JP6838273B2 - Toner, toner accommodating unit and image forming apparatus - Google Patents

Description

The present invention relates to a toner, a toner accommodating unit, and an image forming apparatus.

In the field of electrophotographic image formation technology, the electrostatic image is not only provided with a clear image without image error, but also the machine is operated for a long period of time and the toner for electrostatic image is stored for a long period of time. It is very important that the quality of the image image is stable at a high level even when external addition is added to the toner for a long period of time. In particular, the external additive (external additive) that imparts chargeability, fluidity, etc. to the electrostatic image toner is embedded in the toner or released from the toner in response to the above-mentioned long-term external addition. By doing so, the function tends to be reduced easily.

There are several techniques aimed at preventing the functional deterioration of the external additive applied to the electrostatic image toner. For example, Patent Document 1 defines the average particle size of the inorganic fine particles used as the external additive. By doing so, the embedding of the external additive in the toner and the release from the toner are suppressed.
However, in order to stably provide high-quality images even after long-term use and storage, which are required for toners for electrostatic images in recent years, it is necessary to suppress deterioration of toner quality over time by controlling the average particle size. In particular, it is insufficient as a means for suppressing the embedding of the external additive in the toner, and further improvement is desired by another means.

Further, for example, in Patent Document 2, silica particles produced by the sol-gel method are used as an external additive, and the average particle size and specific gravity of the silica particles are defined to suppress the embedding of the silica particles in the toner. Is disclosed. Further, Patent Document 3 discloses a technique for controlling the viscoelasticity of a toner to control the embedding of an external additive.
However, the former has difficulty in storage stability due to softening of the toner base due to long-term storage, and the latter may not be suitable for achieving both low temperature fixability at a high level at the same time.

As described above, in the toner for electrostatic image development, it is possible to suppress the deterioration of the toner over time caused by the burial of the external additive in the toner due to the environment and external pressure, and to provide the toner with good toner storage stability and image stability. It has become an issue, and it is desired to provide a toner that satisfies all of low temperature fixability, charge stability, etc. at a high level.

The present invention has been made in view of the above problems, has good low-temperature fixability and charge stability, and deteriorates over time due to the burial of an external additive in the toner due to the environment and external pressure and the release of the external additive from the toner. It is an object of the present invention to provide a high-quality toner that can output a stable image at a high level even in a long-term use.

In order to solve the above problems, the present invention is a toner in which inorganic fine particles are externally added to a toner base containing at least a binder resin and a mold release agent, and is measured by GPC of a THF-soluble component of the toner. In the molecular weight distribution, when an arbitrary molecular weight M in the range of 300 or more and 5000 or less is selected, all the molecular weights M in the range of 300 or more and 5000 or less are defined as follows in the range of ± 300 of the molecular weight M. The difference between the maximum value and the minimum value of the peak intensity is 30 or less, the volume average particle size of the inorganic fine particles is 40 nm or more and 300 nm or less, the binder resin contains a polyester resin, and the viscoelasticity of the toner is measured. The value of the ratio tan δ (G ″ / G ′) of the storage elastic modulus G ′ (Pa) and the loss viscosity G ″ (Pa) is 0.40 in the temperature range of the measurement temperature of 120 ° C. or higher and 150 ° C. or lower. to 1.10 Ri der less in differential scanning calorimetry of the toner (DSC), the glass transition point was observed at 40 to 70 ° C. in first heating, when the glass transition point was X ° C., The glass transition point of the second temperature rise is not found in the range of X to X-20 ° C.
However, the molecular weight distribution measured by GPC was determined by using TSK-GEL SUPER HZ2000, TSK-GEL SUPER HZ2500, and TSK-GEL SUPER HZ3000 as columns.
Peak intensity: Relative value when the vertical axis is the intensity and the horizontal axis is the molecular weight distribution curve of the molecular weight, and the maximum intensity value in the range of 20000 or less is set to 100 by GPC measurement.

According to the present invention, low-temperature fixability and charge stability are good, and deterioration of the toner over time caused by the burial of the external additive in the toner due to the environment and external pressure and the release of the external additive from the toner can be suppressed, and the toner can be used for a long period of time. It is also possible to provide high quality toner that can output a stable image at a high level.

It is a schematic diagram which shows an example of the image forming apparatus which concerns on this invention. It is a schematic diagram which shows another example of the image forming apparatus which concerns on this invention. It is a schematic diagram which shows another example of the image forming apparatus which concerns on this invention. It is a schematic diagram which shows another example of the image forming apparatus which concerns on this invention. It is a schematic diagram which shows an example of the evaluation chart in the gloss unevenness evaluation. It is a schematic explanatory drawing which shows an example of GPC measurement in the toner of this invention. It is a schematic explanatory drawing which shows an example of GPC measurement in the conventional toner. It is a schematic explanatory drawing which shows another example of GPC measurement in the toner of this invention. It is the schematic explanatory drawing which shows the other example of GPC measurement in the conventional toner.

Hereinafter, the toner, the toner accommodating unit, and the image forming apparatus according to the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments shown below, and can be modified within the range conceivable by those skilled in the art, such as other embodiments, additions, modifications, and deletions. However, as long as the action and effect of the present invention are exhibited, it is included in the scope of the present invention.

The present invention is a toner in which inorganic fine particles are externally added to a toner base containing at least a binder resin and a mold release agent, and has a molecular weight of 300 or more 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 5000 or less is selected, the difference between the maximum value and the minimum value of the peak intensity defined below in the range of ± 300 of the molecular weight M is 30 or less, and the volume average of the inorganic fine particles. The particle size is 40 nm or more and 300 nm or less.
Peak intensity: Relative value when the vertical axis is the intensity and the horizontal axis is the molecular weight distribution curve of the molecular weight, and the maximum intensity value in the range of 20000 or less is set to 100 by GPC measurement.

According to the present invention, low-temperature fixability and charge stability are good, and deterioration of the toner over time caused by the burial of the external additive in the toner due to the environment and external pressure and the release of the external additive from the toner can be suppressed, and in long-term use. It is also possible to provide high quality toner that can output a stable image at a high level.
Further, in the toner of the present invention, the inorganic fine particles to be added as an external additive by removing a specific molecular weight component of the binder resin contained in the toner to make the toner difficult to be deformed or softened by heat or external pressure. It suppresses burial in toner and release from the toner, achieves high level of toner storage stability and image stability, and achieves high image quality without degrading the quality level even after long-term use and storage. It is possible to provide an image with high resolution.

The details will be described below.
First, in the present invention, when an arbitrary molecular weight M in the range of 300 or more and 5000 or less is selected in the molecular weight distribution measured by GPC of the THF-soluble component, the above definition in the range of ± 300 of the molecular weight M is defined. The feature is that the difference between the maximum value and the minimum value of the peak intensity is 30 or less.

When the difference between the maximum value and the minimum value of the intensity is larger than 30 in the range of the molecular weight M ± 300, the difference in intensity means a peak mainly observed on the low molecular weight side. The peaks on the low molecular weight side of the molecular weight distribution are mainly due to the low molecular weight components derived from the raw materials. For example, in the binder resin, it is derived from an unreacted residual monomer contained in the binder resin, or a dimer or trimmer which is a low polymer. When the difference between the maximum and minimum strength values is greater than 30, that is, it indicates that there are many low molecular weight components contained in the toner, and the low molecular weight components have the characteristic of being easily melted by heat from the outside, so they are used. It is easily softened by the heat generated from the machine and the heat during storage.

Therefore, a toner having a large amount of low molecular weight components has poor heat-resistant storage stability, and toner particles tend to agglomerate due to heat. Furthermore, since low molecular weight components are easily deformed and adhered to external pressure, when toner with a large amount of low molecular weight components is used as a developing agent, it can be used for a long period of time or under high temperature and high humidity. As a result, it adheres to the carrier or the developing member, and the chargeability with time is significantly reduced.
On the other hand, the toner of the present invention deforms and aggregates with respect to external pressure, heat from a machine generated during image image formation, and heat during storage by excluding low molecular weight components contained in the toner. It has characteristics that are difficult to do.

Further, in order to improve the low temperature fixability of the toner, it is necessary to control the toner to have a lower viscosity in the low temperature region. In the present invention, in order to realize low temperature fixability, the weight average molecular weight Mw is preferably 10,000 or less in the molecular weight distribution of the THF-soluble component of the toner. When the weight average molecular weight Mw is larger than 10000, the viscosity of the toner is not sufficiently reduced and the low temperature fixability may be hindered.

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-8220 GPC (manufactured by Tosoh Corporation)
Columns: TSK-GEL SUPER HZ2000, TSK-GEL SUPER HZ2500, TSK-GEL SUPER HZ3000
Temperature: 40 ° C
Solvent: THF
Flow velocity: 0.35 ml / min
Sample: THF sample solution adjusted to 0.15% by mass Sample pretreatment: Dissolve toner in tetrahydrofuran THF (containing stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) at 0.15 wt%, filter with a 0.45 μm filter, and filter the solution. The filtrate is used as a sample. 10 μL to 200 μL of the THF sample solution is injected and measured. 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 count number.
As a standard polystyrene sample for preparing a calibration curve, a standard polystyrene sample for preparing a calibration curve has a molecular weight of 37200, 6200, 2500, 589, TSK standard polystyrene manufactured by Tosoh, and a molecular weight of 28400, 20298, 10900, 4782, 1689, 1309. Showa Denko standard polystyrene and toluene are used. An RI (refractive index) detector was used as the detector.

The GPC measurement results are plotted with the intensity distribution curve on the vertical axis and the molecular weight distribution curve on the horizontal axis, and the strength of the entire molecular weight distribution curve is corrected with the point where the maximum peak intensity is in the range of 20000 or less as 100. .. The difference between the maximum and minimum intensity is calculated from the maximum value-minimum value of the intensity within an arbitrary molecular weight ± 300 range of the obtained molecular weight distribution curve.

In the present invention, when an arbitrary molecular weight M in the range of 300 or more and 5000 or less 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 method for controlling in this way is not particularly limited, and examples thereof include a method of substituting the terminal hydrophilic group of the binder resin with a base oil group and a method of accelerating the reaction conditions of resin synthesis. The method of substituting the terminal hydrophilic group with the parent oil 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 thereof include a method of reacting at a high temperature for a long time and increasing the degree of decompression to remove the monomer.

