JP2015059947A - Toner for electrophotography and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner excellent in low-temperature fixability and heat-resistant storage property.SOLUTION: There is provided a toner having resin fine particles arranged on the surface of each of toner base particles including at least a binder resin, mold release agent, and colorant, where the value of the storage modulus G'A(Pa) of the toner in the first temperature increasing step satisfies the following condition; the value of the storage modulus G'B(Pa) of the resin fine particles in the first temperature increasing step satisfies the following condition; and the relationship between G'A and G'B satisfies the following condition. The storage modulus G'A(60) of the toner in the first temperature increasing step of 60°C: G'A(60):5.0×10<G'A(60)<5.0×10; the storage modulus G'B(60) of the resin fine particles in the first temperature increasing step of 60°C: 1.0×10<G'B(60)<1.0×100; and G'B(60)-G'A(60)≤5.0×10.

Description

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

  In an image forming apparatus such as an electrophotographic apparatus or an electrostatic recording apparatus, a toner image is formed by attaching toner to an electrostatic latent image formed on a photoreceptor, and then the toner image is transferred to a recording medium and heated. To fix. When forming a full-color image, generally, toners of four colors of black, yellow, magenta, and cyan are used to superimpose toner images of respective colors on a recording medium and then fixed by heating. Such toners are required to have low-temperature fixability and heat-resistant storage with the development of electrophotographic technology. In response to these requirements, the binder resin has been reduced in viscosity, but it has problems such as reduced heat-resistant storage stability of the toner and carrier spent in the developing unit during long-term running, resulting in reduced charge. It was.

In recent years, a technique using a crystalline resin and an amorphous resin as a binder resin has been disclosed (Patent Document 1; JP 2005-234046 A, Patent Document 2; JP 2013-050578 A). Has been.
However, these toners mainly use crystalline polyester as a crystalline resin and are compatible with the heat history at the time of fixing and exhibit low-temperature fixability, but high temperature offset is not considered. .
For high temperature offset, for example, a large amount of a release agent is added or a polymer material is used.
However, when the release agent is increased, the release agent exposed on the surface causes aggregation of toners under high temperature and high humidity, or fusion with a carrier, a regulation blade, or the like during long-term running, resulting in a decrease in charge. Further, when a prepolymer is used, the gloss is lowered, the color developability and saturation of the secondary color due to color toner superposition and the like are lowered, and the color reproducibility of the toner is deteriorated.

Japanese Patent Application Laid-Open No. 2005-227672 of Patent Document 3 discloses a toner containing a crystalline resin as a main component for realizing low-temperature fixability and heat-resistant storage stability of toner.
However, although it is said that low temperature fixability can be achieved by using a crystalline resin as a main component, the crystalline resin has time to recrystallize after heating, and therefore has time to cool and solidify after fixing. As a result, there are problems such as soiling the lining of the paper that is overlaid after the paper is discharged, and soiling the conveying member that comes into contact with the paper after fixing.

In order to impart low-temperature fixability, studies have been made to improve the toner base surface. For example, Japanese Patent Application Laid-Open No. 2012-159595 of Patent Document 4 discloses a core in which resin fine particles having a specific particle size and particle size distribution are arranged on the surface by aqueous granulation to achieve both fixing property and heat resistance. Techniques have been proposed that include producing toner having a shell structure.
However, it is not easy to control complicated toner characteristics only by the particle size and particle size distribution of resin fine particles. Japanese Patent Application Laid-Open No. 2006-251359 of Patent Document 5 uses low-temperature fixability and anti-blocking properties by using two types of resin fine particles having a large molecular weight and a small molecular weight in combination and keeping the molecular weight within a certain range. A technique for achieving compatibility is proposed. However, it is difficult to control the toner characteristics only by the molecular weight.

  Furthermore, in Japanese Patent No. 4049679 of Patent Document 6, the resin fine particles are polyester, both the molecular weight and the particle diameter are within a certain range, and the glass transition temperature (Tg) and acid value ( It is disclosed that the fixing property and the storage property can be compatible by setting AV) within a certain range. However, there is still room for improvement in heat resistant storage stability and blocking resistance, and it is desirable to further improve the granulation properties for forming toner base particles.

  The present invention has been made in view of the above, and an object thereof is to provide a toner having excellent low-temperature fixability and heat-resistant storage stability.

The above-mentioned problem is (1) “a toner in which resin fine particles are arranged on the surface of toner base particles containing at least a binder resin, a release agent, and a colorant. The value of the elastic modulus G′A (Pa) satisfies the following conditions, and the value of the storage elastic modulus G′B (Pa) of the resin fine particles at the first temperature increase satisfies the following conditions, and G′A A toner wherein the relationship of G′B satisfies the following conditions.
Storage elastic modulus G′A (60) of toner at first temperature rise of 60 ° C .:
5.0 × 10 ^ 5 <G′A (60) <5.0 × 10 ^ 6
Storage elastic modulus G′A (100) of toner at first temperature rise of 100 ° C .:
1.0 × 10 ^ 4 <G′A (100) <1.0 × 10 ^ 5
Storage elastic modulus G′B (60) of resin fine particles at 60 ° C. for the first temperature increase:
1.0 × 10 ^ 7 <G′B (60) <1.0 × 10 ^ 10
Storage elastic modulus G′B (100) of resin fine particles at 100 ° C. for the first temperature increase:
1.0 × 10 ^ 4 <G′B (100) <1.0 × 10 ^ 6
G′A (60) −G′B (60) ≦ 5.0 × 10 ^ 9
It is solved by G′A (100) −G′B (100) ≦ 5.0 × 10 ^ 5 ”.

  As will be understood from the following detailed and specific description, according to the present invention, an extremely excellent effect of providing a toner excellent in both low-temperature fixability and heat-resistant storage stability is exhibited.

It is a figure which shows an example of the image forming apparatus of this invention. It is a figure which shows another example of the image forming apparatus of this invention. It is a figure which shows the further another example of the image forming apparatus of this invention. It is a diagram showing an example of each tandem developing device in the color image forming means of the present invention.

The “toner” described in (1) of the present invention includes the “toner” described in (2) to (9) below as a part of a preferable embodiment. The present invention also provides an “image forming apparatus” described in (10) below.
(2) “The electrostatic charge developing toner according to (1) above, wherein the resin fine particles have a glass transition temperature (Tg) of 50 to 80 ° C.”
(3) “The electrostatic charge developing toner according to (1) or (2) above, wherein the resin fine particles have an acid value (AV) of 45 to 90 mg KOH / g.”
(4) “The electrostatic charge image developing toner according to any one of (1) to (3) above, wherein the resin fine particles have a particle size of 30 nm to 100 nm.”
(5) “The toner according to any one of (1) to (4), wherein the binder resin includes at least one of a crystalline polyester resin and an amorphous polyester resin.”
(6) “The organic solvent is removed from an emulsified dispersion obtained by dispersing an oil phase containing at least a binder resin precursor composed of a modified polyester resin in an organic solvent in an aqueous medium to which the fine particles are added. The electrophotographic toner according to any one of (1) to (5), wherein the toner is obtained by the above process.
(7) “The release agent contains a wax, and a surface wax amount P (A) obtained by FTIR-ATR measurement of the toner before fixing of the toner and a surface wax amount P (B) of the toner after fixing. The toner for electrophotography according to any one of (1) to (6), wherein the difference is 0.10 ≦ P (B) −P (A) ≦ 0.40.
(8) “The release agent contains wax, and the amount of surface wax P (A) obtained by FTIR-ATR measurement of the toner before fixing of the toner is 0.10 ≦ P (A) ≦ 0.25. The electrophotographic toner according to any one of (1) to (7), wherein the toner is an electrophotographic toner.
(9) “The electrophotographic toner according to any one of (1) to (8) above, wherein the resin fine particles are made of a polyester resin.”
(10) “The electrostatic latent image carrier, the electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the toner according to any one of (1) to (9)” And developing means for developing the electrostatic latent image to form a visible image, transfer means for transferring the visible image onto a recording medium, and fixing the transferred image transferred onto the recording medium. And an image forming apparatus characterized by having a fixing unit.

Hereinafter, the present invention will be described in detail.
In the present invention, the resin fine particles are mainly used for granulating properties, that is, for controlling the appropriate particle size and making the circularity. For this reason, the resin fine particles must be resistant to solvent and have a high molecular weight. Accordingly, the storage elastic modulus of the resin fine particles has a high value, and has been a substance that inhibits low-temperature fixability.
In the present invention, the storage elastic modulus G′A (Pa) of the first temperature increase of the toner and the storage elastic modulus G′B (Pa) of the first temperature increase of the resin fine particles satisfy a certain range, and This means that the difference in storage elastic modulus between the high temperature region and the low temperature region of the resin fine particles is below a certain value, that is, the storage elastic modulus between the toner and the resin fine particles is close. Thereby, it can suppress that low temperature fixability is inhibited with resin fine particles.
Here, the first temperature increase is a process in which the toner in a powder state is given a thermal history and becomes a molten state, that is, from the state in which the amorphous resin and the crystalline resin in the toner are not compatible with each other. The storage elastic modulus is shown. If the storage elastic modulus in the low temperature region at the first temperature increase of the toner is low, that is, the storage elastic modulus G′A (60) at 60 ° C. at the first temperature increase is less than 5.0 × 10 ^ 5, Storage stability deteriorates and problems such as solidification or aggregation occur. On the other hand, if the storage elastic modulus in the low temperature range is high, that is, exceeds 5.0 × 10 ^ 6, the low temperature fixability is inhibited.
Further, when the storage elastic modulus of the resin fine particles in the low temperature region at the first temperature increase is high, that is, the storage elastic modulus G′B (60) at 60 ° C. at the first temperature increase is less than 1.0 × 10 ^ 7, Similarly, when the storage elastic modulus is too low, the storage stability under a high temperature environment deteriorates and problems such as solidification or aggregation occur. On the other hand, if the storage elastic modulus in the low temperature range is high, that is, exceeds 1.0 × 10 ^ 10, the low temperature fixability is inhibited.
When the storage elastic modulus in the high temperature region at the first temperature increase of the toner is low, that is, the storage elastic modulus G′A (100) at 100 ° C. at the first temperature increase is less than 1.0 × 10 ^ 4, the elasticity can be maintained. Therefore, there is a concern that hot offset occurs. On the other hand, if it exceeds 1.0 × 10 ^ 6, there is a concern about low-temperature fixability.
Further, when the storage elastic modulus of the resin fine particles in the high temperature region is high, that is, the storage elastic modulus G′B (100) at the first temperature increase of 100 ° C. is less than 1.0 × 10 ^ 4, the elasticity cannot be maintained. There are concerns that hot offsets will occur. On the other hand, if it exceeds 1.0 × 10 ^ 6, there is a concern about low-temperature fixability.
Further, the difference in storage elastic modulus between the toner of the present invention and the resin fine particles at low and high temperatures, that is, G′A (60) −G′B (60) and G′A (100) −G′B (100). , 5.0 x 10 ^ 9 or less and 5.0 x 10 ^ 5 or less, respectively. When each of the above values is exceeded, the elastic modulus of the resin fine particles becomes high and the deviation from the storage elastic modulus of the toner becomes large, which becomes a factor hindering the low-temperature fixability.
The low-temperature fixability of the electrostatic latent image developing toner is not limited to the Tg or melting temperature of the binder resin or toner, but also the physical properties such as viscosity and fluidity exhibited by the binder resin or toner after being heated above the fixing temperature. It is also known to depend on The same applies to the occurrence of hot offset. It is expressed using storage elastic modulus (low), that is, elasticity (inability) like rubber material, as a means of showing properties such as viscosity and fluidity of the binder resin or toner after being heated. It is also known to do.
However, the storage elastic modulus does not mean a scale for showing the degree of storage stability at room temperature, as understood from the measurement purpose. Furthermore, it was not intended to pay attention to the respective storage elastic moduli before heating for both the toner particles and the resin fine particles located outside thereof.

