JP5453906B2 - Method for producing toner for developing electrostatic image, toner for developing electrostatic image, developer, container with toner for developing electrostatic image, process cartridge, image forming apparatus and image forming method - Google Patents

Description

  The present invention relates to a method for producing an electrostatic charge image developing toner used for image formation in an electrostatic copying process such as a copying machine, a facsimile machine, a printer, etc., an electrostatic charge image developing toner produced by the production method, and the electrostatic charge The present invention relates to a developer containing image developing toner, an image forming apparatus using the electrostatic image developing toner, and an image forming method using the electrostatic image developing toner.

  Conventionally, as an electrophotographic method, many methods are known as described in Patent Documents 1 to 3. In general, a photoconductor using a photoconductive substance is used, an electrostatic latent image is formed on the photoconductor by various means, and then toner is supplied to the electrostatic latent image to form an electrostatic latent image. The toner image is developed and developed. After the toner image is transferred to a recording medium such as paper, the toner image is fixed on the recording medium by heating and pressure to obtain a toner image. Various methods and apparatuses have been developed for fixing the toner image on the recording medium, which is the final step, but the most common method at present is a pressure heating method using a heat roller.

  On the other hand, in recent years, color image forming apparatuses using an electrophotographic method have become widespread, and since the digitized images can be easily obtained, the quality of printed images can be further improved. It is requested. In particular, higher resolution, gradation, color reproducibility, and high gloss are required for images that can be used for digital photo printing. In general, full-color images formed by adopting electrophotography have a narrower color reproduction range compared to full-color images formed by silver salt photography or printing, and in terms of image quality as judged by familiar users. The level has not been reached.

  In order to improve the image quality of a full-color image formed by electrophotography to a level comparable to a full-color image formed by silver salt photography or printing, it is a collection of finer image formation and formed powder. The problem is how to image a toner image as a uniform film. That is, as the toner is present in the image as a granular mass as a powder, color reproducibility decreases due to an increase in scattered light, lack of absorbance, and the like.

  For fine image formation, it is effective to reduce the toner particle size and narrow the particle size distribution. Toners produced by conventional pulverization methods have limitations in fine image formation due to the particle size distribution and shape of the toner obtained, so further spheroidization and smaller particle size are considered in order to form high-definition images. Has been made. Therefore, a so-called polymerized toner manufactured by suspension polymerization method, emulsion polymerization method, dispersion polymerization method or the like capable of reducing the particle size or narrowing the particle size distribution is being adopted (for example, see Patent Document 4).

  The polymerized toner described in Patent Document 4 is effective for reducing the particle size and narrowing the particle size distribution. However, in order to obtain excellent color reproducibility and gloss from the toner image thus obtained, it is necessary to form an image as a uniform film as described above, which is greatly influenced by the thermal properties of the toner and the fixing conditions.

  In order to image a toner image, which is a collection of powders, as a uniform film, a sufficient amount of heat and pressure is applied during fixing to melt the toner, and the toner image is pressed onto the recording medium. It is important that the interface of the toner agglomerates be removed by melting the toners.

  However, since the toner image on the recording medium forms several toner layers, the fixing speed is particularly fast. In a system with a high heating roller temperature, the toner layer contacting the heating roller and the recording medium The temperature difference between the toner layers in contact with the lowermost layer becomes very large. Therefore, when the temperature of the heating roller is high, the toner on the uppermost layer causes an offset phenomenon. On the other hand, when the temperature of the heating roller is low, the toner on the lowermost layer is not sufficiently melted. The phenomenon of low temperature offset occurs without fixing.

  As a method for solving this problem, when the fixing speed is high, a method of increasing the pressure during fixing and anchoring the toner to the recording medium is usually performed. According to this method, the heating temperature of the heating roller can be lowered to some extent, and the high temperature offset phenomenon of the uppermost toner can be prevented. However, since the shearing force applied to the toner becomes very large, the recording medium is wound around the fixing roller, the winding offset, and the image after separation of the member (for example, the separation claw) that separates the recording medium from the fixing roller. And the pressure is high, the line image is crushed at the time of fixing, or the toner is blown off.

  Accordingly, in general, high-speed fixing uses toner having a lower melt viscosity than in low-speed fixing, and lowers the heating temperature and fixing pressure of the heating roller, thereby fixing while preventing high temperature offset and wrapping offset. However, when such a low melt viscosity toner is used for low-speed fixing, an offset phenomenon tends to occur at a high temperature because of its low viscosity. Therefore, in a fixing process by a contact heating method performed using a heating member such as a heat roller, release property (hereinafter referred to as offset resistance) to the heating member is required.

  As a binder resin for toner having good offset resistance while preventing such high temperature offset and wrapping offset, polyester resin excellent in transparency, mechanical strength, and low temperature fixability described in Patent Document 5 A solution has been achieved by using a polyester-modified resin reacted with a precursor.

  However, in the thing of patent document 5, since reaction of a polyester resin precursor is superposition | polymerization of the high molecular weight body by extension reaction (thermal crosslinking) of a prepolymer, reaction is started from the time of oil phase preparation, and reaction rate is slow, In addition, the reaction itself is unstable and it is difficult to control the reaction, and a toner having a large amount of gel is generated. As a result, it was difficult to obtain sufficient transparency and gloss even when using a polyester resin. Further, when a polyester resin having a molecular weight distribution with a weight average molecular weight (Mw) of 10,000 or more is used, the toner composition solution viscosity becomes high, so that it is difficult to reduce the toner diameter and narrow particle size distribution, and stable productivity cannot be obtained. There was a thing.

  The present invention has been made in view of the above circumstances, and has as its object to achieve the following objects. That is, the present invention is compatible with a low-temperature fixing system, has a good offset resistance, a narrow particle size distribution and a small particle size, a high gloss with excellent sharpness, and excellent color reproducibility over a long period of time. An electrostatic image developing toner that can be formed, a method for producing an electrostatic image developing toner capable of easily and reliably producing the toner, a developer containing the toner, a container containing the toner, It is an object to provide a process cartridge, an image forming method, and an image forming apparatus using the toner.

In order to solve the above-mentioned problem, the invention according to claim 1 comprises dissolving or dispersing a toner composition containing at least a binder resin and a radiation crosslinking monomer compatible with the binder resin in an organic solvent. A step of forming a lysate or dispersion, a step of adding the lysate or dispersion to an aqueous medium and emulsifying or dispersing it to prepare an emulsion or dispersion, and the organic solvent from the emulsion or dispersion And a method of producing a toner for developing an electrostatic charge image comprising the step of removing and crosslinking the radiation-crosslinking monomer,
The radiation crosslinking monomer is contained in the toner composition in a mass ratio of binder resin: radiation crosslinking monomer = 92.5: 7.5 to 97.5: 2.5 by mass ratio;
After removing the organic solvent from the emulsion or dispersion and granulating, the radiation crosslinking monomer is subjected to radiation crosslinking at the time of desolvation in which the solid content concentration of the obtained particles is in the range of 80% by mass to 95% by mass. It is characterized by.

The invention of claim 2 is a method for producing a toner for developing an electrostatic charge image according to claim 1,
The toner composition contains a colorant or a release agent.

The invention of claim 3 is the method for producing a toner for developing an electrostatic charge image according to claim 1,
The toner composition contains a colorant and a release agent.

According to a fourth aspect of the present invention, in the method for producing a toner for developing an electrostatic charge image according to any one of the first to third aspects,
The binder resin is a polyester resin.

  According to a fifth aspect of the present invention, there is provided an electrostatic charge image developing toner produced by the method for producing an electrostatic charge image developing toner according to any one of the first to fourth aspects. .

The invention of claim 6 is the toner for developing an electrostatic charge image according to claim 5,
The binder resin has a crosslinked body having a molecular weight of 50,000 or more obtained by radiation-crosslinking a resin having a weight average molecular weight (Mw) of 10,000 or more and 25,000 or less and a radiation crosslinking monomer that does not contain a gel component.

The invention according to claim 7 is the toner for developing an electrostatic charge image according to claim 5 or 6,
The electrostatic charge image developing toner has a volume average particle diameter (Dv) of 4 μm or more and 6 μm or less, and a volume average particle diameter (Dv) / number average particle diameter (Dn) of less than 1.25. .

  The invention of claim 8 is a developer characterized by containing the toner for developing an electrostatic charge image according to any one of claims 5 to 7.

  According to a ninth aspect of the present invention, there is provided a toner-containing container in which the electrostatic image developing toner according to any one of the fifth to seventh aspects is accommodated in a container.

According to a tenth aspect of the present invention, toner is supplied to the electrostatic latent image carrier and the electrostatic latent image formed on the electrostatic latent image carrier to convert the electrostatic latent image into a toner image. In an image forming apparatus provided with a developing device,
The toner according to claim 5, wherein the toner is an electrostatic charge image developing toner.

