JP4331662B2 - Toner, method for producing the same, and image forming method - Google Patents

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.

  Image formation by electrophotography generally forms an electrostatic image on a photoreceptor (electrostatic image carrier), develops the electrostatic image 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. Further, as the toner, a toner produced by a kneading and pulverizing method is generally used in which a thermoplastic resin is melt-kneaded with a release agent such as a pigment and wax, a charge control agent, etc., and then finely pulverized and further classified. Yes. If necessary, inorganic fine particles or organic fine particles may be added to the surface of the toner particles for the purpose of improving fluidity and cleaning properties.

  However, in the kneading and pulverizing method, the toner shape and surface structure obtained are indeterminate, and the toner shape and surface structure are arbitrary although there are some changes depending on the pulverization properties of the materials used and various conditions of the pulverization process It is difficult to control. In addition, in order to obtain a high-resolution and high-gradation image, it is necessary to further narrow the particle size distribution of the toner. However, there are problems such as limit of classification ability, yield and productivity, and cost increase. In addition, it is extremely difficult to produce a toner having a small particle size, particularly a particle size of 6 μm or less.

The irregular toner obtained by the pulverization and kneading method has a different adhesion area to the developing roll for a one-component developer and an adhesion area to a carrier for a two-component developer. In addition, the adhesion force to the carrier is different, and there is a problem that a difference occurs in chargeability, that is, ease of development. Even when the particle diameters of the toners are different, the charge amounts of the individual toner particles are different, so that the development is different.
As described above, when each toner particle is easily developed, easily developable toner is selectively developed, while hard-to-develop toner remains in the developing device, and developability changes with time. There is a problem. Similarly, in transfer to a recording medium, toner that is easily transferred and toner that is difficult to transfer are mixed, and image quality deterioration such as toner scattering tends to occur.

  In the pulverization and kneading method, 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 particles depending on the combination with a thermoplastic resin. In particular, in a combination of a resin that is imparted with elasticity by a high molecular weight component and hardly pulverized, and a brittle wax such as polypropylene, exposure of the wax on the toner particle surface is often observed. Such exposure of the release agent is effective for releasability during fixing and cleaning of the toner remaining on the photoreceptor after transfer, but the fluidizing agent on the toner particle surface is easily moved by mechanical force. Therefore, there is a problem that the developing roll, the photoconductor, the carrier and the like are likely to be contaminated with wax, leading to a decrease in the reliability of the image forming apparatus.

  By the way, the toner image formed on the photoconductor is transferred to a recording medium, but the transfer residual toner remaining on the photoconductor is cleaned by, for example, blade cleaning, fur brush cleaning, roller cleaning, or the like. However, if these cleaning devices are provided, the size of the image forming apparatus inevitably increases, which is against the demand for downsizing the apparatus. In addition, from the viewpoint of nature conservation ecology, a system with a small amount of waste toner to be discarded is desired, and there is a great interest in a toner having excellent chargeability.

In addition, in order to form a high-quality image, it is important to improve the adaptability with members used in the development process, in particular, electrostatic latent image carriers, intermediate transfer members, charging members, etc. Therefore, a toner having a good balance between the image density and the image fog in the development and having a good transfer efficiency is required.
Therefore, for example, spherical toners (see Patent Document 2) that define the shape factors SF-1 and SF-2 and magnetic toners that are made spherical by mechanical impact force (see Patent Document 3) have been proposed.
However, the toner described in Patent Document 2 has no description about transferability, and when an image was formed using the toner, it was recognized that the transfer efficiency was low. In addition, the toner described in Patent Document 3 is still insufficient in transfer efficiency and needs further improvement.

  Accordingly, the present situation is that a spherical toner that has a smooth surface, is excellent in various characteristics such as chargeability and transferability, and can obtain high image quality, and related technology using the toner have not yet been provided. .

US Pat. No. 2,297,691 JP-A 61-279864 Japanese Patent Laid-Open No. 63-235953

  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 provides a spherical toner that has a smooth surface, is excellent in various characteristics such as chargeability and transferability, and obtains high image quality, an efficient manufacturing method thereof, and a high image quality using the toner. An object of the present invention is to provide a developer, 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, a toner material dissolved or dispersed liquid is emulsified or dispersed in an aqueous medium and granulated. Here, the dissolved or dispersed liquid is sheared at 30,000 at 25 ° C. with respect to the dissolved or dispersed liquid. After applying a shearing force at (1 / second) for 30 seconds, the shear rate was changed from 0 (1 / second) to 70 (1 / second) in 20 seconds, and the shear rate was 70 (1 / second). When the viscosity of the toner satisfies 1 to 100 mPa · sec, the surface of the toner can be made smooth, excellent in various characteristics such as chargeability and transferability, and a spherical toner can be obtained that provides high image quality. It is knowledge.