The storage elastic modulus (G ′) can be measured using, for example, the following method. That is, by pressurizing 0.10 g of toner with a tablet molding machine at a pressure of 400 kgf, the toner is molded into a cylindrical sample having a diameter of 8 mm and a height of 1.0 to 1.2 mm to produce a measurement pellet.
Using a viscoelasticity measuring device (rheometer) ARES (manufactured by Rheometrics Scientific), a pellet for measurement was fixed to a parallel plate having a diameter of 8 mm, a frequency of 1 Hz, a temperature of 50 to 180 ° C., a strain of 0.1, a heating rate of 2 ° C. / It is possible to measure the storage elastic modulus G ′ of the toner at each temperature of the toner by measuring in min.

  The glass transition temperature (Tg) of the resin fine particles used in the toner of the present invention is preferably 50 to 80 ° C. When Tg is lower than 50 ° C., the storage elastic modulus in the low temperature region cannot be secured, and the heat resistant storage stability tends to deteriorate. On the other hand, when Tg exceeds 80 ° C., the storage elastic modulus in the high temperature region does not decrease, and the possibility of inhibiting the low temperature fixability increases.

  For the measurement of Tg of toner and resin fine particles used in the present invention, for example, a differential scanning calorimeter (for example, DSC-6220R: Seiko Instruments Inc.) is used. After heating to 150 ° C., let stand at 150 ° C. for 10 min, cool the sample to room temperature, let stand for 10 min, heat again to 150 ° C. at a heating rate of 10 ° C./min, the baseline below the glass transition point, and the glass transition It can be obtained from a curve portion corresponding to a half height of the baseline above the point.

  Further, the acid value (AV) of the resin fine particles is preferably 45 to 90 mgKOH / g. If the AV is less than 45 mgKOH / g, the affinity with the binder resin, which is a toner constituent material, is lowered, so that it does not adhere properly to the toner surface and a problem is likely to occur in granulation properties. On the other hand, when AV exceeds 90 mgKOH / g, polar groups as a resin increase, and it becomes easy to react with water in the atmosphere, so there is a concern about storage stability.

The acid value of the toner composition of the present invention is determined by the following method, and the basic operation conforms to JIS K-0070.
(1) Weigh accurately 0.5 to 2.0 g of the pulverized product of the sample, and let the weight of the polymer component be 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.
(2) Put a sample in a 300 (ml) beaker, add toluene / ethanol (volume ratio 4/1) mixed solution 150 (ml) and dissolve (the polyester resin (L) hardly soluble in the organic solvent is this Since it is substantially insoluble in a toluene-based ethanol mixture, it is separated at this point).
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) 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 calculation formula (1). However, f is a factor of KOH.

  Acid value (mgKOH / g) = [(SB) × f × 5.61] / W Formula (1)

The particle size of the resin fine particles used in the toner of the present invention is preferably 30 to 100 nm. When it is less than 30 nm, it is difficult to perform the function as the resin fine particles, and granulation becomes difficult.
On the other hand, when it exceeds 100 nm, it becomes difficult to adhere to the surface of the toner base, and granulation is also difficult here. As a method for measuring the particle size of the resin fine particles, it can be measured with a nanotrack particle size distribution measuring device UPA-EX150 (manufactured by Nikkiso, dynamic light scattering method / laser Doppler method). As a specific measuring method, the dispersion in which resin fine particles are dispersed is adjusted to a measurement concentration range for measurement. At that time, the background measurement is performed in advance using only the dispersion solvent of the dispersion.

The difference between the surface wax amount P (A) obtained by FTIR-ATR measurement of the toner before fixing and the surface wax amount P (B) of the toner after fixing is 0.10 ≦ P (B) −P (A) ≦ 0.40. It is desirable that When P (B) -P (A) is less than 0.10, the amount of the wax oozing out at the time of fixing is small, and cold offset tends to occur. On the other hand, if it exceeds 0.40, there will be a large amount of wax oozing out during fixing, and there is a possibility of causing in-machine contamination due to volatilized wax.
Further, P (A) is preferably 0.10 ≦ P (A) ≦ 0.25. When P (A) is less than 0.10, the amount of wax present on the surface of the toner particles is too small, and thus cannot function as a release agent during fixing. On the other hand, when it exceeds 0.25, there is a possibility of causing carrier contamination during stirring with the carrier in the development step.
In the present invention, the “toner before fixing” means a toner that is not subjected to a high-temperature heat history after passing through a fixing device.

The surface wax amount of the toner can be obtained by FTIR-ATR (total reflection absorption infrared spectroscopy) method.
From the measurement principle, the analysis depth is about 0.3 μm, and by this analysis, the relative amount of wax in the depth region of 0.3 μm from the surface of the toner particles can be obtained. The method for measuring the toner before fixing is as follows.
First, as a sample, 3 g of toner was pressed with an automatic pellet molding machine (Type M No. 50 BRP-E; manufactured by MAEKAWA TESTING MACHINE CO.) For 1 minute at a load of 6 t to produce a 40 mmφ (about 2 mm thick) pellet. . The toner pellet surface was measured by the FTIR-ATR method. The microscopic FTIR apparatus used was one in which a MultiScope FTIR unit was installed in Spectrum One manufactured by PERKIN ELMER, and measurement was performed with a micro ATR of a germanium (Ge) crystal having a diameter of 100 μm. Measurement was performed with an infrared incident angle of 41.5 °, a resolution of 4 cm ⁻¹ and a total of 20 times.
The intensity ratio (P2850 / P828) between the obtained wax-derived peak (2850 cm ⁻¹ ) and the binder resin-derived peak (828 cm ⁻¹ ) was defined as the relative amount of wax near the toner particle surface. The average value after measuring four times by changing the measurement location was used.
On the other hand, the “toner after fixing” means toner that is fixed on a transfer medium such as paper under a condition that the toner is sufficiently fixed in a state where no offset occurs.
Specifically, it is defined as follows.
An unfixed image having an adhesion amount of 4.0 mg / cm ² was produced with a pre-fixing toner by a copying machine (Imagio Neo C355) manufactured by Ricoh Co., Ltd., and then a copying machine (Imagio Neo C355) manufactured by Ricoh Co., Ltd. Using an external fixing machine that can set the roller temperature freely by modifying the fixing device (oilless system), fixing the paper feed at 120 mm / sec, and changing the temperature from 100 ° C to 140 ° C by 5 ° C enough The toner is observed on the fixing roller and on the paper for the offset phenomenon in which the image is not completely melted and retransferred to the non-image area, and the toner is the toner on the fixed image at the lowest temperature where the image is not retransferred.
The surface wax amount of the toner after fixing was measured by the above-described FTIR-ATR method for the fixed image. The measurement method and analysis method are the same as those for the toner before fixing.

The toner of the present invention is obtained by dispersing an oil phase obtained by dissolving or dispersing a toner material containing at least a polyester resin, a colorant, and a release agent in an organic solvent in an aqueous medium. A toner obtained by removing the organic solvent from the O / W type dispersion is preferred.
The toner material preferably contains a crystalline polyester resin, a binder resin precursor made of a modified polyester resin, and other binder resin components. Further, when obtaining the O / W type dispersion (emulsified dispersion), the oil phase is dissolved in a compound that extends or crosslinks with the binder resin precursor, and then the oil phase is dispersed into a fine particle dispersant. It is preferably dispersed in an aqueous medium in which Furthermore, it is preferable that the binder resin component is subjected to a crosslinking reaction and / or an extension reaction in the lactic acid dispersion.
The binder resin component preferably contains at least one crystalline polyester resin and at least one amorphous polyester resin.

  The two-component developer of the present invention is characterized by including the toner of the present invention, and the carrier contained in the developer is not particularly limited.

  An image forming apparatus according to the present invention includes the toner according to the present invention, and includes an electrostatic latent image forming unit (charging unit and exposure unit), a developing unit, a transfer unit, a fixing unit, and a cleaning unit. It is sufficient if each means is included, and if necessary, a means for performing a process such as a static elimination process, a recycling process, and a control process may be further included.

The electrostatic latent image forming unit is a unit that forms an electrostatic latent image on the image carrier. The material, shape, structure, size and the like of the image carrier can be appropriately selected from known ones. Examples of the material include inorganic substances such as amorphous silicon and selenium, and organic substances such as polysilane and phthalopolymethine. Amorphous silicon is preferable because of its long life. Further, the shape is preferably a drum shape. The electrostatic latent image can be formed by uniformly charging the surface of the image carrier and then exposing it imagewise, and can be performed by an electrostatic latent image forming unit.
The electrostatic latent image forming unit preferably has a charger (charging unit) that uniformly charges the surface of the image carrier and an exposure unit (exposure unit) that exposes the surface of the image carrier.