It is important to select a column for GPC measurement of the THF-soluble component of the toner according to the present invention. In the above column, "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 or more and 5000 or less is selected, the molecular weight M is as follows in the range of ± 300. The result of measuring "toner" (toner A) in which the difference between the maximum value and the minimum value of the defined peak intensity is 30 or less is as shown in FIG. On the other hand, the measurement results for the conventional toner (toner B) not included in the present invention are as shown in FIG.

On the other hand, the above column "(manufactured by Tosoh Corporation) column: TSK-GEL SUPER HZ2000, TSK-GEL SUPER HZ2500, TSK-GEL SUPER HZ3000" was changed to "TSK-GEL SUPER HZM-H three in series". The results of the measurement are shown in FIGS. 8 and 9. FIG. 8 is the measurement for the above-mentioned toner A, and FIG. 9 is the measurement for the above-mentioned conventional toner B. In this column, there is no difference between the above-mentioned toner A and the conventional toner B, and the selection of the column is important.

Further, the volume average particle diameter of the inorganic fine particles to be applied as an external additive is in the range of 40 nm or more and 300 nm or less, which is also effective for suppressing the embedding of the external additive in the toner and the release from the toner. .. In the molecular weight distribution measured by GPC of the THF-soluble component of the toner described above, when an arbitrary molecular weight M having a molecular weight in the range of 300 or more and 5000 or less is selected, the maximum peak intensity in the range of ± 300 of the molecular weight M is obtained. By combining with a toner characterized in that the difference between the value and the minimum value is 30 or less, the range of the volume average particle diameter that can be used is expanded, and the toner of the external additive after long-term use and storage. It gives a characteristic that the effect of suppressing the burial in the toner and the release from the toner is maintained.

Here, if the volume average particle diameter of the inorganic fine particles is less than 40 nm, it is difficult to exert the function of the spacer effect, and even in combination with the binder resin, the external additive is embedded in the toner. Since it is easily caused, it adheres to the carrier or the developing member when used for a long period of time or under high temperature and high humidity, and the chargeability with time is significantly reduced. When the volume average particle diameter of the inorganic fine particles is larger than 300 nm, liberation from the toner tends to occur, and photoconductor filming tends to occur.

The volume average particle size of the inorganic fine particles is 50% of the cumulative frequency of the circle-equivalent diameter obtained by observing 100 inorganic fine particles at a magnification of 40,000 times using a SEM (Scanning Electron Microscope) device. Obtained as the diameter (D50v).
A specific example of the image analysis method of the external additive will be described below. The image analysis method is as follows, using the image analysis software LMeye for Lasertec OPTELICSC130 as the image analysis software.
(1) The image observed by the SEM at 5.0 kV is captured.
(2) Adjust the calibration (scale).
(3) Perform automatic contrast.
(4) Invert.
(5) Edge extraction (sobel) is performed.
(6) Perform edge extraction (sobel) again.
(7) Perform binarization processing (discriminant analysis mode).
(8) The shape features (circularity, absolute maximum length, diagonal width) are calculated by measurement.

Further, it is preferable that the average circularity of the inorganic fine particles is 0.4 or more and 0.8 or less. This means that all of the inorganic fine particles are not spherical or partially non-spherical, and by using such deformed inorganic fine particles, the inorganic particles to the toner are used. The effect of increasing the adhesion of fine particles can be expected. When the average circularity of the inorganic fine particles is 0.4 or more and 0.8 or less, the release of the inorganic fine particles from the toner is suppressed, and the inorganic fine particles move on the toner surface due to external pressure or the like. This can prevent the uneven distribution of inorganic fine particles (for example, silica) in the recesses and the surface exposure of the toner.

Here, the circularity of the inorganic fine particles can be defined as "100 / SF2" calculated by the following formula from the result of the above image analysis.
Circularity (100 / SF2) = 4π × (A / I ² )
In the formula, I represents the peripheral length of the inorganic fine particles on the image, and A represents the projected area of the inorganic fine particles. SF2 represents the shape coefficient. The circularity of the inorganic fine particles can be determined as 50% circularity in the cumulative frequency of the equivalent circle diameters of 100 particles obtained by the above image analysis.

Although details will be described later, it is preferable that the inorganic fine particles contain at least one selected from silica and titania from the viewpoint of imparting chargeability and fluidity.

In the viscous characteristics of the toner, the value of the ratio tan δ (G ″ / G ′) of the storage elastic modulus G ′ (Pa) and the loss viscosity G ″ (Pa) is 120 ° C. or higher and 150 ° C. or lower at the measurement temperature. It is preferably 0.40 or more and 1.10 or less in the temperature range of. When the value of tan δ is smaller than 0.40, it is difficult to keep the glossiness at a high level, and when it is larger than 1.10, uneven gloss is likely to occur.

Gloss unevenness is an image abnormality in which the gloss on a fixed image is not uniform and is partially increased or decreased. This is especially important in the field of product printing, which requires high-quality, high-gloss images. There are various generation mechanisms, but as an example, the history of the immediately preceding image pattern may appear as gloss unevenness on the immediately following image due to the adhesion and accumulation of the release agent on the fixing member.

An explanatory diagram for explaining an example is shown in FIG. FIG. 5 shows an image chart in the case where the immediately preceding image has an image portion and a non-image portion, and the entire solid image comes immediately after the image portion. Since the release agent adheres to the fixing member in the image portion of the immediately preceding image and no release agent adheres to the non-image portion, the history of the immediately preceding image pattern remains as the adhesion of the release agent on the fixing member. Immediately after all the solid images are fixed, this history causes a difference in the amount of mold release agent on the image. Therefore, in places where the amount of mold release agent is large, the releasability becomes excessively good and the gloss becomes relatively high. In the few places, the releasability is usually about, and in some cases, it becomes insufficient and the gloss becomes relatively low, and a difference in gloss occurs.

The tan δ of the toner can be measured using a dynamic viscoelasticity measuring device (for example, ARES (manufactured by TA Instruments)). That is, the sample was molded into pellets having a diameter of 8 mm and a thickness of 1 to 2 mm, fixed on a parallel plate having a diameter of 8 mm, stabilized at 40 ° C., a frequency of 1 Hz (6.28 rad / s), and a strain amount of 0.1. % (Strain amount control mode) was measured by raising the temperature to 200 ° C. at a heating rate of 2.0 ° C./min.

Further, the value of the ratio tan δ (G ″ / G ′) of the storage elastic modulus G ′ (Pa) and the loss viscosity G ″ (Pa) in the viscoelasticity measurement of the toner is tan δA, and is described below (measurement method 1). ), The difference tanδA-tanδB at the same temperature is preferably 0.05 or more and 0.25 or less in the region of 120 ° C. or higher and 150 ° C. or lower.
(Measurement method 1)
Let tan δ of the toner from which all the inorganic fine particles externally attached to the toner base have been peeled off be tan δB.

When the difference tanδA-tanδB is smaller than 0.05, the storage stability is deteriorated due to the inorganic fine particles being buried in the toner base, and when it is larger than 0.25, the adhesive force of the inorganic fine particles is weak and the photoconductor is contaminated / scraped. Is likely to occur.

The toner from which all the attached inorganic fine particles have been peeled off is defined as follows.
(1) 3.75 g of a toner sample is dispersed in 50 mL of a 0.5 mass% polyoxyalkylene alkyl ether dispersion in a 110 mL vial.
(2) Using an ultrasonic homogenizer (trade name: homogenizer, type VCX750, CV33, manufactured by SONICS & MATERIALS Co., Ltd.), the output is set to 80 W at a frequency of 20 Hz, and ultrasonic waves are irradiated for a certain period of time. Further, the amount of energy given at this time is calculated from the product of the output and the irradiation time, and a toner irradiated with ultrasonic waves of 1000 kJ and 1500 kJ is produced. At this time, the treatment is carried out while cooling the toner dispersion liquid in an appropriate manner so that the temperature does not exceed 40 ° C.
(3) The obtained dispersion was suction-filtered with a filter paper (trade name: qualitative filter paper (No. 2, 110 mm), manufactured by Advantech Toyo Co., Ltd.), washed twice with ion-exchanged water, filtered, and released. After removing the inorganic fine particles, the toner is dried.
(4) Use a fluorescent X-ray analyzer (ZSX-100e, manufactured by Rigaku Denki Co., Ltd.) to determine the amount of inorganic fine particles in the toner before and after removal of the inorganic fine particles from the strength by the calibration curve (or the difference in strength before and after removal of the external additive). It is quantified by calculation, and it is confirmed that there is no decrease in the amount of inorganic fine particles at 1000 kJ and 1500 kJ. Further, the surface of the treated toner may be observed with a field emission scanning electron microscope (FE-SEM) to confirm that all the inorganic fine particles are desorbed. If a change is observed, the irradiation energy amount is further increased by 500 kJ and the same treatment is performed.

Further, the value of the ratio tan δ (G ″ / G ′) of the storage elastic modulus G ′ (Pa) and the loss viscosity G ″ (Pa) in the viscoelasticity measurement of the toner is tan δA, and is described below (measurement method 2). ), The difference tanδA-tanδC at the same temperature is preferably 0.05 or more and 0.25 or less in the region of 120 ° C. or higher and 150 ° C. or lower.
(Measurement method 2)
Using a multi-purpose mixer, the toner base and the inorganic fine particles are mixed at 5425 rpm for 10 minutes, and the tan δ of the obtained toner is tan δC.

When the difference tanδA-tanδC is smaller than 0.05, the storage stability is deteriorated by burying the inorganic fine particles in the toner base, and when it is larger than 0.25, the adhesive force of the inorganic fine particles is weak and the photoconductor is contaminated / scraped. Is likely to occur.

The inventors have found that tan δ is increased by adhering inorganic fine particles. Although the cause is not clear, it is considered that the adhesion of the inorganic fine particles is weak and the inorganic fine particles are easily rolled, so that the storage elastic modulus G'(Pa) is lowered and the tan δ is increased. Therefore, in order to maintain storage stability while suppressing an increase in tan δ, the free amount [mass%] of the inorganic fine particles is preferably 0.3 or more and 0.7 or less. If the free amount is less than 0.3, the storage stability deteriorates, and if it is more than 0.7, tan δ increases, which is not preferable.

