granulating a toner by dispersing a solution or dispersion of the toner material prepared by dissolving or dispersing a toner material in an organic solvent as dispersed particles in an aqueous medium, and then dispersing the dispersed particles Removing the organic solvent from
The dissolved or dispersed liquid of the toner material before granulation contains 10.0 to 200% by mass of water of the saturated dissolution amount of water in the organic solvent at 25 ° C.

The toner of the present invention is obtained by the toner production method of the present invention.
In a preferred embodiment of the toner of the present invention, the toner material includes at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the granulation includes the active hydrogen group-containing compound. And a toner that is produced by reacting a polymer capable of reacting with the active hydrogen group-containing compound to produce an adhesive base material while obtaining particles containing at least the adhesive base material.
A toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound is dissolved or dispersed in an organic solvent to prepare a solution or dispersion of the toner material. After preparing an oil-in-water dispersion by dispersing as dispersed particles in an aqueous medium, the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium. To produce particles containing at least an adhesive substrate, obtained by removing the organic solvent from the dispersed particles,
A toner in which the dissolution or dispersion of the toner material before granulation contains 10.0 to 200% by mass of water with respect to the saturated dissolution amount of water in the organic solvent at 25 ° C. is preferable.
Hereinafter, the details of the toner of the present invention will be clarified through the description of the toner production method of the present invention.

-Dissolution or dispersion of toner material-
The solution or dispersion of the toner material is prepared by dissolving or dispersing the toner material in an organic solvent.
The toner material is not particularly limited as long as the toner can be formed, and can be appropriately selected depending on the purpose. For example, the monomer, the polymer, the active hydrogen group-containing compound, and the reaction with the active hydrogen group-containing compound can be selected. It contains at least one of the possible polymers (prepolymers), and further contains other components such as a colorant, a release agent, and a charge control agent as necessary.

The organic solvent is required to be infinitely compatible with the water, and in the dissolved or dispersed liquid of the toner material before granulation, 60% by mass or more of the constituent component of the organic solvent in the dissolved or dispersed liquid However, it is preferable to dissolve 40 g or less of water at 25 ° C. and 100 g, and more preferable to dissolve 2.94 g or less of water at 25 ° C. and 100 g. When exhibiting such solubility, the compatibility in forming the dispersed particles and the ease in removing the organic solvent from the dispersed particles are excellent. Further, when the organic solvent exhibiting the solubility is less than 60% by mass, it becomes difficult to form an organic solvent phase that becomes toner particles, and the toner material flows out into the aqueous medium to be dispersed, and the particle size distribution. Narrow toner may not be obtained.
In addition, as an organic solvent which melt | dissolves 2.94 g or less of water in 25 degreeC and 100 g, the ethyl acetate mentioned later is mentioned, for example.

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 as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.

The organic solvent needs to be removed from the dispersed particles, and is preferably removed during or after toner granulation.
Here, in the method for producing a toner of the present invention, the organic solvent removed from the dispersed particles contains azeotropic water, and 10.0 to 200% by mass of the saturated dissolution amount of water in the organic solvent at 25 ° C. It can be reused as an organic solvent containing water.
The method for removing the organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, (1) The whole reaction system is gradually reduced in pressure and heated to be dispersed. A method of completely evaporating and removing the organic solvent in the particles; (2) spraying the emulsified dispersion in a dry atmosphere to completely remove the water-insoluble organic solvent in the dispersed particles to form toner fine particles; In addition, there is a method of evaporating and removing the aqueous dispersant. If necessary, (3) after removing the organic solvent in the container to some extent (for example, less than 6% against water), it may be combined with a continuous solvent removal system using a thin film distillation method or the like. it can. Among these, the above (1) in which either reduced pressure or elevated temperature is performed is preferable.
Examples of the dry atmosphere in which the emulsified dispersion is sprayed include heated gases such as air, nitrogen, carbon dioxide, and combustion gas, and various air streams heated to a temperature higher than the boiling point of the highest boiling solvent used. It is done. These can sufficiently achieve the intended quality by short-time treatment using a spray dryer, belt dryer, rotary dryer, rotary kiln or the like.

In the dissolution of the toner material or the preparation of the dispersion, when the amount of the organic solvent used is X mass%, the water is gradually added to the organic solvent, and the amount of water added just before phase separation occurs. Is Y mass%, the amount of water added to the solution or dispersion of the toner material satisfies the following formula, 0.4Y (X + Y) to 2.0Y (X + Y) in the solvent mass ratio. It is more preferable that the following formula, 0.6Y (X + Y) to 1.05Y (X + Y) is satisfied.
Specifically, the dissolved or dispersed liquid of the toner material before granulation needs to contain 10.0 to 200% by mass of water with respect to the saturated dissolution amount of water in the organic solvent at 25 ° C.
Further, the dissolved or dispersed liquid of the toner material before granulation preferably contains 1.0% by mass or more of water, preferably 2.0 to 30.0% by mass with respect to the organic solvent. -10.0 mass% is more preferable. If the water content is less than 1.0% by mass, dilution shock may not be suppressed.

  The method for dissolving or dispersing the toner material is not particularly limited and may be appropriately selected according to the purpose. For example, the toner material is dissolved or dispersed in an organic solvent having a water content of less than 1% by mass. A method of adding water to the obtained dispersion or dispersion of the toner material, adding water to an organic solvent having a water content of less than 1% by mass to prepare a water-containing solvent, and then dissolving or dissolving the toner material in the water-containing solvent Examples thereof include a method of dispersing, a method of dissolving or dispersing the toner material in an organic solvent preliminarily hydrated by azeotropy, and the like. These methods may be used alone or in combination of two or more.

  In the method for producing a toner according to the preferred embodiment of the present invention, the dissolution or dispersion of the toner material can be reacted with the active hydrogen group-containing compound and the active hydrogen group-containing compound in the organic solvent. A toner material such as a polymer, the colorant, and the charge control agent can be dissolved or dispersed, and the polymer (pre-polymer) that can react with the active hydrogen group-containing compound in the toner material. Components other than the polymer) may be added and mixed in the aqueous medium in the preparation of the aqueous medium described later, or the dissolution or dispersion of the toner material is added to the aqueous medium. Or you may add to the said aqueous medium with a dispersion liquid.

-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 phase.
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: 0.01-10 are preferable and 100: 0.01-1 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: 0.01-10 are preferable and 100: 0.01-1 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, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially 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 the storage stability of the toner and the low-temperature fixability, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

The polyisocyanate (PIC) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic diisocyanates, araliphatic diisocyanates, and isocyanurates. 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 the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing group are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and preferably 4/1 to 1.2 / 1. More preferred is 3/1 to 1.5 / 1.
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, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 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 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 weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 3,000 to 40,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 4,000 to 30,000 is more preferable. When the weight average molecular weight (Mw) is less than 3,000, the storage stability may be deteriorated, and when it exceeds 40,000, 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 per minute, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 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 Toyo Soda Kogyo Co., Ltd. having a molecular weight of ^{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 those of × 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.

-Other ingredients-
The other component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a colorant, a release agent, a charge control agent, metal oxide, resin fine particles, inorganic fine particles, and a fluidity improver. , Cleaning improvers, magnetic materials, metal soaps, and the like.

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, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, 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 to 15% by mass, and more preferably 3 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, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This 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 organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three roll mill is preferably used.
As content of the said coloring agent in the said masterbatch, it is 80 mass% or less normally, and 30-60 mass% is preferable.

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, long chain hydrocarbons, and the like. 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, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
When the melting point is less than 40 ° C., the release agent may adversely affect storage stability, and when it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the release agent.
If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 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, 0-40 mass% is preferable and 3-30 mass% is 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, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit), quinacridone, azo pigments, other sulfonic acid groups, carbo Sill 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, 0.1-10 mass parts is preferable, and 0.2-5 mass parts is 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.

The metal oxide may be used as a metal oxide solvent dispersion in which the metal oxide is dispersed in a solvent. Examples of the metal oxide solvent dispersion include a wet method (hydrothermal synthesis method, sol-gel method). And the like. The linear / ring-shaped metal oxide hydrogel dispersion synthesized by the above method is subjected to a hydrophobic treatment, and the dispersion solvent is replaced with an arbitrary solvent.
Examples of the metal oxide synthesized by the wet method include silicon dioxide (silica), titanium dioxide (titania), aluminum oxide, zinc oxide, tin oxide, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, and oxidation. Examples include zirconium, parium sulfate, barium carbonate, and calcium carbonate. These may be used individually by 1 type and may use 2 or more types together. Among these, silicon dioxide (silica), titanium dioxide (titania), and aluminum oxide are preferable, and silica is particularly preferable.
The method for hydrophobizing treatment is not particularly limited and may be appropriately selected depending on the intended purpose, but in many cases, a surface treating agent is used. It is necessary to optimize the balance.
Examples of the surface treatment agent include a coupling agent represented by the following formula (Q) x-Si (P) y- (A) z. In the above formula, Q represents a hydrolyzable group such as a halogen atom, an amino group, or an alkoxyl group, A represents an alkyl group or an aryl group, and the organic functional group P represents —BOOC (R ′) C═CH. ₂ , —BNHR ″ or —BNH ₂ , R ′ represents an alkyl group, and R ″ represents an alkyl group or an aryl group. B represents an alkylene group or an alkylene group containing any of —O—, —NH—, and —CO—. x and y are integers of 1 or more, z is an integer of 0 or more, and satisfies x + y + z = 4.
Specific examples of the surface treatment agent include, for example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxy. Propyltrimethoxysilane [γ-glycidoxypropyltrimethoxysilane], 3-glycidoxypropylmethyldiethoxysilane [γ-glycidoxypropylmethyldimethoxysilane], 3-glycidoxypropyltriethoxysilane, p- Styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane [γ-methacryloxypropyltrimethoxysilane], 3-methacryloxypropylmethyldiethoxysilane, 3-methacrylo Cypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane [γ- (2-aminoethyl) aminopropylmethyldimethoxysilane], N-2 (amino Ethyl) 3-aminopropyltrimethoxysilane [γ- (2-aminoethyl) aminopropyltrimethoxysilane], N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane [γ-anilinopropyltrimethoxysilane], N— (Vinylbenzyl) -2-aminoethyl-3-aminop Pyrtrimethoxysilane hydrochloride N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane hydrochloride], octadecyldimethyl (3- (trimethoxysilyl) propyl) ammonium chloride, 3-ureidopropyltri Ethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane (γ-mercaptopropyltrimethoxysilane), bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyl And triethoxysilane. Alternatively, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, or a silicone oil used as a hydrophobizing agent may be used.