  Charging can be performed by applying a voltage to the surface of the image carrier using a charging means (charger). The charger can be appropriately selected according to the purpose, but a known contact charger equipped with a conductive or semiconductive roll, brush, film, rubber blade, etc., or corona discharge such as corotron or scorotron is used. Non-contact chargers and the like.

The exposure can be performed by exposing the surface of the image carrier using an exposure means (exposure device). The exposure device can be appropriately selected according to the purpose, but 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.
It should be noted that an optical back side system in which exposure is performed from the back side of the image carrier may be adopted.

The developing unit is a unit that forms a visible image by developing the electrostatic latent image using the toner of the present invention. The visible image can be formed using a developing unit. The developing means can be appropriately selected from known ones, and preferably has a developing unit that accommodates the toner of the present invention and can apply the toner to the electrostatic latent image in a contact or non-contact manner. The developing device may be a dry development system or a wet development system. Further, it may be a single color developer or a multicolor developer. Specifically, a stirrer for charging the developer by friction stirring and a developer having a rotatable magnet roller can be used. The developer accommodated in the developing device is a developer using the toner of the present invention, but may be a one-component developer or a two-component developer.
In a developing device having a two-component developer, 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 image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the image carrier by an electric attractive force. As a result, the electrostatic latent image is developed with toner, and a visible image is formed with toner on the surface of the image carrier.

The transfer means is a means for transferring a visible image to a recording medium. An intermediate transfer body is used to primarily transfer the visible image onto the intermediate transfer body, and then secondary transfer the visible image onto the recording medium. It is preferable. At this time, the toner used may be monochrome, full color, or transparent toner. Usually, two or more colors are superimposed and developed at the same time. Therefore, a primary transfer process in which a visible image is transferred onto an intermediate transfer member to form a composite transfer image, and a secondary transfer in which the composite transfer image is transferred onto a recording medium. It is more preferable to have a process.
The transfer can be performed by charging the image carrier using a transfer unit. The transfer means preferably has 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. The intermediate transfer member can be appropriately selected from known transfer members according to the purpose, and a transfer belt or the like can be used.
The transfer means preferably has a transfer device that peels and charges the visible image formed on the image carrier to the recording medium side. There may be one transfer means or a plurality of transfer means. Specific 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 can be appropriately selected from known recording media, and recording paper or the like can be used.

  The fixing means is a means for fixing the visible image transferred to the recording medium using the fixing means, and may be fixed each time the toner of each color is transferred to the recording medium, or the toner of each color is laminated. You may fix at once in the state. The fixing unit can be appropriately selected according to the purpose, but a known heating and pressing unit can be used. 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 usually preferably 80 ° C to 200 ° C. A known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

  The neutralization unit is a unit that neutralizes the image by applying a neutralization bias to the image carrier, and can be performed using the neutralization unit. The neutralization means can be appropriately selected from known neutralizers, and a neutralization lamp or the like can be used.

  The cleaning unit is a unit that removes toner remaining on the image carrier. The cleaning means can be appropriately selected from known cleaners, and a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web cleaner, or the like can be used. It is preferable to use a blade cleaner.

The recycling process is a process in which the toner removed by the cleaning unit (process) is recycled by the developing unit, and can be performed using the recycling unit. The recycling means can be appropriately selected according to the purpose, and a known conveying means or the like can be used.
A control process is a process of controlling each process, and can be performed using a control means. The control means can be appropriately selected according to the purpose, and devices such as a sequencer and a computer can be used.

  The process cartridge of the present invention is used in the image forming apparatus of the present invention, and integrally supports an image carrier and at least one unit selected from a charging unit, a developing unit, and a cleaning unit to form the image of the present invention. It is detachable from the main body.

FIG. 1 shows an example of an image forming apparatus used in the present invention. The image forming apparatus 100A includes a drum-shaped photosensitive member 10 as an image carrier, a charging roller 20 as a charging unit, an exposure device 30 as an exposure unit, a developing device 40 as a developing unit, and an intermediate transfer member 50. And a cleaning device 60 as a cleaning means and a static elimination lamp 70 as a static elimination means.
The intermediate transfer member 50 is an endless belt, and is stretched by three rollers 51 so as to be movable in the direction of the arrow. 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. A cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer member 50. In addition, a transfer roller 80 serving as a transfer unit capable of applying a transfer bias for transferring (secondary transfer) a visible image (toner image) to a recording sheet 95 serving as a recording medium is disposed to face the recording paper 95. . Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is in contact with the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. And the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as a developer carrying member, and a black developing device 45K, a yellow developing device 45Y, a magenta developing device 45M, and a cyan developing device 45C provided around the developing belt 41. The black developing device 45K includes a developer container 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing device 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developer 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer accommodating portion 42C, a developer supply roller 43C, and a developing roller 44C. The developing belt 41 is an endless belt, is stretched by a plurality of belt rollers so as to be movable in the direction of the arrow, and a part of the developing belt 41 is in contact with the photoreceptor 10.

  In the image forming apparatus 100A, the charging roller 20 charges the photoreceptor 10 uniformly, and then exposes the photoreceptor 10 using the exposure apparatus 30 to form an electrostatic latent image. Next, the electrostatic latent image formed on the photoreceptor 10 is developed by supplying a developer from the developing device 40 to form a toner image. Further, the toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied by the roller 51, and further transferred (secondary transfer) onto the recording paper 95. As a result, a transfer image is formed on the recording paper 95. The toner remaining on the photoconductor 10 is removed by a cleaning device 60 having a cleaning blade, and the charged charge on the photoconductor 10 is removed by a static elimination lamp 70.

  FIG. 2 shows another example of the image forming apparatus used in the present invention. The image forming apparatus 100B does not include the developing belt 41, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C are arranged around the photoconductor 10 so as to face each other. Other than that, it has the same configuration as that of the image forming apparatus 100A and exhibits the same functions and effects. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals.

FIG. 3 shows another example of the image forming apparatus used in the present invention. The image forming apparatus 100C is a tandem color image forming apparatus. The image forming apparatus 100 </ b> C includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder 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 so as to be able to move clockwise in the drawing. An intermediate transfer body cleaning device 17 for removing toner remaining on the intermediate transfer body 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched by the support rollers 14, 15, and 16 has a tandem type in which image forming means 18 of four colors 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 recording paper conveyed on the secondary transfer belt 24 and the intermediate transfer member 50 can contact each other. It is. 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 image forming apparatus 100C, a sheet reversing device 28 for reversing the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Thereby, images can be formed on both sides of the recording paper.

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

  When a start switch (not shown) is pressed, when a document is set on the automatic document feeder 400, the scanner 300 is driven after the document is conveyed onto the contact glass 32, and the first traveling body 33 and the second traveling body are driven. The body 34 travels. On the other hand, when a document is set on the contact glass 32, the scanner 300 is immediately driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, the reflected light from the original surface of the light irradiated by the first traveling body 33 is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35. As a result, a color original (color image) is read and used as image information for each color of black, yellow, magenta, and cyan. The image information of each color is transmitted to the image forming means 18 of each color in the tandem developing device 120, and a toner image of each color is formed.

  The toner image on the black photoconductor 10K, the toner image on the yellow photoconductor 10Y, the toner image on the magenta photoconductor 10M, and the toner image on the cyan photoconductor 10C are sequentially transferred onto the intermediate transfer member 50. (Primary transfer). Then, the toner images of the respective colors are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  As shown in FIG. 4, the image forming means 18 for each color in the tandem developing device 120 includes a photosensitive member 10, a charger 59 for uniformly charging the photosensitive member 10, and a photosensitive device based on image information of each color. An exposure device that forms an electrostatic latent image on the photoconductor 10 by exposing the photoconductor 10 (L in the figure), and developing the electrostatic latent image using toner of each color, Are provided with a developing device 61 for forming toner images of the respective colors, a transfer charger 62 for transferring the toner images of the respective colors onto the intermediate transfer member 50, a photoconductor cleaning device 63, and a static eliminator 64.

On the other hand, in the paper feed table 200, one of the paper feed rollers 142a is selectively rotated to feed the recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143.
The paper is separated one by one by the separation roller 145a, sent to the paper feed path 146, transported by the transport roller 147, led to the paper feed path 148 in the copier body 150, and abutted against the registration roller 49 and stopped. Alternatively, the paper feed roller 142b is rotated to feed out the recording paper on the manual feed tray 52, separated one by one by the separation roller 145b, 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 time with the color transfer image formed on the intermediate transfer member 50, and the recording paper is fed between the intermediate transfer member 50 and the secondary transfer device 22, thereby being recorded on the recording paper. A color transfer image is formed. The toner remaining on the intermediate transfer member 50 after the transfer is cleaned by the intermediate transfer member cleaning device 17.

  The recording paper on which the color transfer image is formed is conveyed to the fixing device 25 by the secondary transfer device 22, and the color transfer image is fixed on the recording paper by heat and pressure. Thereafter, the recording paper is switched by the switching claw 55 and discharged by the discharge roller 56 and is stacked on the discharge tray 57. Alternatively, the sheet is switched by the switching claw 55, reversed by the sheet reversing device 28, led to the transfer position again, and after the image is formed on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  The average circularity of the toner produced by the production method of the present invention is preferably 0.93 to 0.98, and more preferably 0.94 to 0.96. If it is lower than 0.93, the image uniformity during development deteriorates, or the toner transfer efficiency from the electrophotographic photosensitive member to the intermediate transfer member or from the intermediate transfer member to the recording material decreases, and uniform transfer cannot be obtained. . The toner according to the production method of the present invention is prepared by emulsification in an aqueous medium. In particular, in order to obtain a shape having a smaller particle diameter and an average circularity in the above range in a color toner. It is effective.

  The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner manufactured by the manufacturing method of the present invention is preferably 1.25 or less, for example, 1.00 to 1 .20 is more preferred. When the ratio of the number average particle diameter to the number average particle diameter (Dv / Dn) is less than 1.00, 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 carrier It tends to lead to a decrease in charging ability and deterioration in cleaning performance.