The amount of inorganic fine particles released is determined by mass% of the amount of inorganic fine particles of the toner irradiated with ultrasonic waves of 2400 J by the same method as the treatment of the toner from which all the inorganic fine particles have been peeled off, and the following measurement formula is used. Calculate from.
Measurement formula: Free amount [mass%] = ((mass of inorganic fine particles of toner)-(mass of residual inorganic fine particles after irradiation with a calibration curve of 2400J with a fluorescent X-ray analyzer)) / (mass of inorganic fine particles of toner)

Further, in the present invention, in the differential scanning calorimetry (DSC) of the toner, a glass transition point is observed at 40 to 70 ° C. at the first temperature rise, and when the glass transition point is set to X ° C., the second rise. It is preferable that the temperature glass transition point is not found in the range of X to X-20 ° C.

In the DSC measurement of the toner, in the DSC measurement of the toner, a glass transition point was observed at 40 to 70 ° C. at the first temperature rise, and when the glass transition point was set to X ° C., the glass transition point of the second temperature rise was observed. Is not found in the range of X to X-20 ° C., specifically, it can be achieved by using a crystalline resin as the binder resin or by partially containing it. The fact that the glass transition point is not observed in the range of X to X-20 ° C. at the second temperature rise means that the crystalline resin and the binder resin are compatible with each other, and the glass transition temperature of the binder resin is lowered. This means that excellent low temperature fixability can be achieved.

At this time, the crystalline resin is not particularly limited and may be appropriately selected depending on the intended purpose, but those described below are preferably used.
By including the crystalline resin in the binder resin, it is possible to impart charge stability and sharp meltability to the toner, but the inventors have specified it in the molecular weight distribution obtained by GPC measurement of the THF-soluble component in the binder resin. It has been found that when a large number of molecular weight components of the above are detected as peaks, the heat-resistant storage stability is deteriorated. Although the cause is not clear, the thermal resistance of the toner is caused by the fact that a specific peak component forms a domain for each peak, and the components contained in the peak are collectively compatible with the crystalline resin and act as a plasticizer. It is considered that the toner is significantly lowered and the storage stability of the toner is deteriorated.

Therefore, in the present invention, in the molecular weight distribution measured by GPC of the THF-soluble component of the toner, the difference between the maximum value and the minimum value of the intensity is in the range of any molecular weight ± 300 in the range of the molecular weight of 300 or more and 5000 or less. Since the number is limited to 30 or less, the peak component that can be a plasticizer can be removed, and both low-temperature fixability and storage stability can be achieved at the same time.

Further, from the viewpoint of the balance between low temperature fixability and storage stability, it is preferable that the melting point of the crystalline resin in the toner is in the range of 50 ° C. or higher and 65 ° C. or lower. If the melting point of the crystalline resin is less than 50 ° C., it is somewhat difficult to secure the storability of the toner, and the heat storability and the paper blocking property are liable to deteriorate. If the temperature is higher than 65 ° C., the sharp meltability of the toner is lowered, and the low temperature fixing tends to be deteriorated.

(toner)
The toner of the present invention contains at least a binder resin and a mold release agent in the toner base particles, further contains inorganic fine particles as an external additive, and further contains other components as necessary.
<Toner matrix particles>
The toner base particles contain at least a binder resin and a mold release agent, and further contain other components if necessary.

<< Amorphous polyester 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 / acrylic resin, styrene resin, acrylic resin, epoxy resin, diene resin, phenol. Examples thereof include resins, terpene resins, coumarin resins, amidimide resins, butyral resins, urethane resins, ethylene vinyl acetate resins and the like. These may be used alone or in combination of two or more. Among these, a resin in which a polyester resin or a polyester resin and the above-mentioned other binder resin are combined is preferable in that it has excellent low-temperature fixability and sufficient flexibility even when the molecular weight is reduced.

-Polyester resin-
The polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but unmodified polyester resin and modified polyester resin are preferable. These may be used alone or in combination of two or more.

--Unmodified polyester resin ---
The unmodified polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyol represented by the following general formula (1) and a poly represented by the following general formula (2). Examples thereof include a resin obtained by converting a carboxylic acid into a polyester.

However, in the general formula (1), A represents an aromatic group or a heterocyclic aromatic group which may have an alkyl group, an alkylene group, or a substituent having 1 to 20 carbon atoms, and m is 2 to 2. Represents an integer of 4.
However, in the general formula (2), B represents an aromatic group or a heterocyclic aromatic group which may have an alkyl group, an alkylene group, or a substituent having 1 to 20 carbon atoms, and n is 2 to 2. Represents an integer of 4.

The polyol represented by the general formula (1) is not particularly limited and may be appropriately selected depending on the intended purpose. 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, hydride bisphenol A, hydride bisphenol A ethylene oxide adduct, hydride bisphenol A propylene oxide adduct and the like can be mentioned. These may be used alone or in combination of two or more.

The polycarboxylic acid represented by the general formula (2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid and phthal. Acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebatic 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-naphthalentricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid , 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra ( Methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimeric acid, etc., cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, ethylene glycol Examples include bis (trimeritic acid). These may be used alone or in combination of two or more.

--Modified polyester resin ---
The modified polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an active hydrogen group-containing compound and a polyester capable of reacting with the active hydrogen group-containing compound (hereinafter, “polyester prepolymer””. (Sometimes referred to as), and examples thereof include a resin obtained by an extension reaction and / or a cross-linking reaction. If necessary, the extension reaction and / or the cross-linking reaction may be stopped by a reaction terminator (such as one in which monoamines such as diethylamine, dibutylamine, butylamine, laurylamine, and ketimine compounds are blocked).

--- Active hydrogen group-containing compound ---
The active hydrogen group-containing compound acts as an extender, a cross-linking agent, or the like when the polyester prepolymer undergoes an extension reaction, a cross-linking 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 depending on the intended purpose. However, when the polyester prepolymer is an isocyanate group-containing polyester prepolymer described later. Amines are preferable because they can be made higher in molecular weight.

The active hydrogen group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group and a mercapto group. These may be contained individually by 1 type, and may contain 2 or more types.

The amines, which are the active hydrogen group-containing compounds, are not particularly limited and may be appropriately selected depending on the intended purpose. For example, diamines, trivalent or higher polyamines, aminoalcohols, aminomercaptans, amino acids, and the like. Examples thereof include those in which the amino group of amines is blocked.

Examples of the diamine include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4'diaminodiphenylmethane, etc.); alicyclic diamines (4,4'-diamino-3,3'dimethyldicyclohexylmethane, diaminecyclohexane, etc.). Isophorone diamine, etc.); Aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like can be mentioned.

Examples of the triamine or higher polyamine include diethylenetriamine and triethylenetetramine.

Examples of the amino alcohol include ethanolamine, hydroxyethylaniline and the like.

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 any of the above amines (diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid, etc.) and ketones (acetone, methyl ethyl ketone, etc.). Examples thereof include ketimine compounds and oxazolizone compounds obtained from (methylisobutylketone, etc.). These may be used alone or in combination of two or more.
Among these, the amines are particularly preferably a mixture of diamine, diamine and a small amount of trivalent or higher-valent polyamine.

--- Polymer that can react with active hydrogen group-containing compounds ---
The polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited as long as it has at least a group capable of reacting with the active hydrogen group-containing compound, and can be appropriately selected depending on the intended purpose. However, it is excellent in high 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 toner. ) Is preferable, and an isocyanate group-containing polyester prepolymer is more preferable.

The isocyanate group-containing polyester prepolymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polycondensate of a polyol and a polycarboxylic acid or an active hydrogen group-containing polyester resin is reacted with the polyisocyanate. There are things that can be done.

The polyol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, etc.). 1,6-Hexanediol, etc.), alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diol (1,4-cyclohexanedimethanol, etc.) Hydrogenated bisphenol A, etc.), bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.), alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol, alkylene oxide of the bisphenol (bisphenol A, etc.) Diols such as ethylene oxide, propylene oxide, butylene oxide, etc. adducts; polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.), and trivalent or higher phenols (phenol novolac, cresol, etc.) Novolak, etc.), trivalent or higher polyols such as alkylene oxide adducts of trihydric or higher polyphenols; a mixture of a diol and a trivalent or higher polyol; and the like. These may be used alone or in combination of two or more.

Among these, the polyol is preferably the diol alone or a mixture of the diol and a small amount of the trivalent or higher valent polyol. Examples of the diol include alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols (2 mol adducts of bisphenol A ethylene oxide, 2 mol adducts of bisphenol A propylene oxide, 3 mol adducts of bisphenol A propylene oxide, etc.). Is preferable.

The content of the polyol in the isocyanate group-containing polyester prepolymer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 0.5% by mass to 40% by mass is preferable, and 1% by mass to 1% by mass. 30% by mass is more preferable, and 2% by mass to 20% by mass is particularly preferable. If the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the storage stability of the toner and the low temperature fixability. If the content exceeds 40% by mass, the temperature is low. Fixability may deteriorate.

The polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkylenedicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.). ); Aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.); trivalent or higher valent polycarboxylic acids (trimellitic acid, pyromellitic acid, etc., aromatic polycarboxylic acids having 9 to 20 carbon atoms, etc.), etc. Can be mentioned. These may be used alone or in combination of two or more. Among these, the polycarboxylic acid is preferably an alkenylene dicarboxylic acid having 4 to 20 carbon atoms and an aromatic dicarboxylic acid having 8 to 20 carbon atoms. Instead of the polycarboxylic acid, an anhydride of the polycarboxylic acid, a lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) or the like may be used.

The mixing ratio of the polyol and the polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. However, the hydroxyl group [OH] of the polyol and the carboxyl group [COOH] of the polycarboxylic acid are used. The equivalent ratio [OH] / [COOH] is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.
The polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexanediisocyanate, tetramethylhexane). Diisocyanate, etc.); Alicyclic polyisocyanate (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Aromatic diisocyanate (tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4'-diisocyanate, 4,4 '-Diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, diphenylether-4,4'-diisocyanate, etc.); aromatic aliphatic diisocyanate (α, α, α', α'- Tetramethylxylylene diisocyanate, etc.); Isocyanurates (tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, etc.); these phenol derivatives; those blocked with oxime, caprolactam, etc. can be mentioned. These may be used alone or in combination of two or more.