The invention according to claim 11 supplies toner to the electrostatic latent image carrier and the electrostatic latent image formed on the electrostatic latent image carrier to convert the electrostatic latent image into a toner image. In the process cartridge in which the developing device is connected at least integrally,
The toner supplied to the electrostatic latent image from the developing device is the toner for developing an electrostatic image according to any one of claims 5 to 7.

According to a twelfth aspect of the present invention, an electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and supplying toner to the electrostatic latent image to convert the electrostatic latent image into toner In an image forming method comprising: a developing step for forming an image; a step for transferring the toner image to a recording medium; and a step for fixing the toner image transferred onto the recording medium.
The toner is an electrostatic image developing toner according to any one of claims 5 to 7.

  According to the present invention, the radiation crosslinking monomer is contained in the toner composition in a mass ratio of binder resin: radiation crosslinking monomer = 92.5: 7.5 to 97.5: 2.5, After removing the organic solvent from the emulsion or dispersion and granulating, the radiation crosslinking monomer is subjected to radiation crosslinking at the time of desolvation when the solid content concentration of the obtained particles is in the range of 80% by mass to 95% by mass, It is compatible with low-temperature fixing systems, has good anti-offset properties, narrow particle size distribution and small particle size, high gloss with excellent sharpness and excellent color reproducibility. Charge image developing toner, method for producing electrostatic image developing toner capable of easily and reliably producing the toner, developer containing the toner, container containing the toner, process using the toner Cartridge, it is possible to provide an image forming method and an image forming apparatus.

It is a graph which shows the relationship between solvent removal time and solid content concentration. It is the schematic which shows an example of the process cartridge by this invention. It is a schematic explanatory drawing which shows one example which implements the image forming method of this invention with the image forming apparatus by this invention. It is a schematic explanatory drawing which shows the other example which implements the image forming method of this invention with the image forming apparatus by this invention. It is a schematic explanatory drawing which shows an example which implements the image forming method of this invention with the image forming apparatus (tandem type color image forming apparatus) by this invention. FIG. 6 is a partially enlarged schematic explanatory diagram of the image forming apparatus shown in FIG. 5.

  In order to achieve the above-mentioned object, the present inventors have made various studies, and as a result, dissolved or dissolved a toner composition containing at least a binder resin and a radiation crosslinking monomer compatible with the binder resin in an organic solvent. A solution or dispersion formed by dispersion is prepared, an aqueous medium is added to the solution or dispersion and emulsified or dispersed to prepare an emulsion or dispersion, and the organic solvent is removed from the emulsion or dispersion. When producing the toner for developing an electrostatic charge image by removing and crosslinking the radiation crosslinking monomer, the organic solvent is removed from the emulsion or dispersion and granulated, and then the solid content concentration of the obtained particles It has been found that the above-mentioned object can be appropriately achieved by radiation-crosslinking the radiation-crosslinking monomer at the time of desolvation in the range of 80 mass% to 95 mass%.

  In the method for producing a toner for developing an electrostatic charge image according to the present invention, since a high molecular weight body is formed by radiation crosslinking, the reaction does not proceed until the radiation crosslinking after granulation. The time is very short, and the molecular weight obtained by the particle solid content during the reaction can be appropriately controlled. The higher the particle solids, the lower the molecular weight of the product, and the lower the particle solids. This is presumably because the ease of movement of the radiation crosslinking monomer in the particles changes, and the establishment of contact between functional groups changes. Furthermore, since the binder resin is plasticized with the monomer before the reaction, the oil layer can have a low viscosity even at a high solid content, and productivity can be improved.

  In addition, by blending the binder resin and the radiation crosslinking monomer in a mass ratio of 92.5: 7.5 to 97.5: 2.5, the gloss and color reproducibility of the toner image are affected. It is possible to prevent the generation of a residual monomer that causes problems such as the formation of a gel component giving heat resistance, heat-resistant storage stability, and odor during fixing.

  In addition, the toner according to the present invention is also effective in a so-called transparent toner that does not contain a colorant. In this case, the toner composition does not contain a colorant, and includes a binder resin and a radiation crosslinking monomer, or It can be set as the composition containing binder resin, a radiation crosslinking monomer, and a mold release agent. When a composition containing a binder resin, a radiation crosslinking monomer, a release agent, and a colorant is used as the toner composition, a toner image with improved releasability with respect to a fixing heating roller during fixing is obtained. This is preferable because it can be surely formed.

  Further, by using a polyester resin as the binder resin, it is possible to produce a toner having excellent transparency, low-temperature fixability, and storage stability.

  The toner for developing an electrostatic image according to the present invention has a molecular weight of 50,000 or more obtained by radiation-crosslinking a resin having a weight average molecular weight (Mw) of 10,000 or more and 25,000 or less and a radiation-crosslinking monomer. By having the crosslinked body, the storage elastic modulus at the time of fixing the toner image becomes small, and after fixing, the thinned state can be maintained and good color reproducibility can be obtained.

  The toner for developing an electrostatic charge image according to the present invention has a volume average particle diameter (Dv) of 4 μm or more and 6 μm or less, and a volume average particle diameter (Dv) / number average particle diameter (Dn) of less than 1.25. Fine image formation is possible.

  Hereinafter, the toner for developing an electrostatic image and the method for producing the toner for developing an electrostatic image according to the present invention will be described in detail. The material used will be described later as each component constituting the electrostatic image developing toner of the present invention.

[Toner and toner production method]
As described above, the toner of the present invention is a solution or dispersion formed by dissolving or dispersing a toner composition containing at least a binder resin and a radiation crosslinking monomer compatible with the binder resin in an organic solvent. It is added to an aqueous medium and emulsified or dispersed to prepare an emulsified liquid or dispersion, granulated, and then produced by radiation crosslinking at the time of desolvation when the solid content concentration of the obtained particles is 80 mass% to 95 mass%. Is done.

  The toner composition contains at least a binder resin and a radiation crosslinking monomer, and further contains other components such as a release agent, a colorant, a charge control agent, and a photopolymerization initiator as necessary. Can do. Such a toner composition is used by preparing a solution or dispersion by dissolving or dispersing in an organic solvent.

  The solution or dispersion thus prepared can be granulated by, for example, emulsifying or dispersing it in an aqueous medium together with resin fine particles described later to prepare an emulsion or dispersion. (Preparation of aqueous medium phase). In this case, there is no restriction | limiting in particular as addition amount in the aqueous medium of resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable with respect to an aqueous medium.

(Emulsification or dispersion)
In the dissolution or dispersion of the toner composition in the aqueous medium, the dissolution or dispersion is preferably dispersed in the aqueous medium while stirring. The dispersion method is not particularly limited 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 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 a high-speed shearing disperser is used, there are no particular limitations on conditions such as the number of rotations, dispersion time, and dispersion temperature, and the conditions can be appropriately selected according to the purpose. 000 to 30,000 rpm is preferable, and 5,000 to 20,000 rpm is more preferable. In the case of a batch method, the dispersion time is preferably 0.1 to 5 minutes.

(Removal of organic solvent and crosslinking of radiation crosslinking monomer)
Thus, after emulsifying or dispersing the toner composition, the organic solvent is removed. Then, when the organic solvent is removed and the solid content concentration of the particles is adjusted to a predetermined concentration, a cross-linking reaction of the radiation cross-linking monomer generates a toner adhesive base material that adheres the toner to the recording medium. .

  As the reaction conditions for the radiation crosslinking monomer, it is important to carry out crosslinking by irradiating with radiation at the time of desolvation in which the particle solid content concentration is in the range of 80 mass% to 95 mass%. When the particle solid content concentration is less than 80% by mass, the reaction proceeds too much to generate a gel component. If it is greater than 95% by mass, the contact probability between the monomers decreases, the crosslinking reaction does not proceed, and a large amount of residual monomer remains, preserving property is deteriorated, and offset property is also lowered.

In this case, there is a close relationship between the solvent removal time and the solid content of the particles, and it is effective to confirm the solid content fluctuation (desolvation rate) in advance by the following means.
(1) The slurry immediately after emulsification is sampled in a 10 ml screw bottle to fill the container, and the lid is closed. (Desolvation time 0 hour sample)
(2) 100 parts by mass of the emulsified slurry is charged and stirred in a Kolben equipped with a stirrer and a thermometer. Sample the slurry in the same manner as Sample 1 every 30 minutes.
(3) The sampled slurry is centrifuged at 3000 rpm for 10 minutes in a centrifuge.
(4) A part of the precipitate obtained by discarding and separating the supernatant is weighed and set in gas chromatography to measure the residual solvent.
(5) The remaining sediment is placed on an aluminum petri dish and lightened, dried in a thermostatic bath at 120 ° C. for 1 hour, the dried sample is lightened, and the total solid content concentration is calculated.