[Raw materials used in the production of the toner of the present invention]
(Resin fine particles)
The resin fine particles used in the present invention are preferably polyester resins. The resin fine particles are used as an emulsified polyester dispersion, and examples of the raw material for the polyester resin include the following.
Examples of the alcohol component include polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3,3) -2,2-bis (4-hydroxyphenyl) propane, polyoxy Ethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2,0) -polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane Diols represented by the following general formula (I) such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, isopentyl glycol, hydrogenated bisphenol A, 1,3-butanediol, 1 , 4-butanediol, neopentyl glycol, key Rylene glycol, 1,4-cyclohexanedimethanol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, bis- (β-hydroxyethyl) terephthalate, tris- (β-hydroxyethyl) isocyanurate, 2,2,4 -Trimethylolpentane-1,3-diol and the like, and further a hydroxycarboxylic acid component can be added.

（式中、Ｒ１及びＲ２はエチレン基又はプロピレン基であり、ｘ及びｙは各々１以上の整数であり、且つ、その和の平均値は２〜７である）

(In the formula, R1 and R2 are an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of the sum is 2 to 7)

For example, p-oxybenzoic acid, vanillic acid, dimethylolpropionic acid, malic acid, tartaric acid, 5-hydroxyisophthalic acid and the like.
Specific examples of the acid component include malonic acid, succinic acid, glutaric acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, isophthalic acid dimethyl ester, terephthalic acid dimethyl ester, terephthalic acid monomethyl ester, tetrahydrophthalic acid, methyl tetrahydrophthal Acid, hexahydrophthalic acid, dimethyltetrahydrophthalic acid, endomethylenehexahydrophthalic acid, naphthalenetetracarbic acid, diphenolic acid, trimellitic acid, pyromellitic acid, trimesic acid, cyclopentanedicarboxylic acid, 3,3 ', 4,4'-benzophenonetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 2,2-bis- (4-carboxyphenyl) propane, trimellitic anhydride and 4,4-diaminophenylmethane Diimideca obtained from Isocyanate ring-containing polyimide obtained from trimerization reaction product of trimnic acid anhydride with boric acid, tris- (β-carboxyethyl) isocyanurate, isocyanurate ring-containing polyimide carboxylic acid, tolylene diisocyanate, xylylene diisocyanate or isophorone diisocyanate These are carboxylic acids, and one or more of these are used. Among these, use of a crosslinking component such as a trivalent or higher polyvalent carboxylic acid or polyhydric alcohol may be preferable in terms of stability such as fixing strength and offset resistance.

The polyester resin obtained from these raw materials is manufactured by a normal method.
For example, an acid component and an alcohol component are charged into a reaction vessel at a predetermined ratio, and the reaction is started at a temperature of 150 to 190 ° C. in the presence of an inert gas such as nitrogen gas. By-product low molecular weight compounds are continuously removed from the reaction system. Thereafter, the reaction temperature is further increased to 200 to 250 ° C. to accelerate the reaction, thereby obtaining a target polyester resin.
When producing a polyester resin, when the carboxylic acid component used is a free carboxylic acid containing no ester group, it is represented by an esterification catalyst, for example, an organic metal such as dibutyltin dilaurate or dibutyltin oxide, or tetrabutyl titanate. The metal alkoxide is preferably used in an amount of 0.1 to 1% by weight based on the total amount of raw materials charged. When the carboxylic acid component is a lower alkyl ester, a transesterification catalyst such as zinc acetate, lead acetate or magnesium acetate is used. It is preferable to use 0.005 to 0.05% by weight of a metal oxide, zinc oxide, metal oxide such as antimony oxide, metal alkoxide such as tetrabutyl titanate, etc. with respect to the total amount of raw materials charged.

  In the present invention, two or more of the above polyester resins may be used in combination, or other resins may be added and used. Other resins include silicone resin, epoxy resin, xylene resin, diene resin, styrene resin, acrylic resin, styrene / acrylic resin, phenol resin, terpene resin, coumarin resin, amide resin, amideimide resin, butyral resin, urethane resin And ethylene / vinyl acetate resin.

(Anionic surfactant)
Examples of the anionic surfactant used in the production method of the present invention include alkylbenzene sulfonate, α-olefin sulfonate, phosphate ester, etc., and an anionic surfactant having a fluoroalkyl group is preferable. It is mentioned in. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (having 6 to 6 carbon atoms). 11) Sodium oxy] -1-alkyl (C3-4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl ( Carbon number 11-20) carboxylic acid or metal salt thereof, perfluoroalkyl carboxylic acid (carbon number 7-13) or metal salt thereof, perfluoroalkyl (carbon number 4-12) sulfonic acid or metal salt thereof, perfluorooctane Sulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) par -Fluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number 6-6) 16) Ethyl phosphate and the like.

  Examples of commercially available anionic surfactants having a fluoroalkyl group include Surflon S-111, S-112, and S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC -129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 ( Dainippon Ink Co.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Etc.).

(Binder resin)
For convenience of explanation, the material from the binder resin to the magnetic material described below is sometimes called a toner material.
The binder resin used in the toner production method of the present invention is not particularly limited, and preferably contains at least two kinds of resins. Polyester resin, silicone resin, styrene / acrylic resin, styrene resin, acrylic resin, epoxy resin, diene resin, phenol resin, terpene resin, coumarin resin, amideimide resin, butyral resin, urethane resin, ethylene / vinyl acetate resin, etc. A known binder resin can be used.
Among these, the resin phase for the toner production method of the present invention is preferably a polyester resin that has sufficient flexibility even when the molecular weight is lowered, in that it can sharply melt during fixing and smooth the image surface. Further, other resins may be used in combination with the polyester resin.

  The polyester resin that can be preferably used in the present invention is one or two or more polyols represented by the following general formula (1) and one or two or more polyols represented by the following general formula (2). The polycarboxylic acid is polyesterified.

A- (OH) m ... General formula (1)
[Wherein, A represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, or an aromatic group or heterocyclic aromatic group which may have a substituent. m represents an integer of 2 to 4. ]

B- (COOH) n ... General formula (2)
[Wherein, B represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, or an aromatic group or heterocyclic aromatic group which may have a substituent. n represents an integer of 2 to 4. ]

  Specific polyols represented by the general formula (1) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2, 3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl Propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide addition Products, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, and the like.

  Specific polycarboxylic acids represented by the general formula (2) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid. Azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, Isooctyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5 -Hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxyprop 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, Examples include butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and ethylene glycol bis (trimellitic acid).

(Polymer capable of reacting with active hydrogen group-containing compound)
The polymer that can react with the active hydrogen group-containing compound (hereinafter referred to as “prepolymer”) is not particularly limited as long as it has at least a site that can react with the active hydrogen group-containing compound. Can be selected as appropriate. For example, a polyol resin, a polyacrylic resin, a polyester resin, an epoxy resin, a derivative resin thereof, or the like can be used.
Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.
In addition, these may be used individually by 1 type and may use 2 or more types together.
The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxyl group, an acid chloride Group, and the like. These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable. Among prepolymers, it is easy to adjust the molecular weight of the polymer component, ensuring oil-free low-temperature fixing characteristics for dry toners, especially good release and fixing properties even without a release oil coating mechanism for the heating medium for fixing. In view of the capability, a urea bond-forming group-containing polyester resin (RMPE) is particularly preferable.

As a urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond generating group in the urea bond generating group-containing polyester resin (RMPE) is the isocyanate group, the urea bond generating group-containing polyester resin (RMPE) is particularly an isocyanate group-containing polyester prepolymer (A). Is preferred. There is no restriction | limiting in particular as isocyanate group containing polyester prepolymer (A), According to the objective, it can select suitably. For example, it is a polycondensate of polyol (PO) and polycarboxylic acid (PC), and is obtained by reacting an active hydrogen group-containing polyester resin with polyisocyanate (PIC). There is no restriction | limiting in particular as a polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol ( TO) and the like.
These may be used individually by 1 type and may use 2 or more types together. Among these, diol (DIO) alone or a mixture of diol (DIO) and a small amount of a trivalent or higher polyol (TO) is preferable. Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
As the alkylene glycol, those having 2 to 12 carbon atoms are preferable, and examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. It is done. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of bisphenols include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, and butylene oxide to bisphenols. Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable. Moreover, the mixture of the alkylene oxide adduct of bisphenol and the alkylene oxide adduct of bisphenol and C2-C12 alkylene glycol is especially preferable.
The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trihydric or higher polyhydric aliphatic alcohol, a trihydric or higher polyphenol, an alkylene of a trihydric or higher polyphenol. And oxide adducts. Examples of the trivalent or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and the like. Examples of the trihydric or higher polyphenols include trisphenol bodies (such as Trisphenol PA manufactured by Honshu Chemical Industry Co., Ltd.), phenol novolacs, cresol novolacs, and the like. Examples of the alkylene oxide adduct of trihydric or higher polyphenols include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to trihydric or higher polyphenols.
The mixing mass ratio (DIO: TO) of the diol (DIO) and the trihydric or higher polyol (TO) in the mixture of the diol (DIO) and the trihydric or higher polyol (TO) is 100: 0.01 to 10 Is preferable, and 100: 0.01-1 is more preferable.

There is no restriction | limiting in particular as polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) And a mixture of trivalent or higher valent polycarboxylic acids. These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of dicarboxylic acid (DIC) and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid (DIC) include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like. Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. Moreover, as alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. Moreover, as aromatic dicarboxylic acid, a C8-C20 thing is preferable, for example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned. Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.
The trivalent or higher polycarboxylic acid (TC) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids. Moreover, as an aromatic polycarboxylic acid, a C9-C20 thing is preferable, for example, trimellitic acid, pyromellitic acid, etc. are mentioned.
The polycarboxylic acid (PC) is any one selected from dicarboxylic acid (DIC), trivalent or higher polycarboxylic acid (TC), and a mixture of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid. These acid anhydrides or lower alkyl ester compounds can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.
As a mixing mass ratio (DIC: TC) of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC) in a mixture of dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC), There is no restriction | limiting, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  There is no restriction | limiting in particular as a mixing ratio at the time of making polycondensation reaction of a polyol (PO) and polycarboxylic acid (PC), According to the objective, it can select suitably. For example, the equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] in the polyol (PO) and the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually 2/1 to 1/1. It is preferable that the ratio is 1.5 / 1 to 1/1. Particularly preferred is 1.3 / 1 to 1.02 / 1.

