JP2019164209A - Toner and method for manufacturing the same, developer, and process cartridge using the toner, image forming apparatus, and image forming method - Google Patents

Abstract

To provide a toner excellent in heat-resistant storage property, low-temperature fixability, environmental stability, and image quality.SOLUTION: A toner contains a binder resin and a mold release agent. A mold release agent peak (Wk) and a resin peak (Rk) of a toner heated product obtained by heating the toner when measured by the FTIR-ATR method (total reflection absorption infrared spectroscopy) satisfy a specific relationship; a mold release agent peak (Wn) and a resin peak (Rn) of a non-heated product in which the toner is not heated when measured by the FTIR-ATR method (total reflection absorption infrared spectroscopy) and the mold release agent peak (Wk) and the resin peak (Rk) satisfy a specific relationship; in a molecular weight distribution of a soluble component of tetrahydrofuran (THF) in the toner measured by gel permeation chromatography (GPC), when an arbitrary molecular weight M is selected within a molecular weight range of 300 or more and 5,000 or less, the difference between the maximum value and the minimum value of a peak intensity defined below within a range of ±300 of the molecular weight M is 30 or less.SELECTED DRAWING: None

Description

  The present invention relates to a toner, a manufacturing method thereof, a developer, and a process cartridge, an image forming apparatus, and an image forming method using the toner.

  Currently, in the field of electrophotographic image forming technology, there is a demand for an image forming apparatus capable of high-speed and high-quality image formation. In the image forming apparatus, in order to perform high-speed image formation, the toner is required to have low temperature fixability. Further, in the image forming apparatus, since the toner is subjected to stress due to heat and agitation, durability such as stable charging characteristics and heat-resistant storage stability that can withstand these are required.

  In order to improve the low-temperature fixability of the toner, it is necessary to control the molecular weight, molecular weight distribution, and thermal characteristics of the binder resin that occupies most of the toner. Therefore, for example, it contains at least two kinds of resins having softening points different by 25 ° C. or more, and the molecular weight distribution by GPC determined by the THF soluble content of each resin is between 1,000 and 10,000. And a toner having a molecular weight of 15,000 or less and a chloroform-insoluble content of 5 to 40% has been proposed (for example, see Patent Document 1).

On the other hand, in order to improve the charging stability of the toner, in general, a hydrophobic additive is externally added to the surface of the toner to suppress a decrease in charging of the toner under high humidity. For example, a method for removing a component in the toner that lowers the toner property and a method for improving the contamination resistance of the toner component with respect to the charging member or the carrier are effective.
Therefore, for example, it has been proposed to control the component ratio of the molecular weight of 500 to 1,000 derived from the binder resin in the GPC of the toner and the component ratio of the molecular weight of 500 or less within a specific range (see, for example, Patent Document 2). ).
In addition, it has been proposed to control the content of components having a molecular weight of 500 or less in GPC of the binder resin (see, for example, Patent Document 3).

However, there is a trade-off relationship between low-temperature fixability, heat-resistant storage stability and charging stability.
Thus, toners that satisfy the low-temperature fixability, heat-resistant storage stability, and charge stability, which have been problems so far, have been proposed by using a resin in which a terminal hydrophilic group is substituted with a lipophilic group (for example, patents). Reference 4).
For the toner melt obtained by heating, the relative intensity between the peak derived from the release agent and the peak derived from the binder resin when the ATR method (total reflection method) of the Fourier transform infrared spectroscopic device was measured. By controlling the toner, a toner satisfying low-temperature fixability, heat-resistant storage stability, and charging stability has been proposed (see, for example, Patent Document 5).

  An object of the present invention is to provide a toner excellent in heat-resistant storage stability, low-temperature fixability, environmental stability, and image quality.

The toner of the present invention as means for solving the above problems is
A toner containing a binder resin and a release agent,
The release agent peak (Wk) and the resin peak (Rk) at the time of FTIR-ATR (total reflection absorption infrared spectroscopy) measurement of the heated toner obtained by heating the toner satisfy the relationship of the following formula (1). ,
The release agent peak (Wn), the resin peak (Rn), the release agent peak (Wk), and the above-mentioned when the FTIR-ATR method (total reflection absorption infrared spectroscopy) of the toner non-heated product that does not heat the toner is measured. The resin peak (Rk) satisfies the relationship of the following formula (2),
In the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble component of the toner, when an arbitrary molecular weight M in the range of 300 to 5,000 is selected, the molecular weight M The difference between the maximum value and the minimum value of the peak intensity defined below in the range of ± 300 is 30 or less.
0.20 ≦ Wk / Rk ≦ 0.25 Formula (1)
0.65 ≦ (Wn / Rn) / (Wk / Rk) ≦ 0.84 Formula (2)
Peak intensity: Relative value when GPC measurement is plotted with a molecular weight distribution curve in which the vertical axis is intensity and the horizontal axis is molecular weight, and the maximum intensity value is 100 in the molecular weight range of 20,000 or less.

  According to the present invention, a toner excellent in heat-resistant storage stability, low-temperature fixability, environmental stability, and image quality can be provided.

FIG. 1 is a diagram showing a GPC analysis result of a THF soluble component of the toner of the present invention. FIG. 2 is a diagram showing a GPC analysis result in a THF soluble component of a conventional toner. FIG. 3 is a diagram showing a GPC analysis result in the THF soluble component of the toner of the present invention. FIG. 4 is a diagram showing a GPC analysis result in a THF soluble component of a conventional toner. FIG. 5 is a schematic diagram showing an example of an image forming apparatus according to the present invention. FIG. 6 is a schematic diagram showing another example of the image forming apparatus according to the present invention. FIG. 7 is a schematic diagram showing another example of the image forming apparatus according to the present invention. FIG. 8 is a schematic diagram showing another example of the image forming apparatus according to the present invention. FIG. 9 is a schematic diagram illustrating an example of an evaluation chart in gloss unevenness evaluation. FIG. 10 is a schematic explanatory diagram illustrating an example of a recording medium pressing force measuring apparatus for evaluating toner separation stability.

(toner)
The toner of the present invention is a toner containing at least a binder resin and a release agent.
The release agent peak (Wk) and the resin peak (Rk) at the time of FTIR-ATR (total reflection absorption infrared spectroscopy) measurement of the heated toner obtained by heating the toner satisfy the relationship of the following formula (1). ,
The release agent peak (Wn), the resin peak (Rn), the release agent peak (Wk), and the above-mentioned when the FTIR-ATR method (total reflection absorption infrared spectroscopy) of the toner non-heated product that does not heat the toner is measured. The resin peak (Rk) satisfies the relationship of the following formula (2).
In the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble component of the toner, when an arbitrary molecular weight M in the range of 300 to 5,000 is selected, the molecular weight M The difference between the maximum and minimum peak intensities defined below in the range of ± 300 is 30 or less.
0.20 ≦ Wk / Rk ≦ 0.25 Formula (1)
0.65 ≦ (Wn / Rn) / (Wk / Rk) ≦ 0.84 Formula (2)
Peak intensity: Plotted by GPC measurement with a molecular weight distribution curve with the vertical axis representing the intensity and the horizontal axis representing the molecular weight, and relative values when the maximum intensity value is 100 in the molecular weight range of 20,000 or less. Details will be described.

Japanese Patent Application Laid-Open No. 2006-126196 discloses a toner satisfying low temperature fixability, heat resistant storage stability and charge stability, which has been a problem until now, by using a resin in which a terminal hydrophilic group is substituted with a lipophilic group. Proposed. However, it has been found that the toner containing the resin has difficulty in seeping out the release agent due to its rigidity, and a new problem of uneven gloss is generated by use. For such problems, it has been found that the problem of uneven gloss can be improved by increasing the content of the release agent, but if the total amount of the release agent contained in the toner increases, the binder resin Even if the toner has rigidity, the durability of the toner itself decreases due to the softening of the release agent contained therein. Specifically, toner aggregates are generated over time, resulting in white spots on the image due to the aggregates, or a release agent contained in the toner in the unit. It has been found that density unevenness occurs due to contamination of members and carriers and deterioration of charging ability.
Therefore, the present inventors paid attention to the relationship between the binder resin and the release agent.

<Intensity ratio (W / R)>
In the present invention, the relative intensity ratio regarding the release agent and the binder resin in the toner obtained by FTIR-ATR (total reflection absorption infrared spectroscopy) satisfies the following formulas (1) and (2).
0.20 ≦ Wk / Rk ≦ 0.25 Formula (1)
0.65 ≦ [(Wn / Rn) / (Wk / Rk)] ≦ 0.84 Formula (2)
In the above formulas (1) and (2), Wk is the peak derived from the release agent of the heated toner, Rk is the peak derived from the resin of the heated toner, Wn is the peak derived from the release agent of the non-heated toner, Wn Represents the measured intensity of the resin-derived peak of the non-heated toner.

The heated toner is obtained by the following method. Applying a force of 40 kN, 0.8 g of toner is pressure-molded into a pellet having a diameter of 20 mm, and heated at a heating stage (for example, a microscope cooling heating stage (manufactured by Japan High-Tech)) at a heating rate of 130 ° C./min at 24 ° C. After heating to 160 ° C. and holding for 2 minutes, it can be cooled to room temperature.
The toner non-heated product can be obtained by pressure-molding 0.8 g of toner into a pellet having a diameter of 20 mm by applying a force of 40 kN.

  The ratio (Wk / Rk) represented by the formula (1) is a ratio that takes into account the release agent that has exuded from the inside of the toner when the toner pellets are heated. This shows the ratio of the internal release agent.

The ratio of (Wn / Rn) and (Wk / Rk) represented by the formula (2) is such that the existing ratio of the release agent on the outermost surface of the toner and the existing ratio of the release agent from the outermost surface of the toner to the inside thereof. The ratio is taken.
The larger the value of the ratio expressed by the formula (2), the higher the surface release agent ratio / total release agent ratio of the toner, and the more the release agent is disposed on the surface.

  In the present invention, it is desirable that the ratio of the release agent contained in the toner is not too high, and the ratio of the release agent present on the toner surface is relatively high as compared with the inside of the toner. Even if the toner has a low molecular weight component and is relatively strong in heat-resistant storage, if the percentage of the release agent contained in the toner is high, the toner will be exposed to severe pressure and heat stress in the development unit of a high-speed machine. Deformation of the entire shape is caused, and aggregate formation is caused in the unit. In addition, if the amount of the release agent is small, the release agent does not sufficiently ooze out during fixing due to the rigidity of the toner, the original release agent function cannot be exhibited, and the separation property after fixing becomes poor and glossy. It causes image errors such as unevenness.

Therefore, the present inventors have a relatively high ratio of the release agent present on the toner surface even when the ratio of the release agent contained in the toner is relatively small. Then, it has been found that image errors such as deterioration of separation after fixing and uneven gloss are not caused. However, the disadvantage of increasing the surface release agent ratio is that the surface release agent is exposed more and adheres to the carrier or the developing member while stirring the developer, such as during image formation. It is possible that These disadvantages can be solved by using the toner having a low low molecular weight component. Although the detailed cause is not known, it is considered that the toner is difficult to deform, and the toner is deformed by heat and pressure stress, thereby preventing the release agent present on the toner surface from being excessively exposed to the toner surface. It is done.
If the surface release agent ratio / total release agent ratio of the toner is relatively low, the release agent does not exude to the outermost surface of the toner effectively at the time of fixing. And image errors such as uneven gloss are likely to occur. When the surface release agent ratio / total release agent ratio of the toner is relatively high, the exposure of the release agent to the toner surface becomes excessive, and the carrier due to the release agent in the developing machine is excessive. The charging ability of the developer is reduced due to contamination or the like, causing image errors such as uneven image density.

  Therefore, when the toner satisfies the provisions of the formulas (1) and (2), excessive inclusion of the release agent in the toner can be suppressed, and the release agent can be efficiently disposed near the toner surface. The effect of the release agent can be brought out.