That is, the solid content concentration A calculated in this way is
Solid content concentration A (mass%) = dry matter / initial weight, and solid matter / (solid matter + water + solvent). In this case, it is necessary to perform the operations (4) and (5) as quickly as possible.
(6) The solid content concentration B of the sample excluding moisture is calculated from the residual solvent amount measured in the above (4) and the solid content concentration A (mass%) of the sediment calculated in the above (5). The solid content concentration B is solid matter / (solid matter + solvent). This solid content concentration B is the solid content concentration used in the present invention. Since the solid content concentration starts to change from the emulsification step, the solid content concentration of the sample immediately after emulsification is about 70% by mass even when the solid content concentration of the dissolved or dispersed liquid of the toner composition is 50% by mass.

  FIG. 1 is a graph showing the relationship between the solvent removal time and the solid content concentration. In this figure, the X mark is the result of the first prescription in Example 1 according to the present invention described later, the ◆ mark is the result of the prescription in Example 3 according to the present invention described later, and the ○ mark is according to the present invention described later. The result of the 2nd prescription in Example 1 is shown. From this result, it is clear that there is almost no difference in the dissolution of the toner composition or the change in the solid content concentration of the dispersion in each formulation. Moreover, it turns out that what is necessary is just to perform a solvent removal time within 1-4 hours in order that solid content concentration shall be 80 mass%-95 mass% from this result.

  The amount of radiation irradiation is not particularly limited as long as the crosslinking reaction occurs, but when an electron beam is used, the electron dose is preferably 10 Mrad or less, particularly preferably 5 Mrad or less. When the electron dose is large, there is a concern that the binder resin is decomposed, the coloring power of the coloring agent is decreased, and the like. When ultraviolet rays are used, it is desirable to expose them to the ultraviolet rays while passing through the microtubules because there is a possibility that the ultraviolet rays may not be irradiated to the whole particles due to the colorant.

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

  In the emulsification or dispersion, if necessary, from the viewpoint of stabilizing the dispersion (oil droplets composed of the dissolution or dispersion of the toner composition) and sharpening the particle size distribution while obtaining a desired shape. It is preferable to use a dispersant.

  The organic solvent is removed from the dispersion (emulsified slurry) obtained after irradiation. As a method for removing the organic solvent, (1) the whole is gradually heated to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed in a dry atmosphere. Examples thereof include a method in which the water-insoluble organic solvent in the oil droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation.

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

  The toner has the following volume average particle diameter (Dv), volume average particle diameter (Dv) / number average particle diameter (Dn), penetration, low temperature fixability, non-offset temperature, glass transition temperature (Tg). Etc.).

(Toner particle size)
The toner has a volume average particle diameter (Dv) of preferably 3 to 8 μm, and more preferably 4 to 6 μm. When the volume average particle diameter (Dv) is less than 3 μm, in the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be lowered. In addition, in the case of a one-component developer, toner filming on the developing roller and toner thinning are likely to cause toner fusion to a member such as a blade. When it exceeds 8 μm, 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 become large.

  The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is preferably 1.00 to 1.25, and more preferably 1.00 to 1.20. If the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and the balance of the toner in the developer is reduced. In such a case, the toner particle size may vary greatly. When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.00 to 1.25, the storage stability, the low-temperature fixability, and the hot offset resistance are all excellent. In particular, when used in a full-color copying machine, the glossiness of the image is excellent. With two-component developers, there is little fluctuation in the toner particle diameter in the developer even if the toner balance for a long period of time is achieved, and good and stable developability can be obtained even with long-term stirring in the developing device. Even if the balance of the toner is carried out with the agent, fluctuations in the particle diameter of the toner are reduced, and there is no filming of the toner on the developing roller and no fusion of the toner to the member to the blade for thinning the toner. Even in the long-term use (stirring) of the developing device, good and stable developability can be obtained, so that a high-quality image can be obtained.

  Here, the volume average particle diameter (Dv) and the ratio (Dv / Dn) of the toner can be measured by, for example, a Coulter counter method, and the toner particle diameter and particle size distribution measuring apparatus by the Coulter counter method can be measured. May include Coulter Multisizer III (Beckman Coulter, Inc.).

(Toner storage, fixing, etc.)
The penetration can be used as an index indicating the heat resistant storage stability of the toner. As the penetration, for example, the penetration measured by a penetration test (JIS K2235-1991) is preferably 15 mm or more, and more preferably 20 to 30 mm. When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated.

  The penetration can be measured according to, for example, 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 lower fixing temperature and no offset occurrence, the lower fixing lower temperature is preferable, and the higher the offset non-occurrence temperature is, the more preferable. The temperature range that can be used is that the lower limit fixing temperature is less than 140 ° C., and the non-offset temperature is 200 ° C. or more. The fixing minimum temperature is, for example, an image forming apparatus, a transfer sheet is set, a copy test is performed, and the obtained fixed image is rubbed with a pad. The fixing member temperature is the lower limit fixing temperature.

  The non-offset temperature is adjusted such that, for example, the toner to be evaluated is developed with a predetermined amount using an image forming apparatus, and is adjusted so that the temperature of the fixing member is variable. Can be determined by measuring.

(Toner glass transition temperature, etc.)
The glass transition temperature (Tg) of the toner is preferably 50 to 80 ° C, more preferably 50 to 65 ° C. When the glass transition temperature is in the above range, more excellent heat-resistant storage stability and low-temperature fixability can be exhibited. When the glass transition temperature (Tg) is less than 50 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 80 ° C., the low-temperature fixability may not be sufficient.

  Here, the said glass transition temperature can be measured with the following method, for example using TG-DSC system TAS-100 (made 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 heating rate 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.

  Next, each component constituting the electrostatic image developing toner according to the present invention will be described.

<Binder resin>
The binder resin for binding the electrostatic image developing toner on the recording medium is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyester resins. Polyester is preferred. When a linear polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.

  The weight average molecular weight (Mw) of the polyester resin is preferably 7,500 to 30,000, preferably 10,000 to 25,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Is more preferable. When the weight average molecular weight (Mw) is less than 7,500, the heat resistant storage stability may be deteriorated. On the other hand, when the previous weight average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may be deteriorated.

  As a glass transition temperature of the said polyester resin, 40-70 degreeC is preferable and 50-60 degreeC is more preferable. When the glass transition temperature is less than 40 ° C., the heat-resistant storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient. As a hydroxyl value of the said polyester resin, 5 mgKOH / g or more is preferable, 10-120 mgKOH / g is more preferable, 20-80 mgKOH / g is still more preferable. If the hydroxyl value is less than 5 mgKOH / g, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. Moreover, as an acid value of the said polyester resin, 1.0-50.0 mgKOH / g is preferable and 1.0-30.0 mgKOH / g is more preferable. By giving the toner an acid value in this way, it is generally easy to be negatively charged.

  Examples of the monomer constituting the polyester resin (polyester polymer) include the following. Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned.

  Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And unsaturated dibasic acid anhydrides. Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.

In the present invention, the acid value of the binder resin component of the toner composition is determined by the following methods (A) to (D), and the basic operation conforms to JIS K-0070.
(A) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(B) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(C) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(D) The amount of KOH solution used at this time is S (ml), a blank is measured at the same time, and the amount of KOH solution used at this time is B (ml), which is calculated by the following equation (1). However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (1)

<Radiation crosslinking monomer>
Radiation crosslinking monomers used in the present invention include urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, vinyl, unsaturated polyester oligomers, various polyfunctional acrylates, methacrylates, vinyl esters, ethylene And monomers such as derivatives and allyl compounds. Specific examples include the following.

Examples of bifunctional monomers:
1,4-butanediol acrylate 1,6-hexanediol diacrylate 1,9-nonanediol diacrylate neopentyl glycol diacrylate tetraethylene glycol diacrylate tripropylene glycol diacrylate tripropylene glycol diacrylate polypropylene glycol diacrylate bisphenol A. EO Adduct Diacrylate Glycerin Methacrylate Acrylate Propylene Oxide of Neopentyl Glycol 2 Moleate Diacrylate Diethylene Glycol Diacrylate Polyethylene Glycol (400) Diacrylate Diacrylate of Hydroxypivalic Acid and Neopentyl Glycol 2,2-Bis (4- Acryloxy diethoxyphenyl) propane Diacrylate of neopentyl glycol adipate Diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate Diacrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate 2- (2-hydroxy) -1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxanedia Relate tricyclodecane dimethylol diacrylate tricyclodecane dimethylol diacrylate ε- caprolactone adduct of 1,6-diacrylate diglycidyl ethers of hexanediol

Examples of multifunctional monomers:
Trimethylolpropane triacrylate Pentaerythritol triacrylate Triglycerin PO-added triacrylate Trisacryloyloxyethyl phosphate Pentaerythritol tetraacrylate Triacrylate of trimethylolpropane propylene oxide 3 mol adduct Glyceryl propoxytriacrylate Dipentaerythritol polyacrylate Dipentaerythritol Caprolactone adduct polyacrylate Propionic acid / dipentaerythritol triacrylate Hydroxypivalaldehyde-modified dimethylolpropyne triacrylate Propionic acid / dipentaerythritol tetraacrylate Ditrimethylolpropane tetraacrylate Propionate dipentaerythritol pen Taacrylate Dipentaerythritol hexaacrylate (DPHA)
Ε-caprolactone adduct of DPHA

Examples of oligomers:
Bisphenol A-diepoxyacrylic acid adduct

  These radiation crosslinking monomers are used alone or in admixture of two or more. Among the radiation crosslinking monomers, a material that is compatible with the binder resin is selected. The binder resin is plasticized when mixed with the selected radiation crosslinking monomer and added amount, and the apparent Tg and the viscosity at the time of heat-kneading can be adjusted. It is preferable that a low-viscosity bifunctional or lower radiation crosslinking monomer that functions as a diluent and a high-viscosity polyfunctional crosslinking agent are appropriately mixed and used.