  There is no restriction | limiting in particular as content in the isocyanate group containing polyester prepolymer (A) of a polyol (PO), According to the objective, it can select suitably. For example, 0.5-40 mass% is preferable, 1-30 mass% is more preferable, and 2-20 mass% is especially preferable. This is because if the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner. This is because the low temperature fixability may be deteriorated if the temperature exceeds.

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

  As a mixing ratio when the polyisocyanate (PIC) is reacted with an active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin), an isocyanate group [NCO] in the polyisocyanate (PIC) and a hydroxyl group in the hydroxyl group-containing polyester resin [ The mixing equivalent ratio with [OH] ([NCO] / [OH]) is usually preferably 5/1 to 1/1. 4/1 to 1.2 / 1 is more preferable. Particularly preferred is 3/1 to 1.5 / 1. This is because if the isocyanate group [NCO] exceeds 5, low-temperature fixability may deteriorate, and if it is less than 1, offset resistance may deteriorate.

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

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

The weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is preferably 3,000 to 40,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). 4,000 to 30,000 are more preferable. This is because when the weight average molecular weight (Mw) is less than 3,000, the heat resistant storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.
The molecular weight distribution can be measured by gel permeation chromatography (GPC), for example, as follows. That is, first, the column was stabilized in a 40 ° C. heat chamber, and at this temperature, tetrahydrofuran (THF) was flowed as a column solvent at a flow rate of 1 ml / min to adjust the sample concentration to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 to 200 μl of a tetrahydrofuran sample solution of the resin. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared by several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Or Toyo Soda Kogyo Co., Ltd. having a molecular weight of ^{6 × 10 2, 2.1 × 10} 2, 4 × 10 2, 1.75 × 10 4, 1.1 × 10 5, 3.9 × 10 5, 8.6 It is preferable to use those of × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ and use at least about 10 standard polystyrene samples. An RI (refractive index) detector can be used as the detector.

(Other ingredients)
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 property improvers, magnetic materials , Metal soap, and the like.

(Coloring agent)
The colorant for the toner used in the present invention is not particularly limited and can 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, bengara, red lead, red lead, cadmium red, cadmium mercury red, antimony red, permanent red 4R, para red, phise red, parachlor ortho nitroaniline red, risor fast scarlet G, Reliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon , Oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine Range, 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, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt violet, manganese violet, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridiane, emerald green, pigment green B, naphthol green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Oxidized Chi Tan, zinc white, lithopone and the like. These may be used individually by 1 type and may use 2 or more types together.
The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose. When the content of the colorant is less than 1% by mass, the coloring power of the toner may be reduced. When the content exceeds 15% by mass, poor dispersion of the pigment in the toner occurs, and the coloring power decreases. In some cases, the electrical characteristics of the toner may be degraded.

The colorant may be used as a master batch combined with a resin. There is no restriction | limiting in particular as resin, According to the objective, it can select suitably from well-known things. For example, polyester, styrene or its substituted polymer, styrene copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane, polyamide, Examples thereof include polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type and may use 2 or more types together.
Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene N-acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The master batch can be produced by mixing or kneading a resin for a master batch and a colorant with a high shear force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used. The colorant can be arbitrarily contained in both the first resin phase and the second resin phase by utilizing the difference in affinity for the two resins. It is well known that the colorant deteriorates the charging performance of the toner when present on the toner surface. Therefore, the charging performance (environmental stability, charge retention ability, charge amount, etc.) of the toner can be improved by selectively incorporating a colorant into the first resin phase present in the inner layer.

(Release agent)
There is no restriction | limiting in particular as a mold release agent, Although it can select suitably according to the objective, The low melting-point mold release agent whose melting | fusing point is 50-120 degreeC is preferable. The low melting point release agent, when dispersed with the resin, effectively acts as a release agent between the fixing roller and the toner interface, thereby preventing oilless (a release agent such as oil on the fixing roller). Even if it is not applied), the hot offset property is good.
Preferable examples of the release agent include waxes and waxes. Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin and microcrystalline And natural waxes such as petroleum waxes such as Petrolatum; In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers; Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; poly-n-stearyl methacrylate and poly-n-lauryl which are low molecular weight crystalline polymer resins A homopolymer or copolymer of a polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, or the like may be used. These may be used alone or in combination of two or more.
There is no restriction | limiting in particular as melting | fusing point of a mold release agent, Although it can select suitably according to the objective, 50-120 degreeC is preferable and 60-90 degreeC is 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 120 ° C., a cold offset may easily occur during fixing at a low temperature. The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax. When the melt viscosity is less than 5 cps, the releasability may be lowered, and when it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained. There is no restriction | limiting in particular as content in the said toner of a mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable. When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.
The release agent can be arbitrarily contained in both the first resin phase and the second resin phase by utilizing the difference in affinity for the two resins. By selectively including in the second resin phase present in the outer layer of the toner, the release of the release agent can occur sufficiently even in a short heating time during fixing, so that sufficient release properties can be obtained. Further, by selectively including the release agent in the first resin phase present in the inner layer, the spent of the release agent to other members such as a photoreceptor and a carrier can be suppressed. In the present invention, the arrangement of the release agent may be designed relatively freely, and any arrangement can be taken according to each image forming process.

(Charge control agent)
There is no restriction | limiting in particular as a charge control agent, According to the objective, it can select suitably from well-known things. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus Or a compound thereof, tungsten simple substance or a compound thereof, fluorine-based activator, salicylic acid metal salt, salicylic acid derivative metal salt, and the like. These may be used individually by 1 type and may use 2 or more types together.
A commercially available product may be used as the charge control agent. Examples of the commercially available products include bontron 03, a nigrosine dye, bontron P-51, a quaternary ammonium salt, bontron S-34, a metal-containing azo dye, E-82, an oxynaphthoic acid metal complex, and a salicylic acid metal. E-84 of the complex, E-89 of the phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of the quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, boron complex LR-147 (made by Nippon Carlit), copper phthalocyanine, periree , Quinacridone, azo pigments, sulfonate group, a carboxyl group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.

By selectively containing the charge control agent in the resin phase in the toner particle main body existing in the inner layer, the spent of the charge control agent on other members such as a photoreceptor and a carrier can be suppressed. In the toner manufacturing method of the present invention, the arrangement of the charge control agent may be designed relatively freely, and an arbitrary arrangement may be taken according to each image forming process.
The content of the charge control agent with respect to the toner varies depending on the type of the resin, the presence or absence of the additive, the dispersion method, and the like, and cannot be generally specified. -10 mass parts is preferable, and 0.2-5 mass parts is more preferable. When the content of the charge control agent 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, By reducing the effect, the electrostatic attraction force with the developing roller may increase, leading to a decrease in developer fluidity and a decrease in image density.

(Amorphous polyester resin)
In the present invention, it is preferable to use an amorphous unmodified polyester resin as the binder resin component. It is preferable that at least a part of the modified polyester resin obtained by crosslinking and / or elongation reaction of the binder resin precursor made of the modified polyester resin is compatible with the unmodified polyester resin. Thereby, low temperature fixability and hot offset resistance can be improved. For this reason, it is preferable that the polyol and polycarboxylic acid of the modified polyester resin and the unmodified polyester resin have similar compositions. Further, as the unmodified polyester resin, the non-modified polyester resin used in the crystalline polyester dispersion can also be used as long as it is unmodified.

The acid value of the unmodified polyester resin is usually 1 to 50 KOHmg / g, preferably 5 to 30 KOHmg / g. As a result, since the acid value is 1 KOHmg / g or more, the toner is likely to be negatively charged, and further, the affinity between the paper and the toner is improved at the time of fixing to the paper, and the low-temperature fixability can be improved. . However, if the acid value exceeds 50 KOHmg / g, the charging stability, particularly the charging stability against environmental fluctuations, may be reduced. In the present invention, the unmodified polyester resin preferably has an acid value of 1 to 50 KOHmg / g.
The hydroxyl value of the unmodified polyester resin is preferably 5 KOHmg / g or more.

The hydroxyl value is measured using a method based on JIS K0070-1966. Specifically, first, 0.5 g of a sample is precisely weighed into a 100 ml volumetric flask, and 5 ml of an acetylating reagent is added thereto. Next, after heating in a 100 ± 5 ° C. warm bath for 1-2 hours, the flask is removed from the warm bath and allowed to cool. Furthermore, acetic anhydride is decomposed by adding water and shaking. Next, in order to completely decompose acetic anhydride, the flask is again heated in a warm bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent.
Furthermore, the hydroxyl value was measured at 23 ° C. using an automatic potentiometric titrator DL-53 Titrator (manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00 Analyze using .000. For calibration of the apparatus, a mixed solvent of 120 ml of toluene and 30 ml of ethanol is used.
At this time, the measurement conditions are as follows.
Still
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measurement mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steppes jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential1 No
Potentialial No
Stop for revaluation No

The urea-modified polyester resin can be used in combination with a polyester resin modified with a chemical bond other than a urea bond, for example, a polyester resin modified with a urethane bond, in addition to an unmodified polyester resin.
When the toner composition contains a modified polyester resin such as a urea-modified polyester resin, the modified polyester resin can be produced by a one-shot method or the like.

As an example, a method for producing a urea-modified polyester resin will be described.
First, a polyol and a polycarboxylic acid are heated to 150 to 280 ° C. in the presence of a catalyst such as tetrabutoxy titanate or dibutyltin oxide, and if necessary, water generated while removing pressure is removed to have a hydroxyl group. A polyester resin is obtained. Next, a polyester resin having a hydroxyl group is reacted with polyisocyanate at 40 to 140 ° C. to obtain a polyester prepolymer having an isocyanate group. Furthermore, the polyester prepolymer having an isocyanate group is reacted with amines at 0 to 140 ° C. to obtain a urea-modified polyester resin.
The number average molecular weight of the urea-modified polyester resin is usually 1000 to 10000, preferably 1500 to 6000.

In addition, when making the polyester resin which has a hydroxyl group and polyisocyanate react, and when making the polyester prepolymer which has an isocyanate group, and amines react, a solvent can also be used as needed.
Solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.); ethers (tetrahydrofuran) And the like which are inert with respect to the isocyanate group.