  In the formula (1), if Wk / Rk <0.20, it means that the amount of the release agent contained in the toner is small. For this reason, the release agent does not bleed out sufficiently at the time of fixing, and the original function of the release agent cannot be exerted, which may cause an image error such as deterioration of separation after fixing and uneven gloss. Further, if 0.25 <Wk / Rk, it means that the amount of the release agent is large from the toner surface to the inside. For this reason, when severe pressure and heat stress is applied in the development unit of a high-speed machine, the amount of the release agent contained in the inside causes a deformation of the entire toner shape and the like. Aggregate formation is caused.

In the formula (2), when (Wn / Rn) / (Wk / Rk) <0.65, the ratio (surface release agent ratio / total release agent ratio) is relatively low. means. For this reason, when there is not enough release agent on the outermost surface of the toner at the time of fixing, the release agent does not exist at an effective position around the toner after fixing, and image errors such as deterioration of separation and uneven gloss occur. Sometimes.
Further, when 0.84 <(Wn / Rn) / (Wk / Rk), it means that the ratio of surface release agent / total release agent is relatively high. For this reason, the exposure of the release agent to the toner surface becomes excessive, and the charging ability of the developer may be lowered due to contamination of the carrier by the release agent in the developing machine, and image errors such as image density unevenness may occur.

As a method for measuring the ratio (W / R) related to the formulas (1) and (2), an ATR method of a Fourier transform infrared spectrometer (for example, NICOLET AVATAR 370 DTGS (manufactured by Thermo Scientific)) is used.
As a specific example, a heated or non-heated toner is fixed with an ATR unit, and measured with a Ge crystal crystal, an incident angle of 45 °, a single reflection, a resolution of 4 cm ⁻¹ , and an integration count of 20 times. The relative strength value (W / R) of the release agent / binder resin is determined from the ratio between the characteristic peak absorbance and the characteristic peak absorbance of the binder resin.

As an example of the method for determining the characteristic peak of the release agent and the characteristic peak of the binder resin, a release agent having a methylene group was used, and a binder resin having an aromatic was used. Show the case. In this case, the height of the characteristic peak of the release agent (peak of 2,850 cm ⁻¹ derived from the methylene group) is W (the peak height baseline is in the range of 2,830 cm ^{−1 to} 2870 cm ⁻¹ ). and in pulling), baseline height of the characteristic peak of the binder resin (peak of the aromatic-derived 828 cm ^-1) R (peak height draws in the range of ^{778cm -1 ~898cm} -1 ) And relative strength (W / R) is obtained.

The method for increasing the relative strength value (Wk / Rk) of the release agent / binder resin of the heated toner is not particularly limited and may be appropriately selected depending on the purpose. Etc.
・ Method of increasing the amount of dispersant having a particle size of 2 μm or more in the release agent dispersion ・ Method of increasing the amount of release agent dispersion added ・ Method of reducing the affinity with the binder resin

The method for increasing the relative strength value (W / R) ((Wn / Rn) / (Wk / Rk)) of the release agent / binder resin between the heated toner and the non-heated material is particularly limited. However, it can be appropriately selected depending on the purpose, and examples thereof include the following methods.
・ Method of increasing the ratio of the release agent near the surface by externally adding release agent particles to the toner. ・ Relative near the surface by containing another resin that is more likely to exist inside the toner than the release agent. To increase the proportion of mold release agent

<Peak intensity difference>
As a result of studying the above problems, the present inventors have found that in the molecular weight distribution measured by gel permeation chromatography (GPC, also called gel permeation chromatography) of the tetrahydrofuran (THF) soluble component of the toner, When an arbitrary molecular weight M in the range of 300 to 5,000 is selected, the difference between the maximum and minimum peak intensities defined below in the range of ± 300 of the molecular weight M may be 30 or less. I found it important. As a result, the present inventors have found that the toner has a low low molecular weight component in the toner, has excellent toner rigidity, and can suppress deterioration in chargeability due to long-term use and use under high temperature and high humidity.

That the difference between the maximum value and the minimum value of the molecular weight M in the range of ± 300 is 30 or less means that the low molecular weight component contained in the toner is small.
In the range of the molecular weight M ± 300, when the difference between the maximum value and the minimum value exceeds 30, the difference means a peak mainly observed on the low molecular weight side. The peak seen on the low molecular weight side in the molecular weight distribution is mainly caused by low molecular weight components derived from raw materials. For example, the binder resin is derived from an unreacted residual monomer contained in the binder resin, or a dimer or trimer which is a low polymer.

  A difference between the maximum value and the minimum value exceeding 30 indicates that there are many low molecular weight components contained in the toner, and the low molecular weight components have a characteristic that they are easily melted by heat from the outside. . Therefore, it is easily softened by heat generated from the machine being used, heat during storage, and the like. Therefore, a toner having a large amount of low molecular weight components has poor heat-resistant storage stability, and toner particles are easily aggregated by heat.

  In addition, since low molecular weight components are easily deformed and attached to external pressure, when toners with a large amount of low molecular weight components are used as developers, they can be used for a long time or under high temperature and high humidity. As a result, it adheres to the carrier or the developing member, and the chargeability over time is significantly reduced.

  Then, it is excellent in heat-resistant storage property by making it like this invention. In addition, the toner has excellent rigidity and can be prevented from being deteriorated in chargeability over time by long-term use or use under high temperature and high humidity.

  In the present invention, when an arbitrary molecular weight M in the molecular weight range of 300 to 5,000 is selected in the molecular weight distribution measured by GPC of the THF soluble component of the toner, a peak in the range of ± 300 of the molecular weight M is selected. The difference between the maximum value and the minimum value of the intensity is 30 or less. The control method is not particularly limited, and examples thereof include a method of replacing the terminal hydrophilic group of the binder resin with a lipophilic group and a method of accelerating the reaction conditions for resin synthesis. The method for substituting the terminal hydrophilic group with a lipophilic group is not particularly limited, and examples thereof include a method of substituting the terminal hydroxyl group with phenoxyacetic acid or benzoic acid. The method for accelerating the reaction conditions for resin synthesis is not particularly limited, and examples include a method of reacting at a high temperature for a long time and increasing the degree of vacuum to remove the monomer.

  The molecular weight distribution measured by GPC of the THF soluble component of the toner is measured as follows.

Gel permeation chromatography (GPC) measuring device: GPC-8220GPC (manufactured by Tosoh Corporation)
Column: TSK-GEL SUPER HZ2000, TSK-GEL SUPER HZ2500, TSK-GEL SUPER HZ3000
Temperature: 40 ° C
Solvent: THF
Flow rate: 0.35 ml / min
Sample: THF sample solution adjusted to 0.15% by mass Sample pretreatment: The toner was dissolved in tetrahydrofuran THF (containing a stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) at 0.15% by mass, and then filtered through a 0.45 μm filter. The filtrate is used as a sample.

  The measurement can be performed by injecting 10 μL to 200 μL of the THF sample solution. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts.

  As a standard polystyrene sample for preparing a calibration curve, TSK standard polystyrene made by Tosoh with molecular weight = 37200, 6200, 2500, 589, standard polystyrene made by Showa Denko with molecular weight 28400, 20298, 10900, 4782, 1689, 1309 and toluene are used. . An RI (refractive index) detector is used as the detector.

For the GPC measurement results, the vertical axis is plotted with the intensity, the horizontal axis is the molecular weight distribution curve with the molecular weight, and the point where the peak intensity is maximum in the range where the molecular weight is 20,000 or less is defined as 100. to correct. The difference between the maximum and minimum intensities is calculated from the maximum value-minimum value of the intensity in an arbitrary molecular weight M ± 300 range of the obtained molecular weight distribution curve.
The column selection is important for the GPC measurement of the THF-soluble component of the toner of the present invention. In the column described below, in the molecular weight distribution measured by GPC of the THF soluble component of the toner, when an arbitrary molecular weight M in the range of 300 to 5000 is selected, the molecular weight M is in the range of ± 300. FIG. 1 shows the result of measuring “toner A” in which the difference between the maximum and minimum peak intensities defined below is 30 or less. The measurement result of the conventional toner B (which does not fall within the scope of the present invention) is shown in FIG. The following column "(Tosoh Corporation)
column:
TSK-GEL SUPER HZ2000,
TSK-GEL SUPER HZ2500,
TSK-GEL SUPER HZ3000 "
FIG. 3 and FIG. 4 show the results of the analysis of “TSK-GEL SUPER HZM-H changed to three in series”. In this column, there is no difference between the toner A described herein and the conventional toner B, and selection of the column is important.

<Toner shape and size>
The shape, size, and the like of the toner are not particularly limited and may be appropriately selected depending on the intended purpose. The weight average molecular weight (Mw), average circularity, volume average particle diameter, volume, and the like are as follows. It is preferable to have a ratio of the average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter).

<< Weight Average Molecular Weight (Mw) of Toner >>
The weight average molecular weight (Mw) of the toner is preferably 5,000 to 18,000. When the Mw is 5,000 or more, toner agglomeration is less likely to occur, and the occurrence of abnormal images can be sufficiently suppressed, which is preferable. When the Mw is 18,000 or less, the low-temperature fixability of the toner is improved, and the toner layer on the recording medium side (lower side) where the fixing member does not directly contact is sufficiently melted in the low-temperature region, and image peeling occurs. This is preferable.
As a measuring method of the weight average molecular weight (Mw) of the toner, for example, it can be measured by gel permeation chromatography (GPC). Specifically, the column is stabilized in a 40 ° C. heat chamber. To the column stabilized at this temperature, tetrahydrofuran (THF) as a solvent is flowed at a flow rate of 1 mL / min, and a THF sample solution of toner adjusted to a sample concentration of 0.05% to 0.6% by weight is 50 μL to 200 μL. Inject and measure.
In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , It is appropriate to use 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

<< Average circularity of toner >>
The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected shape as the shape of the toner by the circumference of the actual particles. For example, 0.950 to 0.980 is preferable, and 0.960 to 0 is preferable. .975 is more preferred. In addition, it is preferable that the particles having an average circularity of less than 0.95 are 15% or less.
When the average circularity is 0.950 or more, it is possible to prevent a problem that satisfactory transferability and a high-quality image free from dust cannot be obtained. The following malfunction can be prevented as it is 0.980 or less.
In an image forming system that employs blade cleaning or the like, defective cleaning occurs on the photoreceptor and the transfer belt, and in the case of image formation with a high image area ratio such as dirt on the image, for example, a photographic image, The toner that forms an untransferred image due to poor paper feed, etc., becomes a transfer residual toner on the photoconductor, causing the background stain of the image to be accumulated. Failure to demonstrate charging ability

  The average circularity is measured using a flow type particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation) and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). be able to.

  Specifically, 0.1 to 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, and each toner 0 is added. Add 1 to 0.5 g, stir with microspatel, then add 80 mL of ion-exchanged water. The obtained dispersion is subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner are measured with the FPIA-2100 until the concentration of the dispersion reaches 5,000 to 15,000 / μL.

  In this measurement method, it is important that the concentration of the dispersion is 5,000 to 15,000 / μL from the viewpoint of measurement reproducibility of average circularity. In order to obtain the concentration of the dispersion, 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, and if it is too small, the toner cannot be sufficiently wetted. It will be enough. The amount of toner added varies depending on the particle size, and is small when the particle size is small, and needs to be increased when the particle size is large. By adding 5 g, the dispersion concentration can be adjusted to 5,000 / μL to 15,000 / μL.

<< Volume average particle diameter of toner >>
There is no restriction | limiting in particular as a volume average particle diameter of the said toner, Although it can select suitably according to the objective, For example, 3 micrometers-10 micrometers are preferable, and 4 micrometers-7 micrometers are more preferable. When the volume average particle size is 3 μm or more, the two-component developer can prevent a problem that the toner is fused to the surface of the carrier during a long period of stirring in the developing device and the charging ability of the carrier is lowered. When the thickness is 10 μm or more, it is difficult to obtain a high-resolution and high-quality image, and it is possible to prevent the problem that the toner particle size fluctuates greatly when the balance of the toner in the developer is performed.