(Ratio of binder resin and radiation crosslinking monomer)
The mass ratio of the binder resin and the radiation crosslinking monomer is preferably a blending ratio in the range of 92.5: 7.5 to 97.5: 2.5. When the ratio of the radiation crosslinking monomer is greater than 7.5, the reaction proceeds too much to generate a gel component, which affects transparency and gloss. If it is less than 2.5, the contact probability between the monomers decreases, the crosslinking reaction does not proceed, a large amount of residual monomer remains, the storage stability deteriorates, and the offset property also decreases.

  During the crosslinking reaction, the solid content in the granulated toner particles becomes important. If the solid content at the time of crosslinking is too low, the radiation crosslinking monomer easily moves in the particles, the crosslinking reaction proceeds too much, and the transparency and glossiness of an image that can form a large gel are lowered. If the solid content concentration at the time of crosslinking is too high, the movement of the radiation crosslinking monomer is inhibited, crosslinking inhibition occurs, and uncrosslinked monomer remains. Residual monomers plasticize the binder resin, resulting in poor heat resistance and poor fixability. The solid content concentration during preferred crosslinking is 80% by mass or more and 95% by mass or less. When a crosslinking reaction is carried out at a preferred solid content concentration, the radiation crosslinking monomer is present in the particles as a linear high molecular weight material having a molecular weight of 50,000 to 100,000 suitable for the toner.

(Compatibility of binder resin and radiation monomer)
The compatibility between the binder resin and the radiation monomer is evaluated and judged as follows.
8 parts by mass of the binder resin and 2 parts by mass of radiation monomer are added to 20 parts by mass of ethyl acetate and stirred to prepare a solution having a solid content concentration of 20% by mass. The solution is applied to a transparent PET film having a thickness of 50 μm with a wire bar and dried to form a coating film having a thickness of 10 μm. The haze of the prepared coating film is measured with a haze meter. A haze of less than 5% is compatible and 5% or more is incompatible. When the binder resin and the monomer are incompatible with each other, when the toner is granulated, the monomer may form a domain and become a gel at the time of crosslinking, resulting in a toner that can obtain only an image with low gloss.

<Photopolymerization initiator>
In the present invention, it is preferable to use an electron beam for radiation crosslinking, but it is also possible to use ultraviolet rays. When ultraviolet rays are used, it is necessary to mix a photopolymerization initiator.
Examples of photopolymerization initiators include, but are not limited to, the following.
1. Benzoin ether type Isobutyl benzoin ether Isopropyl benzoin ether Benzoin ethyl ether Benzoin methyl ether 2. α-Acyloxime ester type 1-phenyl-1,2-propanedione-2- (o-ethoxysicarbonyl) oxime Benzyl ketal series 2,2-dimethoxy-2-phenylacetophenone benzyl hydroxycyclohexyl phenyl ketone4. 4. Acetophenone derivative system Diethoxyacetophenone 2-hydroxy-2-methyl-1-phenylpropan-1-one Ketone-(ketone-amine system)
Benzophenone Chlorothioxanthone 2-Chlorothioxanthone Isopropylthioxanthone 2-Methylthioxanthone Chlorine-substituted benzophenone

  These photopolymerization initiators are used alone or in combination of two or more. As addition amount, 0.005-1.0 mass part is preferable with respect to 1 mass part of crosslinking agents, More preferably, it is 0.01-0.5 mass part.

<Photopolymerization accelerator>
In the present invention, a photopolymerization accelerator can be used together with the photopolymerization initiator.
The photopolymerization accelerator used in the present invention has an effect of improving the curing rate with respect to a hydrogen abstraction type photopolymerization initiator such as benzophenone or thioxanthone. For example, an aromatic tertiary class There are amines and aliphatic amines. Specific examples include P-dimethylaminobenzoic acid isoamyl ester, P-dimethylaminobenzoic acid ethyl ester, and the like. These photopolymerization accelerators are used alone or in admixture of two or more. As addition amount, 0.1-5 mass parts is preferable with respect to 1 mass part of photoinitiators, More preferably, it is 0.3-3 mass parts.

<Other ingredients>
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, colorants, mold release agents, charge control agents, inorganic fine particles, fluidity improvers, cleaning improvers, magnetic properties, and the like. Materials, metal soaps, and the like.

<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, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash 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 preferably include pigment reds such as PR122, PR269, PR238, PR146, and PR185; pigment yellows such as PY93, PY128, PY155, PY180, and PY74; PB15: 3 Pigment blue and the like. Among these, as a colorant used as a process color, a PY185 as a yellow pigment, PR122 as a magenta pigment, and PB15: 3 as a cyan pigment are preferably used in an amount of 30% or more of the colorant component from the viewpoint of color resistance.

  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. . A master batch pigment is preferably used as the colorant.

  As a particle size of the colorant in the colorant dispersion after the colorant dispersion, for example, 700 nm or less is preferable. When the particle diameter exceeds 700 nm, when a toner is produced, the image quality may be easily deteriorated, and in particular, the OHP light transmittance may be easily deteriorated. Preferably it is 400 nm or less, More preferably, it is 200 nm or less. It is known that the color resistance deteriorates as the particle size of the colorant becomes smaller. Preferably it is 30 nm or more, More preferably, it is 50 nm or more.

  The particle size of the colorant can be measured using, for example, a laser diffraction / scattering particle size distribution measuring apparatus (“LA-920”, manufactured by Horiba, Ltd.) using a laser light scattering method. The particle size of the colorant in the toner particles after granulation can be confirmed by observing the cross section of the toner by TEM observation. In this case, it is important to determine the pigment diameter from observation of at least 30 toner particles.

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

<Release agent>
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 hydrocarbon waxes and carbonyl group-containing waxes. Among these, hydrocarbon waxes are particularly preferable.

  Examples of the hydrocarbon wax include polyethylene wax, polypropylene wax, paraffin wax, and sazol wax. 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.

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, 50 degreeC or more is preferable, 60-160 degreeC is more preferable, 70-120 degreeC is still more preferable. If the melting point is less than 50 ° C., the wax may adversely affect the heat-resistant storage stability, and if it exceeds 160 ° C., cold offset may easily occur during fixing at a low temperature. The melt viscosity of the release agent is preferably 5 to 500 mPa · s, more preferably 10 to 100 mPa · s, 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 mPa · s, the releasability may be lowered, and if it exceeds 500 mPa · s, 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.

<Charge control agent>
The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferably, for example, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Examples thereof include a single substance or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative. These may be used individually by 1 type and may use 2 or more types together.

  Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, E-89 of a phenol-based condensate (both manufactured by Orient Chemical Industries); TP-302, TP-415 of a quaternary ammonium salt molybdenum complex (both manufactured by Hodogaya Chemical Co., Ltd.); Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, boron complex LR-147 (all manufactured by Nippon Carlit Co., Ltd.); quinacridone, azo pigment Sulfonate group, a carboxyl group, polymer compounds having a quaternary ammonium salt, and the like.

  The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with each component of the toner when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed to 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. 0.1-10 mass parts is preferable with respect to 0.2-5 mass parts. 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.

<Inorganic fine particles>
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 an alkyl fluoride group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. The content of the fluidity improver in the toner is preferably 0.3 to 1.3% by mass.

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, and includes, for example, fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and the like. 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.

  Hereinafter, materials used in the toner manufacturing method of the present invention and materials that may be used to improve manufacturing stability will be described.

<Organic solvent>
The solution or dispersion of the toner composition contains an organic solvent. That is, the toner composition is dissolved or dispersed in the organic solvent to prepare the dissolved or dispersed liquid. 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 composition, 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. Of volatile compounds such as toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Examples include ethyl acetate, 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 compositions, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.

<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.

<Resin fine particles>
The resin fine particles may be mixed in an aqueous medium in order to stabilize the granulated particles.
The resin fine particles are not particularly limited as long as they form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be thermoplastic resins. It may be a thermosetting resin, such as 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. Is mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from vinyl resins, polyurethane resins, epoxy resins, and polyester resins is preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.

  The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like. Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used. The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). ", Sanyo Chemical Industries, Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.

  The volume average particle diameter of the resin fine particles is preferably 5 to 500 nm, and more preferably 10 to 100 nm. When the volume average particle size is less than 5 nm, the molecular weight of the resin becomes small and heat resistant storage stability may be inferior. When the volume average particle size exceeds 500 nm, it does not adhere to the toner surface and the effect as dispersion stable particles cannot be obtained. Sometimes.