In addition, when using unmodified polyester resin together, you may mix to the solution after reaction of the urea modified polyester resin what was manufactured similarly to the polyester resin which has a hydroxyl group.
In the present invention, as the binder resin component contained in the oil phase, a crystalline polyester resin, an amorphous polyester resin, a binder resin precursor, and an unmodified resin may be used in combination. The binder resin component may be contained. The binder resin component preferably contains a polyester resin, and more preferably contains 50% by weight or more of the polyester resin. If the content of the polyester resin is less than 50% by weight, the low-temperature fixability may be lowered. It is particularly preferable that all of the binder resin components are polyester resins.
Examples of binder resin components other than polyester resins include polystyrene, poly (p-chlorostyrene), styrene-substituted polymers such as polyvinyltoluene, styrene-substituted polymers, styrene-p-chlorostyrene copolymers, and styrene-propylene copolymers. Polymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer , Styrene-vinyl methyl ketone copolymer Styrene copolymers such as styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; Methyl acid, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, fat Aromatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like.

(Fluidity improver)
The fluidity improver is an agent that increases the hydrophobicity by performing a surface treatment and prevents deterioration of the flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, modified silicone oil, and the like can be given. Silica and titanium oxide are particularly preferably subjected to surface treatment with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

(Cleaning improver)
The cleaning property improving agent is an agent added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl 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.

(Layered inorganic mineral)
If necessary, a layered inorganic mineral may be contained in the toner. The layered inorganic mineral refers to an inorganic mineral formed by superposing layers having a thickness of several nanometers, and modifying with organic ions refers to introducing organic ions into ions existing between the layers. Specifically, it is described in JP-T-2003-515795, JP-T-2006-500605, and JP-T-2006-503313. This is called intercalation in a broad sense.
As the layered inorganic mineral, smectite group (montmorillonite, saponite, etc.), kaolin group (kaolinite, etc.), magadiite, and kanemite are known. The modified layered inorganic mineral is highly hydrophilic due to its modified layered structure. Therefore, when used in toners that are dispersed in an aqueous medium and granulated without modifying the layered inorganic mineral, the layered inorganic mineral migrates into the aqueous medium and the toner cannot be deformed, but may be modified. Therefore, the modified layered inorganic mineral becomes finer and deformed during the production of the toner, and is particularly present in the surface portion of the toner particles, and it functions as a charge controller and contributes to low-temperature fixing. . At this time, the content of the modified layered inorganic mineral in the toner material is preferably 0.05 to 5% by weight.
The modified layered inorganic mineral used in the present invention is preferably one having a smectite basic crystal structure modified with an organic cation. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.
Examples of the organic ion modifier of the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts and imidazolium salts. A quaternary alkyl ammonium salt is desirable.
Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.
Examples of the organic ion modifier include branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene oxide, propylene oxide, and the like. Sulfates, sulfonates, carboxylates, or phosphates having A carboxylic acid having an ethylene oxide skeleton is desirable.
By modifying at least a part of the layered inorganic mineral with organic ions, the layered inorganic mineral has moderate hydrophobicity, the oil phase containing the toner composition and / or toner composition precursor has non-Nutnian viscosity, Can be modified. At this time, the content of the layered inorganic mineral obtained by modifying a part of the toner material with organic ions is preferably 0.05 to 5% by weight.
The layered inorganic mineral partially modified with organic ions can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.
Commercially available layered inorganic minerals partially modified with organic cations include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite such as (made by Southern Clay), and stearalkonium bentonite such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (made by Southern Clay) Examples include quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA. Further, as the layered inorganic mineral partially modified with an organic anion, a layer modified with an organic anion represented by the following general formula (3) in DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) is particularly preferable. The following general formula (3) includes, for example, Hytenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).

R1 (OR2) nOSO3M General formula (3)
[Wherein R 1 represents an alkyl group having 13 carbon atoms, and R 2 represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element]

  By using the modified layered inorganic mineral, the oil phase having an appropriate hydrophobicity and a toner composition containing the toner composition has a non-Newtonian viscosity in the manufacturing process of the toner, and the toner can be deformed.

(Inorganic fine particles)
The inorganic fine particles are used as an external additive for imparting fluidity, developability, chargeability and the like to the toner particles. The inorganic fine particles are not particularly limited and can be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, 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, silicon carbide, silicon nitride, and the like can be used. These may be used individually by 1 type and may use 2 or more types together.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples. In the examples, “parts” is “parts by weight” unless otherwise specified.

Example 1 Production of Toner 1
(Example of production of emulsified resin fine particle dispersion)
-Production of emulsified resin fine particle dispersion 1-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct 562 parts Bisphenol A propylene oxide 2-mole adduct 95 parts Bisphenol A propylene oxide 3-mole adduct 87 parts Terephthalic acid ... 143 parts adipic acid ... 126 parts, and Dibutyltin oxide: 2 parts were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted at 5 hours under reduced pressure of 10-15 mmHg. Thereafter, 85 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain resin fine particles (I). Polyester (I) obtained had a molecular weight of 3700 and a glass transition temperature of 47 ° C.
The obtained polyester (I) had a glass transition temperature of 65 ° C. and an acid value of 81 mgKOH / g.
200 g of this polyester (I) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 1200 ml of a 1% nonionic surfactant (Neugen EM230D manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature to obtain an emulsified resin fine particle dispersion 1.
The particle diameter of the emulsified resin fine particle dispersion 1 was a volume average particle diameter of 50 nm.

(Adjustment of aqueous phase)
990 parts of water, 83 parts of [Emulsified polyester dispersion 1], 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained.
This is designated as [Aqueous Phase 1].

<Example of resin synthesis>
(Synthesis Example 1 of Amorphous Polyester Resin)
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 67 parts of a 2-mole addition product of ethylene oxide of bisphenol A, 84 parts of a 3-mole addition product of propion oxide of bisphenol A, 270 parts of terephthalic acid, 120 parts of isophthalic acid, and dibutyltin 2 parts of oxide was added and reacted at 270 ° C. under normal pressure for 8 hours. Next, it was made to react for 7 hours under the reduced pressure of 10-15 mmHg, and the polyester resin was synthesize | combined. The obtained polyester resin R1 had an acid value of 19.8 mgKOH / g and a weight average molecular weight Mw of 4200.

(Production of crystalline resin C1)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 241 parts of sebacic acid, 55 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 75 parts was added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 3 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg, the Mw (weight average The reaction was continued until the molecular weight reached about 1200.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and 250 parts of ethyl acetate, 40 parts of hexamethylene diisocyanate (HDI) and 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C1 shown in Table 1.

(Synthesis of intermediate polyester)
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1].
[Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained.

<Synthesis of ketimine compound (active hydrogen group-containing compound)>
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (active hydrogen group-containing compound).
The amine value of the obtained ketimine compound was 418.

[Manufacture of colorant masterbatch]
After mixing 100 parts of amorphous resin A and 100 parts of cyan pigment (CI Pigment blue 15: 3) with a Henschel mixer (Mitsui Mining Co., Ltd.) at 1000 rpm for 5 minutes, an open roll kneader (Mitsui Mine) was used. And 2 mm large pigment dispersion powder was prepared with a rotoplex pulverizer to prepare a master batch.

[Production of Wax Dispersion 1]
20 parts of carnauba wax, 80 parts of amorphous resin A and 120 parts of ethyl acetate were added, heated to 78 ° C. to dissolve sufficiently, cooled to 30 ° C. with stirring for 1 hour, and then further Ultraviscomil (manufactured by IMEX) ), Heated to 40 ° C., and wet pulverized under the conditions of a liquid feeding speed of 1.0 kg / hr, f disk peripheral speed: 10 m / sec, 0.5 mm zirconia bead filling volume of 80% by volume, and 6 passes. Then, a wax dispersion 1 was prepared.

(Manufacture of toner 1)
In a vessel equipped with a thermometer and a stirrer, 20 parts of crystalline resin C1 and 24 parts of ethyl acetate are placed and heated to the melting point of the resin or higher to dissolve well, and a 50% ethyl acetate solution of amorphous resin A is added to 102 parts. 66 parts of [Wax Dispersion 1], 10 parts of Colorant Masterbatch, and 12 parts of [Prepolymer 1] are added at 50 ° C. with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotation speed of 10,000 rpm. The mixture was stirred and uniformly dissolved and dispersed to obtain [Oil Phase 1].
Next, 50 parts of [Oil Phase 1] maintained at 50 ° C. is added to [Aqueous Phase 1], and mixed for 1 minute at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika). Slurry 1] was obtained.
Next, 100 parts of [Composite Particle Slurry 1] of the obtained toner base particles was filtered under reduced pressure, and then the following washing treatments (1) to (4) were performed.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(2) 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), and then filtered under reduced pressure.
(3) 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 6,000 rpm for 5 minutes), and then filtered.
(4) Add 300 parts of ion exchanged water to the filter cake of (3) above, mix with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filter twice to perform [Filter cake 1]. Obtained.
The obtained [Filter cake 1] was dried at 45 ° C. for 48 hours by a circulating dryer. Thereafter, the mixture was sieved with a mesh having a mesh size of 75 μm [Toner base particles 1 were produced.
Next, 1.0 part of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) is mixed with 100 parts of the obtained [toner base particle 1] using a Henschel mixer to obtain a volume average particle diameter of 5. 6 μm of [Toner 1] was produced.

Example 2 Production of Toner 2
A toner 2 was produced in the same manner as in Example 1 except that the emulsion resin fine particle dispersion 1 of Example 1 was changed to the emulsion resin fine particle dispersion 2 produced as follows.

-Production of emulsified resin fine particle dispersion 2-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct 562 parts Bisphenol A propylene oxide 2-mole adduct 90 parts Bisphenol A propylene oxide 3-mole adduct 90 parts terephthalic acid ... 143 parts adipic acid ... 126 parts, and Dibutyltin oxide: 2 parts were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted at 5 hours under reduced pressure of 10-15 mmHg. Thereafter, 60 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain polyester (II). The obtained polyester (II) had a glass transition temperature of 52 ° C. and an acid value of 50 mgKOH / g.
200 g of this polyester (II) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 1800 ml of a 1% nonionic surfactant (Neugen EM230D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature to obtain an emulsified resin fine particle dispersion 2.
The particle diameter of the emulsified resin fine particle dispersion 2 was a volume average particle diameter of 44 nm.

Example 3 Production of Toner 3
A toner 3 was obtained in the same manner as in Example 1 except that the emulsion resin fine particle dispersion 1 of Example 1 was changed to the emulsion resin fine particle dispersion 3 prepared as follows.