Examples of the solvent for dispersing the metal oxide include methanol, ethanol, 1-pentanol, n-butanol, isopropanol, 2-methoxyethanol, isobutanol, methyl ethyl ketone, methyl isobutyl ketone, 2-methyl tetrahydrofuran, cyclohexanone, and formaldehyde. , Dioxane, dimethylformamide, ethyl acetate, n-butyl acetate, methyl methacrylate, diisopropyl ether, dibutyl ether, benzene, toluene and the like. These may be used individually by 1 type and may use 2 or more types together.
It is desirable that the SP value δ _MS of the solvent in the metal oxide solvent dispersion and the SP value δ _PS of the solvent when the metal oxide solvent dispersion is removed are as close as possible, δ _MS and δ _PS needs to satisfy −2.0 <δ _MS −δ _PS <4.0, preferably −0.5 <δ _MS −δ _PS <1.0, and −0 More preferably, 1 <δ _MS −δ _PS <0.3 is satisfied. For example, it is preferable to dissolve or disperse a polymer, a colorant, a release agent and the like in ethyl acetate, and disperse the metal oxide added to the ethyl acetate solution or dispersion in a solvent such as ethyl acetate or methyl ethyl ketone.
When present as a primary particle in a solvent, the dispersibility of the metal oxide is good up to the formation of toner particles and the effect of changing the shape of the toner is greater, so that the dispersibility, stability over time, and productivity are improved. In view of the above, it is particularly preferable to use an organosilica sol as the metal oxide solvent dispersion. The organosilica sol refers to a state in which colloidal silica in which a part of silanol groups on the particle surface is silylated is dispersed in an organic solvent in a stable state or a solution thereof. The detailed description and production method of the organosilica sol are described, for example, in JP-A No. 11-43319.
The pH measurement for dilution with water is performed as follows. First, the metal oxide solvent dispersion is dispersed uniformly. If it is already a sol, it is easy to disperse, but if it is a wet gel, it is crushed with a disper as required. The mixture is diluted with an equal amount of ion-exchanged water and stirred for 3 minutes at a homomixer 2000 rotation, and the pH is measured.

The amount of the metal oxide added to the toner is preferably 0.05 to 50% by mass, and more preferably 0.25 to 10% by mass.
When the addition amount is less than 0.05% by mass, the absolute amount of the metal oxide with respect to the toner particle surface is insufficient, and it may be difficult to obtain a sufficient improvement effect on the toner particle shape change. On the other hand, the amount of the metal oxide present on the surface of the toner particles becomes excessive, and the metal oxide acts as a fixing inhibitor, so that the minimum fixing temperature increases and the low-temperature fixability may be impaired.

The average particle size of the primary particles of the metal oxide is preferably 5 to 200 nm, more preferably 10 to 180 nm.
When the average particle size is less than 5 nm, separation from the organic solvent to the aqueous medium is likely to occur, and it may be difficult to obtain a sufficient improvement effect on toner particle shape change. An interval may be generated between the oxides, which may reduce the effect on the toner particle shape change.
Here, the average particle diameter is a number average particle diameter. The particle diameter of the metal oxide is determined by a particle size distribution measuring device using dynamic light scattering, such as (“DLS-700”; manufactured by Otsuka Electronics Co., Ltd.), (“Coulter N4”; manufactured by Coulter Electronics) Although it is difficult to dissociate secondary aggregation of particles after silicone oil treatment, it can be measured by a scanning electron microscope (SEM) or from a photograph obtained by a transmission electron microscope (TEM). It is preferable to directly determine the particle size. In this case, at least 100 metal oxides are observed, and the average value of the major axis is obtained.
In addition, as the shape of the metal oxide, spherical particles, amorphous particles, linear shapes, network shapes, and the like can be used, and they can be properly used depending on the dispersion state in the organic solvent.

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 resin. , Silicone resin, benzoguanamine resin, nylon resin, and the like.
These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin is preferable because an aqueous dispersion of fine spherical resin 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”). "; Manufactured by Sanyo Chemical Industries Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.

The glass transition temperature (Tg) of the resin fine particles is preferably 40 to 100 ° C., for example, and the weight average molecular weight (Mw) is preferably 9,000 to 200,000.
When the glass transition temperature (Tg) is less than 40 ° C. or the weight average molecular weight (Mw) is less than 9,000, the storage stability is deteriorated, and blocking may occur during storage and in the developing machine. When the Tg exceeds 100 ° C. or the Mw exceeds 200,000, the resin fine particles may inhibit the adhesion with the transfer paper, and the minimum fixing temperature may increase.

There is no restriction | limiting in particular as content (residual amount) in the said toner of the said resin fine particle, Although it can select suitably according to the objective, For example, 0.5-5.0 mass% is preferable.
When the content (residual amount) is less than 0.5% by mass, the storage stability of the toner deteriorates, and blocking may be observed during storage or use. Exceeding the above may cause the resin fine particles to inhibit the exudation of the wax, so that sufficient releasability cannot be obtained and offset may occur.

  The content (residual amount) of the resin fine particles in the toner can be measured by various methods. Substances or functional groups derived only from the resin fine particles can be measured using, for example, a pyrolysis gas chromatograph mass spectrometer. It is possible to calculate from the peak area. There is no restriction | limiting in particular as said detector, Although it can select suitably according to the objective, A mass spectrometer is suitable.

  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 can be suitably used as an external additive for improving the fluidity, developability, chargeability and the like of the toner. The inorganic fine particles are preferably the same type as the inorganic fine particles that can be dispersed in the organic solvent.
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. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 5.0% by mass.

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 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.

-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.

In the aqueous medium, fine particles may be dispersed in order to obtain toner particles having a toner particle size with good chargeability and uniform particle size distribution.
The fine particles are not particularly limited as long as they are present in a solid form hardly soluble in water in the aqueous medium, and can be appropriately selected according to the purpose. The fine particles are preferred.

Among the fine particles, inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
Preferable examples include tricalcium phosphate, calcium carbonate, colloidal titanium oxide, colloidal silica, and hydroxyapatite.
These may be used individually by 1 type and may use 2 or more types together. Among these, hydroxyapatite synthesized by reacting sodium phosphate and calcium chloride in water under basic conditions is particularly preferable.
Among the fine particles, examples of the organic fine particles include microcrystals of low-molecular organic compounds.

The relationship between the size of the toner particles and the fine particles to be fixed to the surface thereof is 5 ≦ R / Rs ≦ 2,000, where R is the particle size of the toner particles and Rs is the particle size of the fine particles. It is necessary to satisfy | fill and it is preferable to satisfy | fill 20 <= R / Rs <= 200. When R and Rs are out of the numerical range, the effect of controlling the particle size of the toner by the fine particles may be significantly reduced.
Further, the amount of the fine particles fixed to the surface of the toner particles is not particularly limited and can be appropriately selected depending on the purpose. For example, 0.1 to 20% by mass with respect to the toner particles is preferable. 1-10 mass% is more preferable.
The volume average particle diameter (Dv) of the fine particles preferably satisfies, for example, 5 μm ≦ Dv ≦ 500 μm, and more preferably satisfies 50 μm ≦ Dv ≦ 200 μm from the viewpoint of particle size control.
The particle size distribution (volume average particle size (Dv) / number average particle size (Dn)) of the fine particles is preferably less than 1.25. When the fine particles satisfying such a particle size distribution are used, the particle size distribution is sharp. A toner can be obtained, and the resin fine particles described above can be suitably used as the fine particles.

-Dispersed particles-
The dispersed particles are dispersions (oil droplets) formed by dissolving or dispersing the toner material in the aqueous medium and formed by dispersing or dissolving the toner material in the aqueous medium, and the composition of the dispersed particles Is the same as the composition of the solution or dispersion of the toner material. That is, the dispersed particles include, for example, at least one of the monomer, the polymer, and a polymer (prepolymer) that can react with the active hydrogen group-containing compound, and if necessary, the colorant, It comprises a toner material containing the other components such as the release agent and the charge control agent.

In the preparation of the oil-in-water dispersion, it is preferable that the dissolved or dispersed liquid of the toner material is dispersed in the aqueous medium while stirring. The dispersion method is not particularly limited and can be appropriately selected according to the purpose. For example, the dispersion can be performed using a known disperser. Examples of the disperser include a low-speed shearing disperser. Machine, high-speed shearing disperser, friction disperser, high-pressure jet disperser, ultrasonic disperser, and the like.
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 3,000 to 30,000 rpm is preferable, 5,000 to 20,000 rpm is more preferable, and the dispersion time is preferably 0.1 to 5 minutes in the case of a batch system, and the dispersion temperature is under pressure. 0-150 degreeC is preferable and 40-98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

  In the method for producing a toner according to the preferred embodiment of the present invention, 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 cross-linking reaction at the time of toner granulation, A substrate is produced.

-Adhesive substrate-
The adhesive base material 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 may contain at least a polymer and may further contain a binder resin appropriately selected from known binder resins.