  Here, the volume average particle diameter of the resin fine particles is, for example, a laser scattering device (for example, LA-920 manufactured by Horiba, Ltd.), a dynamic light scattering device (for example, Microtrac UPA manufactured by Nikkiso Co., Ltd.), a field emission scanning type, or the like. It can be measured with an electron microscope (for example, S-4200 manufactured by Hitachi, Ltd.).

  The content of the resin fine particles in the toner is preferably 0.5% by mass or more, and more preferably 1.0 to 5.0% by mass. When the content of the resin fine particles is in the above range, a sufficient dispersion stabilizing effect of the resin fine particles can be obtained at the time of granulation, and a good particle size distribution can be obtained. When the content is less than 0.5% by mass, the content as a dispersion stabilizer is insufficient, so that sufficient dispersion stability by the resin fine particles cannot be obtained, and the particle size distribution of the toner may be deteriorated. . Here, the measurement of the content of the resin fine particles contained in the toner is not caused by the toner particles, for example, but the substance caused by the resin fine particles is analyzed by a pyrolysis gas chromatograph mass spectrometer and calculated from the peak area. Can be measured. As the detector, a mass spectrometer is preferable.

  The resin fine particles act as a dispersion stabilizer when the toner composition is dispersed or dissolved in an aqueous medium, and therefore advantageously acts when the particles are reduced in size or narrowed.

<Dispersant>
There is no restriction | limiting in particular as a 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, and S-113 (all manufactured by Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, and FC-98. FC-129 (both manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (both manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (both manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (both Chem Products Co., Ltd.); Footage F100, F150 (both manufactured by Neos) 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, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . 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); Unidyne DS-202 (manufactured by Daikin Industries, Ltd.), MegaFuck F-150 F-824 (all manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products); and Frantent 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 a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.

  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 monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like.

  Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like.

  Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate.

  Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds.

  Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride.

  Examples of homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

<Dispersion stabilizer>
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 salts. 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.

<Developer>
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected appropriately. 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 of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and image can be obtained even when the developing device is used (stirred) for a long time. In addition, in the case of the two-component developer using the toner of the present invention, even if the toner balance for a long time is performed, the fluctuation of the toner diameter in the developer is small, and it is good even for long-term stirring in the developing device. And stable developability can be obtained.

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

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, 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 (D50)) is less than 10 μm, in the distribution of carrier particles, the fine powder system increases, the magnetization per particle is lowered, and carrier scattering may occur. If the thickness exceeds 150 μm, the specific surface area may be reduced and toner scattering may occur. In the case of a full color with many solid portions, the reproduction of the solid portions may be particularly poor.

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

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

  The coating amount of the resin layer on the carrier is preferably 0.01 to 5.0% by mass. When the amount is less than 0.01% by mass, it may not be possible to form the uniform resin layer on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes too thick. As a result, 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 contains the toner of the present invention, it is possible to stably form a high-quality image with excellent charging performance during image formation. The developer can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component developing method, a non-magnetic one-component developing method, and a two-component developing method, and the toner-containing container of the present invention described below. It can be particularly suitably used for a process cartridge, an image forming apparatus, and an image forming method.

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

<Process cartridge>
The process cartridge of the present invention forms a visible image by developing an electrostatic latent image carrier carrying an electrostatic latent image and developing the electrostatic latent image carried on the electrostatic latent image carrier with a developer. The developing device is configured to be connected at least integrally, and may be configured such that other means appropriately selected as necessary are integrally connected. The developing device includes a developer container that contains the toner or developer according to 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 mounted on various electrophotographic image forming apparatuses, and is preferably detachably mounted on the image forming apparatus of the present invention described later.

  Here, for example, as shown in FIG. 2, the process cartridge incorporates an electrostatic latent image carrier 101 that is a drum-shaped photosensitive member, and includes an electrostatic latent image carrier 101, a charging unit 102, and a developing device. 104, the transfer unit 108, and the cleaning unit 107 are integrally connected and detachably attached to the image forming apparatus. In the process cartridge according to the present invention, a structure in which the electrostatic latent image carrier 101 and at least the developing device 104 are integrally connected is sufficient, and it is possible to have other means if necessary. is there. In FIG. 2, reference numeral 103 denotes exposure by exposure means, and 105 denotes a recording medium.

  Next, the image forming process using the process cartridge shown in FIG. 2 will be described. The electrostatic latent image carrier 101 is rotated by the charging means 102 while rotating in the direction of the arrow, and the exposure 103 by the exposure means (not shown). An electrostatic latent image corresponding to the exposure image is formed on the surface. This electrostatic latent image is developed into a toner image with toner supplied from the developing roller 104 a of the developing device 104. The obtained visible image, which is a toner image, is transferred to the recording medium 105 by the transfer unit 108 and printed out. Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by the cleaning unit 107, further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

<Image Forming Method and Image Forming Apparatus>
The image forming method of the present invention includes at least the above-described electrostatic latent image forming step, development step, transfer step, and fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, Includes cleaning process, recycling process, control process, etc.

  The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing device, 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 process)
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier. The electrostatic latent image carrier (hereinafter, also referred to as “electrophotographic photoreceptor”, “photoreceptor”, “image carrier”) is particularly limited in terms of material, shape, structure, size, and the like. However, it can be suitably selected from known ones, and the shape thereof is preferably a drum shape, and examples of the material thereof include inorganic photoreceptors such as amorphous silicon and selenium, polysilane, phthalopolymethine and the like. Organic photoreceptors, and the like. Among these, amorphous silicon or the like is preferable in terms of long life.

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

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

(Development process and development device)
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 device.

  The developing device 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 developer capable of bringing the toner or the developer into contact or non-contact with the electrostatic latent image is provided. Etc. are more preferable.

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

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

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

(Transfer process and transfer means)
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable. The transfer can be performed, for example, by charging the electrostatic latent image carrier (photoconductor) with the transfer charger using the visible image, 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 and 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 device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this. There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The heating in the heating and pressurizing means is preferably 80 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.

(Static elimination process and static elimination means)
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.

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

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

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

(Image formation by the image forming apparatus)
One mode of carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 3 includes a photosensitive drum 10 as the electrostatic latent image carrier, a charging roller 20 as the charging unit, an exposure device 30 as the exposure unit, and a developing device. A developing device 40, an intermediate transfer member 50, a cleaning device 60 as the cleaning unit having a cleaning blade, and a static elimination lamp 70 as the static elimination unit.

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

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

  In the image forming apparatus 100 shown in FIG. 3, for example, the charging roller 20 uniformly charges the photosensitive drum 10. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 4 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 3, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and the like around the photoconductor 10. Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 4, the same components as those in FIG. 3 are denoted by the same reference numerals.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 5 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

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

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

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

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); A charging device 160 for uniformly charging the electrostatic latent image carrier 10 and exposing the electrostatic latent image carrier for each color image based on each color image information (reference numeral L in FIG. 6) And an exposure device for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and the electrostatic latent image for each color toner (black toner, yellow toner, magenta toner, and cyan toner). ) A developing device 61 for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, and a static eliminator 64. Each single-color image (black image, yellow image, magenta image, and cyan image) can be formed based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

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

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

  In the image forming apparatus and the image forming method of the present invention, since the above-described toner according to the present invention, which has various properties such as fluidity and fixability and has both excellent low-temperature fixability and heat-resistant storage stability, is used. Can be obtained efficiently.

  An electrostatic charge image developing toner according to an embodiment of the present invention will be described based on examples and comparative examples. The binder resin of the toner used in each of the examples and comparative examples is a polyester copolymer (manufactured by DIC, glass transition point 63.0 ° C., weight average molecular weight (Mw) 12000) as the binder resin A. ), As the binder resin B, a polyester copolymer (manufactured by DIC, glass transition point 63.0 ° C., weight average molecular weight (Mw) 25000) was used.

[Example 1]
(Preparation of master batch (MB))
P. B. After kneading 500 parts by mass of 15: 3 (manufactured by Toyo Ink Co., Ltd.) and 500 parts by mass of the binder resin A with a two roll at 150 ° C. for 30 minutes, the mixture was cooled by cooling and pulverized with a pulverizer (manufactured by Hosokawa μm). A cyan master batch (hereinafter referred to as cyan MB) was prepared.

  Similarly, the pigment blue P.I. B. Magenta masterbatch (hereinafter referred to as magenta MB) prepared by mixing 15: 3 with Pigment Red (PR 122 and PR 269 (both manufactured by DIC)) at 3: 7 to form a magenta colorant, Pigment Yellow P. Y. 74 (manufactured by Clariant) and pigment yellow P.I. Y. 185 (manufactured by BASF) was mixed at 5: 5 to prepare a yellow masterbatch (hereinafter referred to as yellow MB) as a yellow colorant.