-Production of emulsified resin fine particle dispersion 3-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct ... 562 parts Bisphenol A propylene oxide 2-mole adduct ... 98 parts Bisphenol A propylene oxide 3-mole adduct ... 92 parts Terephthalic acid ... 143 parts Adipic acid ...・ 126 parts and 2 parts of dibutyltin oxide ……………………………………………………………………. After 5 hours of reaction, 80 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain polyester (III). The polyester (III) obtained had a glass transition temperature of 78 ° C. and an acid value of 75 mgKOH / g.
200 g of this polyester (III) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 1200 ml of a 1% nonionic surfactant (Neugen EM230D manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature to obtain an emulsified resin fine particle dispersion 3.
The particle diameter of the emulsified resin fine particle dispersion 3 was a volume average particle diameter of 80 nm.

Example 4 Production of Toner 4
A toner 4 was produced in the same manner as in Example 1 except that the emulsion resin fine particle dispersion 1 in Example 1 was changed to the emulsion resin fine particle dispersion 4 produced as follows.

-Production of emulsified resin fine particle dispersion 4-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct ... 562 parts Bisphenol A propylene oxide 2-mole adduct ... 80 parts Bisphenol A propylene oxide 3-mole adduct ... 85 parts Terephthalic acid ... ... 143 parts adipic acid ... 126 parts, and Dibutyltin oxide: 2 parts were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted at 5 hours under reduced pressure of 10-15 mmHg. Thereafter, 80 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain polyester (IV). The polyester (IV) obtained had a glass transition temperature of 46 ° C. and an acid value of 75 mgKOH / g.
200 g of this polyester (IV) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 1400 ml of a 1% nonionic surfactant (Neugen EM230D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature to obtain an emulsified resin fine particle dispersion 4.
The particle diameter of the emulsified resin fine particle dispersion 4 was a volume average particle diameter of 60 nm.

Example 5 Production of Toner 5
A toner 5 was obtained in the same manner as in Example 1 except that the emulsion resin fine particle dispersion 1 in Example 1 was changed to the emulsion resin fine particle dispersion 5 prepared as follows.

-Production of emulsified resin fine particle dispersion 5-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct 562 parts Bisphenol A propylene oxide 2-mole adduct 102 parts Bisphenol A propylene oxide 3-mole adduct 96 parts terephthalic acid ... 143 parts adipic acid ... 126 parts and dibutyl Tin oxide: After 2 parts are added, react for 8 hours at 230 ° C. under normal pressure, and after 5 hours reaction under reduced pressure of 10-15 mmHg Into the reaction vessel, 80 parts of trimellitic anhydride was added and reacted at 180 ° C. and normal pressure for 2 hours to obtain polyester (V). The polyester (V) obtained had a glass transition temperature of 85 ° C. and an acid value of 75 mgKOH / g.
200 g of this polyester (V) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 1400 ml of a 1% nonionic surfactant (Neugen EM230D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature to obtain an emulsified resin fine particle dispersion 5.
The particle diameter of the emulsified resin particle dispersion 5 was a volume average particle diameter of 65 nm.

Example 6 Production of Toner 6
A toner 6 was obtained in the same manner as in Example 1 except that the emulsion resin fine particle dispersion 1 of Example 1 was changed to the emulsion resin fine particle dispersion 6 prepared as follows.

-Production of emulsified resin fine particle dispersion 6-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct ... 562 parts Bisphenol A propylene oxide 2-mole adduct ... 82 parts Bisphenol A propylene oxide 3-mole adduct ... 75 parts terephthalic acid ... 143 parts Adipic acid ...・ 126 parts and 2 parts of dibutyltin oxide ……………………………………………………………………. After 5 hours of reaction, 52 parts of trimellitic anhydride was placed in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain polyester (VI). The obtained polyester (VI) had a glass transition temperature of 60 ° C. and an acid value of 40 mgKOH / g.
200 g of this polyester (VI) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 1500 ml of a 1% nonionic surfactant (Neugen EM230D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature, and an emulsified resin fine particle dispersion 6 was obtained.
The particle diameter of the emulsified resin fine particle dispersion 6 was a volume average particle diameter of 55 nm.

Example 7 Production of Toner 7
A toner 7 was obtained in the same manner as in Example 1 except that the emulsion resin fine particle dispersion 1 of Example 1 was changed to the emulsion resin fine particle dispersion 7 prepared as follows.

-Production of emulsified resin fine particle dispersion 7-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct ... 562 parts Bisphenol A propylene oxide 2-mole adduct ... 76 parts Bisphenol A propylene oxide 3-mole adduct ... 68 parts terephthalic acid ... 143 parts Adipic acid ...・ 126 parts and 2 parts of dibutyltin oxide ……………………………………………………………………. After 5 hours of reaction, 88 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain polyester (VII). The polyester (VII) obtained had a glass transition temperature of 70 ° C. and an acid value of 92 mgKOH / g.
200 g of this polyester (VII) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 1500 ml of a 1% nonionic surfactant (Neugen EM230D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature to obtain an emulsified resin fine particle dispersion 7.
The particle diameter of the emulsified resin fine particle dispersion 7 was a volume average particle diameter of 60 nm.

Example 8 Production of Toner 8
A toner 8 was obtained in the same manner as in Example 1 except that the emulsion resin fine particle dispersion 1 of Example 1 was changed to the emulsion resin fine particle dispersion 8 prepared as follows.

-Production of emulsified resin fine particle dispersion 8-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct ... 562 parts Bisphenol A propylene oxide 2-mole adduct ... 68 parts Bisphenol A propylene oxide 3-mole adduct ... 62 parts terephthalic acid ... 143 parts Adipic acid ...・ 126 parts and 2 parts of dibutyltin oxide ……………………………………………………………………. After 5 hours of reaction, 56 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain polyester (VIII). The polyester (VIII) obtained had a glass transition temperature of 60 ° C. and an acid value of 60 mgKOH / g.
200 g of this polyester (VIII) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 2000 ml of a 1% nonionic surfactant (Neugen EM230D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature to obtain an emulsified resin fine particle dispersion 8.
The particle diameter of the emulsified resin fine particle dispersion 8 was a volume average particle diameter of 22 nm.

Example 9 Production of Toner 9
A toner 9 was obtained in the same manner as in Example 1 except that the emulsion resin fine particle dispersion 1 of Example 1 was changed to the emulsion resin fine particle dispersion 9 prepared as follows.

-Production of emulsified resin particle dispersion 9-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct ... 562 parts Bisphenol A propylene oxide 2-mole adduct ... 70 parts Bisphenol A propylene oxide 3-mole adduct ... 63 parts terephthalic acid ... 143 parts Adipic acid ...・ 126 parts and 2 parts of dibutyltin oxide ……………………………………………………………………. After 5 hours of reaction, 62 parts of trimellitic anhydride was placed in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain polyester (IX). Polyester (IX) obtained had a glass transition temperature of 65 ° C. and an acid value of 70 mgKOH / g.
200 g of this polyester (IX) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 900 ml of a 1% nonionic surfactant (Neugen EM230D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature to obtain an emulsified resin fine particle dispersion 9.
The particle diameter of this emulsified resin fine particle dispersion 9 was a volume average particle diameter of 115 nm.

[Comparative Example 1; Production of Toner 10]
A toner 10 was obtained in the same manner as in Example 1 except that the emulsion resin fine particle dispersion 1 of Example 1 was changed to the emulsion resin fine particle dispersion 10 prepared as follows.

-Production of emulsified resin fine particle dispersion 10-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct 562 parts Bisphenol A propylene oxide 2-mole adduct 52 parts Bisphenol A propylene oxide 3-mole adduct 48 parts terephthalic acid ... 143 parts adipic acid ... 126 parts, and Dibutyltin oxide: 2 parts were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted at 5 hours under reduced pressure of 10-15 mmHg. Thereafter, 62 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain polyester (X). The polyester (X) obtained had a glass transition temperature of 46 ° C. and an acid value of 70 mgKOH / g.
200 g of this polyester (X) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 900 ml of a 1% nonionic surfactant (Neugen EM230D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature to obtain an emulsified resin fine particle dispersion 10.
The particle diameter of the emulsified resin fine particle dispersion 10 was a volume average particle diameter of 120 nm.

[Comparative Example 2; Production of Toner 11]
A toner 11 was obtained in the same manner except that the emulsion resin fine particle dispersion 1 was changed to the emulsion resin fine particle dispersion 11 prepared as follows.

-Production of emulsified resin fine particle dispersion 11-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct ... 562 parts Bisphenol A propylene oxide 2-mole adduct ... 52 parts Bisphenol A propylene oxide 3-mole adduct ... 48 parts terephthalic acid ... 143 parts Adipic acid ...・ 126 parts and 2 parts of dibutyltin oxide ……………………………………………………………………. After 5 hours of reaction, 36 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain polyester (11). The polyester (11) obtained had a glass transition temperature of 45 ° C. and an acid value of 40 mgKOH / g.
200 g of this polyester (11) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 1200 ml of a 1% nonionic surfactant (Neugen EM230D manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature, and an emulsified resin fine particle dispersion 11 was obtained.
The particle diameter of the emulsified resin fine particle dispersion 11 was a volume average particle diameter of 80 nm.

[Comparative Example 3; Production of Toner 12]
A toner 12 was produced in the same manner as in Example 1 except that the emulsion resin fine particle dispersion 1 of Example 1 was changed to the emulsion resin fine particle dispersion 12 produced as follows.

-Production of emulsified resin fine particle dispersion 12-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct ... 562 parts Bisphenol A propylene oxide 2-mole adduct ... 82 parts Bisphenol A propylene oxide 3 mol adduct ... 76 parts terephthalic acid ... 143 parts Adipic acid ...・ 126 parts and 2 parts of dibutyltin oxide ……………………………………………………………………. After 5 hours of reaction, 56 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain polyester (12). The polyester (12) obtained had a glass transition temperature of 85 ° C. and an acid value of 60 mgKOH / g.
200 g of this polyester (12) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 2000 ml of a 1% nonionic surfactant (Neugen EM230D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature to obtain an emulsified resin fine particle dispersion 12.
The particle diameter of the emulsified resin fine particle dispersion 12 was a volume average particle diameter of 20 nm.