The mixing ratio of the polyisocyanate and the active hydrogen group-containing polyester resin (hydroxyl-containing polyester resin) is not particularly limited and may be appropriately selected depending on the intended purpose. ] And the hydroxyl group [OH] of the hydroxyl group-containing polyester resin, the equivalent ratio [NCO] / [OH] is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1. 1 to 1.5 / 1 is particularly preferable. If the equivalent ratio [NCO] / [OH] is less than 1/1, the offset resistance may deteriorate, and if it exceeds 5/1, the low temperature fixability may deteriorate.

The content of the polyisocyanate in the isocyanate group-containing polyester prepolymer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5% by mass to 40% by mass, and 1% by mass. ~ 30% by mass is more preferable, and 2% by mass to 20% by mass is particularly preferable. If the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both storage stability and low-temperature fixability. If it exceeds 40% by mass, low-temperature fixability may be difficult. May get worse.

The average number of isocyanate groups contained in one molecule of the isocyanate group-containing polyester prepolymer is preferably 1 or more, more preferably 1.2 to 5, and even more preferably 1.5 to 4. If the average number is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group may be low, and the hot offset resistance may be deteriorated.

The mixing ratio of the isocyanate group-containing polyester prepolymer and the amines is not particularly limited and may be appropriately selected depending on the intended purpose. However, the isocyanate group [NCO] in the isocyanate group-containing polyester prepolymer. The mixed equivalent ratio [NCO] / [NHx] of the amino group [NHx] in the amines is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, and 1/1. 5 to 1.5 / 1 is particularly preferable. If the mixed equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may decrease, and if it exceeds 3/1, the molecular weight of the urea-modified polyester resin decreases. Hot offset resistance may deteriorate.

--- Method for synthesizing a polymer that can react with an 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 may be appropriately selected depending on the intended purpose. For example, in the case of the isocyanate group-containing polyester prepolymer, the polyol and the above. Polycarboxylic acid is produced by heating to 150 ° C. to 280 ° C. in the presence of a known esterification catalyst (titanium tetrabutoxide, dibutyltin oxide, etc.) and appropriately reduced 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.

The weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the intended purpose. The molecular weight distribution by permeation chromatography) is preferably 3,000 to 40,000, more preferably 4,000 to 30,000. If the weight average molecular weight (Mw) is less than 3,000, the storage stability may be deteriorated, and if it exceeds 40,000, the low temperature fixability may be deteriorated.

The weight average molecular weight of the polymer capable of reacting with the active hydrogen group-containing compound is measured as follows. First, the column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) was flowed as a column solvent at a flow rate of 1 mL / min at this temperature to adjust the sample concentration to 0.05 to 0.6% by mass. Measure by injecting 50 μL to 200 μL of a tetrahydrofuran 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 the calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co., Ltd. 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 resin ---
In order to realize the toner characteristics that the toner has sharp melt property and is advantageous for low temperature fixability, a glass transition point is observed at 40 to 70 ° C. at the first temperature rise in the DSC measurement of the toner, and the glass. When the transition point is set to X ° C, it is preferable that the glass transition point of the second temperature rise is not observed in the range of X to X-20 ° C.
In order to satisfy the above, it is preferable to contain a crystalline resin as the binder resin. Further, crystalline polyester is preferable from the viewpoint of low temperature fixability and charging characteristics.

The crystalline polyester resin is, for example, a saturated aliphatic diol compound having 2 to 12 carbon atoms as an alcohol component, particularly 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-. A dicarboxylic acid having 2 to 12 carbon atoms or 2 carbon atoms having at least a double bond (C = C bond) as an acidic component with at least one selected from decanediol, 1,12-dodecanediol and derivatives thereof. ~ 12 saturated dicarboxylic acids, especially fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1,12 dodecanedioic acid and A crystalline polyester synthesized using at least one selected from these derivatives is preferable.

Among them, one kind of aliphatic alcohol component such as 1,4-butanediol, 1,6-hexanediol, and 1,9-nonanediol is particularly important in reducing the difference between the heat absorption peak temperature and the heat absorption shoulder temperature. It is preferably composed of only one type of aliphatic dicarboxylic acid component such as sebacic acid and 1,12-dodecanedioic acid.

Further, as a method for controlling the crystallinity and softening point of the crystalline polyester resin, a polyhydric alcohol having a trivalent or higher valence such as glycerin as an alcohol component and a polyvalent or higher valent as an acid component such as trimellitic anhydride as an acid component during polyester synthesis Examples thereof include designing and using a non-linear polyester or the like which has undergone polycondensation by adding a valent carboxylic acid.

The molecular structure of the crystalline polyester resin of the present invention can be confirmed by NMR measurement using a solution or solid, X-ray diffraction, GC / MS, LC / MS, IR measurement, or the like.

The content of the crystalline polyester resin in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3% by weight to 15% by weight, more preferably 5% by weight to 10% by weight. preferable. When the content is 3% by weight or more, the effect on low-temperature fixability is sufficiently obtained, and when it is 15% by mass or less, deterioration of heat-resistant storage stability is less likely to occur, which is preferable.

-Release agent-
The release agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, plant wax (carnauba wax, cotton wax, wood wax, rice wax, etc.), animal wax (honey wax, lanolin, etc.), mineral wax (ozokelite, celsine, etc.), petroleum wax (paraffin, microcrystallin, petrolatum, etc.) ) And other waxes and waxes; synthetic hydrocarbon waxes (Fishertropsh wax, polyethylene wax, etc.), synthetic waxes (esters, ketones, ethers, etc.) and other non-natural waxes; 1,2-hydroxystearic acid amide, Fatty acid amides such as stearate amides, phthalate anhydrides, chlorinated hydrocarbons; homopolymers or copolymers of polyacrylates such as low molecular weight crystalline polymers such as n-stearyl polymethacrylate and n-lauryl polymethacrylate ( Crystalline polymers having a long-chain alkyl group in the side chain, such as n-stearyl-ethyl methacrylate copolymer, etc.).
Among these, Fischer-Tropsch wax, paraffin wax, microcrystalline wax, monoester wax, and rice wax are preferable in that unnecessary volatile organic compounds are less generated during fixing.

As the release agent, a commercially available product can be used. Examples of the microcrystalline wax include "HI-MIC-1045", "HI-MIC-1070", "HI-MIC-1080", "HI-MIC-1090", manufactured by Nippon Seiro Co., Ltd., and Toyo Adre Co., Ltd. Examples include "B-Square 180 White" and "B-Square 195" manufactured by WAX Petrolife, "BARECO C-1035" manufactured by WAX Petrolife, and "CRAY VALLAC WN-1442" manufactured by Cray Valley.

The melting point of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C to 100 ° C, more preferably 65 ° C to 90 ° C. When the melting point is 60 ° C. or higher, the exudation of the release agent from the toner base can be suppressed even during high-temperature storage at about 30 to 50 ° C., and the heat-resistant storage stability can be maintained well. When the temperature is 100 ° C. or lower, cold offset is unlikely to occur during fixing at a low temperature, which is preferable.

The release agent preferably exists in a state of being dispersed in the toner matrix particles, and for that purpose, it is preferable that the release agent and the binder resin are incompatible with each other. The method for finely dispersing the mold release agent in the toner matrix particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the release agent is dispersed by applying the shearing force of kneading during toner production. The method etc. can be mentioned.

The dispersed state of the release agent can be confirmed by observing a thin film section of the toner particles with a transmission electron microscope (TEM). The dispersion diameter of the release agent is preferably small, but if it is too small, exudation at the time of fixing may be insufficient. Therefore, if the release agent can be confirmed at a magnification of 10,000 times, the release agent is present in a dispersed state. If the release agent cannot be confirmed at 10,000 times, even if it is finely dispersed, the dyeing at the time of fixing becomes insufficient.

The content of the release agent in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3% by mass to 15% by mass, more preferably 5% by mass to 10% by mass. .. If the content is less than 3% by mass, the hot offset resistance may be deteriorated, which is not preferable. If the content exceeds 15% by mass, the amount of the release agent exuded at the time of fixing tends to be excessive. It is not preferable because the heat-resistant storage property tends to deteriorate.

-Wax dispersant-
The toner preferably contains a wax dispersant. By containing the wax dispersant, the dispersibility of the wax in the binder resin is improved, and the dispersion state of the wax can be easily controlled by the contents of the wax and the wax dispersant. Further, the toner preferably contains the polyester resin in an amount of 50% by mass to 100% by mass, but when the polyester resin and the wax have almost no compatibility, when the wax dispersant is not used, the toner is used. When the toner is produced, the wax is not finely dispersed at the particle interface but is unevenly distributed, and the amount of the wax on the surface of the toner increases, which may cause contamination of other members. From these aspects, it is preferable to use the wax dispersant.

The wax dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. However, the graft weight of the resin (D) described below and the resin (E) different from the resin (D) It is preferably a coalescence, and a graft polymer having a structure in which the resin (D) is used as a main chain and the resin (E) is used as a side chain is preferable.

The resin (D) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include wax.
Examples of the wax include polyolefin resins and heat-reduced polyolefin resins. Among these, heat-reduced molded polyolefin resin is preferable.
Examples of the olefins constituting the polyolefin resin include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and the like.
Examples of the polyolefin resin include polymers of olefins, oxides of polymers of olefins, modified products of polymers of olefins, copolymers of other monomers copolymerizable with olefins, and the like. Can be mentioned. Examples of the olefin polymers include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, and propylene / 1-hexene copolymer.
Examples of the modified product of the polymer of the olefins include a maleic acid derivative adduct of the polymer of the olefins.
Examples of the maleic acid derivative include maleic anhydride, monomethyl maleate, monobutyl maleate, and dimethyl maleate.
Examples of the copolymer with the other monomer copolymerizable with the olefins include a copolymer of a monomer such as an unsaturated carboxylic acid and an unsaturated carboxylic acid alkyl ester and the olefins. Be done.
Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, maleic anhydride and the like.
Examples of the unsaturated carboxylic acid alkyl ester include (meth) acrylic acid alkyl (C1 to C18) ester and maleic acid alkyl (C1 to C18) ester.
Further, in the polymer of the olefins, the polymer structure may have a polyolefin structure, and the monomer does not necessarily have to have an olefin structure. For example, polymethylene (sazole wax or the like) or the like can be used.