(Synthesis of ketimine (the active hydrogen group-containing compound))
Into a reaction vessel equipped with a stirrer and a thermometer, 30 parts by mass of isophoronediamine and 70 parts by mass of methyl ethyl ketone are charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound). did. The amine value of the obtained ketimine compound (the active hydrogen machine-containing compound) was 423.

(Dissolution of toner composition or preparation of dispersion)
In a beaker, 88.5 parts by mass of the binder resin A, 2.5 parts by mass of a polyfunctional monomer mixture (KAYARAD DPHA-2C, manufactured by Nippon Kayaku Co., Ltd.), bisphenol A. 5 parts by mass of EO adduct diacrylate (KAYARAD R-551, manufactured by Nippon Kayaku Co., Ltd.) and 100 parts by mass of ethyl acetate were added and stirred to dissolve. Next, 5 parts by mass of paraffin wax (molecular weight = 1,800, acid value = 2.5 mg KOH / g, penetration = 1.5 mm (40 ° C.), melting point 86 ° C.) and 8 parts by mass of cyan MB were charged. Using a bead mill ("Ultra Visco Mill", manufactured by Imex Co., Ltd.), the raw material is passed through 3 passes under the condition that the liquid feeding speed is 1 kg / hr, the disk peripheral speed is 6 m / s, and the diameter of 0.5 mm zirconia beads is 80% by volume. A solution was prepared, and 2.7 parts by mass of the ketimine was added and dissolved to prepare a toner composition solution or dispersion.

  Similarly, a magenta toner composition solution or dispersion in which 8 parts by mass of cyan MB is 15 parts by mass of magenta MB, and a solution or dispersion of yellow toner composition in which 8 parts by mass of cyan MB are 16 parts by mass of yellow MB are prepared. Prepared. In addition, the amount of the binder resin A was adjusted to be the same prescription amount for each color according to the mixing amount of the master batch.

(Preparation of resin fine particle emulsion)
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by weight of water, 11 parts by weight of sodium salt of an ethylene oxide adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 79 parts by weight of styrene , 79 parts by weight of methacrylic acid, 105 parts by weight of butyl acrylate, 13 parts by weight of divinylbenzene, and 1 part by weight of ammonium persulfate were stirred and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to vinyl resin (a copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) An aqueous dispersion (fine particle dispersion) was obtained. When the obtained fine particle dispersion was measured with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.), the volume average particle size was 105 nm. A part of the fine particle dispersion was dried to isolate the resin component. The resin component had a glass transition temperature (Tg) of 95 ° C., a number average molecular weight of 140,000, and a weight average molecular weight of 980,000.

(Preparation of aqueous medium phase)
Aqueous medium phase was prepared by mixing and stirring 306 parts by mass of ion-exchanged water, 60 parts by mass of the fine particle dispersion, and 4 parts by mass of sodium dodecylbenzenesulfonate, and dissolving them uniformly.

(Emulsification or preparation of dispersion)
150 parts by mass of the aqueous medium phase is put in a container, and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), in which 100 parts by mass of the toner composition is dissolved or dispersed. Part was added and mixed for 10 minutes to prepare an emulsified or dispersed liquid (emulsified slurry).

(Removal of organic solvent and radiation crosslinking)
In a Kolben equipped with a stirrer and a thermometer, 100 parts by mass of the emulsified slurry was charged, and after desolvation at 30 ° C. for 3 hours while stirring at a stirring peripheral speed of 20 m / min (the solid content concentration of the particles at this time is (95% by mass) The electron beam was irradiated so that the total irradiation amount was 5 Mrad. The solid content concentration was determined in advance by confirming the relationship between the solvent removal time and the particle solid content. Further, the solvent was removed at 30 ° C. for 10 hours while stirring at a stirring peripheral speed of 20 m / min.

(Washing and drying)
After 100 parts by mass of the emulsified slurry are filtered under reduced pressure, 100 parts by mass of ion-exchanged water is added to the filter cake and mixed with a TK type homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd. for 10 minutes at a rotational speed of 12,000 rpm). And then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. To the obtained filter cake, 20 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. Furthermore, 20 mass parts of 10 mass% hydrochloric acid was added to the obtained filter cake, mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes) and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filtered twice to obtain a final filter cake. The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours, and sieved with a mesh opening of 75 μm, and toner base particles of yellow (Y), magenta (M), and cyan (C) of Example 1 were used. Got. The volume average particle diameter of the obtained particles was 5.5 μm, aiming at 5.5 μm.

[Example 2]
(Dissolution of toner composition or preparation of dispersion)
In a beaker, 91.0 parts by mass of the binder resin A, 2.5 parts by mass of a polyfunctional monomer mixture (KAYARAD DPHA-2C, manufactured by Nippon Kayaku Co., Ltd.), bisphenol A. 2.5 parts by mass of EO adduct diacrylate (KAYARAD R-551, manufactured by Nippon Kayaku Co., Ltd.) and 100 parts by mass of ethyl acetate were added and stirred to dissolve. Next, 5 parts by mass of paraffin wax (molecular weight = 1,800, acid value = 2.5 mg KOH / g, penetration = 1.5 mm (40 ° C., melting point 86 ° C.)) and 8 parts by mass of cyan MB were charged, and bead mill ("Ultra Viscomill", manufactured by IMEX Co., Ltd.) is used to dissolve the raw material in 3 passes under the condition that the liquid feeding speed is 1 kg / hr, the disk peripheral speed is 6 m / s, and 80% by volume of 0.5 mm zirconia beads are filled. A liquid was prepared, and 2.7 parts by mass of the ketimine was added and dissolved to prepare a toner composition solution or dispersion.

  Similarly, a magenta toner composition solution or dispersion liquid in which cyan MB was 15 parts by mass of magenta MB, and a yellow toner composition solution or dispersion liquid in which cyan MB was 16 parts by mass of yellow MB were prepared. The Y, M, and C toner base particles of Example 2 were prepared in the same manner as in Example 1 except that the amount of binder resin A was adjusted to be the same prescription amount for each color by the mixing amount of the master batch. Obtained. The obtained particles had a volume average particle size of 5.5 μm, aimed at 5.5 μm.

Example 3
(Dissolution of toner composition or preparation of dispersion)
In a beaker, 93.5 parts by mass of the binder resin B, 1.5 parts by mass of a polyfunctional monomer mixture (KAYARAD DPHA-2C, manufactured by Nippon Kayaku Co., Ltd.), bisphenol A. 1.0 part by mass of EO adduct diacrylate (KAYARAD R-551, manufactured by Nippon Kayaku Co., Ltd.) and 100 parts by mass of ethyl acetate were added and dissolved by stirring. Next, 5 parts by mass of paraffin wax (molecular weight = 1,800, acid value = 2.5 mg KOH / g, penetration = 1.5 mm (40 ° C., melting point 86 ° C.)) and 8 parts by mass of cyan MB were charged, and bead mill ("Ultra Viscomill", manufactured by IMEX Co., Ltd.) is used to dissolve the raw material in 3 passes under the condition that the liquid feeding speed is 1 kg / hr, the disk peripheral speed is 6 m / s, and 80% by volume of 0.5 mm zirconia beads are filled. A liquid was prepared, and 2.7 parts by mass of the ketimine was added and dissolved to prepare a toner composition solution or dispersion.

(Removal of organic solvent and radiation crosslinking)
In a Kolben equipped with a stirrer and a thermometer, 100 parts by mass of the emulsified slurry was charged, and after desolvation at 30 ° C. for 1 hour while stirring at a stirring peripheral speed of 20 m / min (the solid content concentration of the particles at this time is 82 mass%) The electron beam was irradiated so that the total irradiation amount was 5 Mrad. The solid content concentration was determined in advance by confirming the relationship between the solvent removal time and the particle solid content. Further, Y, M, and C toner base particles of Example 3 were obtained in the same manner as in Example 1 except that the solvent was removed at 30 ° C. for 10 hours while stirring at a stirring peripheral speed of 20 m / min. The volume average particle size of the obtained particles was 5.8 μm, targeting 5.5 μm.

[Comparative Example 1]
(Synthesis of unmodified polyester (low molecular polyester))
In a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, and dibutyltin 2 parts by mass of oxide was added and allowed to react at 230 ° C. for 8 hours under normal pressure. Next, the reaction solution was reacted for 5 hours under a reduced pressure of 10 to 15 mmHg to synthesize an unmodified polyester. The obtained unmodified polyester had a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 5,600, and a glass transition temperature (Tg) of 55 ° C.

(Preparation of master MB)
1,000 parts by weight of water; B. 540 parts by mass of 15: 3 (manufactured by Toyo Ink Co., Ltd.) and 1,200 parts by mass of the unmodified polyester were mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded with a two-roller at 150 ° C. for 30 minutes, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa μm) to prepare cyan MB.

  Similarly, the above-mentioned P.I. B. 15: 3 and P.I. R. 122 and P.I. R. 269 (both manufactured by DIC) at a ratio of 3: 7 to obtain a magenta colorant. Y. 74 (manufactured by Clariant) and P.I. Y. 185 (manufactured by BASF) was mixed at 5: 5 to prepare yellow MB as a yellow colorant.