[Comparative Example 4; Production of Toner 13]
A toner 13 was obtained in the same manner as in Example 1 except that the emulsion resin fine particle dispersion 1 of Example 1 was changed to the emulsion resin fine particle dispersion 13 prepared as follows.

-Production of emulsified resin fine particle dispersion 13-
In an autoclave equipped with a thermometer and stirrer,
Bisphenol A ethylene oxide 2-mole adduct 562 parts Bisphenol A propylene oxide 2-mole adduct 66 parts Bisphenol A propylene oxide 3-mole adduct 59 parts Terephthalic acid ... 143 parts adipic acid ... 126 parts, and Dibutyltin oxide: 2 parts were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted at 5 hours under reduced pressure of 10-15 mmHg. Thereafter, 36 parts of trimellitic anhydride was put into a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain polyester (13). The polyester (13) obtained had a glass transition temperature of 70 ° C. and an acid value of 42 mgKOH / g.
200 g of this polyester (13) was dissolved in 300 g of tetrahydrofuran at room temperature.
Subsequently, 10 g of 40 wt% aqueous KOH solution was added.
While stirring this mixture, 800 ml of a 1% nonionic surfactant (Neugen EM230D, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) aqueous solution was added at room temperature. In order to remove tetrahydrofuran, the temperature was raised to 65 ° C. with nitrogen flow, and the temperature was maintained for 1 hour. This was cooled to room temperature, and the emulsion resin fine particle dispersion 13 had a volume average particle size of 200 nm.

[Comparative Example 5; Production of Toner 14]
A toner 14 was obtained in the same manner as in Example 1 except that the amount of [Prepolymer 1] added to the toner was changed to 18 parts.
Table 1 summarizes the characteristics of the toners of Examples and Comparative Examples and the resin fine particles used.

[Toner characteristics measurement method]
(Volume average particle diameter (Dv) and number average particle diameter (Dn))
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.) at an aperture diameter of 100 μm, and analysis software (Beckman Coulter) is used. Analysis was performed using Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) was added to a glass 100 ml beaker, 0.5 g of each toner was added, and the mixture was stirred with a micropartel. Subsequently, 80 ml of ion-exchanged 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) 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.

(Average circularity)
The average circularity of the toner is defined by the average circularity SR = (peripheral length of a circle having the same area as the particle projection area / perimeter length of the particle projection image) × 100%. Measurement was performed using a flow particle image analyzer (“FPIA-3000”; manufactured by Sysmex Corporation), and analysis was performed using analysis software (FPIA-3000 Data Processing Program for FPIA version 00-10). Specifically, 0.1 to 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, and each toner 0.1 to 0 is added. 0.5 g was added and stirred with a microspatel, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). Using the FPIA-3000, the dispersion was measured for toner shape and distribution until a density of 5000 to 15000 / μl was obtained. In this measurement method, it is important that the concentration of the dispersion liquid is 5000 to 15000 / μl from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated. It will be enough. Further, the toner addition amount differs from the particle size, and it is necessary to decrease the small particle size and increase the large particle size. When the toner particle size is 3 to 7 μm, the toner amount is 0.1 to 0. By adding 0.5 g, the dispersion concentration can be adjusted to 5000 to 15000 / μl.

(Granulation property evaluation)
The particle size (Dv), particle size distribution (Dv / Dn), and average circularity are determined as follows.
Dv;
5.0 to 5.4 μm is ◎,
4.7 to 4.9 μm and 5.5 to 5.7 μm are ○,
4.4 to 4.6 μm and 5.8 to 6.0 μm are Δ,
The other range is x.
Dv / Dn;
1.00 to 1.15 is ◎,
1.16 to 1.20 are ○
1.21-1.25 is △,
The other range is x.
Average circularity;
0.95-0.96 is ◎,
0.93 to 0.94 and 0.97 to 0.98 are ○,
The other range is x.

(Fixability evaluation)
- a two-component developers obtained in the low-temperature fixability Evaluation of Ricoh Company, Ltd. Co. copier coating weight 4.0 mg / cm ² at (Imagio Neo C355), creates an unfixed image, then Corporation Using an external fixing machine that can set the roller temperature freely by modifying the fixing device (oilless system) of the Ricoh Copier (Imagio Neo C355), the paper feed is fixed at 120 mm / sec and from 100 ° C to 140 ° C The temperature was changed by 1 ° C. At this time, the offset phenomenon in which the image was not fully melted and the image was retransferred to the non-image portion was observed on the fixing roller and the paper, and the temperature at which the image was not retransferred was defined as the low-temperature non-offset temperature. At this time, the non-offset temperature is
◎ less than 110 ℃,
110 ° C. or more and less than 120 ° C.,
△ at 120 ° C or higher and lower than 130 ° C
130 degreeC or more was made into x.

(Preservation evaluation)
10 g of the above toner was weighed into a 200 CC screw vial and allowed to stand in a 35 ° C./80% environment for 1 month to obtain an evaluation toner. The toner for evaluation was spread on an opening of 75 μm, and the state of the toner remaining on the shaker was observed by shaking for 1 minute.
X, a lot of aggregated toner
Somewhat seen △,
Those that were not observed at all were marked with ◯.
The evaluation results are shown in Table 2.

  As can be seen from the above results, the toners of the examples had good results, although their levels differed.

(About Fig. 1 and Fig. 2)
DESCRIPTION OF SYMBOLS 100A Image forming apparatus 100B Image forming apparatus 10 Photoconductor 20 Charging roller 30 Exposure apparatus 40 Developing means (developing apparatus)
41 Development Belt 42C Developer Storage Unit 42M Developer Storage Unit 42Y Developer Storage Unit 42K Developer Storage Unit 43C Developer Supply Roller 43M Developer Supply Roller 43Y Developer Supply Roller 43K Developer Supply Roller 44C Development Roller 44M Development Roller 44Y Developing roller 44K Developing roller 45C Cyan developing unit (developing unit)
45M magenta developer (development unit)
45Y Yellow developer (development unit)
45K black developer (development unit)
50 Intermediate transfer member 51 Roller 58 Corona charger 60 Cleaning means (cleaning device)
70 Static elimination means (static elimination lamp)
80 Transfer means (transfer roller)
90 Cleaning device 95 Recording medium (recording paper)
(About Fig. 3 and Fig. 4)
100C Image forming apparatus 10K Photoconductor for black 10Y Photoconductor for yellow 10M Photoconductor for magenta 10C Photoconductor for cyan 14 Intermediate transfer member support roller 15 Intermediate transfer member support roller 16 Intermediate transfer member support roller 17 Intermediate transfer member cleaning device 18 Image Forming means 21 Exposure device 22 Secondary transfer device 23 Roller pair 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 49 Registration roller 50 Intermediate transfer member 52 Manual feed tray 53 Manual feed path 55 Switching claw 56 Ejection roller 57 Ejection tray 59 Charger 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 120 Tandem developer 130 Document platen 142a Paper feed roller 142b Paper feed roller 143 Paper bank 144 Paper feed cassette 145a Separation roller 145b Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copying device main body 200 Paper feed table 300 Scanner 400 Automatic document feeder L exposure

JP 2005-234046 A JP 2013-050578 A JP 2005-227672 A JP 2012-159595 A JP 2006-251359 A Japanese Patent No. 4049679

Claims (10)

A toner in which resin fine particles are arranged on the surface of toner base particles containing at least a binder resin, a release agent, and a colorant, and the value of the storage elastic modulus G′A (Pa) of the first temperature increase of the toner The following conditions are satisfied, the value of the storage elastic modulus G′B (Pa) at the first temperature rise of the resin fine particles satisfies the following conditions, and the relationship between G′A and G′B satisfies the following conditions: Toner.
Storage elastic modulus G′A (60) of toner at first temperature rise of 60 ° C .:
5.0 × 10 ^ 5 <G′A (60) <5.0 × 10 ^ 6
Storage elastic modulus G′A (100) of toner at first temperature rise of 100 ° C .:
1.0 × 10 ^ 4 <G′A (100) <1.0 × 10 ^ 5
Storage elastic modulus G′B (60) of resin fine particles at 60 ° C. for the first temperature increase:
1.0 × 10 ^ 7 <G′B (60) <1.0 × 10 ^ 10
Storage elastic modulus G′B (100) of resin fine particles at 100 ° C. for the first temperature increase:
1.0 × 10 ^ 4 <G′B (100) <1.0 × 10 ^ 6
G′B (60) −G′A (60) ≦ 5.0 × 10 ^ 9
G′B (100) −G′A (100) ≦ 5.0 × 10 ^ 5   2. The electrostatic charge developing toner according to claim 1, wherein the resin fine particles have a glass transition temperature (Tg) of 50 to 80 ° C. 3.   The electrostatic charge developing toner according to claim 1, wherein the resin fine particles have an acid value (AV) of 45 to 90 mg KOH / g.   4. The electrostatic image developing toner according to claim 1, wherein the resin fine particles have a particle diameter of 30 nm to 100 nm.   The toner according to claim 1, wherein the binder resin includes at least one of a crystalline polyester resin and an amorphous polyester resin.   It is obtained by removing the organic solvent from an emulsified dispersion obtained by dispersing an oil phase containing at least a binder resin precursor composed of a modified polyester resin in an organic solvent in an aqueous medium to which the fine particles are added. The electrophotographic toner according to claim 1, wherein the toner is an electrophotographic toner.   The release agent contains a wax, and the difference between the surface wax amount P (A) obtained by FTIR-ATR measurement of the toner before fixing of the toner and the surface wax amount P (B) of the toner after fixing is 0. The toner for electrophotography according to claim 1, wherein 10 ≦ P (B) −P (A) ≦ 0.40.   The release agent contains a wax, and the surface wax amount P (A) obtained by FTIR-ATR measurement of the toner before fixing of the toner satisfies 0.10 ≦ P (A) ≦ 0.25. The electrophotographic toner according to claim 1, wherein the toner is an electrophotographic toner.   9. The toner for electrophotography according to claim 1, wherein the resin fine particles are made of a polyester resin.   An electrostatic latent image carrier, electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and the toner according to claim 1, Developing means for developing a latent image to form a visible image, transfer means for transferring the visible image onto a recording medium, and fixing means for fixing the transferred image transferred onto the recording medium An image forming apparatus.

Images