The polyolefin resin is preferably a polymer of olefins, an oxide of a polymer of olefins, or a modified product of a polymer of olefins, and is preferably polyethylene, polymethylene, polypropylene, ethylene / propylene polymer, oxidized polyethylene, or oxidized type. Polypropylene and maleated polypropylene are more preferable, and polyethylene and polypropylene are particularly preferable.

Examples of the resin (E) include acrylic resin and the like.
Examples of the monomer constituting the acrylic resin include alkyl (1 to 5 carbon atoms) esters of unsaturated carboxylic acids and vinyl ester-based monomers.
Examples of the alkyl (carbon number 1 to 5) ester of the unsaturated carboxylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
Examples of the vinyl ester-based monomer include vinyl acetate. Among these, alkyl (meth) acrylate is preferable, and alkyl (meth) acrylate having an alkyl chain having 1 to 5 carbon atoms is more preferable.

Examples of the aromatic vinyl monomer used in combination with the alkyl (meth) acrylic acid having 1 to 5 carbon atoms in the alkyl chain as the monomer constituting the acrylic resin include styrene-based monomers. Examples of the styrene-based monomer include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, and phenylstyrene. Examples include benzyl styrene. Of these, styrene is particularly preferable.

The mass ratio (D) / (E) of the resin (D) of the wax dispersant and the resin (E) in the toner is not particularly limited and may be appropriately selected depending on the intended purpose. However, 1 to 50 is preferable. If the mass ratio (D / E) exceeds 50, the compatibility between the wax dispersant and the binder resin may deteriorate, and if it is less than 1, the wax dispersant may be added to the added wax. May not be sufficiently compatible with each other and the dispersion of the wax may decrease.

The glass transition temperature of the wax dispersant is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 55 ° C to 80 ° C, more preferably 55 ° C to 70 ° C. If the glass transition temperature of the wax dispersant exceeds 80 ° C., the low temperature fixability may be impaired, and if it is less than 55 ° C., the hot offset resistance may decrease.

The content of the wax dispersant is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.01 parts by mass to 8 parts by mass with respect to 100 parts by mass of the toner. More preferably, 5 parts by mass to 6 parts by mass. When the content is within the more preferable range, the amount of the wax present on the surface of the toner is appropriately maintained, and in particular, the releasability from the fixing roller and the belt is improved, and the smear resistance is excellent. It can be effective.

The content of the wax dispersant is preferably 20 parts by mass to 100 parts by mass with respect to 100 parts by mass of the wax.

-Colorant-
The colorant used for the toner is not particularly limited, and a known colorant can be appropriately selected depending on the intended purpose.
The color of the colorant of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. It can be at least one type selected from black toner, cyan toner, magenta toner and yellow toner, and the toner of each color can be obtained by appropriately selecting the type of colorant, but the color toner is the color toner. preferable.

Examples for black include carbon black (CI pigment black 7) such as furnace black, lamp black, acetylene black, and channel black, copper, iron (CI pigment black 11), titanium oxide, and the like. Metals, organic pigments such as aniline black (CI pigment black 1) and the like can be mentioned.

Examples of the magenta coloring pigment 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 and the like can be mentioned.

Examples of the cyan pigment include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; C.I. I. Bat Blue 6; C.I. I. Examples thereof include a copper phthalocyanine pigment in which 1 to 5 phthalimide methyl groups are substituted in the acid blue 45 or phthalocyanine skeleton, green 7, green 36 and the like.

Examples of the yellow coloring pigment 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; C.I. I. Bat Yellow 1, 3, 20, Orange 36 and the like can be mentioned.

The content of the colorant in the toner is preferably 1% by mass to 15% by mass, more preferably 3% by mass to 10% by mass. If the content is less than 1% by mass, the coloring power of the toner may be lowered, and if it exceeds 15% by mass, poor dispersion of the pigment in the toner occurs, and the coloring power is lowered and the electricity of the toner is reduced. May lead to deterioration of characteristics.

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

The masterbatch can be produced by mixing or kneading a resin and a colorant by applying a high shearing force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Further, the so-called flushing method is also preferable in that the wet cake of the colorant can be used as it is and does not need to be dried. The flushing method is a method in which an aqueous paste containing water as a colorant is mixed or kneaded 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 disperser such as a three-roll mill can be used.

-Charge control agent-
It is also possible to add a charge control agent to the toner, if necessary, in order to impart an appropriate chargeability to the toner.
As the charge control agent, any known charge control agent can be used. Since the color tone may change when a colored material is used, a material close to colorless to white is preferable. For example, a triphenylmethane dye, a molybdic chelate pigment, a rhodamine dye, an alkoxy amine, or a quaternary ammonium salt (fluorine). (Including modified quaternary ammonium salts), alkylamides, phosphorus alone or its compounds, tungsten alone or its compounds, fluoroactive agents, salicylic acid metal salts, salicylic acid derivative metal salts and the like. These may be used alone or in combination of two or more.

The content of the charge control agent is determined by the type of the binder resin and the toner manufacturing method including the dispersion method, and is not uniquely limited, but is 0. 01% by mass to 5% by mass is preferable, and 0.02% by mass to 2% by mass is more preferable. If the amount added exceeds 5% by mass, the chargeability of the toner is too large, the effect of the charge control agent is diminished, the electrostatic attraction with the developing roller is increased, the fluidity of the developer is lowered, and the image is displayed. The density may decrease, and if it is less than 0.01% by mass, the charge rising property and the charge amount are not sufficient, and the toner image may be easily affected.

<External agent>
The external additive is not particularly limited and may be appropriately selected from known ones in combination of one or a plurality of types depending on the intended purpose. For example, silica fine particles, hydrophobicized silica fine particles, and fatty acids. Metal salts (eg, zinc stearate, aluminum stearate, etc.); metal oxides (eg, titania, alumina, tin oxide, antimony, etc.) or their hydrophobics, fluoropolymers, and the like.
Among these, hydrophobicized silica fine particles, titania particles, and hydrophobicized titania fine particles are preferably mentioned.
Further, from the viewpoint of toner storage stability and image stability, the inorganic fine particles need to have a volume average particle size in the range of 40 nm or more and 300 nm or less. Further, it is preferable that the inorganic fine particles contain at least one selected from silica and titania.

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

The content of the external additive is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.3 parts by mass to 3.0 parts by mass with respect to 100 parts by mass of the 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 matrix particles is not particularly limited, but is preferably 50% to 90%, more preferably 60% to 80%.

<Toner manufacturing method>
As the method and material for producing the toner in the present invention, all known methods and materials can be used as long as the conditions are satisfied, and the toner particles are not particularly limited. 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 or the like and placed in an aqueous medium. Dissolution suspension method for dispersing or emulsifying; 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 contains resin fine particles. A method of emulsifying or dispersing in an aqueous medium and reacting the active hydrogen group-containing compound with the reactive group-containing prepolymer in the aqueous medium (production method (I)); suitable for a resin or a resin precursor. Phase inversion emulsification method in which water is added to a solution consisting of an emulsifier to invert the phase; resin particles obtained by these methods are agglomerated in a dispersed state in an aqueous medium and granulated into particles of a desired size by heat melting or the like. Such as the agglomeration method. Among these, the toner obtained by the dissolution / suspension method, the production method (I), and the agglutination method is preferable from the viewpoint of granulation property (particle size distribution control, particle shape control, etc.), and the production method (I) is used. The resulting toner is more preferred.

The details of these manufacturing methods will be described below.
The kneading and pulverizing method is a method for producing the base particles of the toner by, for example, melting and kneading a toner material having at least a colorant, a binder resin, and a mold release agent, pulverizing and classifying the toner material.

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 type kneader using a roll mill can be used. For example, KTK type twin-screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin-screw extruder manufactured by Ktk Inc., PCM type twin-screw extruder manufactured by Ikegai Iron Works, Conider manufactured by Bus Co., Ltd., etc. are suitable. Used. It is preferable that this melt-kneading is performed under appropriate conditions so as not to cause breakage of the molecular chain of the binder resin. Specifically, the melt-kneading temperature is performed with reference to the softening point of the binder resin, and if the temperature is too high above 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 product is first roughly pulverized and then finely pulverized. At this time, a method is preferably used in which particles are crushed by colliding with a collision plate in a jet stream, particles are crushed by colliding with each other in a jet stream, or crushing is performed in a narrow gap between a mechanically rotating rotor and a stator.
In the classification, the pulverized product obtained by the pulverization is classified into particles having a predetermined particle size. The classification can be performed by removing the fine particle portion with, for example, a cyclone, a decanter, a centrifuge, or the like.
After the pulverization and classification are completed, the pulverized product can be classified into an air stream by centrifugal force or the like to produce toner matrix particles having a predetermined particle size.

In the dissolution / suspension method, for example, an oil phase composition obtained by dissolving or dispersing a toner composition containing at least a binder resin or a resin precursor, a colorant, and a mold release agent in an organic solvent is prepared in an aqueous system. This is a method for producing a parent particle of a toner by dispersing or emulsifying it in a medium.
The organic solvent used when dissolving or dispersing the toner composition is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of facilitating subsequent removal of the solvent.

Examples of the organic solvent include ester-based or ester-ether-based solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, and ethyl cellosolve acetate, diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl. Ether solvents such as ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, ketone solvents such as cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2 -Alcohol-based solvents such as ethylhexyl alcohol and benzyl alcohol, and mixed solvents of two or more of these can be mentioned.

In the above-mentioned dissolution / suspension method, an emulsifier or a dispersant may be used, if necessary, when the oil phase composition is dispersed or emulsified in an aqueous medium.

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 (alkylbenzene sulfonic acid, phosphoric acid ester, etc.), a cationic surfactant (quaternary ammonium salt type, amine salt type, etc.), and an amphoteric surfactant (carboxylic acid). Acid type, sulfate ester salt type, sulfonate type, phosphate ester salt type, etc.), nonionic surfactant (AO addition type, polyhydric alcohol type, etc.) and the like can be mentioned. As the surfactant, one kind alone or two or more kinds of surfactants may be used in combination.