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> A toner material dissolved or dispersed in an aqueous medium is emulsified or dispersed and granulated,
After applying a shearing force to the dissolved or dispersed liquid at 25 ° C. and a shear rate of 30,000 (1 / second) for 30 seconds, the shear rate was changed from 0 (1 / second) to 70 (1 / second) to 20 Change in seconds,
A toner manufacturing method, wherein the viscosity of the dissolved or dispersed liquid is 1 to 100 mPa · sec when the shear rate is 70 (1 / sec).
<2> The method for producing a toner according to <1>, wherein the solution or dispersion of the toner material contains an organic solvent, and the organic solvent is removed during or after granulation.
<3> 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,
Granulation is carried out by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium to produce an adhesive base material, and then forming particles by the adhesive base material. The method for producing a toner according to any one of <1> to <2>, wherein the toner is obtained by obtaining the toner.
<4> The viscosity of the dissolved or dispersed liquid is 0.05 to 20 mPa · s when a shearing force is applied to the dissolved or dispersed liquid of the toner material at 25 ° C. at a shear rate of 30,000 (1 / second) for 20 seconds. The toner production method according to any one of <1> to <3>, wherein the toner is seconds.
<5> The method for producing a toner according to any one of <1> to <4>, wherein the toner material includes a colorant, and the colorant is dispersed by a pigment dispersant.
<6> The method for producing a toner according to <5>, wherein the pigment dispersant is a polymer dispersant.
<7> The method for producing a toner according to <6>, wherein the polymer dispersant is a modified polyurethane dispersant.
<8> The method for producing a toner according to <7>, wherein the modified polyurethane dispersant is compatible with the adhesive base material.
<9> The toner production method according to any one of <6> to <8>, wherein the blending amount of the polymer dispersant with respect to the colorant is 1 to 100% by mass.
<10> A toner produced by the toner production method according to any one of <1> to <9>.
<11> The toner according to <10>, wherein the toner has a volume average particle diameter of 3 to 8 μm.
<12> The toner according to any one of <10> to <11>, wherein the toner has a volume average particle diameter (Dv) / number average particle diameter (Dn) of 1.00 to 1.25.
<13> The toner according to any one of <10> to <12>, wherein the toner has an average circularity of 0.970 to 1.000.
<14> The toner according to any one of <10> to <13>, wherein the toner has a BET specific surface area of 0.5 to 3.0 m ² / g.
<15> A developer comprising the toner according to any one of <10> to <14>.
<16> A toner-containing container filled with the toner according to any one of <10> to <14>.
<17> 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 <10> to <14> to be a visible image And a developing means for forming the process cartridge.
<18> 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 <10> to <14> 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, The image forming apparatus is characterized by having at least.
<19> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image is formed using the toner according to any one of <10> to <14>. 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.

In the toner production method of the present invention, a toner material dissolved or dispersed liquid is emulsified or dispersed in an aqueous medium and granulated.
After applying a shearing force to the dissolved or dispersed liquid at 25 ° C. and a shear rate of 30,000 (1 / second) for 30 seconds, the shear rate was changed from 0 (1 / second) to 70 (1 / second) to 20 Change in seconds,
When the shear rate is 70 (1 / second), the viscosity of the dissolved or dispersed liquid is 1 to 100 mPa · sec. In the method for producing the toner, a solution or dispersion of the toner material is emulsified or dispersed in the aqueous medium, and then the toner is granulated. At this time, after applying a shearing force as a solution or dispersion at a shear rate of 30,000 (1 / second) at 25 ° C. for 30 seconds, the shear rate is changed from 0 (1 / second) to 70 (1 / second). The solution or dispersion is used in which the viscosity is 1 to 100 mPa · sec when the shear rate is 70 (1 / sec). As a result, a spherical toner having a smooth surface, excellent properties such as transferability and chargeability, and high image quality can be efficiently produced.
In the method for producing a toner of the present invention, the toner material includes 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. In the case where the reaction is carried out by reacting a polymer capable of reacting with the active hydrogen group-containing compound to produce an adhesive base material, particles obtained by the adhesive base material are further obtained. In addition, a toner that is excellent in various properties such as fluidity, transferability, and fixability and that can obtain high image quality is efficiently produced.
In addition, the dissolution or dispersion of the toner material contains an organic solvent, and the organic solvent is removed during or after granulation. For the dissolution or dispersion, a shear rate of 30,000 (1 / The viscosity of the solution or dispersion is 0.05 to 20 mPa · sec when a shearing force is applied for 20 seconds at a second), the toner material contains a colorant, and the colorant is dispersed by a pigment dispersant. Embodiments, embodiments in which the pigment dispersant is a polymer dispersant, embodiments in which the polymer dispersant is a modified polyurethane dispersant, embodiments in which the modified polyurethane dispersant is compatible with the adhesive substrate, and the polymer An embodiment in which the blending amount of the dispersant with respect to the colorant is 1 to 100% by mass is preferable.

  The toner of the present invention is produced by the toner production method of the present invention. For this reason, the toner has a smooth surface, excellent properties such as transferability and chargeability, high image quality, and a spherical shape. In addition, when the toner includes an adhesive substrate obtained by reacting a polymer capable of reacting with the active hydrogen group-containing compound to form particles, aggregation resistance, charging property, fluidity, transfer Excellent properties such as fixability and fixability. 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, a spherical toner that can solve various problems in the prior art, has a smooth surface, is excellent in various characteristics such as chargeability and transferability, and has high image quality, and an efficient manufacturing method thereof. In addition, 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 using the toner.

(Toner and toner production method)
The toner of the present invention is obtained by the toner production method of the present invention.
In the toner production method of the present invention, a toner material dissolved or dispersed liquid is emulsified or dispersed in an aqueous medium and granulated.
After applying a shearing force to the dissolved or dispersed liquid at 25 ° C. and a shear rate of 30,000 (1 / second) for 30 seconds, the shear rate was changed from 0 (1 / second) to 70 (1 / second) to 20 Change in seconds,
When the shear rate is 70 (1 / second), the viscosity of the dissolved or dispersed liquid is 1 to 100 mPa · sec.
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.

  In the present invention, a shearing force is applied to the dissolved or dispersed liquid of the toner material at a shear rate of 30,000 (1 / second) at 25 ° C. for 30 seconds, and then the shear rate is changed from 0 (1 / second). The viscosity of the dissolved or dispersed liquid is required to be 1 to 100 mPa · sec when the shear rate is 70 (1 / sec) and the viscosity is 1 to 100 mPa · sec. -Seconds are preferred. When the viscosity is less than 1 mPa · s, the toner particle size may be too small, and when it exceeds 100 mPa · s, the surface property of the toner may be deteriorated and a spherical shape may not be obtained.