The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, and more preferably 1.00 to 1.15.
The volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) are measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.). The measurement can be performed with an aperture diameter of 100 μm and the analysis can be performed with analysis software (Beckman Coulter Multisizer 3 Version 3.51).

  Specifically, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml beaker made of glass, and 0.5 g of each toner is added. Stir with a microspatel and then add 80 ml of ion-exchanged water. The obtained dispersion is subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion is measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution.

  In the measurement, the toner sample dispersion is dropped so that the concentration indicated by the apparatus is 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.

<Toner raw material>
In the toner of the present invention, for example, a toner base containing at least a binder resin and a release agent can contain other components as necessary, and an external additive is added as necessary. is there.

<< Binder resin >>
The binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyester resin, silicone resin, styrene / acryl resin, styrene resin, acrylic resin, epoxy resin, diene resin, phenol Resins, terpene resins, coumarin resins, amideimide resins, butyral resins, urethane resins, ethylene vinyl acetate resins and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

The binder resin preferably contains a resin (A) and a block copolymer (B) that can be present inside the toner from a release agent.
The block copolymer (B) is preferably a copolymer of a resin (L1) compatible with the resin (A) and a resin containing a resin (L2) that is hardly soluble in ethyl acetate.

  In the copolymer, the blending mass ratio of the resin (L1) and the resin (L2) is preferably 2 ≦ L2 / L1 ≦ 4. When the blending mass ratio of the resin (L1) and the resin (L2) is within this range, the proportion of the copolymer present in the toner increases, and the mass ratio of the copolymer to the toner is Can be reduced. Therefore, the influence of the copolymer on the physical properties of the entire toner is reduced, which is desirable.

The resin (L1) having compatibility with the resin (A) can be specifically determined by the following method.
(1) Weigh 10 g of resin (L1) compatible with resin (A) in a weight ratio of 9/1, 8/2, 7/3 in a 50 mL screw vial (2) 150 degrees with block heater, Mix with a spatula while heating for 1 hour (3) Pour the molten resin into a Teflon sheet and cool it at room temperature for about 1 hour (cool down enough to break by hand)
(4) Disintegration (5) DSC measurement of resin (A), resin (L1) alone having compatibility with resin (A), and a mixture of resin (A) and resin (L1) When compatible The Tg of the compatible resin other than the glass transition point (Tg) peak of the resin (A) and the resin (A) alone is observed.

Using Shimadzu TA-60WS and DSC-60 as measuring devices, the measurement was performed under the following measurement conditions.
Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
The measurement result is analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The glass transition point is analyzed by specifying a range of ± 5 ° C around the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve when the temperature is raised, and using the peak analysis function of the analysis software Find the temperature. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the glass transition point of the toner.

The ethyl acetate hardly soluble resin (L2) can be specifically determined by the following method.
In a 50 mL screw vial, 45 g of ethyl acetate and 5 g of ethyl acetate hardly soluble resin (L2) are weighed and stirred for 10 hours while warming to 50 ° C. in a water bath. Then, the contents of the screw vial were suction filtered with filter paper (trade name: qualitative filter paper (No. 2, 110 mm), manufactured by Advantech Toyo Co., Ltd.), and 50 ml of ethyl acetate was suction filtered as it was, and the filter paper was sufficiently dried. Then, the weight increase before and after the filtration is 0.5 mg or more, and it is determined that the resin (L2) is hardly soluble in ethyl acetate.

-Polyester resin-
There is no restriction | limiting in particular as said polyester resin, Although it can select suitably according to the objective, An unmodified polyester resin and a modified polyester resin are preferable. These may be used individually by 1 type and may use 2 or more types together.
The resin (A) is preferably an unmodified polyester resin, and the block copolymer (B) is preferably a modified polyester resin.

--Unmodified polyester resin--
There is no restriction | limiting in particular as said unmodified polyester resin, According to the objective, it can select suitably, For example, the polyol represented by following General formula (1), and poly represented by following General formula (2) Examples thereof include resins obtained by polyesterifying carboxylic acid and crystalline polyester resins.
However, in the said General formula (1), A represents the aromatic group or heterocyclic aromatic group which may have a C1-C20 alkyl group, an alkylene group, and a substituent, m is 2- Represents an integer of 4.
However, in said general formula (2), B represents the C1-C20 alkyl group, alkylene group, the aromatic group which may have a substituent, or a heterocyclic aromatic group, and n is 2-2. Represents an integer of 4.

  There is no restriction | limiting in particular as a polyol represented by the said General formula (1), According to the objective, it can select suitably, For example, 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-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, and the like. These may be used alone or in combination of two or more.

  There is no restriction | limiting in particular as polycarboxylic acid represented by the said General formula (2), According to the objective, it can select suitably, For example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalate Acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, 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-di Ruboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empor trimer Examples include acids, etc., cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, ethylene glycol bis (trimellitic acid), and the like. These may be used alone or in combination of two or more.

  In the present invention, when an arbitrary molecular weight M in the range of 300 to 5000 is selected in the molecular weight distribution measured by GPC of the THF soluble component of the toner, the peak intensity in the range of ± 300 of the molecular weight M is selected. The difference between the maximum value and the minimum value is 30 or less. The control method is not particularly limited, and examples thereof include a method of replacing the terminal hydrophilic group of the binder resin with a lipophilic group and a method of accelerating the reaction conditions for resin synthesis. The method for substituting the terminal hydrophilic group with a lipophilic group is not particularly limited, and examples thereof include a method of substituting the terminal hydroxyl group with phenoxyacetic acid or benzoic acid. The method for accelerating the reaction conditions for resin synthesis is not particularly limited, and examples include a method of reacting at a high temperature for a long time and increasing the degree of vacuum to remove the monomer.

--Modified polyester resin--
There is no restriction | limiting in particular as said modified polyester resin, According to the objective, it can select suitably, For example, polyester (henceforth "polyester prepolymer" which can react with an active hydrogen group containing compound and the said active hydrogen group containing compound) And a resin obtained by an extension reaction and / or a crosslinking reaction. The extension reaction and / or the cross-linking reaction may be stopped by a reaction terminator (blocked monoamine such as diethylamine, dibutylamine, butylamine, laurylamine, ketimine compound, etc.) as necessary.

--- Active hydrogen group-containing compound ---
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent or the like when the polyester prepolymer undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous phase.

  The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected according to the purpose. However, when the polyester prepolymer is an isocyanate group-containing polyester prepolymer described later. An amine is preferable in that a high molecular weight can be obtained.

  There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be contained singly or in combination of two or more.

  The amines that are the active hydrogen group-containing compounds are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamines, trivalent or higher polyamines, amino alcohols, amino mercaptans, amino acids, and the like. The thing etc. which blocked the amino group of amines are mentioned. Examples of the diamine include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine, etc.); aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like. Examples of the trivalent or higher polyamine include diethylenetriamine and triethylenetetramine. Examples of the amino alcohol include ethanolamine and hydroxyethylaniline. Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid include aminopropionic acid and aminocaproic acid. Examples of the blocked amino groups of these amines include, for example, any of these amines (diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid, etc.) and ketones (acetone, methyl ethyl ketone, And ketimine compounds and oxazolyzone compounds obtained from methyl isobutyl ketone and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, the amines are particularly preferably diamine and a mixture of a diamine and a small amount of a trivalent or higher polyamine.

--- Polymer capable of reacting with active hydrogen group-containing compound ---
The polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited as long as it is a polymer having at least a group capable of reacting with the active hydrogen group-containing compound, and can be appropriately selected according to the purpose. However, it has excellent fluidity and transparency when melted, it is easy to adjust the molecular weight of the polymer component, and it is excellent in oilless low-temperature fixability and releasability in dry toners. ) Is preferred, and an isocyanate group-containing polyester prepolymer is more preferred.

--- Method for synthesizing polymer capable of reacting with active hydrogen group-containing compound ---
The method for synthesizing the polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited and can be appropriately selected according to the purpose. For example, in the case of the isocyanate group-containing polyester prepolymer, the polyol and the Polycarboxylic acid is produced in the presence of a known esterification catalyst (titanium tetrabutoxide, dibutyltin oxide, etc.), heated to 150 ° C. to 280 ° C. while appropriately reducing the pressure as necessary, and water is distilled off to contain a hydroxyl group. Examples thereof include a method of synthesizing the polyester by reacting the hydroxyl group-containing polyester with the polyisocyanate at 40 ° C. to 140 ° C. after obtaining the polyester.

There is no restriction | limiting in particular as a weight average molecular weight (Mw) of the polymer which can react with the said active hydrogen group containing compound, Although it can select suitably according to the objective, Tetrahydrofuran (THF) soluble GPC (gel) The molecular weight distribution by permeation chromatography) is preferably 3,000 to 40,000, and more preferably 4,000 to 30,000. When the weight average molecular weight (Mw) is less than 3,000, the storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated. The weight average molecular weight (Mw) can be measured, for example, as follows. First, the column was stabilized in a 40 ° C. heat chamber, and at this temperature, tetrahydrofuran (THF) as a column solvent was flowed at a flow rate of 1 mL / min, and the sample concentration was adjusted to 0.05 to 0.6% by mass. Measurement is performed by injecting 50 μL to 200 μL of a tetrahydrofuran sample solution. 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.

<< Crystalline polyester resin >>
Since the toner has sharp melt properties and realizes toner properties advantageous for low-temperature fixability, it can contain a crystalline polyester.
Examples of the crystalline polyester resin include saturated aliphatic diol compounds having 2 to 12 carbon atoms as alcohol components, particularly 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10- Decanediol, 1,12-dodecandiol and derivatives thereof, and a dicarboxylic acid having 2 to 12 carbon atoms or a saturated dicarboxylic acid having 2 to 12 carbon atoms having at least a double bond (C═C bond) as an acidic component Especially using fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1, -8 octanedioic acid, 1,10-decanedioic acid, 1,12 dodecanedioic acid and their derivatives Synthesized crystalline polyester is preferred.

  Among these, one kind of aliphatic alcohol component such as 1,4-butanediol, 1,6-hexanediol, and 1,9-nonanediol is particularly preferable in that the difference between the endothermic peak temperature and the endothermic shoulder temperature is further reduced. And only one kind of aliphatic dicarboxylic acid component such as sebacic acid or 1,12-dodecanedioic acid.

<< Releasing agent >>
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably. For example, plant wax (carnauba wax, cotton wax, wood wax, rice wax, etc.), animal wax (beeswax, lanolin, etc.), mineral wax (ozokerite, cercin etc.), petroleum wax (paraffin, microcrystalline, petrolatum, etc.) ) Waxes and waxes; synthetic hydrocarbon waxes (Fischer-Tropsch wax, polyethylene wax, etc.), synthetic waxes other than natural waxes (esters, ketones, ethers, etc.); 1,2-hydroxystearic acid amide, Fatty acid amides such as stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; homopolymers or copolymers of polyacrylates such as poly (n-stearyl methacrylate) and poly (n-lauryl methacrylate) which are low molecular weight crystalline polymers ( Acrylic acid n- Crystalline polymer having a stearyl over long chain alkyl group in the side chain of ethyl methacrylate copolymer, etc.) and the like; and the like.

  Among these, Fischer-Tropsch wax, paraffin wax, microcrystalline wax, monoester wax, and rice wax are preferable because less unnecessary volatile organic compounds are generated during fixing.

  A commercial item can be used for the mold release agent. Examples of the microcrystalline wax include “HI-MIC-1045”, “HI-MIC-1070”, “HI-MIC-1080”, “HI-MIC-1090” manufactured by Nippon Seiki Co., Ltd. “Bsquare 180 White”, “Bsquare 195” manufactured by Co., Ltd., “BARECO C-1035” manufactured by WAX Petrolife, “CRAYVALLAC WN-1442” manufactured by Cray Valley, and the like.