Examples of the water-soluble polymer include cellulose-based compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and their saponified products), gelatin, starch, dextrin, gum arabic, chitin, and chitosan. , Polyvinyl alcohol, Polypolypyrrolidone, Polyethylene glycol, Polyethyleneimine, Polyacrylamide, Acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, partial neutralized sodium hydroxide of polyacrylate , Sodium acrylate-acrylic acid ester copolymer), sodium hydroxide (partial) neutralized product of styrene-maleic anhydride copolymer, water-soluble polyurethane (polyethylene glycol, polycaprolactone diol, etc.) and polyisocyanate reaction product Etc.) and so on.
Further, the above-mentioned organic solvent, plasticizer and the like can be used in combination as an auxiliary agent for emulsification or dispersion.

The toner according to the present invention is 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 mold release agent in the dissolution and suspension method. The oil phase composition containing the above is dispersed or emulsified in an aqueous medium containing resin fine particles, and the active hydrogen group-containing compound contained in the oil phase composition and / or the aqueous medium and the reactive group-containing prepolymer. It is preferable to obtain by granulating the base particles of the toner by a method (manufacturing method (I)) of reacting with.

The resin fine particles can be formed by using a known polymerization method, but it is preferably obtained as an aqueous dispersion of the resin fine particles. Examples of the method for preparing the aqueous dispersion of the resin fine particles include the methods shown in (a) to (h) below.

(A) A method for directly preparing an aqueous dispersion of resin fine particles by a polymerization reaction of any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method using a vinyl monomer as a starting material.
(B) After dispersing a precursor (monomer, oligomer, etc.) of a heavy addition or condensation resin such as a polyester resin, a polyurethane resin, or an epoxy resin or a solvent solution thereof in an aqueous medium in the presence of an appropriate dispersant, A method of preparing an aqueous dispersion of resin fine particles by heating or adding a curing agent and curing.
(C) In a precursor (monomer, oligomer, etc.) of a heavy addition or condensation resin such as a polyester resin, a polyurethane resin, or an epoxy resin, or a solvent solution thereof (preferably a liquid, which may be liquefied by heating). A method of preparing an aqueous dispersion of resin fine particles by dissolving an appropriate emulsifier in the resin and then adding water for phase inversion emulsification.
(D) A resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-open polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized using a mechanical rotary type or jet type fine pulverizer and classified. A method of preparing an aqueous dispersion of resin fine particles by dispersing the resin fine particles in water in the presence of an appropriate dispersant.
(E) Resin fine particles are formed by spraying a resin solution prepared by dissolving a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent in the form of a mist. After that, the resin fine particles are dispersed in water in the presence of an appropriate dispersant to prepare an aqueous dispersion of the resin fine particles.
(F) A poor solvent is added to a resin solution prepared by dissolving a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, or the solvent is preheated. Resin fine particles are precipitated by cooling the dissolved resin solution, the solvent is removed to form resin fine particles, and then the resin fine particles are dispersed in water in the presence of an appropriate dispersant to carry out aqueous dispersion of the resin fine particles. How to prepare the liquid.
(G) A resin solution prepared by dissolving a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent is used as an aqueous medium in the presence of an appropriate dispersant. A method of preparing an aqueous dispersion of resin fine particles by dispersing the resin in the resin and then removing the solvent by heating, reducing the pressure, or the like.
(H) A suitable emulsifier is dissolved in a resin solution prepared by dissolving a resin synthesized in advance 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 polycondensation and emulsification.

The volume average particle size 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 and when it exceeds 300 nm, the particle size distribution of the toner may be deteriorated, which is not preferable.

The solid content concentration of the oil phase is preferably about 40 to 80%. If the concentration is too high, it becomes difficult to dissolve or disperse, and if the concentration is too low, the viscosity becomes high and it is difficult to handle. If the concentration is too low, the manufacturability of the toner is lowered.

Toner compositions other than the binder resin such as the colorant and the mold release agent, and their master batches and the like are individually dissolved or dispersed in an organic solvent and then mixed with the binder resin solution or the dispersion. You may.

As the water-based medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellsolves (methylcellsolve, etc.), lower ketones (acetone, methylethylketone, etc.) and the like.
The method of dispersion or emulsification in the aqueous medium is not particularly limited, but known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. Above all, 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 rotation speed is not particularly limited, but is usually 1000 to 30,000 rpm, preferably 5000 to 20000 rpm. The temperature at the time of dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

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

A known technique is used as a method for washing and drying the parent particles of the toner dispersed in the aqueous medium. That is, after solid-liquid separation with a centrifuge, filter press, etc., the obtained toner cake is redistributed in ion-exchanged water at room temperature to about 40 ° C., and the pH is adjusted with acid or alkali as necessary. Toner powder is obtained by removing impurities and surfactants by repeating the process of solid-liquid separation again several times, and then drying with an air flow dryer, a circulation dryer, a vacuum dryer, a vibration flow dryer, or the like. .. At this time, the fine particle components of the toner may be removed by centrifugation or the like, and after drying, a known classifier can be used to obtain a desired particle size distribution.

In the agglomeration method, for example, a resin fine particle dispersion made of at least a binder resin, a colorant particle dispersion, and a release agent particle dispersion, if necessary, are mixed and agglomerated to produce toner matrix particles. is there. The resin fine particle dispersion is obtained by a known method such as emulsion polymerization, seed polymerization, phase inversion emulsion, etc., and the colorant particle dispersion and the release agent particle dispersion are known wet dispersion methods. It can be obtained by dispersing a colorant or a mold release agent in an aqueous medium.
For controlling the agglutinated state, methods such as applying heat, adding a metal salt, and adjusting the pH are preferably used.

The metal salt is not particularly limited, and is a monovalent metal constituting a salt such as sodium or potassium; a divalent metal constituting a salt such as calcium or magnesium; a trivalent metal constituting a salt such as aluminum, or the like. Can be mentioned.

Examples of anions constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion, and sulfate ion, and among these, magnesium chloride, aluminum chloride, and a complex or multimer thereof are preferable. ..
Further, it is possible to promote the fusion of the resin fine particles by heating during the aggregation or after the aggregation is completed, which is preferable from the viewpoint of toner uniformity. Further, the shape of the toner can be controlled by heating, and usually, the toner becomes closer to a spherical shape when it is heated more.
As a method for washing and drying the parent particles of the toner dispersed in the aqueous medium, the above-mentioned method or the like can be used.

Further, in order to improve the fluidity, storage stability, developability, and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder are further added and mixed with the toner base particles produced as described above.
A general powder mixer is used for mixing the additives, but it is preferable to equip a jacket or the like to control the internal temperature. In order to change the history of the load applied to the additive, the additive may be added in the middle or gradually. In this case, the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. Further, a strong load may be applied first, and then a relatively weak load may be applied, and vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a locking mixer, a Reedige mixer, a Nauter mixer, a Henschel mixer, and the like. Next, coarse particles and agglomerated particles are removed by passing through a sieve of 250 mesh or more to obtain toner.

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

-Average circularity of toner-
The average circularity is a value obtained by dividing the peripheral length of an equivalent circle having the same projected area as the shape of the toner by the peripheral length of existing particles, and is preferably 0.950 to 0.980, preferably 0.960 to 0. .975 is more preferred. It is preferable that 15% or less of the particles have an average circularity of less than 0.95.

If the average circularity is less than 0.950, a high-quality image without satisfactory transferability and dust may not be obtained, and if it exceeds 0.980, image formation using blade cleaning or the like may not be obtained. In the system, poor cleaning of the photoconductor and the transfer belt occurs, and in the case of stains on the image, for example, in the case of image formation with a high image area ratio such as a photographic image, an untransferred image is formed due to poor feeding or the like. The transferred toner may become a transfer residual toner on the photoconductor, causing background stains on the accumulated image, or contaminating the charging roller or the like that contact-charges the photoconductor, thereby reducing the original charging ability. It may not be possible to demonstrate it.

The average circularity is measured using a flow-type particle image analyzer (“FPIA-2100”, manufactured by Sysmex), and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). It was. Specifically, 0.1% by mass of a 10% by mass surfactant (alkylbenzenesulfonate, Neogen SC-A, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added to a 100 ml glass beaker, and 0.1 of each toner was added. ~ 0.5 g was added and stirred with microspartel, then 80 mL of ion-exchanged water was added. The obtained dispersion was dispersed for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Corporation). The shape and distribution of the toner were measured with the FPIA-2100 of the dispersion until a concentration of 5,000 to 15,000 / μL was obtained.

In this measurement method, it is important that the concentration of the dispersion liquid is 5,000 to 15,000 / μL from the viewpoint of measurement reproducibility of average circularity. In order to obtain the dispersion liquid concentration, it is necessary to change the conditions of the dispersion liquid, that is, the amount of the surfactant to be added and the amount of the toner. As with the measurement of toner particle size described above, the required amount of surfactant differs depending on the hydrophobicity of the toner. If a large amount is added, noise due to bubbles is generated, and if a small amount is added, the toner cannot be sufficiently wetted, resulting in poor dispersion. Will be enough. The amount of toner added varies depending on the particle size, and is small in the case of a small particle size and needs to be increased in the case of a large particle size. When the toner particle size is 3 μm to 10 μm, the toner amount is 0.1 g to 0. By adding 5 g, the concentration of the dispersion can be adjusted to 5,000 / μl to 15,000 / μl.

-Volume average particle size of toner-
The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 3 μm to 10 μm is preferable, and 4 μm to 7 μm is more preferable. If the volume average particle size is less than 3 μm, the toner may be fused to the surface of the carrier in the two-component developer during long-term stirring in the developing apparatus, and the charging ability of the carrier may be lowered. If it exceeds 10 μm. It becomes difficult to obtain a high-resolution and high-quality image, and when the toner in the developing agent is balanced, the particle size of the toner may fluctuate greatly.