There is no restriction | limiting in particular as a weight average molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 3,000 or more are preferable and 5,000-1,000,000 are more preferable. 7,000 to 500,000 are particularly preferred.
When the weight average molecular weight is less than 3,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said adhesive base material, Although it can select suitably according to the objective, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable. In the toner, since a polyester resin subjected to a crosslinking reaction and an extension reaction coexists, the toner exhibits good storage stability even when the glass transition temperature is lower than that of a conventional polyester toner.
When the glass transition temperature (Tg) is less than 30 ° C., the storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.

  The glass transition temperature can be measured by, for example, the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. can do.

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 resin comprises 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. Obtained by reacting in phase.
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.

--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 resistance to hot offset.

The weight 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 preferred. When the weight average molecular weight (Mw) is less than 1,000, the storage stability may be deteriorated. Therefore, the content of the component having the weight 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 weight 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 to 70 ° C. When the glass transition temperature is less than 35 ° C., the storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5, it may be difficult to achieve both storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is usually 1.0 to 30.0 mgKOH / g, and preferably 5.0 to 20.0 mgKOH / g. Generally, it becomes easy to be negatively charged by giving the toner an acid 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. -25/75 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 may be deteriorated. .

  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)). A solution or dispersion of the toner material is emulsified or dispersed in the aqueous medium together with the active hydrogen group-containing compound (for example, the amines (B)) to form the dispersed particles, and both in the aqueous medium. (2) The dispersion or dispersion of the toner material is emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance, and the dispersion is performed. It may be formed by forming particles and subjecting both to an extension reaction or a crosslinking reaction in the aqueous medium, or (3) a solution or dispersion of the toner material. After adding and mixing in the aqueous medium, the active hydrogen group-containing compound is added to form the dispersed particles, and these are formed by extending or cross-linking both from the particle interface in the aqueous medium. May be. 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 to 150 ° C, more preferably 40 to 98 ° C.

  Examples of a method for stably forming the dispersed particles containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)) in the aqueous medium include, for example, the aqueous system. In the medium, the toner material such as a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, the charge control agent, and the unmodified polyester resin. And a method of adding a solution or dispersion liquid of the toner material prepared by dissolving or dispersing the toner material in the organic solvent and dispersing the toner material by a shearing force.

In the emulsification or dispersion, the amount of the aqueous medium used is preferably 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner material.
If the amount used is less than 50 parts by mass, the toner material may be poorly dispersed and toner particles having a predetermined particle size may not be obtained. If the amount used exceeds 2,000 parts by mass, the production cost will be high. May be.

In the emulsification or dispersion, a dispersant is preferably used from the viewpoint of stabilizing the dispersed particles and sharpening the particle size distribution while obtaining a desired shape, if necessary.
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 and the like, and those having a fluoroalkyl group are preferable. 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 (manufactured by Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nihon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, amino alcohol 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. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. 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 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M Co.); Unidyne DS-202 (manufactured by Daikin Industries Ltd.), MegaFuck F-150 F-824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products); Footgent F-300 (manufactured by Neos).

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 hydroxyl groups, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and compounds containing carboxyl groups, 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 the homopolymer or copolymer 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 the preparation of the oil-in-water 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 oil-in-water dispersion, the 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 oil-in-water dispersion (emulsified slurry).
The organic solvent is removed, for example, when the toner is produced by a known dissolution suspension method or the toner production method of the preferred embodiment of the present invention.
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 by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.
The obtained unnecessary fine particles or coarse particles can be returned to the kneading step and used for the formation of toner particles. At this time, the fine particles or the coarse particles may be in a wet state.

Thus, the obtained toner particles are mixed with particles of the colorant, the release agent, the charge control agent, etc., and further, a mechanical impact force is applied to the release particles from the surface of the toner particles. It is possible to prevent the particles such as the agent 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 for 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 is lowered, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

  The toner obtained by the toner production method of the present invention has the following volume average particle diameter (Dv), volume average particle diameter (Dv) / number average particle diameter (Dn), average circularity, penetration, It preferably has low temperature fixability, non-offset temperature, thermal characteristics, glass transition temperature, acid value, image density, and the like.

The volume average particle size (Dv) of the toner is preferably 3 to 7 μm, and more preferably 4 to 5 μm, for example.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. If the thickness exceeds 7 μm, the resolution is high and high. It becomes difficult to obtain an image of an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is preferably 1.25 or less, and more preferably 1.05 to 1.20.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is less than 1.05, in the two-component developer, the toner is fused to the surface of the carrier during long-term stirring in the developing device, The chargeability of the carrier may be reduced, and the cleaning property may be deteriorated. In the case of a one-component developer, the filming of the toner on the developing roller and the thinning of the toner are performed. Toner fusion may easily occur, and if it exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and toner particles in the case where the balance of the toner in the developer is performed Variation in diameter may be large.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.05 to 1.20, the storage stability, the low-temperature fixability, and the hot offset resistance are all excellent. In particular, when used in a full-color copying machine, the glossiness of the image is excellent. With two-component developers, there is little fluctuation in the toner particle diameter in the developer even if the toner balance for a long period of time is achieved, and good and stable developability can be obtained even with long-term stirring in the developing device. Even if the balance of the toner is carried out with the agent, fluctuations in the particle diameter of the toner are reduced, and there is no filming of the toner on the developing roller and no fusion of the toner to the member to the blade for thinning the toner. Even in the long-term use (stirring) of the developing device, good and stable developability can be obtained, so that a high-quality image can be obtained.

  The volume average particle diameter and the ratio (Dv / Dn) between the volume average particle diameter and the number average particle diameter are measured using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can do.

The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected area as the shape of the toner by the circumference of the actual particles, and is preferably 0.92 to 0.99, for example, 0.94 to 0 .97 is more preferred.
If the average circularity is less than 0.92, a satisfactory transferability and a high-quality image free from dust may not be obtained. If the average circularity exceeds 0.99, image formation employing blade cleaning or the like may be performed. In the system, defective cleaning occurs on the photoconductor and transfer belt, and in the case of image formation with a high image area ratio such as photographic images, an untransferred image is formed due to poor paper feed, etc. As a result, the accumulated toner may become a transfer residual toner on the photoconductor, which may cause background smearing of the image, or may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.
The average circularity is measured, for example, by an optical detection band method in which a suspension containing toner is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).

The toner preferably has a plurality of indentations on the surface. Due to the presence of the recess, the cleaning property and the transfer property are improved.
The indentation can be measured, for example, by observing an SEM image with a scanning electron microscope (SEM).
The major diameter of the recess is, for example, ½ or less of the toner particle diameter, and specifically, 1.0 to 5.0 μm is preferable. As the depth of the depression, for example, 1/10 or more of the major axis is preferable, and 1/8 or more is more preferable. In general, in concavo-convex particles formed by pulverized toner or emulsion polymerization, additives such as silica that are added for the purpose of improving fluidity tend to accumulate in the concave portions, and the additives are stirred and mixed with a high-speed mixer. In such a case, the additive is difficult to be fixed and may be released from the toner, causing problems such as photoconductor contamination and adhesion to the carrier. However, if the major axis of the dent is 1 μm or more and the depth is shallow, the occurrence of the problems such as accumulation and release of additives is suppressed.

As said penetration, the penetration measured by the penetration test (JIS K2235-1991) needs to be 15 mm or more, for example, and 20-30 mm is more preferable.
If the penetration is less than 15 mm, the storage stability may deteriorate.
The penetration can be measured according to JIS K2235-1991. Specifically, a 50 ml glass container is filled with toner and left in a thermostatic bath at 50 ° C. for 20 hours. The penetration can be measured by cooling the toner to room temperature and performing a penetration test. In addition, it has shown that the said storage stability is excellent, so that the said penetration value is large.

As the low temperature fixability, from the viewpoint of achieving both a reduction in the fixing temperature and the occurrence of no offset, it is preferable that the lower limit temperature for fixing is lower, and more preferable that the temperature at which no offset is generated is higher. As a temperature range in which both can be achieved, the minimum fixing temperature is less than 150 ° C., and the non-offset temperature is 200 ° C. or more.
The fixing lower limit temperature is, for example, an image forming apparatus, a transfer sheet is set, a copy test is performed, and the remaining ratio of the image density after rubbing the obtained fixed image with a pad is 70% or more. The fixing member temperature is the lower limit fixing temperature.
The offset non-occurrence temperature is adjusted such that the toner to be evaluated is developed with a predetermined amount by using an image forming apparatus, and is adjusted so that the temperature of the fixing member is variable, so that no offset is generated. Can be determined by measuring.

The thermal characteristics are also called flow tester characteristics, and are evaluated as, for example, a softening temperature (Ts), an outflow start temperature (Tfb), a 1/2 method softening point (T1 / 2), and the like.
These thermal characteristics can be measured by an appropriately selected method. For example, the thermal characteristics can be obtained from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
There is no restriction | limiting in particular as said softening temperature (Ts), According to the objective, it can select suitably, For example, 30 degreeC or more is preferable and 50-90 degreeC is more preferable. Storage stability may deteriorate that the said softening temperature (Ts) is less than 30 degreeC.
There is no restriction | limiting in particular as said outflow start temperature (Tfb), According to the objective, it can select suitably, For example, 60 degreeC or more is preferable and 80-120 degreeC is more preferable. When the outflow start temperature (Tfb) is less than 60 ° C., at least one of storage stability and offset resistance may deteriorate.
The 1/2 method softening point (T1 / 2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 ° C. or higher is preferable, and 100 to 170 ° C. is more preferable. When the 1/2 method softening point (T1 / 2) is less than 90 ° C., the offset resistance may be deteriorated.

There is no restriction | limiting in particular as said glass transition temperature, Although it can select suitably according to the objective, For example, 40-70 degreeC is preferable and 45-65 degreeC is more preferable. When the glass transition temperature (Tg) is less than 40 ° C., the storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.
The glass transition temperature can be measured using, for example, a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation).