(Synthesis of urea-modified polyester)
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, 22 parts by mass of merit 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 obtained intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,600, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl group. The value was 49 mgKOH / g.

  Next, 411 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 are heated at 100 ° C. for 5 hours. By reacting, a urea-modified polyester (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized. The free isocyanate content of the obtained urea-modified polyester was 1.60% by mass, and the solid content concentration of the urea-modified polyester (after standing at 150 ° C. for 45 minutes) was 50% by mass.

(Dissolution of toner composition or preparation of dispersion)
In a beaker, 15 parts by mass of the urea-modified polyester, 60 parts by mass of the unmodified polyester, and 100 parts by mass of ethyl acetate were stirred and dissolved. Next, 10 parts by mass of carnauba wax (molecular weight = 1,800, acid value = 2.5 mg KOH / g, penetration = 1.5 mm (40 ° C., melting point 86 ° C.)) and 8 parts by mass of cyan MB were charged. Using a bead mill ("Ultra Visco Mill", manufactured by Imex Co., Ltd.), the raw material is passed through 3 passes under the condition that the liquid feeding speed is 1 kg / hr, the disk peripheral speed is 6 m / s, and the diameter of 0.5 mm zirconia beads is 80% by volume. A solution was prepared, and 2.7 parts by mass of the ketimine was added and dissolved to prepare a cyan toner composition solution or dispersion.

  Similarly, a magenta toner composition solution or dispersion with cyan MB as magenta MB 15 parts by mass and a yellow toner composition solution or dispersion with cyan MB as yellow MB 20 parts were prepared.

(Preparation of resin fine particle emulsion)
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by weight of water, 11 parts by weight of sodium salt of an ethylene oxide adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 79 parts by weight of styrene , 79 parts by weight of methacrylic acid, 105 parts by weight of butyl acrylate, 13 parts by weight of divinylbenzene, and 1 part by weight of ammonium persulfate were stirred and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to vinyl resin (a copolymer of sodium salt of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate) An aqueous dispersion (fine particle dispersion) was obtained. When the obtained fine particle dispersion was measured with a laser diffraction particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.), the volume average particle size was 105 nm. A part of the fine particle dispersion was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 95 ° C., the number average molecular weight (Mn) 140,000, and the weight average molecular weight (Mw) 980,000.

(Preparation of aqueous medium phase)
Aqueous medium phase was prepared by mixing and stirring 306 parts by mass of ion-exchanged water, 60 parts by mass of the fine particle dispersion, and 4 parts by mass of sodium dodecylbenzenesulfonate, and dissolving them uniformly.

(Emulsification or preparation of dispersion)
150 parts by mass of the aqueous medium phase is put in a container, and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Mass parts were added and mixed for 10 minutes to prepare an emulsified or dispersed liquid (emulsified slurry).

(Removal of organic solvent)
100 parts by mass of the emulsified slurry was charged in a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min.

(Washing 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 and mixed with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) for 10 minutes at 12,000 rpm. ) And then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. To the obtained filter cake, 20 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. Furthermore, 20 mass parts of 10 mass% hydrochloric acid was added to the obtained filter cake, mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes) and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filtered twice to obtain a final filter cake. The obtained final filter cake was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh having a mesh size of 75 μm to obtain Y, M, and C toner base particles of Comparative Example 1. The obtained particles had a volume average particle size of 5.5 μm, aimed at 5.5 μm.

[Comparative Example 2]
Comparative Example 1 except that 15 parts by mass of urea-modified polyester was changed to 5 parts by mass and 60 parts by mass of the unmodified polyester were changed to 70 parts by mass in “Dissolution of toner composition or preparation of dispersion” in Comparative Example 1. In the same manner, Y, M, and C toner base particles of Comparative Example 2 were produced. The obtained particles had a volume average particle size of 5.5 μm, aimed at 5.5 μm.

[Comparative Example 3]
Comparative Example 1 is the same as Comparative Example 1 except that 15 parts by mass of the urea-modified polyester is changed to 2 parts by mass and 60 parts by mass of the unmodified polyester is changed to 73 parts by mass in “Dissolution of toner composition or preparation of dispersion” in Comparative Example 1. In the same manner, Y, M, and C toner base particles of Comparative Example 3 were produced. The volume average particle diameter of the obtained particles was 5.5 μm, aiming at 5.5 μm.

[Comparative Example 4]
The toner base particles of Y, M, and C of Comparative Example 4 were prepared in the same manner as in Example 1 except that the electron beam irradiation of Example 1 was performed immediately after the emulsification or dispersion preparation. The volume average particle diameter of the obtained particles was 5.5 μm, aiming at 5.5 μm. The solid content of the particles immediately after preparation was 76% by mass.

[Comparative Example 5]
The toner base particles of Y, M, and C of Comparative Example 5 are the same as Example 1 except that the electron beam irradiation of Example 1 is carried out after the preparation of the emulsified or dispersed liquid and after desolvation at 30 ° C. for 12 hours. Was made. The volume average particle diameter of the obtained particles was 5.5 μm, aiming at 5.5 μm. In addition, solid content of the particle | grains which removed the solvent for 12 hours at 30 degreeC after preparation was 98 mass%.

[Comparative Example 6]
In Example 1, “Dissolution of toner composition or preparation of dispersion”, except that 88.5 parts by mass of binder resin A was changed to 96 parts by mass, and 2.5 parts by mass of the mixture of radiation crosslinking monomers was changed to 0 parts by mass. In the same manner as in Example 1, Y, M, and C toner base particles of Comparative Example 6 were prepared. The volume average particle size of the obtained particles was 7.0 μm, aiming at 5.5 μm.

[Comparative Example 7]
In Example 1 "Dissolution of toner composition or preparation of dispersion liquid", 88.5 parts by mass of binder resin A was changed to 86.0 parts by mass, and 2.5 parts by mass of the mixture of polyfunctional monomers was changed to 5 parts by mass, respectively. Except that, Y, M, and C toner base particles of Comparative Example 7 were produced in the same manner as in Example 1. The volume average particle diameter of the obtained particles was 5.5 μm, aiming at 5.5 μm.

[Comparative Example 8]
In Example 1 “Dissolution of toner composition or preparation of dispersion”, 88.5 parts by mass of binder resin A is 96 parts by mass, 2.5 parts by mass of a mixture of polyfunctional monomers is 1.0 part by mass, and bisphenol A. . Y, M, and C toner base particles of Comparative Example 8 were produced in the same manner as in Example 1 except that 5 parts by mass of EO adduct diacrylate was changed to 1.0 part by mass. The volume average particle diameter of the obtained particles was 6.5 μm, aiming at 5.5 μm.

[Addition of external additives to toner base particles]
1.0 part by mass of hydrophobic silica (“H2000”, manufactured by Clariant Japan) as an external additive is added to 100 parts by mass of the obtained toner base particles of Examples 1 to 3 and Comparative Examples 1 to 8 in a Henschel mixer. (Mitsui Mining Co., Ltd.), 5 cycles of mixing for 30 seconds at a peripheral speed of 30 m / s and resting for 1 minute, sieving with a mesh of 35 μm, each toner of Examples 1 to 3 and Comparative Examples 1 to 8 Was made.

<Measurement of toner volume average particle size and particle size distribution>
The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner are measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm, and analysis software (Beckman Coulter Multisizer) is used. 3 Version 3.51). Specifically, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a glass 100 ml beaker, and 0.5 g of each toner is added to make microscopic. The mixture was stirred with a spatula, and then 80 ml of ion exchange water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

  In this experiment, since the target of the volume average particle size is set to 5.5 μm, the volume average particle size is determined to be ◯ if the volume average particle size is 5.4 to 5.6 μm, and the others are determined to be ×, and the particle size distribution (Dv / Dn) is 1. .. Less than 2 is judged as ◯.

<Measurement of glass transition temperature of toner>
The glass transition temperature of the toner was measured by the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, 10 mg of toner was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample was left at 150 ° C. for 10 minutes, and the sample was cooled to room temperature and left for 10 minutes. Then, the DSC curve was measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a heating 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. did.

<Heat resistant storage stability (Penetration)>
Each toner was filled in a 50 ml glass container and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JIS K2235-1991) and evaluated based on the following criteria. In addition, it shows that heat-resistant storage stability is excellent, so that the said penetration value is large, and when a penetration is 5 mm or less, possibility that a problem in use will generate | occur | produce is high.

(Evaluation criteria)
○: Needle penetration 15 mm or more Δ: Needle penetration 5 mm or more and less than 15 mm ×: Needle penetration less than 5 mm

[Creation of carrier]
To 100 parts by mass of toluene, 100 parts by mass of a silicone resin (“organostraight silicone”), 5 parts by mass of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by mass of carbon black are added. A coating layer forming solution was prepared by dispersing for a minute. The obtained coating layer forming liquid was coated on the surface of 1,000 parts by mass of spherical magnetite having a particle diameter of 50 μm using a fluid bed type coating apparatus to produce a magnetic carrier.