  The viscosity of the solution or dispersion after applying a shearing force to the solution or dispersion of the toner material at 25 ° C. at a shear rate of 30,000 (1 / second) for 20 seconds is 0.05 to 20 mPa. Second is preferable, and 0.05 to 10 mPa · second is more preferable. When the viscosity is less than 0.05 mPa · s, the particle size of oil droplets when the dissolved or dispersed liquid is emulsified or dispersed in the aqueous medium is 1 μm or less, and the toner may not function. When the viscosity exceeds 20 mPa · sec, it becomes difficult to emulsify the dissolved or dispersed liquid in the aqueous medium, and even if it can be emulsified, the oil droplets obtained have a large particle diameter of 20 μm or more, and the toner The surface of may become rough.

  The toner material is dissolved or the viscosity of the dispersion is measured by applying the shearing force using a parallel plate rheometer (“AR2000”; manufactured by TA Instruments Japan) as a measuring device, It can be measured with a parallel plate.

-Dissolution or dispersion of toner material-
The toner material solution is obtained by dissolving the toner material in a solvent, and the toner material dispersion liquid is obtained by dispersing the toner material in a solvent.
The toner material is not particularly limited as long as the toner can be formed, and can be appropriately selected according to the purpose. Examples thereof include monomers, polymers, active hydrogen group-containing compounds, and active hydrogen group-containing compounds. It contains at least one of the polymers capable of reacting with the compound, preferably contains a colorant, and further contains other components such as a mold release agent and a charge control agent as necessary.

The dissolved or dispersed liquid of the toner material preferably contains an organic solvent. That is, it is preferable to prepare the solution or dispersion by dissolving or dispersing the toner material in the organic solvent.
When the organic solvent is contained, the organic solvent is preferably removed during or after the toner granulation.
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.

  When the toner material contains a colorant, it is preferable to disperse the colorant with the pigment dispersant in the preparation of the dispersion of the toner material. By dissolving or dispersing the colorant using the pigment dispersant, a shearing force was applied to the dissolved or dispersed liquid of the toner material at 25 ° C. at a shear rate of 30,000 (1 / second) for 30 seconds. Thereafter, the shear rate is changed from 0 (1 / second) to 70 (1 / second) in 20 seconds, and the viscosity of the dissolved or dispersed liquid is 1 to 100 mPa when the shear rate is 70 (1 / second). -It is possible to control to be seconds.

  The blending ratio of the colorant and the organic solvent in the dispersion liquid of the toner material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 5:95 to 50:50 is preferable. If the blending amount of the colorant is less than 5:95, the amount of the solution or dispersion may increase during the production of the toner, and the toner production efficiency may decrease. Dispersion may be insufficient.

--Colorant--
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 Degreen Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Hana, Litobon, and a mixture thereof.
These may be used individually by 1 type and may use 2 or more types together.
Further, examples of colorants that can be used particularly suitably include pigment red such as PR122, PR269, PR184, PR57: 1, PR238, PR146, and PR185; and pigment yellow such as PY93, PY128, PY155, PY180, and PY74. A pigment blue such as PB15: 3;

The colorant may be used as a colorant dispersion obtained by previously dispersing only the colorant in the solvent, or may be directly dispersed in the solvent together with the binder resin, the adhesive base material, and the like. You may let them. Further, even when the colorant is dispersed in advance, the viscosity may be adjusted by adding a part of the binder resin, the adhesive base material or the like in order to apply an appropriate shearing force when dispersing the pigment. .
The particle size of the colorant in the colorant dispersion after the colorant dispersion is preferably 1 μm or less, for example. When the particle diameter exceeds 1 μm, when the toner is manufactured, the particle diameter of the colorant is increased, and the image quality may be easily deteriorated. In particular, the optical transparency of OHP may be easily decreased. .
The particle size of the colorant can be measured using a laser diffraction / scattering particle size distribution measuring apparatus (“LA-920”; manufactured by Horiba, Ltd.) using a laser light scattering method.

The colorant is preferably subjected to a surface treatment in order to enhance the interaction with the modified polyurethane-based dispersant described later and stabilize the dispersion of the colorant.
Examples of the surface treatment agent for the colorant include natural rosins such as gum rosin, wood rosin, and tall rosin; abietic acid derivatives such as abietic acid, levopimaric acid, and dextropimaric acid; and calcium salts, sodium salts, potassium salts of the abietic derivatives Metal salts such as magnesium salts; rosin-modified maleic acid resin, rosin-modified phenolic acid resin, and the like. Among these, an acidic surface treatment agent is preferable in order to increase the affinity with the pigment dispersant.
The addition amount of the surface treatment agent is, for example, preferably 1 to 100% by mass and more preferably 1 to 10% by mass with respect to the colorant.

The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose.
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.

--- Pigment dispersant--
By using the pigment dispersant separately from the binder resin or the adhesive substrate, the pigment having an amine value that is likely to be positively charged because most of the pigment dispersant is adsorbed to the pigment particles. Since the amount of the dispersant present on the toner surface is reduced, it is possible to prevent the negative chargeability from being disturbed particularly in the negatively chargeable toner.

The pigment dispersant is not particularly limited as long as the colorant can be dispersed in a solvent, and can be appropriately selected according to the purpose. Examples thereof include polymer dispersants and synergists. Among these, a polymer dispersant is preferable.
There is no restriction | limiting in particular as said polymer dispersing agent, According to the objective, it can select suitably, For example, (1) A part of isocyanate group and hydroxyl group of the polyisocyanate compound of Japanese Patent Publication No. 2-19844 are included. And reacting a compound having one and further reacting an unreacted part with a compound having active hydrogen at both ends of the isocyanate group, and after these reactions, a substituent having an unreacted isocyanate group and active hydrogen, and Dispersant obtained by reacting a compound having a tertiary amino group or heterocyclic group, (2) monocarboxylic acid compound and monoepoxy compound, acid anhydride, and lactone described in JP-A-4-227774 A polyester having a hydroxyl group at the molecular end obtained by reacting with a compound, a compound having a monohydric alcohol, a monoepoxy compound and a lacquer. It is obtained by reacting a diisocyanate compound with a polyester having a hydrogen group at the molecular end obtained by further reacting with an acid anhydride if necessary, and further reacting with a hydroxyl group-containing copolymerizable monomer. Obtained by copolymerizing polyester macromer or polyester macromer obtained by reacting acid anhydride with either of the above polyesters and reacting with glycidyl (meth) acrylate and tertiary amino group-containing copolymerizable monomer. (3) a reaction product of a monocarboxylic acid compound and a lactone, a reaction product of a monocarboxylic acid compound, an acid anhydride, and a monoepoxy compound, a monohydric alcohol and a lactone, as described in JP-A-9-87537 The compound obtained by reacting an acid anhydride with the reaction product and a polymerizable vinyl group-containing monomer are converted into a carboxyl group and a Organic compound having one secondary amino group in the molecule by reacting one of the compounds having a carboxyl group at one end obtained by polymerization using a radical chain transfer agent having a capto group and a polyepoxy compound Examples thereof include a dispersant obtained by reacting an amino compound, and a polyurethane-based polymer dispersant obtained by these reactions is preferable, and a modified polyurethane-based dispersant is particularly preferable.