  The acid value of the toner is, for example, preferably 4.0 to 40.0 (KOH mg / g), and more preferably 10.0 to 30.0. When the acid value is less than 4.0 (KOHmg / g), the reaction between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound is accelerated, and a toner having a narrow particle size distribution is obtained. When it exceeds 40.0 (KOHmg / g), it becomes difficult to ensure the releasability at high temperature.

The image density is, for example, preferably 1.40 or more, more preferably 1.45 or more, and 1.50 or more, as measured by a spectrometer (X-Light, 938 Spectrodensitometer). Is more preferable.
If the image density is less than 1.40, the image density may be low and high image quality may not be obtained.
The image density is, for example, a tandem color electrophotographic apparatus (“IPSIO Color 8100”; manufactured by Ricoh Co., Ltd.), and a developer adhesion amount of 1 on copy paper (“Type 6200”; manufactured by Ricoh Co., Ltd.). A solid image of .00 ± 0.1 mg / cm ² was formed at a surface temperature of the fixing roller of 160 ± 2 ° C., and the image density at any five positions in the obtained solid image was measured by a spectrometer (manufactured by X-Light). , 938 Spectrodensitometer), and the average value can be calculated.

  The coloration of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner and yellow toner. This toner can be obtained by appropriately selecting the type of the colorant.

As the amount of fine powder produced when the toner is produced by the toner production method of the present invention, for example, the amount of fine powder having a volume average particle diameter (Dv) of less than 3 μm is preferably 10.0% by number or less. Is more preferably 0.0% by number or less, and even more preferably 7.0% by number.
When the fine powder amount exceeds 10.0% by number, toner scattering and fogging are likely to occur, and a high-quality image may not be obtained.
The amount of fine powder is, for example, the average circularity of fine powder, a suspension containing fine powder is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Sysmex Corporation).

  The method for producing a toner of the present invention comprises dispersing the toner material dissolved or dispersed in a water-based medium as dispersed particles prepared by dissolving or dispersing the toner material in a solvent, granulating the toner, and then dispersing the dispersed particles. In this case, the solution or dispersion of the toner material before granulation contains 10.0 to 200% by mass of water with respect to the saturated dissolution amount of water in the organic solvent. The occurrence of a phenomenon (dilution shock) in which the toner material aggregates and inhibits uniform dispersion during dispersion in the aqueous medium is suppressed, and the amount of fine powder that causes toner scattering and fogging can be reduced. Toner with small particle size and narrow particle size distribution that is excellent in various characteristics such as chargeability and transferability, has less toner scattering and fogging, achieves both low-temperature fixability and storage stability, and provides high image quality. Is always stable It is. Further, when the organic solvent is removed from the dispersed particles, the removed organic solvent can be reused as the organic solvent used for dissolving or dispersing the toner material, and the amount of the organic solvent used as a waste liquid is reduced. It is reduced, and the burden on the environment due to waste liquid treatment can be reduced.

  The toner of the present invention has a small particle size and a narrow particle size distribution, is excellent in various properties such as chargeability and transferability, has little toner scattering and fogging, has both low temperature fixability and storage stability, and has high quality. An image can be formed. When the toner of the present invention contains particles containing at least the adhesive base material obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous phase, Excellent properties such as anti-aggregation, charging, fluidity, releasability, and fixing properties. Therefore, the toner of the present invention can be suitably used in various fields, and can be more suitably used for image formation by electrophotography. The following toner-containing container, developer, and process of the present invention are described below. It can be particularly suitably used for a cartridge, an image forming apparatus, and an image forming method.

(Developer)
The developer of the present invention contains at least the toner of the present invention and other components appropriately selected such as the carrier. 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 according to the present invention, the toner particle diameter hardly fluctuates even if the balance of the toner is performed, and the filming of the toner on the developing roller or the toner is made thin. Therefore, toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.

  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 high magnetization 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, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The core material has a volume average particle diameter of preferably 10 to 150 μm, more preferably 40 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 150 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 can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester 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 a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like, if 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 coating method include a dipping 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, cersol 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 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 the 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. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.

Since the developer of the present invention contains the toner, it is excellent in transferability, fixability and the like, and can stably form a high-quality image.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Toner container)
The toner-containing container of the present invention is formed by filling the container of the toner of the present invention or the developer.
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, etc. of the container body containing toner is not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. The spiral surface irregularities are 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 toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(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 developer to form a visible image. At least a developing means for forming the film, and 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 of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably provided detachably in the image forming apparatus of the present invention described later.

(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 transferring step, and a fixing step, preferably including a cleaning step, and other steps appropriately selected as necessary. For example, a static elimination process, a recycling process, a control process, etc. are included.
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, and a fixing unit, and preferably includes a cleaning unit. In addition, other means appropriately selected as necessary, for example, static elimination means, recycling means, control means and the like are provided.

-Electrostatic latent image forming step and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, the surface hardness is high, high sensitivity to long-wavelength light (770 to 800 nm) such as a semiconductor laser, and the electrostatic latent image carrier has a layer made of amorphous silicon in terms of long life. Is preferred.

  The amorphous silicon photoconductor (sometimes referred to as “a-Si photoconductor”) is, for example, a conductive support heated to 50 to 400 ° C., and a vacuum deposition method, a sputtering method, It can be manufactured by forming a photoconductive layer made of a-Si by a film forming method such as an ion plating method, a thermal CVD method, a photo CVD method, or a plasma CVD method. Among the film forming methods, an a-Si photosensitive member is manufactured using a plasma CVD method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge, and an a-Si deposited film is formed on the support. Is preferred.

As an example of the electrostatic latent image carrier (photoconductor), a schematic explanatory diagram of a layer structure of the amorphous silicon photoconductor is shown in FIG.
An electrophotographic photoreceptor 500 shown in FIG. 1A has a photoconductive layer 502 made of a-Si (H, F, O) and having photoconductivity on a support 501.
An electrophotographic photoreceptor 510 shown in FIG. 1B has a photoconductive layer 502 and an amorphous silicon-based surface layer 503 on a support 501.
An electrophotographic photoreceptor 520 shown in FIG. 1C has a photoconductive layer 502, the amorphous silicon-based surface layer 503, and an amorphous silicon-based charge injection blocking layer 504 on a support 501.
An electrophotographic photoreceptor 530 shown in FIG. 1D has the photoconductive layer 502 on a support 501. The photoconductive layer 502 includes a charge generation layer 505 and a charge transport layer 506 made of a-Si (H, F, O), and has the amorphous silicon-based surface layer 503 thereon.

The support 501 may be conductive or electrically insulating.
Examples of the conductive support include those formed of metals such as Al, Cr, Mo, Au, In, Nb, Te, V, Ti, Pt, Pd, Fe, and alloys thereof (for example, stainless steel). Is mentioned.
Examples of the electrically insulating support include those formed of a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polystyrene, polyamide, glass, ceramic, and the like. .
Moreover, you may use the support body which electrically conductively processed the surface of the said electrically insulating support body at least which forms the photosensitive layer.
There is no restriction | limiting in particular as a shape of the said support body 501, According to the objective, it can select suitably, For example, a smooth surface, an uneven | corrugated surface, cylindrical shape, plate shape, endless belt shape etc. are mentioned.
The thickness of the support 501 is not particularly limited and may be appropriately selected depending on the purpose. However, when flexibility as an image forming photoconductor is required, the thickness of the support 501 functions as a support. It is preferable to make it as thin as possible within a range where it can be sufficiently exerted. In view of manufacturing and handling, the mechanical strength is usually 10 μm or more.

The photoconductive layer 502 is formed on the undercoat layer as necessary.
The thickness of the photoconductive layer 502 is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 100 μm, more preferably 20 to 50 μm in terms of electrophotographic characteristics and economic effects. 23 to 45 μm is particularly preferable.

The amorphous silicon surface layer 503 has a free surface, and mainly exhibits moisture resistance, continuous repeated use characteristics, electrical pressure resistance, use environment characteristics, durability, and the like.
There is no restriction | limiting in particular as thickness of the said surface layer 503, According to the objective, it can select suitably, Usually, 0.01-3 micrometers is preferable, 0.05-2 micrometers is preferable, and 0.1-1 micrometer is more. preferable.
When the thickness is less than 0.01 μm, the surface layer may be lost due to wear or the like during use of the photoreceptor. When the thickness exceeds 3 μm, electrophotographic characteristics such as increase in residual potential may be deteriorated. There is.

The charge injection blocking layer 504 is provided between the conductive support 501 and the photoconductive layer 502 as necessary for the purpose of blocking injection of charges from the conductive support 501 side. . That is, the charge injection blocking layer 504 has a function of blocking charge injection from the support 501 side to the photoconductive layer 502 side when the photosensitive layer is subjected to a charging process with a constant polarity on its free surface. And has a so-called polarity dependency that does not exhibit such a function when subjected to a reverse polarity charging process. In order to provide such a function, the charge injection blocking layer 504 needs to contain a relatively large amount of atoms for controlling conductivity as compared with the photoconductive layer 502.
The thickness of the charge injection blocking layer 504 is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 to 5 μm in terms of electrophotographic characteristics and economic effects, 3-4 micrometers is more preferable and 0.5-3 micrometers is especially preferable.

The charge generation layer 505 is a layer that mainly exhibits a function of generating charges when the photoconductive layer 502 is functionally separated. The charge generation layer 505 is made of a-Si (H) containing at least silicon atoms, substantially not containing carbon atoms, and optionally containing hydrogen atoms, and has photoconductive properties, in particular, charge generation properties and charge. Shows transport properties.
The thickness of the charge generation layer 505 is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 to 15 μm from the viewpoint of electrophotographic characteristics and economic effects, and is preferably 1 to 10 μm. Is more preferable, and 1 to 5 μm is particularly preferable.