[Production of developer]
5 parts by mass of each of the toners of Examples 1 to 3 and Comparative Examples 1 to 8 after the external additive treatment and 95 parts by mass of the carrier were mixed by a ball mill, and each of Examples 1 to 13 and Comparative Examples 1 to 5 were mixed. A component developer was prepared. Using each developer thus obtained, fixability (offset generation temperature and minimum fixing temperature) and heat-resistant storage stability were evaluated as follows. The results are shown in Table 1.

<Image quality evaluation (fixing temperature range, glossiness, color characteristics evaluation)>
A device that has been tuned so that the temperature and linear velocity can be adjusted by removing the silicone oil application mechanism from the fixing unit of the tandem color image forming apparatus (“Imagio Neo C350”, manufactured by Ricoh) and remodeling it to an oilless fixing system. The fixing properties (offset non-occurrence temperature and fixing lower limit temperature) were evaluated using art paper (Tokuhishi Art Double Side, manufactured by Mitsubishi Paper Industries Co., Ltd.). The tandem color image forming apparatus can continuously print 35 sheets of A4 size paper per minute. At this time, the linear velocity of the fixing roller was set to 125 mm / s, and the evaluation was performed by changing the roller temperature.

-Fixing temperature range-
For image formation, the solid image of each single color of yellow, magenta, cyan, and black is printed on the plain paper using the tandem-type color electrophotographic apparatus in a single color of 0.85 ± 0.3 mg / cm ² . The toner was adjusted so as to be developed. The obtained image is fixed by changing the temperature of the heating roller, and after fixing the obtained fixed image with a dedicated cloth pad, a fixing roll temperature at which the residual ratio of the image density becomes 70% or more, The fixing temperature at which offset occurs (offset generation temperature) was measured and evaluated based on the following criteria.

(Fixing temperature range evaluation criteria)
A: 40 ° C. or more Δ: Less than 40 ° C. 30 ° C. or more

(Maximum gloss evaluation criteria)
◎: 40 or more Δ: less than 40 20 or more x: less than 20

-Color characteristic evaluation-
Image formation is performed using the tandem-type color electrophotographic apparatus with a single solid color image of 0.40 ± 0.3 mg / cm ² for each single color of yellow, magenta, cyan, and black on the art paper. The toner was adjusted so as to be developed. The temperature of the heating roller was set to the temperature at which the maximum glossiness was obtained in cyan in the fixing temperature range evaluation, and the color characteristics of the output image were measured by X-Rite. The saturation c * was calculated as c * = √ (a * ² + b * ² ). ) The greater the saturation c *, the higher the color reproducibility.

(Color reproducibility evaluation standard (c *))
Yellow (Y)
A: 100 or more Δ: Less than 100 95 or more x: Less than 95 Magenta (M)
A: 76 or more Δ: Less than 76 72 or more ×: Less than 72 Cyan (C)
A: 62 or more Δ: Less than 62 60 or more: Less than 60, and the result of the color with the lowest evaluation was determined as the overall result.

  As is apparent from the results in Table 1 above, when urea-modified polyester was used as the binder resin shown in Comparative Examples 1 and 2, a large amount of gel was generated, the maximum glossiness and saturation were poor, and good image quality was achieved. No toner image can be obtained. In the case where urea modified polyester and unmodified polyester are used as the binder resin shown in Comparative Example 3, although the gel amount is reduced, the heat resistant storage stability is poor. In addition, when the electron beam irradiation shown in Comparative Example 4 is just after the preparation of the emulsification or dispersion and the solid content concentration is 76% by mass, a gel is generated and the maximum glossiness and saturation are poor, and a toner image with good image quality. Can't get. In the case where the electron beam irradiation of Comparative Example 5 was subjected to solvent removal treatment at 30 ° C. for 12 hours after emulsification or dispersion preparation, the solid concentration was as high as 96% by mass, and therefore the penetration was 0 mm and heat resistant storage stability. In addition, gel is generated and the maximum glossiness and saturation are poor, and a toner image with good image quality cannot be obtained. In the thing which is not using the radiation crosslinking monomer of the comparative example 6, a particle size will become larger than the target. In Comparative Example 7, when the amount of the radiation crosslinking monomer used is as large as 10% by mass, the maximum glossiness and saturation are poor, and a toner image with good image quality cannot be obtained. When the amount of the radiation crosslinking monomer used in Comparative Example 8 is as small as 2% by mass, the heat-resistant storage stability is poor, the maximum glossiness and the saturation are poor, and a good quality toner image cannot be obtained.

  On the other hand, in each of the examples according to the present invention, the heat resistant storage stability is good, the fixing temperature range is large, and good offset resistance is exhibited. It is clear that both toner images are good and a good quality toner image is obtained.

10 Electrostatic latent image carrier (photosensitive drum)
10K Black electrostatic latent image carrier 10Y Yellow electrostatic latent image carrier 10M Magenta electrostatic latent image carrier 10C Cyan electrostatic latent image carrier 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 belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling body 34 Second Traveling body 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Development roller 44Y Development roller 4 M Developing 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 Manual feed path 54 Manual tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Charger lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 101 Photoconductor 102 Charging means 103 Exposure 104 Developing means 105 Recording medium 107 Cleaning means 108 Transfer means 120 Tandem developer 121 Heating roller 122 Fixing roller 123 Fixing belt 124 Pressure roller 125 Heating source 126 Cleaning roller 12 Temperature sensor 130 Document base 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Carriage roller 148 Paper feed path 150 Copier main body 160 Charging device 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF) )

US Pat. No. 2,297,691 Japanese Patent Publication No.42-23910 Japanese Patent Publication No.43-24748 Japanese Patent No. 3486707 Japanese Patent No. 3640918

Claims (12)

A step of dissolving or dispersing a toner composition containing at least a binder resin and a radiation-crosslinking monomer compatible with the binder resin in an organic solvent to form a solution or dispersion; and the solution or dispersion Is added to an aqueous medium and emulsified or dispersed to prepare an emulsion or dispersion, and the organic solvent is removed from the emulsion or dispersion to crosslink the radiation crosslinking monomer. In the method for producing a developing toner,
The radiation crosslinking monomer is contained in the toner composition in a mass ratio of binder resin: radiation crosslinking monomer = 92.5: 7.5 to 97.5: 2.5 by mass ratio;
After removing the organic solvent from the emulsion or dispersion and granulating, the radiation crosslinking monomer is subjected to radiation crosslinking at the time of desolvation in which the solid content concentration of the obtained particles is in the range of 80% by mass to 95% by mass. A method for producing a toner for developing an electrostatic charge image. The method for producing a toner for developing an electrostatic charge image according to claim 1,
The method for producing a toner for developing an electrostatic charge image, wherein the toner composition contains a colorant or a release agent. The method for producing a toner for developing an electrostatic charge image according to claim 1,
The method for producing a toner for developing an electrostatic charge image, wherein the toner composition contains a colorant and a release agent. In the manufacturing method of the electrostatic charge image development toner according to any one of claims 1 to 3.
A method for producing a toner for developing an electrostatic charge image, wherein the binder resin is a polyester resin.   An electrostatic image developing toner produced by the method for producing an electrostatic image developing toner according to claim 1. In the electrostatic image developing toner according to claim 5,
The electrostatic charge characterized in that the binder resin has a resin having a weight average molecular weight (Mw) of 10,000 to 25,000 and a crosslinked product having a molecular weight of 50,000 or more obtained by radiation-crosslinking the radiation crosslinking monomer. Toner for image development. In the electrostatic image developing toner according to claim 5 or 6,
The electrostatic charge image developing toner has a volume average particle diameter (Dv) of 4 μm or more and 6 μm or less, and a volume average particle diameter (Dv) / number average particle diameter (Dn) of less than 1.25. Toner for developing electrostatic images.   A developer comprising the electrostatic image developing toner according to claim 5.   8. A toner-containing container, wherein the electrostatic image developing toner according to claim 5 is contained in the container. In an image forming apparatus comprising an electrostatic latent image carrier and a developing device that supplies toner to the electrostatic latent image formed on the electrostatic latent image carrier to convert the electrostatic latent image into a toner image ,
An image forming apparatus, wherein the toner is an electrostatic image developing toner according to claim 5. An electrostatic latent image carrier and a developing device that supplies toner to the electrostatic latent image formed on the electrostatic latent image carrier and converts the electrostatic latent image into a toner image are connected at least integrally. In the process cartridge,
The process cartridge according to claim 5, wherein the toner supplied from the developing device to the electrostatic latent image is the electrostatic image developing toner according to claim 5. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, a developing step of supplying toner to the electrostatic latent image to convert the electrostatic latent image into a toner image, and the toner In an image forming method comprising a step of transferring an image to a recording medium, and a step of fixing a toner image transferred onto the recording medium.
The image forming method according to claim 5, wherein the toner is an electrostatic image developing toner according to claim 5.

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