The modified polyurethane-based dispersant is preferably compatible with the binder resin or the adhesive substrate in terms of improving pigment dispersibility.
The weight average molecular weight of the modified polyurethane-based dispersant is, for example, the maximum molecular weight of the main peak in terms of styrene in GPC (gel permeation chromatography), preferably 500 or more, more preferably 2,000 or more, In view of improving pigment dispersibility, 3,000 or more is more preferable. More specifically, about 500 to 100,000 is preferable, and 2,000 to 10,000 is more preferable.
When the molecular weight is less than 500, the polarity becomes high and the dispersibility of the colorant may be easily lowered. When the molecular weight exceeds 100,000, the affinity with the solvent is increased, and Dispersibility may be easily reduced.

As the modified polyurethane dispersant, for example, a silane coupling agent having an amino group, a modified polyurethane derivative such as polyurethane modified with isocyanate, and the like are preferable.
As addition amount of the said modified polyurethane derivative, 1-50 mass parts is preferable with respect to 100 mass parts of said coloring agents, for example, and 5-30 mass parts is more preferable.
When the addition amount is less than 1 part by mass, the dispersion performance may be lowered, and when it exceeds 50 parts by mass, the chargeability may be lowered.
Specific examples of the modified polyurethane-based dispersant include, for example, “EFKA-4060”, “EFKA-4080”, “EFKA-7462”, “EFKA-4015”, “EFKA-4046”, and “EFKA-4046” manufactured by EFKA CHEMICALS. EFKA-4047 "," EFKA-4055 "," EFKA-4050 ", etc. are mentioned.

There is no restriction | limiting in particular as the compounding quantity in the said toner of this invention of the said modified polyurethane type dispersing agent, Although it can select suitably according to the objective, For example, 0.1-10 mass% is preferable.
When the blending amount is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it exceeds 10% by mass, the chargeability under high humidity may be deteriorated.

The said polymer dispersing agent may be used individually by 1 type, may use 2 or more types together, and may use it together with another dispersing agent.
Examples of other dispersants that can be used in combination include polyester dispersants, polymers of acrylic acid, methacrylic acid and esters thereof, and derivatives of colorants.
The addition amount of the colorant derivative is preferably 0.1 to 100% by mass, and preferably 0.1 to 10% by mass with respect to the colorant.

There is no restriction | limiting in particular as the compounding quantity with respect to the said coloring agent of the said polymer dispersant or the said synergist, Although it can select suitably according to the objective, 1-100 mass% is preferable, and 5-40 mass% is more. preferable.
When the blending amount is less than 1% by mass, the interaction between the pigments increases, the viscosity increases, and the toner surface smoothness is impaired when the toner is granulated in the aqueous medium. If it exceeds 100% by mass, the viscosity of the toner material dissolved or dispersed at the time of high shear becomes extremely low, and a toner having a desired particle size may not be obtained.

-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.

-Emulsification or dispersion-
The dissolution or dispersion of the toner material in the aqueous medium is preferably performed by dispersing the dissolution or dispersion in the aqueous medium while stirring.
The dispersion method is not particularly limited and may be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction disperser. High pressure jet disperser, ultrasonic disperser, and the like. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 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.

-Granulation-
The granulation method is not particularly limited, and can be appropriately selected from known methods. For example, the toner can be obtained using a suspension polymerization method, an emulsion polymerization aggregation method, a dissolution suspension method, or the like. Examples thereof include a granulating method, a method of granulating toner by obtaining particles based on the adhesive substrate while producing an adhesive substrate described later, and among these, the adhesive substrate is produced. A method of granulating the toner is preferred.

The method of granulating the toner while forming the adhesive base material, the toner material includes an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound,
Granulation is carried out by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in an aqueous medium to produce an adhesive base material, and then forming particles by the adhesive base material. Done by getting.
The toner formed by using such a granulation method includes an adhesive base material, preferably a colorant, and other components such as a release agent and a charge control agent, which are appropriately selected as necessary. Comprising.

-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 heat-resistant 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-based resin includes an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. In this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When the urea bond is less than 10, the hot offset resistance may be deteriorated.

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

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

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

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

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

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

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

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

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

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

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

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

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

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 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 deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

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 heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

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

  The weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 1,000 to 30,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 1,500-15,000 are more preferable. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, 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.

---- 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 heat resistant storage stability may be deteriorated. Therefore, as described above, the content of the component having the weight average molecular weight (Mw) of less than 1,000. 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 usually 30 to 70 ° C, more preferably 35 to 60 ° C, and still more preferably 35 to 50 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, 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 heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1.0 to 50.0 mgKOH / g, and more preferably 1.0 to 30.0. 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. .

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, a release agent, a charge control agent, resin fine particles, inorganic fine particles, a fluidity improver, a cleaning property improver, a magnetic property Examples include materials, metal soaps, and the like.

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.
If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability, and if it exceeds 160 ° C., a cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 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 wax.
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 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. , Etc.
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 resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. 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.