The charge transport layer 506 is a layer mainly expressing a function of transporting charges when the photoconductive layer 502 is functionally separated. The charge transport layer 506 includes a-SiC (H, F, O) including at least silicon atom, carbon atom, and fluorine atom, and optionally including hydrogen atom and oxygen atom, and has photoconductive properties, in particular, It shows charge retention characteristics, charge generation characteristics and charge transport characteristics. The image forming apparatus of the present invention particularly preferably contains oxygen atoms.
The thickness of the charge transport layer 506 is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 to 50 μm, and preferably 10 to 40 μm in terms of electrophotographic characteristics and economic effects. More preferably, 20-30 micrometers is especially preferable.

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 Preferably, a developer containing at least a developer and having at least a developing unit capable of contacting or non-contacting the toner or the developer with the electrostatic latent image is provided, and includes the toner container according to the present invention. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. Well, for example, those having a stirrer that frictionally stirs and charges the toner or the developer and a rotatable magnet roller, those having a power source capable of applying an alternating electric field, etc. Preferably mentioned.

  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).

In a developing device having a power source to which the alternating electric field can be applied, for example, a vibration bias voltage obtained by superimposing an AC voltage on a DC voltage as a developing bias is applied to the developing sleeve by the power source. The background portion potential and the image portion potential are located between the maximum value and the minimum value of the vibration bias potential. For this reason, an alternating electric field whose direction changes alternately is formed in the developing portion. In the alternating electric field, the toner of the developer and the carrier vibrate vigorously, and the toner shakes off the electrostatic restraining force on the developing sleeve and the carrier to form an electrostatic latent image carrier (photoconductor). It flies and adheres corresponding to the electrostatic latent image on the electrostatic latent image carrier (photoconductor). 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).
Here, the difference (peak-to-peak voltage) between the maximum value and the minimum value of the vibration bias voltage is preferably, for example, 0.5 to 5 kV, and the frequency is preferably, for example, 1 to 10 kHz. As the vibration bias waveform, a rectangular wave, a sine wave, a triangular wave, or the like can be used.
As described above, the DC voltage component of the vibration bias voltage is a value between the background part potential and the image part potential, but the background part potential region is closer to the background part potential than the image part potential. This is preferable in that the fog toner can be prevented from adhering to the surface.
When the waveform of the vibration bias voltage is a rectangular wave, the duty ratio is preferably 50% or less. Here, the duty ratio is a ratio of time for the toner to go to the electrostatic latent image carrier (photoconductor) during one cycle of the vibration bias. By setting the duty ratio to 50% or less, it is possible to increase the difference between the peak value at which the toner is directed to the photoconductor and the time average value of the bias, and the movement of the toner is further activated. The toner adheres faithfully to the potential distribution on the latent image surface, and can improve roughness and resolution. Further, the difference between the peak value of the carrier having the charge opposite to that of the toner and the bias toward the photoconductor and the time average value of the bias can be reduced. For this reason, the movement of the carrier can be calmed down, and the adhesion of the carrier to the background portion of the latent image can be suppressed.

  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).

-Fixing process and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, 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.
The fixing unit is not particularly limited and may be appropriately selected depending on the purpose. A known heating and pressing unit may be used, and a heating member, a film in contact with the heating member, At least a pressure member arranged in pressure contact with the heating member via a film, and fixing the transfer image by passing a recording medium on which a transfer image is formed between the film and the pressure member Preferably.
Examples of the known 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, and the like.
The heating in the heating and pressing means is usually 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.

As the fixing means having at least the heating member, a film in contact with the heating member, and a pressure member disposed in pressure contact with the heating member through the film, for example, as shown in FIG. And a so-called surf fixing device that fixes the transferred image by rotating the.
A surf fixing device 600 shown in FIG. 2 includes a heating body 610, a pressure roller 620, and a fixing film 630.
The fixing film 630 is an endless belt-shaped heat-resistant film, is stretched by a driving roller 631 and a driven roller 632 that are rotatably disposed therein, is fixedly supported by a heating body 610, and is heated to a predetermined temperature. The fixing film 630 is rotationally driven in the clockwise direction in FIG. 2 by the driving force of the driving roller 631. At this time, the rotational driving speed is adjusted so that the recording medium and the fixing film 630 move at the same speed in the fixing nip region L where the fixing film 630 and the pressure roller 620 are in contact with each other.
The fixing film 630 is preferably excellent in heat resistance, releasability, durability, and the like. The fixing film 630 is preferably thin, and the thickness is preferably 100 μm or less, more preferably 40 μm or less. Specifically, for example, a heat-resistant resin single layer film such as polyimide, polyetherimide, PES (polyether sulfide), PFA (tetrafluoroethylene perfluoroalkyl vinyl ether copolymer resin), or a composite layer film, for example, A 20 μm thick film with at least 10 μm thickness of a release coating layer obtained by adding a conductive material to a fluororesin such as PTFE (tetrafluoroethylene resin) and PFA on the image contact surface side, fluororubber, silicon rubber, etc. And those having an elastic layer.
The heating body 610 includes a flat substrate 611, a fixing heater 612, and a fixing temperature sensor 613 attached to the opposite side of the fixing heater 612 on the flat substrate 611, and the temperature can be adjusted by the temperature sensor 613. Designed to. The flat substrate 611 is made of a material having high thermal conductivity and high electrical resistivity, such as alumina, and a fixing heater 612 is installed in the longitudinal direction on the surface in contact with the fixing film 630. The fixing heater 612 is composed of a resistance heating element, and for example, an electric resistance material such as Ag / Pd or Ta ₂ N is applied in a linear or belt shape by screen printing or the like. In addition, electrodes (not shown) are formed at both ends of the fixing heater 612, and the resistance heating element generates heat when energized between the electrodes. The fixing temperature sensor 613 is constituted by a thermistor, and the temperature information of the flat substrate 611 detected by the fixing temperature sensor 613 is sent to a control means (not shown) and is supplied to the fixing heater 612 by the control means. The amount is controlled so that the heating element 610 is held at a predetermined temperature.
The pressure roller 620 abuts on the outside of the fixing film 630 and on the outer surface of the fixing film 630 so as to press the flat substrate 611 in the heating body 610 and is rotatably arranged.

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 electrophotographic toner remaining on the electrostatic latent image carrier and cleaning the surface of 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. Examples include a brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner. The second cleaning blade includes two blades of a first cleaning blade and a second cleaning blade. A cleaning means is preferably a polishing blade.

The cleaning means including two blades includes at least a first cleaning blade and a second cleaning blade in order from the upstream side in the rotation direction of the electrostatic latent image carrier, and the second cleaning blade is used for polishing. It is a blade.
The first cleaning blade mainly removes transfer residual toner and paper dust on the electrostatic latent image carrier (photoconductor).
The second cleaning blade is a polishing blade having a two-layer structure comprising a blade base layer and an abrasive particle-containing layer, and the polishing surface formed by the abrasive particle-containing layer is disposed in contact with the photoreceptor. Is done. When the polishing surface of the abrasive particle-containing layer is in contact with the photoconductor, film abrasion of the photoconductor becomes uniform, and there are few adverse effects on the photoconductor. When compared with a polishing blade whose surface is coated with an abrasive, there is no problem of the abrasive being peeled off or scraped off in a short time, so the cleaning means maintains an excellent cleaning function over the long term. can do.
The second cleaning blade removes adhering substances on the photoconductor such as the inorganic fine particles detached from the toner, a filming substance, and the like by scraping with a polishing surface. In addition, toner, paper dust, and the like that have been missed by the first cleaning blade can be removed at the same time.

There is no restriction | limiting in particular as said 1st cleaning blade, Although it can select suitably according to the objective, As a material, a metal, resin, rubber | gum etc. are preferable, for example. Preferred examples of the rubber include fluorine rubber, silicone rubber, butyl rubber, butadiene rubber, isoprene rubber, and urethane rubber. Among these, urethane rubber is particularly preferable.
The second cleaning blade is a two-layer polishing blade comprising a blade base layer and an abrasive particle-containing layer.
Examples of the material of the blade base layer include rubber, resin, metal, and the like. Among these, like the first cleaning blade, rubber is preferable, and urethane rubber is particularly preferable.
The abrasive particle-containing layer is formed by dispersing abrasive particles in rubber.
When the blade base layer is formed of rubber, the hardness of the rubber used for the abrasive particle-containing layer is preferably 65 to 85 degrees. When the hardness is less than 65 degrees, the blade wear proceeds rapidly, and when the hardness exceeds 85 degrees, the blade edge may be easily chipped.

Examples of the abrasive particles include nitrides such as silicon nitride; silicates such as aluminum silicate, magnesium silicate, and calcium silicate; calcareous substances such as calcium carbonate and gypsum; silicon carbide, boron carbide, tantalum carbide, titanium carbide, Examples thereof include carbides such as aluminum carbide and zirconium carbide; oxides such as cerium oxide, chromium oxide, titanium oxide, and aluminum oxide. Among these, cerium oxide is preferable in terms of excellent polishing power.
The average particle size of the abrasive particles is preferably 0.05 to 100 μm. When the average particle size is less than 0.05 μm, the particles are too fine, and it may be difficult to uniformly disperse in the rubber, or the polishing force as a polishing blade may not be sufficiently obtained, and exceeds 100 μm. In addition, since the polishing force is too large, the surface of the electrostatic latent image carrier (photoconductor) may be damaged.
The content of the abrasive particles in the abrasive particle-containing layer is preferably 0.5 to 50% by mass. When the content is less than 0.5% by mass, dispersion of the abrasive particles becomes sparse and uniform polishing may not be possible. When the content exceeds 50% by mass, the density of the abrasive particles becomes high. In other words, it may be easily peeled off and may increase the cost.