  There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 60 to 100 degreeC is preferable and 65 to 90 degreeC is more preferable. When the melting point is 60 ° C. or more, even when stored at a high temperature of about 30 ° C. to 50 ° C., it is possible to suppress the exudation of the release agent from the toner base material and to maintain good heat resistant storage stability. When the temperature is 100 ° C. or lower, it is preferable because cold offset hardly occurs at the time of fixing at a low temperature.

  The releasing agent is preferably present in a dispersed state in the toner base particles. The method for finely dispersing the release agent in the toner base particles is not particularly limited and may be appropriately selected depending on the purpose. For example, the release agent is dispersed by applying a kneading shear force during toner production. The method etc. are mentioned.

  The dispersion state of the release agent can be confirmed by observing a thin film slice of toner particles with a transmission electron microscope (TEM). The dispersion diameter of the release agent is preferably small, but if it is too small, there are cases where bleeding during fixing is insufficient. Therefore, if the release agent can be confirmed at a magnification of 10,000, the release agent is present in a dispersed state. When the release agent cannot be confirmed at 10,000 times, even when finely dispersed, the dyeing at the time of fixing becomes insufficient.

  There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 3 mass%-15 mass% are preferable, and 5 mass%-10 mass% are more preferable. . When the content is 3 mass or more, it is possible to prevent a problem that hot offset resistance is deteriorated. When the amount is 15% by mass or less, the exudation amount of the releasing agent at the time of fixing tends to be excessive, and the problem that the heat resistant storage stability is deteriorated can be prevented.

<< Other ingredients >>
Examples of the other components include a colorant and a charge control agent.

-Colorant-
There is no restriction | limiting in particular as a coloring agent used for the said toner, According to the objective, it can select suitably from a well-known coloring agent.

  There is no restriction | limiting in particular as a color of the colorant of the said toner, According to the objective, it can select suitably. The toner can be at least one selected from black toner, cyan toner, magenta toner, and yellow toner, and each color toner can be obtained by appropriately selecting the type of colorant. preferable.

  Examples of the black colorant include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, iron (CI pigment black 11), and titanium oxide. And organic pigments such as aniline black (CI Pigment Black 1).

  Examples of the magenta colorant include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 177, 179, 184, 202, 206, 207, 209, 211, 269; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of cyan colorants include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, green 7 and green 36, and the like.

  Examples of the colorant for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is 1% by mass or more, it is possible to prevent a problem that the coloring power of the toner is reduced. When the content is 15% by mass or less, poor dispersion of the pigment in the toner occurs, and the coloring power is reduced. In addition, the electrical characteristics of the toner can be prevented from deteriorating.

  The colorant may be used as a master batch combined with a resin. Such a resin is not particularly limited, but it is preferable to use a binder resin or a resin having a structure similar to the binder resin from the viewpoint of compatibility with the binder resin.

  The masterbatch can be produced by applying a high shear force and mixing or kneading the resin and the colorant. 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. The 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 water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

-Charge control agent-
In addition, in order to impart an appropriate charging ability to the toner, a charge control agent can be contained in the toner as necessary.
Any known charge control agent can be used as the charge control agent. Since the color tone may change when a colored material is used, a colorless or nearly white material is preferable. For example, a triphenylmethane dye, a molybdate chelate pigment, a rhodamine dye, an alkoxyamine, a quaternary ammonium salt (fluorine) Modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine-based activators, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The content of the charge control agent is determined by the toner production method including the type of the binder resin and the dispersion method, and is not uniquely limited. 01 mass%-5 mass% are preferable, and 0.02 mass%-2 mass% are more preferable. When the addition amount is 5% by mass or less, the chargeability of the toner is too large, the effect of the charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is decreased, The decrease in image density can be prevented, and if it is 0.01% by mass or more, the charge rising property and the charge amount are not sufficient, and the toner image can be prevented from being affected.

<< External additive >>
There is no restriction | limiting in particular as said external additive, According to the objective, it can select suitably from well-known things. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (eg, zinc stearate, aluminum stearate, etc.); metal oxides (eg, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoro Examples thereof include polymers. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the hydrophobized silica fine particles include HDK H2000T, HDK H2000 / 4, HDK H2050EP, HVK21, and HDK H1303VP (all manufactured by Clariant Japan); R972, R974, RX200, RY200, R202, R805, R812. NX90G (all manufactured by Nippon Aerosil Co., Ltd.). Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.). MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.) and the like can be mentioned. Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF- 1500T (all manufactured by Fuji Titanium Industrial Co., Ltd.); MT-100S, MT-100T (all manufactured by Teika Co., Ltd.); IT-S (manufactured by Ishihara Sangyo Co., Ltd.) and the like.

  There is no restriction | limiting in particular as content of the said external additive, Although it can select suitably according to the objective, 0.3 mass part-3.0 mass parts are preferable with respect to 100 mass parts of toner base particles. 0.5 parts by mass to 2.0 parts by mass is more preferable.

  The total coverage of the external additive with respect to the toner base particles is not particularly limited, but is preferably 50% to 90%, and more preferably 60% to 80%.

<Toner production method>
The toner production method and materials in the present invention can be any known ones as long as they satisfy the conditions, and are not particularly limited. For example, the toner particles may be mixed in a kneading and pulverization method or an aqueous medium. There is a so-called chemical method of granulating.
Examples of the chemical method include a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, a dispersion polymerization method, etc., in which a monomer is used as a starting material; a resin or a resin precursor is dissolved in an organic solvent and the like in an aqueous medium. Dispersing or emulsifying dissolution suspension method; in the dissolution suspension method, an oil phase composition containing a resin precursor (reactive group-containing prepolymer) having a functional group capable of reacting with an active hydrogen group is contained in resin fine particles. A method of emulsifying or dispersing in an aqueous medium and reacting the active hydrogen group-containing compound and the reactive group-containing prepolymer in the aqueous medium (production method (I)); Phase inversion emulsification method in which water is added to a solution composed of an emulsifier; the resin particles obtained by these methods are aggregated in a state of being dispersed in an aqueous medium and granulated into particles of a desired size by heating and melting. Aggregation And the like. Among these, the toner obtained by the dissolution suspension method, the production method (I), and the aggregation method is preferable from the viewpoint of granulation properties (particle size distribution control, particle shape control, etc.), and the production method (I). The resulting toner is more preferred.
In the following, detailed description of these production methods will be given.

  The kneading and pulverizing method is, for example, a method of producing the toner base particles by pulverizing and classifying a toner material having at least a colorant, a binder resin, and a release agent melted and kneaded.

  In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay, a PCM type twin screw extruder manufactured by Ikegai Iron Works, and a Kneader manufactured by Buss Co., Ltd. are suitable. Used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.

  In the dissolution suspension method, for example, an oil phase composition in which a toner composition containing at least a binder resin or a resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent is used. This is a method of producing toner base particles by producing an oil-in-water (O / W type) emulsion by dispersing or emulsifying in a medium.

The organic solvent used for dissolving or dispersing the toner composition is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later.
Examples of the organic solvent include ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl. Ether solvents such as ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2 -Alcohol solvents, such as ethyl hexyl alcohol and benzyl alcohol, and these 2 or more types of mixed solvents are mentioned.

In the dissolution suspension method, when the oil phase composition is dispersed or emulsified in an aqueous medium, an emulsifier or a dispersant may be used as necessary.
As the emulsifier or dispersant, known surfactants, water-soluble polymers and the like can be used. The surfactant is not particularly limited, and is an anionic surfactant (alkyl benzene sulfonic acid, phosphate ester, etc.), a cationic surfactant (quaternary ammonium salt type, amine salt type, etc.), an amphoteric surfactant (carbon carboxyl). Acid salt type, sulfate ester type, sulfonate salt type, phosphate ester salt type, etc.), nonionic surfactants (AO addition type, polyhydric alcohol type, etc.) and the like. One surfactant may be used alone, or two or more surfactants may be used in combination.
Examples of the water-soluble polymer include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, chitosan. , Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partially neutralized sodium hydroxide of polyacrylic acid) , Sodium acrylate-acrylic acid ester copolymer), sodium hydroxide of styrene-maleic anhydride copolymer ( Min) neutralized product water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.
Moreover, said organic solvent, a plasticizer, etc. can also be used together as an auxiliary | assistant of emulsification or dispersion | distribution.

  The toner according to the present invention includes at least a binder resin, a binder resin precursor having a functional group capable of reacting with an active hydrogen group (reactive group-containing prepolymer), a colorant, and a release agent in a dissolution suspension method. An active phase group-containing prepolymer and an active hydrogen group-containing compound contained in the oil phase composition and / or the aqueous medium are dispersed or emulsified in an aqueous medium containing resin fine particles. It is preferable to obtain the toner base particles by a method of reacting with (the production method (I)).

The resin fine particles can be formed using a known polymerization method, but is preferably obtained as an aqueous dispersion of resin fine particles. Examples of the method for preparing an aqueous dispersion of resin fine particles include the methods shown in the following (a) to (h).
(A) A method in which an aqueous dispersion of resin fine particles is directly prepared from a vinyl monomer as a starting material by any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method.
(B) After dispersing a precursor of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin (monomer, oligomer, etc.) or a solvent solution thereof in an aqueous medium in an aqueous medium, A method of preparing an aqueous dispersion of resin fine particles by heating or adding a curing agent to cure.
(C) Polyaddition or condensation resin precursors (monomers, oligomers, etc.) such as polyester resins, polyurethane resins, and epoxy resins, or solvent solutions thereof (preferably liquids, which may be liquefied by heating). A method for preparing an aqueous dispersion of resin fine particles by dissolving a suitable emulsifier in the mixture and then adding water to effect phase inversion emulsification.
(D) A resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized and classified using a mechanical rotary type or jet type fine pulverizer. A method of preparing an aqueous dispersion of resin fine particles by obtaining resin fine particles and then dispersing in water in the presence of an appropriate dispersant.
(E) Fine resin particles are formed by spraying a resin solution in which a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Then, resin fine particles are dispersed in water in the presence of a suitable dispersant to prepare an aqueous dispersion of resin fine particles.
(F) A poor solvent is added to a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, or heated to a solvent in advance. By cooling the dissolved resin solution, the resin fine particles are precipitated, the solvent is removed to form the resin fine particles, and then the resin fine particles are dispersed in water in the presence of an appropriate dispersant to disperse the resin fine particles in water. A method for preparing a liquid.
(G) A resin solution obtained by dissolving a resin previously synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent in the presence of an appropriate dispersant. A method of preparing an aqueous dispersion of resin fine particles by dispersing in a solvent and then removing the solvent by heating, decompression or the like.
(H) A suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, and then water To prepare an aqueous dispersion of resin fine particles by phase inversion emulsification.

  The volume average particle diameter of the resin fine particles is preferably 10 nm or more and 300 nm or less, and more preferably 30 nm or more and 120 nm or less. When the volume average particle size of the resin fine particles is less than 10 nm or more than 300 nm, the particle size distribution of the toner may be deteriorated.

  The solid content concentration of the oil phase is preferably about 40 to 80%. If the concentration is too high, dissolution or dispersion becomes difficult, and the viscosity becomes high and difficult to handle. If the concentration is too low, the productivity of the toner decreases.

  The toner composition other than the binder resin such as the colorant and the release agent, and the masterbatch thereof are individually dissolved or dispersed in an organic solvent, and then mixed with the binder resin solution or dispersion. May be.

  As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The dispersion or emulsification method in the aqueous medium is not particularly limited, and known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable from the viewpoint of reducing the particle size of the particles. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

  In order to remove the organic solvent from the obtained emulsified dispersion, there is no particular limitation, and a known method can be used. For example, the whole system is gradually raised while stirring the whole system under normal pressure or reduced pressure. A method of warming and completely evaporating and removing the organic solvent in the droplets can be employed.