As an example of the method for producing the toner, a method for granulating the toner by producing particles with the adhesive substrate while producing the adhesive substrate will be described below.
In the method of granulating toner while producing the adhesive substrate, for example, preparation of an aqueous medium phase, preparation of a solution or dispersion of a toner material, emulsification or dispersion, production of the adhesive substrate, organic solvent And others (synthesis of a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound, synthesis of the active hydrogen group-containing compound, etc.).

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin microparticles | fine-particles, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
In the organic solvent, the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, the colorant, the release agent, and the charge control are prepared. It can be carried out by dissolving or dispersing a toner material such as an agent and the unmodified polyester resin.
In the toner material, components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound are added when the resin fine particles are dispersed in the aqueous medium in the preparation of the aqueous medium phase. You may add and mix in an aqueous medium, or when adding the said solution or dispersion to the said aqueous medium phase, you may add to the said aqueous medium phase with this solution or dispersion.

The emulsification or dispersion can be performed by emulsifying or dispersing the previously prepared solution or dispersion of the toner material in the previously prepared aqueous medium phase. When the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an elongation reaction or a crosslinking reaction during the emulsification or dispersion, the adhesive base material is generated.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). A solution or dispersion of the toner material is emulsified or dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and the aqueous medium phase (2) A solution or dispersion of the toner material may be emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance. May be formed by subjecting both to an extension reaction or a crosslinking reaction in the aqueous medium phase, or (3) dissolving or dispersing the toner material before After being added and mixed in the aqueous medium, the active hydrogen group-containing compound is added to form a dispersion, and the resultant may be produced by subjecting both to an extension reaction or a crosslinking reaction from the particle interface in the aqueous medium phase. Good. 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.

In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, In an aqueous medium phase, a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, the mold release agent, the charge control agent, the unmodified Examples thereof include a method of adding the solution or dispersion prepared by dissolving or dispersing the toner material such as polyester resin in the organic solvent and dispersing the solution by shearing force.
The dispersion is not particularly limited as a method thereof, and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction type. Examples include a disperser, a high-pressure jet disperser, and an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1 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 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, if necessary, the dispersion (oil droplets formed by dissolving or dispersing the toner material) is stabilized to obtain a desired shape and sharpen the particle size distribution. It is preferable to use an agent.
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 emulsification or 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 emulsification or dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

  The organic solvent is removed from the obtained dispersion (emulsified slurry). The organic solvent is removed by (1) a method of gradually raising the temperature of the entire reaction system to completely evaporate and remove the organic solvent in the oil droplets, and (2) spraying the emulsified dispersion in a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions 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.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board, etc. are mentioned. As an apparatus used 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 has the following volume average particle diameter (Dv), volume average particle diameter (Dv) / number average particle diameter (Dn), average circularity, BET specific surface area, penetration, low temperature fixability, offset. It preferably has non-generated temperature, thermal characteristics, image density, and the like.

The volume average particle diameter (Dv) of the toner is preferably, for example, 3 to 8 μm, and more preferably 4 to 7.
When the volume average particle size is less than 3 μm, in the two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring 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, and if it exceeds 8 μm, the resolution is high and the resolution is high. It becomes difficult to obtain an image having 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, for example, preferably 1.00 to 1.25, more preferably 1.05 to 1.25. preferable.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.00 to 1.25, the two-component developer has a toner balance over a long period of time. The toner particle size does not fluctuate little, and good and stable developability is obtained even with long-term agitation in the developing device. Even if the toner balance is achieved with a one-component developer, the toner particle size fluctuates little In addition, there is no filming of toner on the developing roller and no toner fusion to a member such as a blade for thinning the toner, and the developing device has good and stable developability even in long-term use (stirring). As a result, a high-quality image can be obtained. On the other hand, when it exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle size may increase.

The volume average particle diameter and the ratio (Dv / Dn) of the volume average particle diameter to the number average particle diameter are, for example, as follows using a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can be measured.
First, 0.1 to 5 ml of a surfactant (for example, an alkylbenzene sulfonate is preferably used) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic aqueous solution is prepared by preparing a 1% by mass NaCl aqueous solution using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter, Inc.) can be used. Next, about 2 to 20 mg of a measurement sample is added. The electrolytic aqueous solution in which the sample is suspended is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and the number of toner particles or toner are measured using a 100 μm aperture as an aperture by “Multisizer II”. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.
In addition, as a channel, it is less than 2.00-2.52 micrometer; 2.52-3.17 micrometer; 3.17-4.00 micrometer; 4.00-5.04 micrometer; 5.04-6.35 micrometer 6.35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Using 13 channels of less than 25.40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30;

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 0.970 to 1.000, for example, 0.975 to 1. .000 is more preferable. The particles having an average circularity of less than 0.940 are preferably 15% or less.
When the average circularity is less than 0.970, satisfactory transferability and a high-quality image free from dust may not be obtained. When the average circularity exceeds 0.995, image formation employing blade cleaning or the like is employed. 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 BET specific surface area in the toner, for example, preferably ^{0.5~3.0m 2 / g, 0.5~2.5m 2 /} g is more preferable.
The BET specific surface area is less than 0.5 m 2 / ^g, the effect of the external additive can not be obtained which is added to the toner, there is the fluidity and chargeability of the toner is deteriorated, 3.0 m ² / If it exceeds g, transferability may deteriorate.
The specific surface area of the toner can be measured according to the BET method. For example, the specific surface area measuring device Tristar 3000 (manufactured by Shimadzu Corporation) is used to adsorb nitrogen gas on the sample surface and the BET multipoint method is used. can do.

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.
When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated.
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 heat-resistant preservation | save property 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 140 ° 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. When the softening temperature (Ts) is less than 30 ° C., the heat resistant storage stability may be deteriorated.
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 heat resistant storage stability and offset resistance may be deteriorated.
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 heat-resistant 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 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, such that a tandem type color electrophotographic apparatus (“Imagio Neo 450”; manufactured by Ricoh Co., Ltd.) is used, and the amount of developer attached to copy paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) is 1 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 with a spectrometer (X-Light, Inc.) , 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.