  The thickness of each of the blade base layer and the abrasive particle-containing layer can be arbitrarily set. The thickness of the abrasive particle-containing layer is 0.5 to 50 of the total thickness of the second cleaning blade. % Is preferable. When the thickness of the abrasive particle-containing layer is less than 0.5%, there is no allowance for blade wear, and thus the quality over time may not be maintained. When the thickness exceeds 50%, the rubber originally has. The function of elasticity may not be exhibited, and the electrostatic latent image carrier may not be uniformly polished.

  When the blade base layer in the first cleaning blade and the second cleaning blade is made of rubber, it is preferable that the rubber hardness of the blade base layer is higher than the rubber hardness of the first cleaning blade. In this case, adhered substances, filming substances, and the like that cannot be removed by the first cleaning blade can be removed with a stronger polishing force.

It is preferable that both the first cleaning blade and the second cleaning blade are brought into contact with the electrostatic latent image carrier (photosensitive member) in a counter manner. In this case, the first cleaning blade efficiently removes transfer residual toner and paper dust on the photoconductor, and the second cleaning blade is caused by an impact when the second cleaning blade hits the photoconductor. It is possible to remove adhering substances and the like on the photoconductor to obtain a good cleaning property.
At this time, the contact angle of the second cleaning blade to the photosensitive member is preferably, for example, 5 to 25 degrees. If the contact angle is less than 5 degrees, the blade may hit the belly and the polishing function may not be exhibited over time due to the creep phenomenon. If the contact angle exceeds 25 degrees, the reverse of the photoreceptor at the end of the job, Blade turning may occur.
The contact pressure of the second cleaning blade to the photoreceptor is preferably 10 to 60 kgf / cm, for example. If the contact pressure is less than 10 kgf / cm, the contact pressure is low, the adhering substance on the photoreceptor is likely to slip through the second cleaning blade, and the adhering substance may not be sufficiently removed. If it exceeds 1, the amount of film scraping of the photoreceptor increases, which may shorten the life of the photoreceptor.
The amount of biting into the photoconductor of the second cleaning blade obtained from the relationship between the hardness of the second cleaning blade and the contact pressure to the photoconductor is preferably, for example, 0.2 to 1.5 mm. . By setting the biting amount within the above range, it is possible to remove adhering substances without excessively increasing the amount of film scraping of the photoreceptor.

  In addition, the first cleaning blade and the second cleaning blade are brought into contact with the electrostatic latent image carrier (photosensitive member) so that the first cleaning blade is a counter type and the second cleaning blade The blade may be a trailing type. In this case, as compared with the case where the second cleaning blade is of the counter type, the ability to remove the adhered substance on the photoreceptor is slightly lowered. However, since there is almost no toner input to the second cleaning blade, the blade is likely to be turned over. However, the trailing contact can prevent the blade from turning up. The contact pressure of the second cleaning blade to the photosensitive member is the same as in the counter method.

  The mode of contact of the second cleaning blade with the photosensitive member is not particularly limited and may be appropriately selected according to the purpose. The second cleaning blade may be always contacted or intermittently with appropriate timing. You may contact | abut. In the case of the intermittent contact, it is necessary to provide a separation mechanism using a solenoid, a cam or the like. By the intermittent contact, the amount of film scraping of the photosensitive member can be reduced and the life of the photosensitive member can be extended.

The second cleaning blade preferably includes a swing mechanism. In this case, even if there is a slight deviation in the dispersion of the abrasive particles in the abrasive particle-containing layer, the deviation can be compensated for and the film scraping of the photoreceptor can be made uniform. At this time, it is preferable that the first cleaning blade also includes the same swinging mechanism and swings together. Although the abrasive particles are not contained in the first cleaning blade, the film scraping of the photosensitive member is slightly generated. Therefore, the film scraping can be made uniform by the swing mechanism.
Further, it is preferable that the first cleaning blade and the second cleaning blade are oscillated at different phases in order to make the film shaving of the photoreceptor more uniform. In this case, for example, a cam surface having a different phase may be provided on the inner side of the cam surface of the gear with the rocking cam, and may be rocked by different cam surfaces.

An example of the cleaning means having two cleaning blades is shown in FIG.
A cleaning device 700 shown in FIG. 3 includes a first cleaning blade 720 and a second cleaning blade 730 that can contact the photoconductor in order from the upstream side in the rotation direction of the photoconductor 710, and have been cleaned. A toner collection blade 740 for collecting the toner and a collection coil 741 for conveying the collected toner are provided.
The first cleaning blade 720 is formed of urethane rubber, and the second cleaning blade 730 has a two-layer structure including a blade base layer 731 and an abrasive particle-containing layer 732 as shown in FIG. The blade base layer 731 is made of urethane rubber, and the abrasive particle-containing layer 732 is formed by dispersing cerium oxide as abrasive particles in urethane rubber.
The first cleaning blade 720 and the second cleaning blade 730 are arranged so as to be able to come into contact with the photoconductor 710 by a counter method, and the second cleaning blade 730 has an abrasive fine particle-containing layer 732 on the photoconductor 710. Arranged in contact. Further, the first cleaning blade 720 and the second cleaning blade 730 are swung together by the same swinging mechanism 750. As shown in FIG. 3, the swing mechanism 750 supports the second cleaning blade 730 with a pressure holder (not shown), includes a bearing at the crimping tip of the pressure holder, and a cam surface 752 of the gear 751 with the swing cam. It is provided so as to abut. When the photoconductor 710 rotates in the direction of arrow A in FIG. 3, the gear 751 with the swing cam rotates in the direction of arrow B, and the second cleaning blade 730 swings in the direction of arrow C according to the rotation.
Then, untransferred toner and adhering substances remaining on the photoconductor 710 are scraped off by the first cleaning blade 720 and then the second cleaning blade 730, respectively, and recovered by the toner recovery blade 740. The collected toner is conveyed by a collection coil 741.

The recycling step is a step of recycling the electrophotographic color toner removed in 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 means is a process for controlling the respective steps, and can be suitably performed by the control means.
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 for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 4 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and an exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. 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. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 52 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the 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. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 4, 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 of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 5 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 1, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and the like around the photoconductor 10. Except that the cyan developing unit 45C is disposed directly opposite, it has the same configuration as that of the image forming apparatus 100 shown in FIG. In FIG. 5, the same components as those in FIG. 4 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 of the present invention will be described with reference to FIG. A tandem image forming apparatus 100 shown in FIG. 6 is a tandem color image forming apparatus. The tandem image forming apparatus 100 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. 6. 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 100, 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. Yes.

  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 means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. 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 photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. An exposure device that exposes the photoconductor for each color image corresponding image (L in FIG. 7) and forms an electrostatic latent image corresponding to each color image on the photoconductor; A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image of each color toner, and the toner image is transferred to the intermediate transfer member 5. The image forming apparatus includes a transfer charger 62 for transferring the image on the surface, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta image) based on image information of each color. And cyan images) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. 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 feeding roller 150 is rotated to feed out the sheets (recording paper) on the manual feed tray 51, separated one by one by the separation roller 52, 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.

  The image forming apparatus and the image forming method of the present invention are excellent in various properties such as chargeability and transferability, are less likely to cause toner scattering and fogging, have both low temperature fixability and storage stability, and have a small particle size and particle size. Since the toner of the present invention having a narrow distribution is used, high image quality can be obtained efficiently.

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

Example 1
<Adhesive substrate production process>
A toner was produced as follows.

-Dissolution of toner material or preparation of dispersion-
--- Synthesis of unmodified polyester (low molecular weight polyester)-
229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propion oxide 3-mole adduct, 208 parts by mass of terephthalic acid, 48 parts by mass of adipic acid And 2 parts by mass of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, the reaction solution was reacted for 6 hours under a reduced pressure of 20 mmHg or less, and then 44 parts by weight of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. Polyester was synthesized.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,400, a weight average molecular weight (Mw) of 6,800, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25 mgKOH / g.

-Preparation of master batch (MB)-
1200 parts by mass of water and 1000 parts by mass of carbon black (“Printex35”; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5) were mixed using a Henschel mixer (manufactured by Mitsui Mining). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

-Preparation of organic solvent phase-
In a reaction vessel equipped with a stir bar and a thermometer, 50 parts by mass of ester wax, 30 parts by mass of CCA (“salicylic acid metal complex E-84”; manufactured by Orient Chemical Industries), and 330 parts by mass of ethyl acetate were charged and stirred. The temperature was raised to 80 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 250 parts by mass of the master batch was charged into a reaction vessel and mixed for 1 hour to obtain a raw material solution.
132 parts by mass of the resulting raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia. The carbon black and the ester wax were dispersed in 6 to 24 passes under the condition of 80% by volume of beads. Subsequently, 200 parts by mass of a 70% by mass ethyl acetate solution of the unmodified polyester, 80 parts by mass of ethyl acetate, and 10 parts by mass of water were added to the dispersion. The organic solvent phase was prepared by performing 3 passes in a bead mill under the same conditions as described above and dispersing.
The solid content concentration of the obtained organic solvent phase (measurement condition: 150 ° C., after standing for 60 minutes) was 48% by mass.

--Synthesis of prepolymer--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined.
The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,600, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.60% by mass, and the solid content concentration of the prepolymer (after standing at 150 ° C. for 45 minutes) was 50% by mass.

--Synthesis of ketimine (the active hydrogen group-containing compound)-
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
The amine value of the obtained ketimine compound (the active hydrogen machine-containing compound) was 423.

  In a reaction vessel, 749 parts by mass of the organic solvent phase, 115 parts by mass of the prepolymer, and 2.9 parts by mass of the ketimine compound are charged, and 5,000 rpm is obtained using a TK type homomixer (manufactured by Special Machine Industries). For 1 minute to prepare a solution or dispersion of the toner material.