  As a method of washing and drying the toner base particles dispersed in the aqueous medium, a known technique is used. That is, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion exchange water at about room temperature to about 40 ° C., and after adjusting the pH with acid or alkali as necessary, After removing the impurities and surfactants by repeating the process of solid-liquid separation again and again, the toner powder is obtained by drying with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. . At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

  In the agglomeration method, for example, a toner base particle is produced by mixing and aggregating a resin fine particle dispersion comprising at least a binder resin, a colorant particle dispersion, and a release agent particle dispersion as necessary. is there. The resin fine particle dispersion is obtained by a known method such as emulsion polymerization, seed polymerization, phase inversion emulsification, and the like. The colorant particle dispersion and the release agent particle dispersion are obtained by a known wet dispersion method. It can be obtained by dispersing a colorant or a release agent in an aqueous medium.

For the control of the aggregation state, methods such as applying heat, adding a metal salt, and adjusting pH are preferably used.
There is no restriction | limiting in particular as said metal salt, The monovalent metal which comprises salts, such as sodium and potassium; The bivalent metal which comprises salts, such as calcium and magnesium; The trivalent metal which comprises salts, such as aluminum, etc. Is mentioned.
Examples of the anion constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion, and sulfate ion. Among these, magnesium chloride, aluminum chloride, and complexes and multimers thereof are preferable. .
Also, heating between the agglomeration and after completion of the agglomeration can promote fusion between the resin fine particles, which is preferable from the viewpoint of toner uniformity. Furthermore, the shape of the toner can be controlled by heating. Normally, the toner becomes more spherical when heated further.

  As the method for washing and drying the toner base particles dispersed in the aqueous medium, the above-described method and the like can be used.

Further, in order to improve the fluidity, storage stability, developability, and transferability of the toner, the coalesced particles are added to and mixed with the toner base particles produced as described above. Inorganic fine particles may be added and mixed.
For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

(Developer)
The developer mounted on the image forming apparatus of the present invention contains at least the toner, and contains other appropriately selected components such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.

  In the case of the one-component developer using the toner, toner aggregation does not easily occur over time against stress caused by the developing means, and toner filming on the developing roller as the developer carrying member In addition, there is no fusion of toner to a layer thickness regulating member such as a blade for thinning the toner, and good and stable image quality can be obtained by maintaining good image density stability and transferability. . In addition, in the case of the two-component developer using the toner, toner aggregation does not easily occur over time even with agitation stress caused by the developing means, and the occurrence of abnormal images is suppressed, and the image density is stable. Good and stable image quality can be obtained by maintaining good properties and transferability.

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

<< Core particle >>
The core particles are not particularly limited as long as they are magnetic core particles, and can be appropriately selected according to the purpose. Examples thereof include ferromagnetic metals such as iron and cobalt; oxidation of magnetite, hematite, ferrite, and the like. Iron; resin particles in which magnetic materials such as various alloys and compounds are dispersed in a resin. Among these, Mn-based ferrite, Mn-Mg-based ferrite, Mn-Mg-Sr-based ferrite and the like are preferable from the viewpoint of environmental considerations.

-Weight average particle diameter Dw of core particles-
The weight average particle diameter Dw of the core particles refers to the particle diameter at an integrated value of 50% in the particle size distribution of the core particles obtained by a laser diffraction or scattering method. There is no restriction | limiting in particular as the weight average particle diameter Dw of the said core particle, Although it can select suitably according to the objective, 10 micrometers-80 micrometers are preferable, and 20 micrometers-65 micrometers are more preferable.

The weight average particle diameter Dw of the core particles is measured by using a microtrac particle size distribution meter (HRA9320-X100, manufactured by Honeywell) as a particle size distribution (relationship between number frequency and particle size) of particles measured on a number basis. And measured under the conditions described below, and calculated using the following formula (III). Each channel represents a length for dividing the particle size range in the particle size distribution chart into measurement width units, and the lower limit value of the particle size stored in each channel is adopted as the representative particle size.
Dw = {1 / Σ (nD3)} × {Σ (nD4)} (III)
In the formula (III), D represents the representative particle size (μm) of the core particles present in each channel, and n represents the total number of core particles present in each channel.
[Measurement condition]
[1] Particle size range: 100 μm to 8 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

<< Coating layer >>
The coating layer contains at least a resin, and may contain other components such as a filler as necessary.

-Resin-
The resin for forming the carrier coating layer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyolefin (for example, polyethylene, polypropylene, etc.) and modified products thereof, polystyrene, acrylic resin, acrylonitrile, Crosslinkable copolymer containing vinyl acetate, vinyl alcohol, vinyl chloride, vinyl carbazole, vinyl ether, etc .; silicone resin composed of organosiloxane bond or modified product thereof (for example, alkyd resin, polyester resin, epoxy resin, polyurethane, polyimide, etc.) Modified products); polyamides; polyesters; polyurethanes; polycarbonates; urea resins; melamine resins; benzoguanamine resins; epoxy resins; ionomer resins; These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is preferable.

There is no restriction | limiting in particular as said silicone resin, According to the objective from the silicone resin generally known, it can select suitably according to the objective, For example, straight silicone resin which consists only of organosiloxane bonds, alkyd, polyester , Silicone resins modified with epoxy, acrylic, urethane and the like.
Examples of the straight silicone resin include KR271, KR272, KR282, KR252, KR255, KR152 (manufactured by Shin-Etsu Chemical Co., Ltd.), SR2400, SR2405, SR2406 (manufactured by Toray Dow Corning Silicone). Specific examples of the modified silicone resin include epoxy-modified product: ES-1001N, acrylic-modified silicone: KR-5208, polyester-modified product: KR-5203, alkyd-modified product: KR-206, and urethane-modified product: KR-. 305 (manufactured by Shin-Etsu Chemical Co., Ltd.), epoxy-modified product: SR2115, alkyd-modified product: SR2110 (manufactured by Toray Dow Corning Silicone), and the like.

  The silicone resin can be used alone, but a crosslinking reactive component, a charge amount adjusting component, and the like can be used at the same time. Examples of the crosslinking reactive component include a silane coupling agent. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, aminosilane coupling agent, and the like.

-Filler-
There is no restriction | limiting in particular as said filler, According to the objective, it can select suitably, For example, a conductive filler, a nonelectroconductive filler, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferable to contain a conductive filler and a non-conductive filler in the coating layer.

The conductive filler refers to a filler having a powder specific resistance value of 100 Ω · cm or less.
The said nonelectroconductive filler points out the filler whose powder specific resistance value exceeds 100 ohm * cm.
The powder specific resistance value of the filler is measured by a powder resistance measuring system (MCP-PD51, manufactured by Dia Instruments) and a resistivity meter (4-terminal 4-probe system, Loresta GP, manufactured by Mitsubishi Chemical Analytech). Was measured under the conditions of a sample of 1.0 g, an electrode interval of 3 mm, a sample radius of 10.0 mm, and a load of 20 kN.

--Conductive filler--
The conductive filler is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tin oxide or oxide may be applied to a substrate such as aluminum oxide, titanium oxide, zinc oxide, barium sulfate, silicon oxide, or zirconium oxide. Examples thereof include a conductive filler formed using indium as a layer; a conductive filler formed using carbon black, and the like. Among these, a conductive filler containing aluminum oxide, titanium oxide, and barium sulfate is preferable.

--Non-conductive filler--
There is no restriction | limiting in particular as said nonelectroconductive filler, According to the objective, it can select suitably, For example, it forms using aluminum oxide, titanium oxide, barium sulfate, zinc oxide, silicon dioxide, zirconium oxide etc. Non-conductive filler etc. are mentioned. Among these, non-conductive fillers containing aluminum oxide, titanium oxide, and barium sulfate are preferable.

<< Carrier manufacturing method >>
There is no restriction | limiting in particular as a manufacturing method of the said carrier, Although it can select suitably according to the objective, The said resin and the said filler are contained in the surface of the said core particle using a fluid bed type coating apparatus. The method of manufacturing by apply | coating a coating layer forming solution is preferable. In addition, when apply | coating the said coating layer forming solution, you may advance condensation of the resin contained in the said coating layer, and after apply | coating the said coating layer forming solution, condensation of the resin contained in the said coating layer You may proceed. There is no restriction | limiting in particular as the condensation method of the said resin, According to the objective, it can select suitably, For example, the method etc. which give a heat | fever, light, etc. to the said coating layer formation solution, etc. are mentioned. .

-Weight average particle diameter Dw of carrier-
The weight average particle diameter Dw of the carrier refers to the particle diameter at an integrated value of 50% in the particle size distribution of the core particles obtained by a laser diffraction / scattering method. There is no restriction | limiting in particular as the weight average particle diameter Dw of the said carrier, Although it can select suitably according to the objective, 10 micrometers-80 micrometers are preferable, and 20 micrometers-65 micrometers are more preferable.

For the measurement of the weight average particle diameter Dw of the carrier, the particle size distribution (relationship between the number frequency and the particle diameter) of the particles measured on the basis of the number is used using a Microtrac particle size distribution meter (HRA9320-X100, manufactured by Honeywell). Measured under the conditions described below, and calculated using the following formula (V). Each channel represents a length for dividing the particle size range in the particle size distribution chart into measurement width units, and the lower limit value of the particle size stored in each channel is adopted as the representative particle size.
Dw = {1 / Σ (nD3)} × {Σ (nD4)} (V)
In the above formula (V), D represents the representative particle size (μm) of carriers present in each channel, and n represents the total number of carriers present in each channel.
[Measurement condition]
[1] Particle size range: 100 nm to 8 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

  When the developer is a two-component developer, the mixing ratio of the toner and the carrier in the two-component developer is preferably such that the mass ratio of the toner to the carrier is 2.0 to 12.0% by mass, More preferably, it is 2.5-10.0 mass%.

(Image forming method and image forming apparatus)
The image forming method used in the present invention includes at least an electrostatic latent image forming step (charging step and exposure step), a developing step, a transfer step, and a fixing step, and other types appropriately selected as necessary. The process includes, for example, a static elimination process, a cleaning process, a recycling process, a control process, and the like.
The image forming apparatus of the present invention includes an electrostatic latent image carrier, a charging unit for charging the surface of the electrostatic latent image carrier, and exposing the surface of the electrostatic latent image carrier to expose the electrostatic latent image. An exposure means for forming the electrostatic latent image, a developing means for sequentially developing the electrostatic latent image with a plurality of colors of toner to form a visible image, a transfer means for transferring the visible image to a recording medium, and a recording medium. And at least fixing means for fixing the transferred image, and other means appropriately selected as necessary, for example, static elimination means, cleaning means, recycling means, control means, and the like.

-Electrostatic latent image forming process and electrostatic latent image forming means-
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
The electrostatic latent image carrier (sometimes referred to as “electrophotographic photosensitive member” or “photosensitive member”) is not particularly limited in terms of material, shape, structure, size, etc. Although it can be selected as appropriate, the shape thereof is preferably a drum shape, and examples of the material thereof include inorganic photoreceptors such as amorphous silicon and selenium, organic photoreceptors (OPC) such as polysilane and phthalopolymethine, and the like. Is mentioned. Among these, an organic photoreceptor (OPC) is preferable in that a higher definition image can be obtained.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by electrostatic latent image forming means. Can do.
The electrostatic latent image forming unit includes, for example, a charging unit (charger) that uniformly charges the surface of the electrostatic latent image carrier, and an exposure that exposes the surface of the electrostatic latent image carrier imagewise. Means (exposure unit).

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotrons and corotrons.
The charger is preferably one that is arranged in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying a direct current and an alternating voltage.
Further, the charger is a charging roller disposed in a non-contact proximity to the electrostatic latent image carrier via a gap tape, and the electrostatic latent image is carried by applying a direct current and an alternating voltage to the charging roller. Those that charge the body surface are preferred.