The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) of the toner is preferably 1.00 to 1.25, more preferably 1.00 to 1.15.
The volume average particle size and the ratio of the volume average particle size to the number average particle size (volume average particle size / number average particle size) are determined by using a particle size measuring instrument (“Multisizer III”, manufactured by Beckman Coulter). , The particle size was measured with an aperture diameter of 100 μm, and the analysis was performed with analysis software (Beckman CounterMlitizer 3 Version 3.51). Specifically, 0.5 ml of a 10 mass% surfactant (alkylbenzenesulfonate, Neogen SC-A, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was added to a 100 ml glass beaker, and 0.5 g of each toner was added to Microspartel. Stir with water, then 80 ml of ion-exchanged water was added. The obtained dispersion was dispersed for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as a measurement solution. In the measurement, the toner sample dispersion was added dropwise so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important to set the concentration to 8 ± 2% from the viewpoint of measurement reproducibility of the particle size. Within this concentration range, there is no error in the particle size.

-Volume average particle size of external additive-
The average particle size of the inorganic fine particles attached as an external additive is the equivalent circle diameter obtained by observing 100 inorganic fine particles at a magnification of 40,000 times using a SEM (Scanning Electron Microscope) device and performing image analysis. It is calculated as a 50% diameter (D50v) in the cumulative frequency.
A specific example of the image analysis method of the external additive will be described below. As the method of image analysis, the following method can be performed using the image solution software LMeye for Lasertec OPTELICSC130 as the image analysis software.
(1) The image observed by the SEM at 5.0 kV is captured.
(2) Adjust the calibration (scale).
(3) Perform automatic contrast.
(4) Invert.
(5) Edge extraction (sobel) is performed.
(6) Perform edge extraction (sobel) again.
(7) Perform binarization processing (discriminant analysis mode).
(8) The shape features (circularity, absolute maximum length, diagonal width) are calculated by measurement.

-Average roundness of the external additive-
The circularity of the inorganic fine particles can be defined as "100 / SF2" calculated by the following (formula) from the result of the above image analysis.
Circularity (100 / SF2) = 4π × (A / I ² )
[In the formula, I represents the peripheral length of the inorganic fine particles on the image, A represents the projected area of the inorganic fine particles, and SF2 represents the shape coefficient. ]

The circularity of the inorganic fine particles is obtained as 50% circularity in the cumulative frequency of the equivalent circle diameters of 100 particles obtained by the above image analysis.

-Glass transition point, melting point of crystalline resin, melting point of wax-
Here, the glass transition point, the melting point of the crystalline resin, and the melting point of the wax in the present invention are specifically determined by the following procedure. TA-60WS and DSC-60 manufactured by Shimadzu Corporation were used as measuring devices, and the measurement was performed under the following measurement conditions.

Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5 mg
Reference: Aluminum sample pan (alumina 10 mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature conditions-First temperature rise-
Starting temperature: 20 ° C
Temperature rise rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Cooling temperature: 10 ° C / min
End temperature: 20 ° C
-Second temperature rise-
Holding time: None Heating rate: 10 ° C / min
End temperature: 150 ° C

The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The method of analyzing the glass transition point is to specify the range of ± 5 ° C centering on the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve at the time of temperature rise, and use the peak analysis function of the analysis software to peak. Find the temperature. Next, the maximum endothermic temperature of the DSC curve is obtained by using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. on the DSC curve. The temperature shown here corresponds to the glass transition point of the toner.

The melting point of the crystalline resin is the first endothermic peak temperature that was seen at the first temperature rise and disappeared at the second temperature rise on the DSC curve. As a specific analysis method, the first endothermic temperature of the DSC curve is used. The maximum endothermic temperature of the DSC curve is obtained by using the peak analysis function of the analysis software for the first endothermic peak that was seen by the temperature rise and disappeared by the second temperature rise. The temperature shown here corresponds to the melting point of the crystalline resin.

The melting point of the wax is the endothermic peak temperature of the second temperature rise on the DSC curve, and as a specific analysis method, the endothermic peak of the second temperature rise of the DSC curve is analyzed using the peak analysis function of the analysis software. Find the maximum endothermic temperature of the DSC curve. The temperature shown here corresponds to the melting point of the wax.

(Developer)
The developer in the present invention contains at least the toner, and contains other components such as carriers, which are appropriately selected. The developer may be a one-component developer or a two-component developer, but when used in a high-speed printer or the like corresponding to an improvement in information processing speed in recent years, the service life is improved. The two-component developer is preferable in terms of the above.

In the case of the one-component developer using the toner, agglomerates of the toner are less likely to be formed over time even under stress caused by the developing means, and the toner is filmed on a developing roller as a developing agent carrier. , Toner is not fused 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. .. Further, in the case of the two-component developer using the toner, the toner is less likely to agglomerate over time even under agitation stress caused by the developing means, the generation 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)
The carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but those having core particles and a resin layer (coating layer) for coating the core particles are preferable.

<Core particles>
The core particles are not particularly limited as long as they are magnetic core particles and can be appropriately selected depending on the intended purpose. For example, ferromagnetic metals such as iron and cobalt; oxidation of magnetite, hematite, ferrite and the like. Iron; Examples thereof include resin particles in which magnetic substances 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 consideration for the environment.

-Weight average particle size of core particles Dw-
The weight average particle size Dw of the core particles refers to the particle size at an integrated value of 50% in the particle size distribution of the core particles obtained by a laser diffraction or scattering method. The weight average particle size Dw of the core particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10 μm to 80 μm, more preferably 20 μm to 65 μm.

To measure the weight average particle size Dw of the core particles, use a Microtrack particle size distribution meter (HRA9320-X100, manufactured by Honewell) to measure the particle size distribution (relationship between the number frequency and the particle size) of the particles measured on a number basis. It was measured under the conditions described below and calculated using the following formula (I). Each channel represents a length for dividing the particle size range in the particle size distribution map into measurement width units, and the representative particle size adopts the lower limit of the particle size stored in each channel.
Dw = {1 / Σ (nD3)} × {Σ (nD4)} ・ ・ ・ (I)
However, in the above formula (I), D represents the representative particle size (μm) of the core particles existing in each channel, and n represents the total number of core particles existing 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, if necessary.

-Resin-
The resin for forming the coating layer of the carrier is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyimide (for example, polyethylene, polypropylene, etc.) or a modified product thereof, polystyrene, acrylic resin, acrylonitrile, etc. Crosslinkable copolymer containing vinyl acetate, vinyl alcohol, vinyl chloride, vinyl carbazole, vinyl ether, etc .; using a silicone resin composed of an organosiloxane bond or a modified product thereof (for example, alkyd resin, polyester resin, epoxy resin, polyurethane, polyimide, etc.) Modified products); polyamide; polyester; polyurethane; polycarbonate; urea resin; melamine resin; benzoguanamine resin; epoxy resin; ionomer resin; polyimide resin, and derivatives thereof. These may be used alone or in combination of two or more. Among these, silicone resin is preferable.

The silicone resin is not particularly limited and may be appropriately selected from generally known silicone resins according to the purpose. For example, a straight silicone resin consisting only of an organosiloxane bond, and alkyds and polyesters. , Silicone resin 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 Co., Ltd.) and the like. Specific examples of the modified silicone resin include epoxy-modified silicone: ES-1001N, acrylic-modified silicone: KR-5208, polyester-modified product: KR-5203, alkyd-modified product: KR-206, and urethane-modified product: KR-. 305 (all manufactured by Shin-Etsu Chemical Industry Co., Ltd.), epoxy modified product: SR2115, alkyd modified product: SR2110 (manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like can be mentioned.

The silicone resin can be used alone, but it is also possible to use a cross-linking reactive component, a charge amount adjusting component, and the like at the same time. Examples of the cross-linking reactive component include a silane coupling agent and the like.
Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, aminosilane coupling agent and the like.

-Filler-
The filler is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include conductive fillers and non-conductive fillers. These may be used alone or in combination of two or more. Among these, it is preferable that the coating layer contains a conductive filler and a non-conductive filler.
The conductive filler refers to a filler having a powder resistivity value of 100 Ω · cm or less.
The non-conductive filler refers to a filler having a powder resistivity value of more than 100 Ω · cm.
The powder resistivity value of the filler is measured by a powder resistance measurement system (MCP-PD51, manufactured by Dia Instruments) and a resistivity meter (4-terminal 4-probe method, Loresta-GP, manufactured by Mitsubishi Chemical Analytech). Was used for measurement under the conditions of 1.0 g of sample, 3 mm of electrode spacing, 10.0 mm of sample radius, and 20 kN of load.

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

--Non-conductive filler ---
The non-conductive filler is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is formed by using aluminum oxide, titanium oxide, barium sulfate, zinc oxide, silicon dioxide, zirconium oxide or the like. Examples include non-conductive fillers. Among these, a non-conductive filler containing aluminum oxide, titanium oxide, and barium sulfate is preferable.

<Manufacturing method of carrier>
The method for producing the carrier is not particularly limited and may be appropriately selected depending on the intended purpose. However, the resin and the filler are contained on the surface of the core particles by using a fluidized bed coating device. A method of producing by applying a coating layer forming solution is preferable. When the coating layer forming solution is applied, the resin contained in the coating layer may be condensed, or after the coating layer forming solution is applied, the resin contained in the coating layer is condensed. May proceed. The method for condensing the resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method in which heat, light or the like is applied to the coating layer forming solution to condense the resin. ..

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

(Toner storage unit)
The toner accommodating unit in the present invention means a unit accommodating toner in a unit having a function of accommodating toner. Here, examples of the toner storage unit include a toner storage container, a developing device, a process cartridge, and the like.
The toner containing container means a container containing toner.
A developer has a means for accommodating and developing toner.
The process cartridge is a cartridge in which at least an image carrier and a developing means are integrated, accommodates toner, and is detachable from an image forming apparatus. The process cartridge may further include at least one selected from charging means, exposing means, and cleaning means.

By mounting the toner accommodating unit of the present invention on an image forming apparatus to form an image, an image is formed using the toner of the present invention. Therefore, low temperature fixability and charge stability are good, and it depends on the environment and external pressure. It is possible to suppress the deterioration of the toner over time caused by the embedding of the external additive in the toner and the release of the external additive from the toner, and it is possible to output a stable image at a high level even in long-term use.