-Preparation of aqueous medium phase-
--Preparation of fine particle dispersion--
In a reaction vessel in which a stir bar and a thermometer are set, 680 parts by mass of water, 11 parts by weight of sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30" manufactured by Sanyo Chemical Industries), 69 parts by mass of styrene Then, 110 parts by mass of methacrylic acid, 69 parts by mass of butyl acrylate, and 1 part by mass of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Next, 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, so that vinyl resin particles (copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) An aqueous dispersion of polymer) (fine particle dispersion) was prepared.
The volume average particle diameter of the fine particles contained in the obtained fine particle dispersion was measured with a particle size distribution measuring apparatus (“LA-920”; manufactured by Horiba, Ltd.) using a laser light scattering method, and found to be 0.11 μm. there were. Further, a part of the fine particle dispersion was dried to isolate the resin component, and the glass transition temperature (Tg) of the resin component was measured.

  240 parts by mass of water, 13 parts by mass of the fine particle dispersion, 40 parts by mass of a 50% by mass aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and 25 parts by mass of ethyl acetate were mixed and stirred. As a result, a milky white liquid (aqueous medium) was obtained.

-Preparation of oil-in-water dispersion-
150 parts by mass of the aqueous medium phase is placed in a container, and stirred at a rotational speed of 11,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). The mixture was added and mixed for 10 minutes to prepare an oil-in-water dispersion (emulsified slurry).

-Removal of organic solvent-
The emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours.
At this time, a dispersion (desolvent slurry) containing toner particles and a water-containing solvent (desolvent ethyl acetate) obtained by desolvation were obtained. The solvent-free ethyl acetate was kept at 25 ° C., and the water content was measured. From the analysis by gas chromatography, the peak ratio between ethyl acetate and water was determined, and the water content of the solvent-free ethyl acetate was 2.8 gH ₂ O / 100 gAcOEt. In addition, the solubility of water with respect to ethyl acetate at 25 ° C. is 2.94 gH ₂ O / 100 g AcOEt, and the water content of the desolvated ethyl acetate is 95% by mass of the saturated solubility of water.
Next, the solvent removal slurry was aged at 60 ° C. for 10 hours to obtain a dispersion slurry.

-Cleaning and drying-
After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filtered twice. To the obtained filter cake, 20 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filtered twice. Furthermore, 20 mass parts of 10 mass% hydrochloric acid was added to the obtained filter cake, mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with an opening of 75 μm mesh to obtain toner base particles of Example 1.

-External additive treatment-
Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) was prepared by adding 0.7 parts by mass of hydrophobic silica as an external additive and 0.3 parts by mass of hydrophobized titanium oxide to 100 parts by mass of the obtained toner base particles of Example 1. The toner of Example 1 was manufactured by mixing with a sieve and sieving with a mesh of 35 μm.

  With respect to the obtained toner, the volume average particle size (Dv), number average particle size (Dn), particle size distribution (volume average particle size (Dv) / number average particle size (Dn)), and fine powder amount are measured by the following methods. did. The results are shown in Table 1.

<Toner particle size>
The volume average particle diameter (Dv) of the toner and the number average particle diameter (Dn) of the toner were measured using a particle size measuring device (“Multisizer II”; manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm. From these results, the particle size distribution (volume average particle diameter (Dv) / number average particle diameter (Dn)) was calculated. As a result, the volume average particle size was 5.8 μm, the number average particle size was 5.1 μm, and the particle size distribution (Dv / Dn) was 1.14.

<Amount of fine powder>
The amount of fine powder of toner was measured as a mean circularity using a flow type particle image analyzer (“FPIA-2000”; manufactured by Toa Medical Electronics Co., Ltd.). Specifically, 0.1 to 0.5 ml of a surfactant (alkylbenzene sulfonate) as a dispersant is added to 100 to 150 ml of water from which impure solids have been removed in advance, and each toner is further added. 0.1 to 0.5 g was added and dispersed. The obtained dispersion was subjected to a dispersion treatment with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.) for about 1 to 3 minutes so that the concentration of the dispersion was 3000 to 10,000 / μl, and the volume average particle diameter (Dv) The amount of toner having a particle size of 3 μm or less (amount of fine powder) was measured. As a result, it was 6.7% by number.

(Example 2)
In Example 1, the toner of Example 2 was produced in the same manner as in Example 1 except that the organic solvent phase and the aqueous medium phase were replaced with the organic solvent phase and the aqueous medium phase prepared by the following method. Further, various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.

-Preparation of organic solvent phase-
In a reaction vessel equipped with a stir bar and a thermometer, 50 parts by mass of ester wax, 30 parts by mass of CCA (“salicylic acid metal complex E-84”; manufactured by Orient Chemical Industries), and 330 parts by mass of ethyl acetate were charged and stirred. The temperature was raised to 80 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 250 parts by mass of the master batch was charged into a reaction vessel and mixed for 1 hour to obtain a raw material solution.
132 parts by mass of the resulting raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia. The carbon black and the ester wax were dispersed in 6 to 24 passes under the condition of 80% by volume of beads. Next, 70 parts by mass of 140 parts by mass of the unmodified polyester was added to a mixed solution of 32 parts by mass of ethyl acetate and 28 parts by mass of the desolvated ethyl acetate obtained by removing the organic solvent in Example 1. A 200% by weight aqueous solution of ethyl acetate and 100 parts by weight of the desolvated ethyl acetate were added. The organic solvent phase was prepared by performing 3 passes in a bead mill under the same conditions as described above and dispersing. The solid content concentration of the obtained organic solvent phase (measurement condition: 150 ° C., after standing for 60 minutes) was 48% by mass.
In addition, 749 parts by mass of the organic solvent phase, 115 parts by mass of the prepolymer, and 2.9 parts by mass of the ketimine compound were charged in a reaction vessel, and TK type homomixer (manufactured by Special Machine Industries) was used. The toner material was dissolved or dispersed by mixing at 000 rpm for 1 minute.

-Preparation of aqueous medium phase-
By removing 238 parts by weight of water, 13 parts by weight of the fine particle dispersion, 40 parts by weight of a 50% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries) and the organic solvent in Example 1 27 parts by mass of the obtained solvent-free ethyl acetate was mixed and stirred to prepare a milky white liquid (aqueous medium).

The obtained toner material solution or dispersion was emulsified or dispersed in an aqueous medium phase to form dispersed particles. Thereafter, a toner was produced in the same manner as in Example 1.
In Example 2, the amount of the solvent-removed ethyl acetate obtained in Example 1 in the total ethyl acetate (organic solvent) used for dissolving or dispersing the toner material is 54.6% by mass. By reusing solvent-free ethyl acetate, the amount of ethyl acetate waste liquid is reduced and the environmental load is also reduced.

(Comparative Example 1)
In Example 1, a toner of Comparative Example 1 was produced in the same manner as in Example 1 except that the organic solvent phase was replaced with an organic solvent phase containing no water prepared by the following method. Further, various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.

-Preparation of organic solvent phase-
In a reaction vessel equipped with a stir bar and a thermometer, 50 parts by mass of ester wax, 30 parts by mass of CCA (“salicylic acid metal complex E-84”; manufactured by Orient Chemical Industries), and 330 parts by mass of ethyl acetate were charged and stirred. The temperature was raised to 80 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 250 parts by mass of the master batch was charged into a reaction vessel and mixed for 1 hour to obtain a raw material solution.
132 parts by mass of the resulting raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia. The carbon black and the ester wax were dispersed in 6 to 24 passes under the condition of 80% by volume of beads. Next, 200 parts by mass of a 70% by mass ethyl acetate solution of the unmodified polyester and 80 parts by mass of ethyl acetate were added. The organic solvent phase was prepared by performing 3 passes in a bead mill under the same conditions as described above and dispersing.
The resulting organic solvent phase had a solid content concentration of 49% by mass (measurement condition: 150 ° C. under reduced pressure, after standing for 60 minutes).
In addition, 749 parts by mass of the organic solvent phase, 115 parts by mass of the prepolymer, and 2.9 parts by mass of the ketimine compound were charged in a reaction vessel, and TK type homomixer (manufactured by Special Machine Industries) was used. The toner material was dissolved or dispersed by mixing at 000 rpm for 1 minute.
The obtained toner material solution or dispersion was emulsified or dispersed in the aqueous medium phase to form dispersed particles. Thereafter, a toner was produced in the same manner as in Example 1.

Next, a carrier was produced as follows.
200 parts by mass of toluene, 200 parts by mass of silicone resin (“SR2400”; made by Toray Dow Corning Silicone, nonvolatile content 40% by mass), 7 parts by mass of aminosilane (“SH6020”; made by Toray Dow Corning Silicone), and 4 parts by mass of carbon black was added and dispersed using a stirrer for 10 minutes. The obtained liquid and 5,000 parts by mass of Mn ferrite particles (weight average diameter 35 μm) are provided in a coating apparatus which is provided with a rotating bottom plate disk in a fluidized bed and a stirring blade and performs coating while forming a swirling flow. Then, a coating film was formed on the Mn ferrite particles. The obtained coated material was baked at 250 ° C. for 2 hours in an electric furnace to prepare a carrier.

  Using a turbuler mixer of a type in which 7.5 parts by weight of each of the toners of Examples 1 and 2 and Comparative Example 1 that have been treated with external additives and 100 parts by weight of the carrier are agitated by rolling and stirring. The developers of Examples 1 and 2 and Comparative Example 1 were produced by mixing and charging.

  Using the obtained developers, (a) fixability (offset non-occurrence temperature and fixing lower limit temperature), (b) cleaning property, (c) transfer property, and (d) image graininess, as follows. And sharpness, (e) fog, (f) toner scattering, (g) storage stability (blocking resistance), and (h) chargeability (charge stability). The results are shown in Tables 2-3.

(A) Fixability (offset non-occurrence temperature and fixing lower limit temperature)
Remove the fixing oil application unit from the color electrophotographic apparatus (“IPSIO Color 8100”; manufactured by Ricoh Co., Ltd.), remodel it into an oil-less fixing system, and use plain paper (“Type 6200”; manufactured by Ricoh Co., Ltd.). ) And a thick transfer paper ("copy printing paper <135>"; manufactured by NBS Ricoh Co., Ltd.), the fixability (offset non-occurrence temperature and fixing lower limit temperature) was evaluated.