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

-Development process and development means-
The developing step is a step of developing the electrostatic latent image with the toner to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner, and can be performed by the developing unit.
The developing unit preferably includes, for example, at least a developing unit that accommodates the toner and can apply the toner to the electrostatic latent image in a contact or non-contact manner, and includes a toner-containing container. Etc. are more preferable.

The developing device may be a monochromatic developing device or a multi-color developing device, and has, for example, an agitator that frictionally agitates and charges the toner and a rotatable magnet roller. A thing etc. are mentioned suitably.
In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

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

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

―Fixing process and fixing means―
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the developer of each color is transferred to the recording medium, or the developer of each color. On the other hand, it may be carried out at the same time in a state where these are laminated.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt.
The fixing device includes a heating body including a heating element, a film in contact with the heating body, and a pressure member in pressure contact with the heating body through the film, and the film and the pressure member It is preferably a unit that heats and fixes a recording medium on which an unfixed image is formed. The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

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

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

The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit. There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.
The control step is a step of controlling each step, and each step can be suitably performed by a control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  FIG. 5 shows a first example of the image forming apparatus of the present invention. The image forming apparatus 100A includes a photosensitive drum 10, a charging roller 20, an exposure device (not shown), a developing device 40, an intermediate transfer belt 50, a cleaning device 60 having a cleaning blade, and a static elimination lamp 70. Prepare.

  The intermediate transfer belt 50 is an endless belt stretched by three rollers 51 arranged on the inner side, and can move in the direction of the arrow in the figure. A part of the three rollers 51 also functions as a transfer bias roller that can apply a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Further, a cleaning device 90 having a cleaning blade is disposed in the vicinity of the intermediate transfer belt 50. Further, a transfer roller 80 capable of applying a transfer bias (secondary transfer bias) for transferring the toner image to the transfer paper 95 is disposed opposite to the intermediate transfer belt 50. Further, around the intermediate transfer belt 50, a corona charging device 58 for applying a charge to the toner image transferred to the intermediate transfer belt 50 is connected to the photosensitive drum 10 with respect to the rotation direction of the intermediate transfer belt 50. It is disposed between the contact portion of the intermediate transfer belt 50 and the contact portion of the intermediate transfer belt 50 and the transfer paper 95.

  The developing device 40 includes a 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 provided around the developing belt 41. Each color developing unit 45 includes a developer container 42, a developer supply roller 43, and a developing roller (developer carrier) 44. The developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can move in the direction of the arrow in the figure. Further, a part of the developing belt 41 is in contact with the photosensitive drum 10.

  Next, a method for forming an image using the image forming apparatus 100A will be described. First, the charging roller 20 is used to uniformly charge the surface of the photosensitive drum 10, and then the exposure light L is exposed to the photosensitive drum 10 using an exposure device (not shown) to form an electrostatic latent image. Form. Next, the electrostatic latent image formed on the photosensitive drum 10 is developed with the toner supplied from the developing device 40 to form a toner image. Further, after the toner image formed on the photosensitive drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by the transfer bias applied from the roller 51, the transfer bias applied from the transfer roller 80 is used. Then, it is transferred (secondary transfer) onto the transfer paper 95. On the other hand, the photosensitive drum 10 on which the toner image is transferred to the intermediate transfer belt 50 is discharged by the discharging lamp 70 after the toner remaining on the surface is removed by the cleaning device 60.

  FIG. 6 shows a second example of the image forming apparatus used in the present invention. In the image forming apparatus 100B, the black developing unit 45K, the yellow developing unit 45Y, the magenta developing unit 45M, and the cyan developing unit 45C are arranged directly facing each other around the photosensitive drum 10 without providing the developing belt 41. Other than that, the configuration is the same as that of the image forming apparatus 100A.

FIG. 7 shows a third example of the image forming apparatus used in the present invention. The image forming apparatus 100 </ b> C is a tandem type color image forming apparatus, and includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The intermediate transfer belt 50 provided at the center of the copying apparatus main body 150 is an endless belt stretched around three rollers 14, 15 and 16, and can move in the direction of the arrow in the figure. In the vicinity of the roller 15, a cleaning device 17 having a cleaning blade for removing toner remaining on the intermediate transfer belt 50 on which the toner image has been transferred onto the recording paper is disposed. While facing the intermediate transfer belt 50 stretched by the rollers 14 and 15, image forming units of yellow, cyan, magenta and black are juxtaposed along the transport direction. An exposure device 21 is disposed in the vicinity of the image forming unit 120. Further, the secondary transfer belt 24 is disposed on the side of the intermediate transfer belt 50 opposite to the side on which the image forming unit 120 is disposed. The secondary transfer belt 24 is an endless belt stretched around a pair of rollers 23, and the recording paper and the intermediate transfer belt 50 conveyed on the secondary transfer belt 24 are between the rollers 16 and 23. Can touch. Further, in the vicinity of the secondary transfer belt 24, a fixing device 25 is provided with a fixing belt 26 that is an endless belt stretched between a pair of rollers, and a pressure roller 27 that is arranged to be pressed against the fixing belt 26. Is arranged. A sheet reversing device 28 for reversing the recording paper when an image is formed on both sides of the recording paper is disposed in the vicinity of the secondary transfer belt 24 and the fixing device 25.

  Next, a method for forming a full-color image using the image forming apparatus 100C will be described. First, a color document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a color document is set on the contact glass 32 of the scanner 300 to automatically convey the document. The device 400 is closed. When a start switch (not shown) is pressed, when an original is set on the automatic document feeder 400, the original is conveyed and moved onto the contact glass 32, and then the original is set on the contact glass 32. In this case, the scanner 300 is immediately driven, and the first traveling body 33 including the light source and the second traveling body 34 including the mirror travel. At this time, the reflected light from the original surface of the light irradiated from the first traveling body 33 is reflected by the second traveling body 34 and then received by the reading sensor 36 via the imaging lens 35, whereby the original is received. It is read and image information of black, yellow, magenta and cyan is obtained.

The image information for each color is transmitted to the image forming unit 120 for each color, and a toner image for each color is formed. As shown in FIG. 8, the image forming units 120 for the respective colors are each based on the photosensitive drum 10, the charging roller 160 for uniformly charging the photosensitive drum 10, and the image information for each color. An exposure device that exposes the exposure light L to form an electrostatic latent image of each color; a developing device 61 that develops the electrostatic latent image with a developer of each color to form a toner image of each color; A transfer roller 62 for transferring onto the transfer belt 50, a cleaning device 63 having a cleaning blade, and a static elimination lamp 64 are provided.
The toner images of the respective colors formed by the image forming units 120 of the respective colors are sequentially transferred (primary transfer) onto the intermediate transfer body 50 that is stretched and moved by the rollers 14, 15, and 16, and superimposed to form a composite toner image. It is formed.

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, and one sheet at a time by the separation roller 145. The paper is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 to stop. Alternatively, the paper feed roller is rotated to feed out the recording paper on the manual feed tray 54, separated one by one by the separation roller 52, guided to the manual paper 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 in order to remove paper dust from the recording paper. Next, by rotating the registration roller 49 in synchronization with the composite toner image formed on the intermediate transfer belt 50, the recording paper is sent between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is sent. The toner image is transferred onto the recording paper (secondary transfer). The toner remaining on the intermediate transfer belt 50 to which the composite toner image has been transferred is removed by the cleaning device 17.

  The recording paper on which the composite toner image has been transferred is conveyed by the secondary transfer belt 24 and then the composite toner image is fixed by the fixing device 25. Next, the conveyance path of the recording paper is switched by the switching claw 55, and the recording paper is discharged onto the paper discharge tray 57 by the discharge roller 56. Alternatively, the recording path of the recording paper is switched by the switching claw 55, reversed by the sheet reversing device 28, an image is similarly formed on the back side, and then discharged onto the discharge tray 57 by the discharge roller 56. .

  The image forming apparatus of the present invention can provide high-quality images over a long period of time.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to these. However, “part” represents “part by mass” unless otherwise specified, and “%” represents “mass%” unless otherwise specified.

-Synthesis of Binder Resin A-1-
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 346 parts of bisphenol A propylene oxide 2 mol adduct and 94 parts of bisphenol A propylene oxide 3 mol adduct were in a molar ratio (bisphenol A 80/20 propylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct), 116 parts isophthalic acid and 44 parts adipic acid in a molar ratio (isophthalic acid / adipic acid) 70/30, OH / COOH = 1.33, and the mixture was reacted with 500 ppm of titanium tetraisopropoxide at 230 ° C. for 10 hours at normal pressure. Next, 26 parts of benzoic acid was added to the reaction vessel and reacted at a reduced pressure of 10 mmHg to 15 mmHg for 5 hours. Then, 11 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. and normal pressure for 3 hours. A-1] was obtained.

-Synthesis of Binder Resin A-2-
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 346 parts of bisphenol A propylene oxide 2 mol adduct and 94 parts of bisphenol A propylene oxide 3 mol adduct are in a molar ratio (bisphenol A propylene. Oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct) 80/20, 116 parts isophthalic acid and 44 parts adipic acid in a molar ratio (isophthalic acid / adipic acid) 70/30, OH / COOH = The mixture was charged to 1.33 and reacted with 500 ppm of titanium tetraisopropoxide at 230 ° C. for 10 hours at normal pressure. Next, after 5 hours of reaction at a reduced pressure of 10 mmHg to 15 mmHg, 11 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. and normal pressure for 3 hours to obtain [Binder Resin A-2].

-Synthesis of Binder Resin A-3-
In the synthesis of binder resin A-1, 216 parts of bisphenol A propylene oxide 2 mol adduct and 235 parts of bisphenol A propylene oxide 3 mol adduct (molar ratio (bisphenol A propylene oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct) 50/50), to 166 parts isophthalic acid and 0 parts adipic acid (molar ratio (isophthalic acid / adipic acid) 100/0), except that OH / COOH was changed to 1.29. In the same manner as in the synthesis of the fixing resin A-1, [Binder resin A-3] was obtained.

-Synthesis of Binder Resin B-1-
2.8 parts of binder resin A-3 and 5.2 parts of bis (2-hydroxyethyl) terephthalate (hereinafter abbreviated as “BHET”) are put into a three-necked separable flask and decompressed. Under heating with a mantle heater at 150 ° C. for 10 minutes, drying was performed. Next, with the dry distillation tube attached, the mixture was cooled to 50 ° C., and then ethyl acetate was added and stirred to dissolve the reagent. After dissolution, 2.3 parts of isophorone diisocyanate (hereinafter abbreviated as “IPDI”) was added over 3 minutes, and 0.05 part of tin catalyst (Tin (II) 2-ethylhexanoate) was added. After confirming that the temperature did not rapidly increase, the temperature of the solution was gradually raised, and after confirming that the temperature was stable at 80 ° C., the mixture was stirred for 5 hours to synthesize [Binder Resin B-1]. This reaction had a ratio of NCO / OH = 0.95.
In addition, the resin part produced | generated when BHET and IPDI react was ethyl acetate hardly soluble.

-Synthesis of Binder Resin B-2-
In the synthesis of the binder resin B-1, except that the binder resin A-2 was changed to 1.5 parts and the BHET was changed to 6.5 parts, the same as the binder resin B-1, B-2] was synthesized.

-Synthesis of Binder Resin B-3-
In the synthesis of the binder resin B-1, except that the binder resin A-2 is changed to 1.6 parts and the BHET is changed to 6.4 parts, the binder resin B-1 is used. B-3] was synthesized.

-Synthesis of Binder Resin B-4-
In the synthesis of Binder Resin B-1, [Binder Resin B-4] was synthesized.

-Synthesis of Binder Resin B-5-
In the synthesis of the binder resin B-1, except that the binder resin A-2 was changed to 2.0 parts and the BHET was changed to 6.0 parts, the same as the binder resin B-1, B-5] was synthesized.