  In the toner production method of the present invention, a solution or dispersion of a toner material is dispersed in an aqueous medium and granulated, and the solution or dispersion is granulated at 25 ° C. at a shear rate of 30,000 (1 / second). After applying a shearing force for 30 seconds, the shear rate is changed from 0 (1 / second) to 70 (1 / second) in 20 seconds, and the dissolution or dispersion when the shear rate is 70 (1 / second) Since the viscosity of the liquid is 1 to 100 mPa · sec, a spherical toner having a smooth surface, excellent properties such as transferability and chargeability, and high image quality can be efficiently produced.

  Since the toner of the present invention has a smooth surface, it has excellent properties such as transferability and chargeability, and can form a high-quality image. The toner of the present invention includes the adhesive base 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 medium to form particles. Furthermore, it is further excellent in various properties such as transferability and fixability. 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, chargeability, etc., 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 detachably provided in the electrophotographic 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 transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.
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 further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.

-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, amorphous silicon and the like are preferable in terms of long life.

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

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

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

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, the toner or developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention 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 multicolor developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

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

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

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

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

-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 intended purpose, but a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is 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.

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 can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

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. An image forming apparatus 100 shown in FIG. 1 includes a photosensitive drum 10 (hereinafter referred to as “photosensitive member 10”) as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and 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 58 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. 1, 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. 2 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 Except for the fact that the cyan developing unit 45C is disposed directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 2, the same components as those in FIG. 1 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. An image forming apparatus 100 shown in FIG. 3 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. 3. 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 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. The photosensitive member is exposed to each color image corresponding image (L in FIG. 4), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. 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.

  In the image forming apparatus and the image forming method of the present invention, the surface is smooth, excellent in various properties such as transferability and chargeability, and since the spherical toner of the present invention 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 by obtaining particles from the adhesive substrate while producing an adhesive substrate 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, 46 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, after reacting the reaction solution under a reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts by mass of trimellitic anhydride was added to the reaction vessel, and the reaction was performed at 180 ° C. for 2 hours under normal pressure. A modified polyester was synthesized.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 25.

--Preparation of pigment dispersion--
1,200 parts by mass of ethyl acetate, C.I. I. Pigment Red (“PR269”; manufactured by Dainippon Ink & Chemicals, Inc.) 540 parts by mass, Modified polyurethane-based dispersant (“EFKA-4080”; manufactured by EFKA Chemicals) as the polymer dispersant, 486 parts by mass, and polyester resin 1200 Mass parts were mixed using a disper (manufactured by Tokushu Kika Kogyo Co., Ltd.), and the mixture was dispersed using a dyno mill (manufactured by Shinmaru Enterprises Co., Ltd.) to prepare a pigment dispersion.

In a reaction vessel in which a stir bar and a thermometer were set, 378 parts by mass of the unmodified polyester, 110 parts by mass of carnauba wax, 22 parts by mass of CCA (“salicylic acid metal complex E-84”; manufactured by Orient Chemical Industries), and ethyl acetate 947 parts by mass were charged, and the temperature was raised to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts by mass of the pigment dispersion and 500 parts by mass of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a raw material solution.
1324 parts by mass of the obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”; manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 0.5 mm zirconia. Three passes under the condition that 80% by volume of beads were filled, and the C.I. I. Pigment red and carnauba wax were dispersed. Next, 1324 parts by mass of a 65% by mass ethyl acetate solution of the unmodified polyester was added to the wax dispersion. One pass was performed in a bead mill under the same conditions as described above, and the mixture was dispersed to prepare a toner material dissolved or dispersed liquid.
The solid content concentration (130 ° C., 30 minutes) of the obtained toner material dissolved or dispersed liquid was 50 mass%.

The viscosity or viscosity of the obtained toner material dissolved or dispersed liquid was measured as follows. The results are shown in Table 1.
A parallel plate type rheometer (“AR2000”; manufactured by D.A. Instruments Japan) having a parallel plate of 20 mmφ with respect to the dissolution or dispersion of the toner material (the content of the polymer dispersant is 90 parts by mass). After applying a shearing force at 25 ° C. and a shear rate of 30,000 (1 / second) for 30 seconds, the shear rate was changed from 0 (1 / second) to 70 (1 / second) in 20 seconds. And the viscosity when a shear rate is 70 (1 / second) was measured. As a result, the viscosity was 9.8 mPa · sec.
Further, the viscosity after applying a shearing force for 20 seconds at a shear rate of 30,000 (1 / second) at 25 ° C. to the dissolution or dispersion of the toner material (content of the polymer dispersant is 90 parts by mass). The parallel plate rheometer (“AR2000”; manufactured by TA Instruments Japan) was used. As a result, the viscosity was 0.13 mPa · sec.

-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 9,500, 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 1.53% 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 418.

  In a reaction container, 749 parts by mass of the toner material dissolved or dispersed liquid, 115 parts by mass of the prepolymer, and 2.9 parts by mass of the ketimine compound were charged, and the mixture was prepared using a TK homomixer (manufactured by Special Machine). The oil phase mixture was obtained by mixing at 1,000 rpm for 1 minute.

-Preparation of aqueous medium-
--Preparation of fine particle dispersion--
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts by weight of water, 11 parts by weight of sodium salt of ethylene oxide methacrylate adduct sulfate ("Eleminol RS-30"; manufactured by Sanyo Chemical Industries), 83 parts by weight of styrene , 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, and 1 part by weight 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 aqueous ammonium persulfate solution was added, and the mixture was aged at 75 ° C. for 5 hours to give vinyl resin particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt. An aqueous dispersion (fine particle dispersion) was prepared.
The volume average particle size 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 105 nm. . Further, a part of the fine particle dispersion was dried to isolate the resin, and the glass transition temperature (Tg) of the resin was measured. As a result, it was 59 ° C. and the weight average molecular weight (Mw) was measured. 000.