<Temperature without offset>
Image formation is performed using the color electrophotographic apparatus on the transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) on each of single colors of yellow, magenta, cyan, and black, and red, blue, and green as intermediate colors. The solid image was adjusted so that 1.0 ± 0.1 mg / cm ² of toner was developed for each single color. The obtained image was fixed by changing the temperature of the fixing belt (heating roller), and the upper limit temperature at which no offset occurred (temperature at which no offset occurred) was measured. In addition, it was judged that the offset non-occurrence temperature was 200 ° C. or higher.

<Fixing temperature limit>
For the image, the above-described color electrophotographic apparatus was used to set the above-mentioned thick transfer paper (“copy printing paper <135>”; manufactured by NBS Ricoh Co., Ltd.), and a copy test was performed. The fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more was determined as the minimum fixing temperature. In addition, it was judged that the fixing lower limit temperature was 140 ° C. or less.

(B) Cleanability Transfer residual toner on the photoconductor that has passed the cleaning process after outputting 1,000 sheets of a 95% image area ratio chart is transferred to white paper with Scotch tape (manufactured by Sumitomo 3M Limited), and this is reflected by Macbeth reflection. It measured with the densitometer (RD514 type | mold) and evaluated based on the following reference | standard.
〔Evaluation criteria〕
A: Difference from blank is less than 0.005 B: Difference from blank is 0.005-0.010
(Triangle | delta): The difference with a blank is 0.011-0.02.
X: The difference from the blank exceeds 0.02.

(C) Transferability After transferring the 20% image area ratio chart from the photoconductor to the paper, the transfer residual toner on the photoconductor immediately before cleaning is transferred to white paper with Scotch tape (manufactured by Sumitomo 3M Limited), and this is reflected by Macbeth reflection. It measured with the densitometer (RD514 type | mold) and evaluated based on the following reference | standard.
〔Evaluation criteria〕
A: Difference from blank is less than 0.005 B: Difference from blank is 0.005-0.010
(Triangle | delta): The difference with a blank is 0.011-0.02.
X: The difference from the blank exceeds 0.02.

(D) Image granularity and image sharpness A photographic image was output in a single color, and the degree of image granularity and image sharpness was visually observed and evaluated based on the following criteria.
〔Evaluation criteria〕
◎: Same as offset printing ○: Slightly worse than offset printing △: Much worse than offset printing ×: Very bad with conventional electrophotographic images

(E) Fog An image forming apparatus (“IPSIO Color 8100”; manufactured by Ricoh Co., Ltd.) was used for each toner in an environment of temperature 10 ° C. and humidity 15%, using an evaluation machine remodeled to an oilless fixing method. Then, after conducting an output durability test on a continuous 100,000 sheets sheet with an image area ratio of 5%, the degree of toner contamination on the surface of the transfer paper was visually observed (loupe) and evaluated based on the following criteria.
〔Evaluation criteria〕
A: Toner stains are not observed at all and are in a good state. O: Slight stains are not a problem. Δ: Slight stains are observed. X: Very dirty outside the allowable range. There is a problem

(F) Toner scattering An image forming apparatus (“IPSIO Color 8100”; manufactured by Ricoh Co., Ltd.) was used to tune each toner in an environment of a temperature of 40 ° C. and a humidity of 90% using an evaluation machine that was tuned by modifying the oil-less fixing method. Then, after carrying out a continuous 100,000 sheet output durability test with a 5% image area ratio chart, the toner contamination inside the copying machine was visually observed and evaluated based on the following criteria.
〔Evaluation criteria〕
A: Toner stains are not observed at all and are in a good state. O: Slight stains are not a problem. Δ: Slight stains are observed. X: Very dirty outside the allowable range. There is a problem

(G) Storage stability (blocking resistance)
Each 10 mg of toner was weighed, each toner was filled in a 20 ml glass bottle, tapped the glass bottle 100 times, and then left in a constant temperature bath set at a temperature of 55 ° C. and a humidity of 80% for 24 hours. The penetration (mm) of this toner was measured by a penetration test (JIS K2235-1991). Also, the toner stored in a low-temperature and low-humidity environment (10 ° C., 15%) is similarly evaluated for the penetration, and the value with the lower penetration is adopted in the high-temperature and high-humidity and low-temperature and low-humidity environments. Evaluation was based on criteria.
〔Evaluation criteria〕
◎: Needle penetration 20 mm or more ○: Needle penetration 15 mm or more and less than 20 mm △: Needle penetration 10 mm or more and less than 15 mm ×: Needle penetration less than 10 mm

(H) Chargeability (charge stability)
A continuous 100,000 sheet output durability test was conducted using a character image pattern with an image area ratio of 12% using each toner. A small amount of developer was collected from the developing sleeve, the change in charge amount was measured by the blow-off method, and evaluated based on the following criteria.
〔Evaluation criteria〕
○: Change in charge amount is 5 μC / g or less Δ: Change in charge amount is 10 μC / g or less X: Change in charge amount exceeds 10 μC / g

From the results of Tables 1 to 3, the following is clear. That is, in Examples 1 and 2, since the dissolution or dispersion of the toner material contains 10.0 to 200% by mass of water with respect to the saturated dissolution amount of water in the organic solvent at 25 ° C., the amount of fine powder is small. A toner having a small particle size and a narrow particle size distribution was obtained. In addition, the toner has excellent transferability and cleanability, good chargeability (charge stability), no fogging or toner scattering, low temperature fixability and storage stability, and image granularity. The evaluation results of the property and sharpness were also good, and it was found that high image quality was obtained.
On the other hand, it was found that the toner obtained in Comparative Example 1 was inferior in charging stability, and fogging and toner scattering occurred.
In Example 2, since the solvent-removed ethyl acetate obtained in Example 1 was reused as an organic solvent in the dissolution or dispersion of the toner material, the amount of ethyl acetate waste liquid was reduced, and the environment was reduced. The load is also reduced.

The toner production method of the present invention reduces the amount of fine powder, generates less toner scattering and fogging, can stably and efficiently obtain a toner having a small particle size and a narrow particle size distribution, and recycles the organic solvent. It can be used and the environmental impact of waste liquid treatment is small.
The toner of the present invention is excellent in various properties such as chargeability and transferability, is less likely to cause toner scattering and fogging, and is compatible with both low-temperature fixability and storage stability. The The developer, toner-containing container, process cartridge, image forming apparatus and image forming method of the present invention using the toner of the present invention are suitably used for high-quality image formation.

FIG. 1 is a schematic explanatory view showing an example of an electrostatic latent image carrier (photosensitive member) in the image forming apparatus of the present invention. FIG. 2 is a schematic explanatory view showing an example of a fixing unit (surf fixing device) in the image forming apparatus of the present invention. FIG. 3 is a schematic explanatory view showing an example of a cleaning unit in the image forming apparatus of the present invention. FIG. 4 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. 5 is a schematic explanatory view showing another example in which the image forming method of the present invention is implemented by the image forming apparatus of the present invention. FIG. 6 is a schematic explanatory view showing an example in which the image forming method of the present invention is implemented by the image forming apparatus (tandem color image forming apparatus) of the present invention. FIG. 7 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 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 roller 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 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 Developer roller 44Y Developer roller 44M Developer 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 Corona charger 53 Constant current source 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Separating roller 60 Cleaning device 61 Developing device 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 120 Tandem type developer 130 Document base 142 Feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Carriage roller 148 Paper feed path 150 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)
500 Electrophotographic photosensitive member 501 Support 502 Photoconductive layer 503 Amorphous silicon surface layer 504 Amorphous silicon charge injection blocking layer 505 Charge generation layer 506 Charge transport layer 600 Surf fixing device 610 Heating body 612 Fixing heater 620 Pressure roller 630 Fixing film 700 Cleaning device 720 First cleaning blade 730 Second cleaning blade 731 Blade base layer 732 Abrasive particle-containing layer 750 Oscillation mechanism

Claims (6)

at least,
<1> A method of adding water to a solution or dispersion of a toner material obtained by dissolving or dispersing a toner material in an organic solvent having a water content of less than 1% by mass; <2> an organic solvent having a water content of less than 1% by mass A step of preparing a water-soluble solvent, preparing a water-containing solvent, and then preparing a solution or dispersion of the toner material by one or more methods selected from a method of dissolving or dispersing the toner material in the water-containing solvent.
Adding or dissolving a dispersion or dispersion of the toner material prepared in the above step into an aqueous medium, dispersing the particles, granulating the dispersed particles, and removing the organic solvent from the dispersed particles;
A method for producing a toner, wherein the toner material dissolved or dispersed in the step contains 10.0 to 200% by mass of water in a saturated amount of water dissolved in the organic solvent at 25 ° C.   The method for producing a toner according to claim 1, wherein the solution or dispersion of the toner material before granulation contains 1.0% by mass or more of water with respect to the organic solvent.   The method for producing a toner according to claim 1, wherein 60% by mass or more of a constituent component of the organic solvent in the toner material dissolved or dispersed solution dissolves 40 g or less of water at 25 ° C. and 100 g.   4. The method for producing a toner according to claim 3, wherein 60% by mass or more of the constituent component of the organic solvent in the toner material dissolved or dispersed solution dissolves 2.94 g or less of water at 25 ° C. and 100 g.   The method for producing a toner according to any one of claims 3 to 4, wherein the constituent of 60 mass% or more of the organic solvent in the solution or dispersion of the toner material is ethyl acetate. The toner material includes at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound,
By granulating, by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound to produce an adhesive base material, particles containing at least the adhesive base material are obtained. The method for producing a toner according to claim 1, wherein the toner is produced.

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