-Synthesis of polyester prepolymer-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen insertion tube, 720 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 90 parts by mass of bisphenol A propylene oxide 2 mol adduct, 290 parts by mass of terephthalic acid, and tetrabutoxy titanate 1 A mass part was added, and the reaction was carried out for 8 hours while distilling off the generated water at 230 ° C. and normal pressure under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 10-15 mmHg for 7 hours, and intermediate polyester was obtained. The obtained intermediate polyester had a weight average molecular weight (Mw) of 9,300.

  Next, 400 parts by mass of the obtained intermediate polyester, 95 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate were placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen insertion tube. The mixture was reacted at 80 ° C. for 8 hours to obtain a 50% by mass ethyl acetate solution of [polyester prepolymer] having an isocyanate group at the terminal. The obtained polyester prepolymer had a free isocyanate mass% of 1.47%.

(Example 1)
<Manufacture of toner 1>
-Preparation of masterbatch (MB)-
1,200 parts of water, carbon black (made by Printex 35 Dexa) [DBP oil absorption =
42 mL / 100 mg, pH = 9.5] 540 parts and [Polyester resin A-1] are added in 1,200 parts, mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.), and the mixture is 150 ° C. using two rolls. After kneading for 30 minutes, it was rolled and cooled and pulverized with a pulverizer to obtain a [masterbatch].

-Preparation of release agent dispersion-
70 parts by weight of carnauba wax (WA-05, manufactured by Celalica Noda), 290 parts by weight of binder resin A, and 290 parts by weight of ethyl acetate are placed in a container in which a stir bar and a thermometer are set. The temperature was raised and held at 75 ° C. for 1.5 hours, then cooled to 30 ° C. in 1 hour, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), the liquid feeding speed was 5 kg / hr, and the disk peripheral speed was 6 m. / Sec, filled with 80% by volume of 0.5 mm zirconia beads and dispersed under the conditions of 3 passes to obtain a [release agent dispersion].

-Production of oil phase 1-
In a container equipped with a thermometer and a stirrer, 113 parts by weight of [Binder Resin A-1], 40 parts by weight of [Binder Resin B-1], 40 parts by weight of [Releasing Agent Dispersion], [Masterbatch] After 42 parts by mass and 150 parts by mass of ethyl acetate were added and pre-dispersed with a stirrer, the mixture was stirred at a rotational speed of 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) and dissolved uniformly. Dispersion gave [Oil Phase 1].

-Production of aqueous dispersion of resin fine particles-
In a reaction vessel equipped with a stirrer and a thermometer, 600 parts by mass of water, 120 parts by mass of styrene, 100 parts by mass of methacrylic acid, 45 parts by mass of butyl acrylate, sodium salt of alkylallylsulfosuccinate (Eleminol JS-2, Sanyo Chemical Industries) 10 parts by mass) and 1 part by mass of ammonium persulfate were charged and stirred at 400 rpm for 20 minutes to obtain a white emulsion. This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours. Further, 30 parts by mass of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 6 hours to obtain [Aqueous dispersion of resin fine particles]. The volume average particle diameter of the particles contained in this [resin fine particle aqueous dispersion] was 60 nm, the weight average molecular weight of the resin component was 140,000, and Tg was 73 ° C.

-Preparation of aqueous phase-
990 parts by mass of water, 83 parts by mass of an aqueous dispersion of resin fine particles, 37 parts by mass of a 48.5% by mass aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries), and 90 parts by mass of ethyl acetate Parts were mixed and stirred to obtain [Aqueous phase].

-Emulsification or dispersion-
To 393 parts by mass of [Oil Phase 1], 58 parts by mass of an ethyl acetate solution of [Polyester Prepolymer] and 3.5 parts by mass of a 50% by mass ethyl acetate solution of isophorone diamine were added, and a TK homomixer (specialized machine) was added. The product was stirred at a rotational speed of 5,000 rpm and uniformly dissolved and dispersed to obtain [Oil Phase 1 ′]. Next, 550 parts by mass of [Aqueous Phase] is put in another container in which a stirrer and a thermometer are set, and while stirring at 11,000 rpm with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), [Oil Phase] 1 '] was added and emulsified for 1 minute to obtain [Emulsified slurry 1].

-Solvent removal-Washing-Drying-
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Slurry 1]. The obtained [Slurry 1] was kept at 40 ° C. for 4 hours, then filtered under reduced pressure, and the following washing treatment was performed.
(1) 100 parts by mass 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) After adding 100 parts by mass of ion-exchanged water to the filter cake of (1) and mixing with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), 1% by mass hydrochloric acid is about pH 3.3 with stirring. The mixture was added until the mixture was stirred, and stirring was continued for 1 hour in that state, followed by filtration.
(3) Add 300 parts by mass of ion-exchanged water to the filter cake of (2) above, mix with a TK homomixer (5 minutes at 6,000 rpm) and then filter twice to obtain filter cake 1 It was.

  The obtained filter cake 1 was dried at 40 ° C. for 48 hours in a circulating dryer. Thereafter, the mixture was sieved with a 75 μm mesh to produce [Toner Base Particles 1].

-Mixed-
Hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) is added to the above [toner base particle 1] in an amount of 1.5 parts with respect to 100 parts of the base particle, and a 20 L Henschel mixer (manufactured by Mitsui Mining). Mixing was performed at a peripheral speed of 33 m / s for 5 minutes. The above was air sieved with a 500 mesh sieve to obtain [Toner 1].

(Examples 2 to 13, Comparative Examples 2 to 5)
In Example 1 -Preparation of oil phase-, toners of Examples 2 to 13 and Comparative Examples 2 to 5 were obtained in the same manner as in Example 1 except that the composition shown in Table 1 was used. Further, the following physical properties were measured for each of the obtained toners. The measurement results are also shown in Table 1.

(Comparative Example 1)
A toner of Comparative Example 1 was obtained in the same manner as in Example 1 except that [Binder Resin A-1] was replaced with [Binder Resin A-2] in the entire production of the toner of Example 1. . The obtained toner was measured for the following physical properties. The measurement results are also shown in Table 1.

<Infrared total reflection absorption measurement of heated toner (FTIR-ATR)>
-Preparation of heated toner-
0.8 g of each of the obtained toners was pressure-molded into a pellet having a diameter of 20 mm by applying a force of 40 kN. The pressure-molded product is heated from 24 ° C. to 160 ° C. at a heating rate of 130 ° C./min on a microscope cooling and heating stage (manufactured by Japan High-Tech), held for 2 minutes, cooled to room temperature, and heated with toner I got a thing.
−Preparation of non-heated toner−
0.8 g of each obtained toner was pressure-molded into a pellet having a diameter of 20 mm by applying a force of 40 kN to obtain a non-heated toner.

-Relative strength value (strength value of release agent for heated toner / strength value of binder resin (Wk / Rk), or strength value of release agent for non-heated toner / strength value of binder resin (Wn / Rn))-
The peak intensity ratios Wk / Rk and Wn / Rn were obtained from spectra measured using a Fourier transform infrared spectroscopic measurement apparatus (Avatar 370 / Thermo Scientific) ATR method (total reflection method). The spectrum is obtained by measuring the obtained heated toner or non-heated toner fixed with an ATR unit.
Measurement conditions were as follows.
[Measurement condition]
Incident angle: 45 °
ATR prism: Ge crystal Reflection: Reflection once Resolution: 4 cm ^-1
Number of integrations: 20 times The target peak is a peak derived from a release agent, a peak at 2,850 cm ⁻¹ derived from a methylene group, and a peak derived from a binder resin is a peak at 828 cm ⁻¹ derived from an aromatic ring. is there. The relative intensity value was determined from the ratio of these absorbance heights.

<Relationship between heated toner and non-heated toner (formula (2))>
Relative intensity ratio of the heated toner (peak intensity (Wk) derived from the release agent of the heated toner / peak intensity (Rk) derived from the binder resin) and relative intensity ratio of the non-heated toner (of the non-heated toner) Also in the ratio [(Wn / Rn) / (Wk / Rk)] of the peak intensity derived from the release agent (Wn) / peak intensity derived from the binder resin (Rn)), the peak intensity obtained above Calculated from the ratio.

<GPC signal intensity difference (maximum)>
The molecular weight distribution measured by GPC of the THF soluble component of the toner was measured as follows.

Gel permeation chromatography (GPC) measuring device: GPC-8220GPC (manufactured by Tosoh Corporation)
Column: TSK-GEL SUPER HZ2000, TSK-GEL SUPER HZ2500, TSK-GEL SUPER HZ3000
Temperature: 40 ° C
Solvent: THF
Flow rate: 0.35 mL / min
Sample: THF sample solution adjusted to 0.15% by mass Sample pretreatment: The toner was dissolved in tetrahydrofuran THF (containing a stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) at 0.15% by mass, and then filtered through a 0.45 μm filter. The filtrate was used as a sample.

  The measurement was performed by injecting 10 μL to 200 μL of the THF sample solution. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts.

  As a standard polystyrene sample for preparing a calibration curve, Tosoh's TSK standard polystyrene with molecular weight = 37200, 6200, 2500, 589, Showa Denko standard polystyrene with toluene with molecular weight 28400, 20298, 10900, 4782, 1689, 1309 and toluene are used. It was. An RI (refractive index) detector was used as the detector.

<Mass ratio of block copolymer (L2 / L1)>
About mass ratio (L2 / L1) of a block copolymer, it computed by raw material ratio (ratio of resin A-1 to A-3 and BHET) in resin B-1 to B-5.

  Next, the obtained toner was evaluated for heat-resistant storage stability, low-temperature fixability, environmental stability, and image quality as follows. Evaluation of image quality is based on evaluation of gloss unevenness, separation stability, absence of abnormal images (pochi), and image density unevenness. The evaluation results are shown in Table 2.

<Heat resistant storage stability>
The toner was stored at 50 ° C. for 8 hours, and then sieved with a 42 mesh sieve for 2 minutes. The residual ratio on the wire mesh was used as an index for heat resistant storage stability.
The heat resistant storage stability was evaluated in the following four stages.

[Evaluation criteria]
A: Less than 5%. No problem at all ○: 5 to 10%. No problem at all Δ: 10 to 25%. Slightly poor storability, but practically acceptable level ×: 25% or more. Problematic level as a high quality toner

<Low temperature fixability>
The image is obtained by using an evaluation machine tuned by modifying the image forming apparatus (“IPSIO Color 8100”; manufactured by Ricoh Co., Ltd.) into an oilless fixing method, and using cardboard (“copy printing paper <135>”; (Manufactured by NBS Ricoh Co., Ltd.) was set and adjusted so that 1.0 ± 0.1 mg / cm ² of toner was developed with a solid image. The fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more was determined as the minimum fixing temperature.

[Evaluation criteria]
A: Fixing lower limit is less than 120 ° C. ○: Fixing lower limit is 120 ° C. or more and less than 135 ° C. Δ: Fixing lower limit is 135 ° C. or more and less than 150 ° C. ×: Fixing lower limit is 150 ° C. or more.

<Gloss unevenness>
First, using the image forming apparatus, the evaluation chart (FIG. 9) was applied to a Mondi Color Copy 300 (basis weight: 300 g / m ² ) manufactured by mondi at an adhesion amount of 1.00 ± 0.03 mg / cm ² . The first image and the second solid image are formed in succession, and the fixing temperature is changed by changing the linear velocity of paper feed: 400 mm / second, surface pressure: 1.6 kgf / cm ² , and nip width: 15 mm. The second fixed image at each fixing temperature was used as an evaluation image for gloss unevenness. The evaluation of the gloss afterimage is performed by measuring the 60 degree glossiness at each of the evaluation sites (1) and (2) of the evaluation image using a gloss meter VG-7000 (manufactured by Nippon Denshoku Industries Co., Ltd.). Then, the average glossiness of each was obtained, and the fixing temperature at which the difference in glossiness was 20% or more was examined.