  990 parts by weight of water, 83 parts by weight of the fine particle dispersion, 37 parts by weight of a 48.5% by weight aqueous solution of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7”; manufactured by Sanyo Chemical Industries), and 90 parts by weight of ethyl acetate, Mixing and stirring were performed to obtain a milky white liquid (aqueous medium).

-Emulsification / Dispersion-
1200 parts by mass of the aqueous medium was added to 867 parts by mass of the oil phase mixed liquid, and the mixture was mixed with the TK homomixer at a rotational speed of 13,000 rpm for 20 minutes to prepare a dispersion (emulsified slurry).

Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain a dispersed slurry.
The obtained dispersion slurry had a volume average particle size of 5.7 μm and a number average particle size of 5.0 μm as measured by Multisizer II (manufactured by Beckman Coulter, Inc.).

-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.
10 mass% hydrochloric acid was added to the obtained filter cake, pH was adjusted to 2.8, it mixed with TK type homomixer (10 minutes at 12,000 rpm), and then filtered.
Further, 300 parts by mass of ion-exchanged water was added to the obtained filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered twice to obtain a final filter cake. It was.
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 used with 100 parts by mass of the obtained toner base particles of Example 1 using 1.0 part by mass of hydrophobic silica as an external additive and 0.5 parts by mass of hydrophobic titanium oxide. The toner of Example 1 was manufactured by using the mixture.
The obtained toner was observed with a scanning electron microscope (SEM) (FE-SEM “S-4200”; manufactured by Hitachi, Ltd.). The SEM photograph at this time is shown in FIG. From the SEM photograph, it was confirmed that the toner of Example 1 was excellent in surface smoothness and had a true spherical shape.

  The obtained toner has a volume average particle diameter (Dv), a number average particle diameter (Dn), a particle size distribution (volume average particle diameter (Dv) / number average particle diameter (Dn)), an average circularity, and a BET specific surface area. It measured by the following method. The results are shown in Table 2.

<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 4.9 μm, the number average particle size was 4.65 μm, and the particle size distribution (Dv / Dn) was 1.05.

<Average circularity>
The average circularity of the toner was measured using a flow particle image analyzer (“FPIA-1000”; 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 is dispersed for about 1 to 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.), so that the concentration and the distribution of the toner are 3,000 to 10,000 / μl. It was measured. The average circularity was calculated from these measurement results. As a result, the average circularity was 0.983.

<BET specific surface area>
According to the BET method, nitrogen gas was adsorbed on the surface of each toner base (sample) using a specific surface area measuring device (“Tristar 3000”; manufactured by Shimadzu Corporation), and measurement was performed by the BET multipoint method. As a result, it was 1.3 m ² / g.

(Example 2)
Example 1 is the same as Example 1 except that the content of the modified polyurethane-based dispersant (“EFKA-4080”; manufactured by EFKA Chemicals) as the polymer dispersant is changed from 486 parts by mass to 216 parts by mass. In the same manner, toner base particles of Example 2 were prepared and subjected to an external additive treatment to produce the toner of Example 2. Further, various physical properties and the like were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2.

(Example 3)
Example 1 is the same as Example 1 except that the content of the modified polyurethane-based dispersant (“EFKA-4080”; manufactured by EFKA Chemicals) as the polymer dispersant is changed from 486 parts by mass to 54 parts by mass. In the same manner, toner base particles of Example 3 were prepared and subjected to an external additive treatment to produce the toner of Example 3. Further, various physical properties and the like were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2.

(Example 4)
In Example 1, except that the content of the modified polyurethane-based dispersant (“EFKA-4080”; manufactured by EFKA Chemicals) as the polymer dispersant was changed from 486 parts by mass to 27 parts by mass, In the same manner, toner base particles of Example 4 were prepared and subjected to external additive treatment, whereby the toner of Example 4 was produced. Further, various physical properties and the like were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2.

(Comparative Example 1)
A toner base particle of Comparative Example 1 was produced in the same manner as in Example 1 except that the pigment dispersion was replaced with a master batch prepared by the following method in Example 1, and subjected to external additive treatment. 1 toner was produced. Further, various physical properties and the like were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2.

  The master batch contains 1200 parts by mass of water, C.I. I. 540 parts by mass of Pigment Yellow (“CI.PY74”; manufactured by Clariant) and 1200 parts by mass of a polyester resin were mixed using a Henschel mixer (manufactured by Mitsui Mining). The mixture was kneaded with two rolls at 150 ° C. for 30 minutes, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

  The obtained toner of Comparative Example 1 was observed with a scanning electron microscope (SEM) FE-SEM “S-4200” (manufactured by Hitachi, Ltd.). The SEM photograph at this time is shown in FIG. From the SEM photograph, it was confirmed that the toner of Comparative Example 1 had a rough surface and a shape far from a true spherical shape.

(Comparative Example 2)
In Example 1, except that the content of the modified polyurethane-based dispersant (“EFKA-4080”; manufactured by EFKA Chemicals) as the polymer dispersant was changed from 486 parts by mass to 10 parts by mass. Similarly, toner base particles of Comparative Example 2 were prepared and subjected to external additive treatment to produce a toner of Comparative Example 2. Further, various physical properties and the like were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2.

(Comparative Example 3)
In Example 1, except that the content of the modified polyurethane dispersant (“EFKA-4080”; manufactured by EFKA Chemicals) as the polymer dispersant was changed from 486 parts by mass to 810 parts by mass, Similarly, toner base particles of Comparative Example 3 were produced.
When the particle size of the obtained toner base particles was measured using a laser diffraction / scattering particle size distribution measuring device (“LA-920”; manufactured by Horiba, Ltd.), the particle size was as small as 1 μm or less. The toner base particles that can withstand the evaluation could not be obtained.
Table 1 shows the measurement results of the dissolution of the toner material and the viscosity of the dispersion.