[Evaluation criteria]
A: Fixing temperature at which the gloss difference is 20% or more is 190 ° C. or higher, or the gloss difference is not 20% or more ○: A fixing temperature at which the gloss difference is 20% or more is 180 ° C. or more Less than 190 ° C. Δ: The fixing temperature at which the gloss difference is 20% or more is 170 ° C. or more and less than 180 ° C. ×: The fixing temperature at which the gloss difference is 20% or more is less than 170 ° C. thing

<Separation stability>
The separation resistance required to peel the recording medium from the fixing roller was measured using a recording medium pressing force measuring apparatus shown in FIG. 10 to evaluate the separation stability.
In the measuring device for the pressing force of the recording medium, the recording medium S is conveyed in a form of being pressed against the measuring claw 405 when a load 406 is applied as shown in the figure. At this time, the pressing force of the recording medium is read by the load cell 403 provided at the other end of the measurement claw 405 via the fulcrum 404. The value read by the load cell 403 is the separation resistance. The measurement claw 405 is provided on the fixing roller 401 side immediately after the nip portion N between the fixing roller 401 and the pressure roller 402.

At this time, the measuring device for the pressing force of the recording medium was fixed to the fixing portion of the image forming apparatus so that the measuring claw 405 was at an appropriate position by a jig. Further, A4 paper type 6200 paper (manufactured by Ricoh) was used as the recording medium S, and a 3 cm × 10 cm unfixed solid image with a toner adhesion amount of 0.85 ± 0.01 mg / cm ² was measured 3 cm from the top to the left and right. Created in the center of the direction. The separation resistance generated when this unfixed solid image was fixed at a fixing temperature of 160 ° C. was measured and evaluated according to the following criteria.

[Evaluation criteria]
A: Separation resistance is less than 200 gf B: Separation resistance is 200 gf or more and 300 gf or less Δ: Separation resistance is greater than 300 gf, 400 gf or less ×: Separation resistance is more than 400 gf

<Environmental stability>
An image was formed under the following conditions using an apparatus modified so that the linear speed of the developing roller in the developing machine of the image forming apparatus (Ricoh MP C305SP, manufactured by Ricoh Co., Ltd.) could be changed. Unless otherwise noted, the agent capacity was 110 g, and the linear velocity of the developing roller in the developing machine was 266 mm / sec.
0% to less than 10,000 sheets at 23 ° C, 50% RH, 10,000 sheets to less than 20,000 sheets at 28 ° C, 85% RH, 20,000 sheets to less than 30,000 sheets at 15 ° C The image area ratio 5% image and the image area ratio 20% image were alternately output every 1,000 sheets under the condition of 30% RH. Up to 90,000 images were created in three sets for this actual machine.
A small amount of developer was sampled from the sleeve after the 10,000 image formation and 90,000 image formation, and the change in charge amount was determined by the blow-off method and evaluated according to the following criteria.

[Evaluation criteria]
A: Change in charge amount is less than 2.0 μc / g ○: Change in charge amount is less than 5.0 μc / g Δ: Change in charge amount is less than 8.0 μc / g X: Change in charge amount is 8.0 μc / g more than g

<No abnormal image (Pochi)>
Using the image forming apparatus, 1 sheet or more and less than 10,000 sheets at 23 ° C., 50% RH, 10,000 sheets or more and less than 20,000 sheets at 28 ° C., 85% RH, 20,000 sheets or more Up to 1,000 sheets, images with an image area ratio of 5% and an image area ratio of 20% were alternately output every 1,000 sheets under the condition of 30% RH at 15 ° C. Up to 90,000 images were created in three sets for this actual machine. Thereafter, all solid images were output as sample images to three A3 size papers, and white spots and streaks were visually evaluated.
About the evaluation, it performed by the sensory evaluation method which compares the solid image for the rank sample created beforehand with a sample image visually.

[Evaluation criteria]
A: No white spots or streaks are observed in the image, and there is no problem. No level Δ: White spots with a diameter of 0.5 mm or less are observed in a part of the image (approximately 10 to 25 as a guide as a guide), but there is no problem in practical use ×: White spots are seen in the image (all 25 or more in the image), white spots with a diameter of 0.5 mm or more are seen, or there are streaks that are missing in the image.

<Image density unevenness>
Using the image forming apparatus, 50,000 test images having a printing rate of 6% were continuously output on A3 size paper. Thereafter, halftone images were output as sample images to three A3 size papers, and the blur in each was visually evaluated. The evaluation was performed by a sensory evaluation method in which a halftone image for a rank sample prepared in advance and a sample image were compared visually.

[Evaluation criteria]
◎: Level in which no roughness is seen in the image and no problem at all ○: Level slightly coarse in a part of the image (approximately 5% of all images as a guide), but no problem at all Δ: Part of the image ( Some roughness is seen in about 10 to 25% of all images as a guideline, but there is no problem in practical use. ×: Roughness is seen in the image (25% or more of all images as a guideline), and there is a problem as a high-quality toner Level with

<Comprehensive evaluation>
The evaluation criteria for comprehensive evaluation are as follows. A case where all items were ◯ or ◎ was judged as ◎, a case where there was one or more △ but no problem in use was judged as ○, and a case where x was one or more was judged as ×.

[Evaluation criteria]
◎: very good ○: excellent △: withstands practical use ×: cannot withstand practical use

  For Examples 1 to 13 which are the present invention, heat-resistant storage stability, low-temperature fixability, gloss unevenness, separation stability, environmental stability, absence of abnormal images (pochi), and image density unevenness are sufficiently excellent. . Among these, the results of Examples 11, 12, and 13 are particularly excellent. On the other hand, as for the toners of Comparative Examples 1 to 5, any one of heat-resistant storage stability, gloss unevenness, separation stability, environmental stability, absence of abnormal image (pochi), and image density unevenness is a high quality toner. Has a practically problematic result.

As an aspect of this invention, it is as follows, for example.
<1> A toner containing a binder resin and a release agent,
The release agent peak (Wk) and the resin peak (Rk) at the time of FTIR-ATR (total reflection absorption infrared spectroscopy) measurement of the heated toner obtained by heating the toner satisfy the relationship of the following formula (1). ,
The release agent peak (Wn), the resin peak (Rn), the release agent peak (Wk), and the above-mentioned when the FTIR-ATR method (total reflection absorption infrared spectroscopy) of the toner non-heated product that does not heat the toner is measured. The resin peak (Rk) satisfies the relationship of the following formula (2),
In the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble component of the toner, when an arbitrary molecular weight M in the range of 300 to 5,000 is selected, the molecular weight M A toner characterized in that a difference between a maximum value and a minimum value of peak intensity defined below in a range of ± 300 is 30 or less.
0.20 ≦ Wk / Rk ≦ 0.25 Formula (1)
0.65 ≦ (Wn / Rn) / (Wk / Rk) ≦ 0.84 Formula (2)
Peak intensity: Relative value obtained by plotting with a molecular weight distribution curve in which the vertical axis is intensity and the horizontal axis is molecular weight by GPC measurement, and the maximum intensity value is 100 in the molecular weight range of 20,000 or less. 2> The binder resin includes a resin (A) and a block copolymer (B),
The toner according to <1>, wherein the block copolymer (B) contains a resin compatible with the resin (A) and a resin hardly soluble in ethyl acetate.
<3> In the block copolymer (B), the blending mass ratio of the resin (L1) compatible with the resin (A) and the ethyl acetate hardly soluble resin (L2) is 2 ≦ L2 / L1 ≦. The toner according to <2>, which is 4.
<4> The toner according to any one of <1> to <3>, including a step of dispersing the liquid containing the binder resin in an aqueous medium to produce an oil-in-water (O / W type) emulsion. A toner manufacturing method characterized by manufacturing the toner.
<5> A developer comprising the toner according to any one of <1> to <3>.
<6> an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier;
Developing means for developing the electrostatic latent image with toner to form a visible image;
Transfer means for transferring the visible image to a recording medium;
Fixing means for fixing the transferred image transferred to the recording medium,
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <3>.
<7> An image forming apparatus, comprising: an electrostatic latent image carrier; and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. A process cartridge that is attachable to and detachable from a main body, wherein the toner is the toner according to any one of <1> to <3>.
<8> an electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
A developing step of developing the electrostatic latent image with toner to form a visible image;
A transfer step of transferring the visible image to a recording medium;
Fixing the transferred image transferred to the recording medium, and
An image forming method, wherein the toner is the toner according to any one of <1> to <3>.

  <1> to <3> toner, <4> toner production method, <5> developer, <6> image forming apparatus, <7> The process cartridge described in <5> and the image forming method described in <8> above can solve the above problems and achieve the object of the present invention.

10 Electrostatic latent image carrier (photosensitive drum)
10K Black electrostatic latent image carrier 10Y Yellow electrostatic latent image carrier 10M Magenta electrostatic latent image carrier 10C Cyan electrostatic latent image carrier 14 Roller 15 Roller 16 Roller 17 Cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading Sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developing roller 44M Developing roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer belt 51 Roller 52 Separating roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Ejection roller 57 Ejection tray 58 Corona charging device 60 Cleaning device 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100A, 100B, 100C Image forming device 120 Image forming unit 130 Document base 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Paper feed path 147 Conveyance Roller 148 Paper feed path 150 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)
401 fixing roller 402 pressure roller 403 load cell 404 fulcrum 405 measuring claw 406 load S recording medium N nip

Japanese Patent No. 4118498 Japanese Patent No. 4156759 Japanese Patent No. 4993533 Japanese Patent Laid-Open No. 2006-126196 JP 2017-151185 A

Claims (8)

A toner containing a binder resin and a release agent,
The release agent peak (Wk) and the resin peak (Rk) at the time of FTIR-ATR (total reflection absorption infrared spectroscopy) measurement of the heated toner obtained by heating the toner satisfy the relationship of the following formula (1). ,
The release agent peak (Wn), the resin peak (Rn), the release agent peak (Wk), and the above-mentioned when the FTIR-ATR method (total reflection absorption infrared spectroscopy) of the toner non-heated product that does not heat the toner is measured. The resin peak (Rk) satisfies the relationship of the following formula (2),
In the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble component of the toner, when an arbitrary molecular weight M in the range of 300 to 5,000 is selected, the molecular weight M A toner characterized in that a difference between a maximum value and a minimum value of peak intensity defined below in a range of ± 300 is 30 or less.
0.20 ≦ Wk / Rk ≦ 0.25 Formula (1)
0.65 ≦ (Wn / Rn) / (Wk / Rk) ≦ 0.84 Formula (2)
Peak intensity: Relative value when GPC measurement is plotted with a molecular weight distribution curve in which the vertical axis is intensity and the horizontal axis is molecular weight, and the maximum intensity value is 100 in the molecular weight range of 20,000 or less. The binder resin includes a resin (A) and a block copolymer (B),
The toner according to claim 1, wherein the block copolymer (B) contains a resin compatible with the resin (A) and a resin hardly soluble in ethyl acetate.   In the block copolymer (B), the blending mass ratio of the resin (L1) compatible with the resin (A) and the ethyl acetate hardly soluble resin (L2) is 2 ≦ L2 / L1 ≦ 4. The toner according to claim 2.   4. The toner according to claim 1, comprising a step of dispersing the liquid containing the binder resin in an aqueous medium to produce an oil-in-water (O / W type) emulsion. 5. A method for producing toner.   A developer comprising the toner according to claim 1. An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means for developing the electrostatic latent image with toner to form a visible image;
Transfer means for transferring the visible image to a recording medium;
Fixing means for fixing the transferred image transferred to the recording medium,
The image forming apparatus according to claim 1, wherein the toner is the toner according to claim 1.   An electrostatic latent image carrier, and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image, and is attached to and detached from the main body of the image forming apparatus A process cartridge capable of being used, wherein the toner is the toner according to claim 1. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
A developing step of developing the electrostatic latent image with toner to form a visible image;
A transfer step of transferring the visible image to a recording medium;
Fixing the transferred image transferred to the recording medium, and
The image forming method according to claim 1, wherein the toner is the toner according to claim 1.