  Next, a conventional method is performed from 5% by mass of each of the toners of Examples 1 to 4 and Comparative Examples 1 and 2 that have been treated with external additives and 95% by mass of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin. Thus, developers of Examples 1 to 4 and Comparative Examples 1 to 2 were produced.

  Using each of the obtained developers, (a) transferability, (b) charge amount, (c) image density, and (d) fog were evaluated as follows. The results are shown in Table 3.

(A) Transferability An image was formed on a transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) using a tandem color electrophotographic apparatus (“imagio Neo 450”; manufactured by Ricoh Co., Ltd.). During the transfer of the image onto the transfer paper, the electrophotographic apparatus was stopped, the amount of the developer remaining on the photoreceptor was visually observed, and evaluation was performed based on the following criteria.
〔Evaluation criteria〕
◎: Very little transfer residual toner and excellent transferability ○: Low transfer residual toner and good transferability △: Same transferability as conventional toner ×: Very much transfer residual toner Inferior to

(B) Charge amount 6 g of the developer was weighed, charged in a metal cylinder capable of being sealed, and blown to obtain the charge amount. The toner concentration was adjusted to 4.5 to 5.5% by mass.

(C) Image density Using a tandem color electrophotographic apparatus (“Imagio Neo 450”; manufactured by Ricoh Co., Ltd.), the amount of each developer adhered to transfer paper (“Type 6200”; manufactured by Ricoh Co., Ltd.) is 1. A solid image of 00 ± 0.1 mg / cm ² was formed at a surface temperature of the fixing roller of 160 ± 2 ° C. The image density of arbitrary 5 places in the obtained solid image was measured using a spectrometer (“938 Spectrodensitometer, manufactured by X-Rite”. The image density value is an average value of the image densities of 5 places. It means that the higher the obtained image density value, the higher the image density and the higher density image can be formed, and that the image density is 1.4 or more is a practical level. Is recognized.

(D) Cover Using a tandem type color electrophotographic apparatus (“Imagio Neo 450”; manufactured by Ricoh Co., Ltd.), the electrophotographic apparatus is stopped while developing a blank paper image, and the developer on the photoconductor after development is taped. In addition, the difference from the image density of the tape to which toner was not attached was measured with a spectrometer (“938 Spectrodensitometer”; manufactured by X-Light).

  From the results in Table 3, the following is clear. That is, in Examples 1 to 4, excellent transferability, uniform chargeability, and spherical toner were obtained. Further, it was found that the toner is excellent in fog, the evaluation result of the image density is good, and high image quality can be obtained. The toner of Example 1 was found to have a smooth surface.

  Since the toner of the present invention has a smooth surface, excellent properties such as transferability and chargeability, and a spherical shape, the toner is suitably used for high quality image formation. 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 in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 2 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 3 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. 4 is a partially enlarged schematic explanatory diagram of the image forming apparatus shown in FIG. FIG. 5 is an SEM photograph showing the shape of the toner produced in Example 1. FIG. 6 is an SEM photograph showing the shape of the toner produced in Comparative Example 1.

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 Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Constant current source 55 Switching claw 56 Discharging roller 57 Discharging tray 58 Corona charger 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 110 Belt type fixing device 120 Tandem type developer 130 Original platen 142 paper feed roller 143 paper bank 144 paper feed cassette 145 separation roller 146 paper feed path 147 transport roller 148 paper feed path 150 copying machine main body 200 paper feed table 300 scanner 400 automatic document Conveyor (ADF)

Claims (17)

(I) A solution or dispersion of a toner material containing at least a binder resin and a colorant, an active hydrogen group-containing compound, and a polymer capable of reacting with the active hydrogen group-containing compound are emulsified or dispersed in an aqueous medium.
(Ii) A method for producing a toner, wherein the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted to form an adhesive base material and granulate.
(Iii) After applying a shearing force to the dissolved or dispersed liquid at a shear rate of 30,000 (1 / second) at 25 ° C. for 30 seconds, the shear rate was changed from 0 (1 / second) to 70 (1 / second). ) In 20 seconds until
A toner manufacturing method, wherein the viscosity of the dissolved or dispersed liquid is 1 to 100 mPa · sec when the shear rate is 70 (1 / second).   The method for producing a toner according to claim 1, wherein the toner material is dissolved or dispersed in an organic solvent, and the organic solvent is removed during or after granulation. The viscosity of the solution or dispersion is 0.05 to 20 mPa · sec when a shearing force is applied to the solution or dispersion of the toner material at 25 ° C. at a shear rate of 30,000 (1 / second) for 20 seconds. The method for producing a toner according to claim 1. 4. The method for producing a toner according to claim 1, wherein the toner material contains a pigment dispersant. The method for producing a toner according to claim 4, wherein the pigment dispersant is a polymer dispersant. The method for producing a toner according to claim 5, wherein the polymer dispersant is a modified polyurethane dispersant. The method for producing a toner according to claim 6, wherein the modified polyurethane-based dispersant is compatible with the adhesive base material. The method for producing a toner according to claim 5, wherein the blending amount of the polymer dispersant with respect to the colorant is 1 to 100% by mass. A toner produced by the toner production method according to claim 1. The toner according to claim 9, wherein the toner has a volume average particle diameter of 3 to 8 μm. The toner according to claim 9, wherein the toner has a volume average particle diameter (Dv) / number average particle diameter (Dn) of 1.00 to 1.25. The toner according to claim 9, wherein the toner has an average circularity of 0.970 to 1.000. The BET specific surface area of the toner is 0.5 to 3.0 m ² The toner according to claim 9, which is / g. A developer comprising the toner according to claim 9. A toner-filled container filled with the toner according to claim 9. An electrostatic latent image carrier, and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using the toner according to claim 9 to form a visible image. A process cartridge having at least 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 according to any one of claims 9 to 13 to form a visible image An image forming method comprising: a developing step for forming the 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.