(Image forming method and image forming device)
The image forming method used in the present invention includes an electrostatic latent image forming step (charging step and exposure step) for forming an electrostatic latent image on an electrostatic latent image carrier, and the electrostatic latent image using a toner. It has at least a developing step of developing to form a visible image, a transfer step of transferring the visible image to a recording medium, and a fixing step of fixing the transferred image transferred to the recording medium. Further, it has other steps appropriately selected as necessary, such as a static elimination step, a cleaning step, a recycling step, a control step and the like.
The image forming apparatus of the present invention includes an electrostatic latent image carrier, electrostatic latent image forming means (charging means and exposure means) for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic. A developing means for developing a latent image with toner to form a visible image, a transfer means for transferring the visible image onto a recording medium, and a fixing means for fixing the transferred image transferred on the recording medium. And have at least. Further, it has other means appropriately selected as necessary, such as 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 an electrostatic latent image carrier.
The material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as "electrophotographic photosensitive member" or "photoreceptor") are not particularly limited, and among known ones. Although it can be appropriately selected, the shape thereof is preferably drum-shaped, and the material thereof is, for example, an inorganic photoconductor such as amorphous silicon or selenium, an organic photoconductor (OPC) such as polysilane or phthalopolymethine, or the like. Can be mentioned. Among these, an organic photoconductor (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 exposing it to an image, and by using an electrostatic latent image forming means. Can be done.
The electrostatic latent image forming means includes, for example, a charging means (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 in an image manner. It is provided with at least means (exposure device).

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging device.
The charger is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a contact charge known per se including a conductive or semi-conductive roll, brush, film, rubber blade or the like. Examples include non-contact chargers that utilize corona discharge such as vessels, corotrons, and scorotrons.
As the charger, it is preferable that the charger is arranged in contact or non-contact state with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by superimposing and applying DC and AC voltages.

Further, the charger is a charging roller that is non-contactly arranged on the electrostatic latent image carrier via a gap tape, and the electrostatic latent image is supported by superimposing and applying direct current and alternating voltage to the charging roller. Those that charge the body surface are preferable.

The exposure can be performed, for example, by exposing the surface of the electrostatic latent image carrier as an image using the exposure device.
The exposure device is not particularly limited as long as the surface of the electrostatic latent image carrier charged by the charger can be exposed to an image to be formed, and may be appropriately selected depending on the intended purpose. However, examples thereof include 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.
In the present invention, an optical back surface method may be adopted in which the back surface side of the electrostatic latent image carrier is exposed in an image-like manner.

-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 with the toner, and can be performed by the developing means.
The developing means preferably has, for example, a developer that accommodates the toner and is capable of contacting or non-contacting the toner to the electrostatic latent image, and is provided with a container containing the toner. Etc. are more preferable.
The developer may be a monochromatic developer or a multicolor developer, and has, for example, a stirrer for frictionally agitating and charging the toner, and a rotatable magnet roller. Those and the like are preferably mentioned.

In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by the friction at that time and is held in a spiked state on the surface of a rotating magnet roller to form a magnetic brush. .. Since the magnet roller is arranged in the vicinity of the electrostatic latent image carrier (photoreceptor), 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 (photoreceptor) by force. As a result, the electrostatic latent image is developed by the toner, and a visible image by the toner is formed on the surface of the electrostatic latent image carrier (photoreceptor).

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image to a recording medium. After using an intermediate transfer body to primary transfer the visible image onto the intermediate transfer body, the visible image is transferred onto the recording medium. A mode of secondary transfer to the medium is preferable, and a primary transfer step of transferring a visible image onto an intermediate transfer body to form a composite transfer image by using two or more colors, preferably a full-color toner as the toner, and the composite. A mode including a secondary transfer step of transferring the transferred image onto a recording medium is more preferable.

The transfer can be performed, for example, by charging the electrostatic latent image carrier (photoreceptor) with the transfer charger using the transfer charger, and can be performed by the transfer means. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer body to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Aspects are preferred.
The intermediate transfer material is not particularly limited and may be appropriately selected from known transfer materials according to the purpose. For example, a transfer belt or the like is preferably used.

The transfer means (the primary transfer means, the secondary transfer means) transfers and charges the visible image formed on the electrostatic latent image carrier (photoreceptor) to the recording medium side. It is preferable to have at least a vessel. The transfer means may be one or two or more.
Examples of the transfer device include a corona transfer device by corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, an adhesive transfer device, and the like.
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 by using a fixing device, and may be performed every time the developer of each color is transferred to the recording medium, or the developer of each color. On the other hand, this may be carried out at the same time in a state of being laminated.
The fixing device is not particularly limited and may be appropriately selected depending on the intended purpose, but known heating and pressurizing means are suitable. Examples of the heating and pressurizing means include a combination of a heating roller and a pressurizing roller, a combination of a heating roller, a pressurizing roller and an endless belt, and the like.

The fixing device has a heating body including a heating element, a film in contact with the heating body, and a pressure member that presses against the heating body via the film, and the film and the pressure member It is preferable that the means is to heat and fix the film by passing it through a recording medium on which an unfixed image is formed. The heating in the heating and pressurizing 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 fixing means, depending on the purpose.

-Other processes and other means-
The static electricity elimination step is a step of applying a static electricity elimination bias to the electrostatic latent image carrier to perform static electricity elimination, and can be preferably performed by the static electricity elimination means.
The static eliminating means is not particularly limited as long as it can apply a static eliminating bias to the electrostatic latent image carrier, and can be appropriately selected from known static eliminators, for example, a static eliminating lamp or the like. Preferred.

The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier, and can be preferably performed by a cleaning means.
The cleaning means is not particularly limited as long as it can remove the toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners, for example, a magnetic brush cleaner. , Electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web cleaner and the like are preferable.

The recycling step is a step of causing the developing means to recycle the toner removed by the cleaning step, and can be preferably performed by the recycling means. The recycling means is not particularly limited, and examples thereof include known transportation means.

The control step is a step of controlling each of the steps, and each step can be preferably performed by a control means.
The control means is not particularly limited as long as the movement of each of the means can be controlled, and can be appropriately selected depending on the intended purpose. Examples thereof include devices such as sequencers and computers.

FIG. 1 shows a first example of the image forming apparatus of the present invention. The image forming apparatus 100A includes a photoconductor drum 10, a charging roller 20, an exposure apparatus, a developing apparatus 40, an intermediate transfer belt 50, a cleaning apparatus 60 having a cleaning blade, and a static elimination lamp 70.

The intermediate transfer belt 50 is an endless belt stretched by three rollers 51 arranged inside, and can be moved in the direction of the arrow in the drawing. A part of the three rollers 51 also functions as a transfer bias roller capable of applying a transfer bias (primary transfer bias) to the intermediate transfer belt 50. Further, a cleaning device 90 having a cleaning blade is arranged 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 arranged so as to face 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 provided with the photoconductor drum 10 in the rotation direction of the intermediate transfer belt 50. It is arranged between the contact portion of the intermediate transfer belt 50 and the contact portion between the intermediate transfer belt 50 and the transfer paper 95.

The developing device 40 includes a developing belt 41, a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C, which are arranged around the developing belt 41. The developing unit 45 for each color includes a developing agent accommodating portion 42, a developing agent supply roller 43, and a developing roller (developer carrier) 44. Further, the developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can be moved in the direction of an arrow in the drawing. Further, a part of the developing belt 41 is in contact with the photoconductor drum 10.

Next, a method of forming an image using the image forming apparatus 100A will be described. First, the surface of the photoconductor drum 10 is uniformly charged using the charging roller 20, and then the exposure light L is exposed to the photosensitive drum 10 using an exposure device (not shown) to obtain 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, the toner image formed on the photoconductor drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by the transfer bias applied from the roller 51, and then transferred by the transfer bias applied from the transfer roller 80. , Transferred on transfer paper 95 (secondary transfer). On the other hand, the photoconductor drum 10 on which the toner image is transferred to the intermediate transfer belt 50 is statically eliminated by the static elimination lamp 70 after the toner remaining on the surface is removed by the cleaning device 60.

FIG. 2 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 directly opposed to each other around the photoconductor drum 10 without providing the developing belt 41. Other than that, it has the same configuration as the image forming apparatus 100A.

FIG. 3 shows a third example of the image forming apparatus used in the present invention. The image forming apparatus 100C 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 transporting apparatus (ADF) 400.

The intermediate transfer belt 50 provided in the central portion of the copying apparatus main body 150 is an endless belt stretched on the three rollers 14, 15 and 16, and can be moved in the direction of the arrow in the drawing. In the vicinity of the roller 15, a cleaning device 17 having a cleaning blade for removing the toner remaining on the intermediate transfer belt 50 on which the toner image is transferred to the recording paper is arranged. Yellow, cyan, magenta, and black image forming units 120Y, 120C, 120M, and 120K are juxtaposed along the transport direction while facing the intermediate transfer belt 50 stretched by the rollers 14 and 15.

Further, an exposure device 21 is arranged in the vicinity of the image forming unit 120. Further, the secondary transfer belt 24 is arranged on the side of the intermediate transfer belt 50 opposite to the side on which the image forming unit 120 is arranged. The secondary transfer belt 24 is an endless belt stretched on 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 be contacted.

Further, in the vicinity of the secondary transfer belt 24, a fixing device 25 including a fixing belt 26 which is an endless belt stretched on a pair of rollers and a pressure roller 27 which is pressed and arranged by the fixing belt 26. Is placed. A sheet reversing device 28 for reversing the recording paper when an image is formed on both sides of the recording paper is arranged in the vicinity of the secondary transfer belt 24 and the fixing device 25.

Next, a method of forming a full-color image using the image forming apparatus 100C will be described. First, a color document is set on the platen 130 of the automatic document transfer device (ADF) 400, or a color document is set on the contact glass 32 of the scanner 300 by opening the automatic document transfer device 400 and automatically transporting the document. Close device 400.
When the start switch is pressed, when the original is set in the automatic document transfer device 400, the original is conveyed and moved onto the contact glass 32, and then the original is set on the contact glass 32. Immediately, the scanner 300 is driven, and the first traveling body 33 including the light source and the second traveling body 34 including the mirror travel. At this time, after the light reflected from the document surface of the light emitted from the first traveling body 33 is reflected by the second traveling body 34, the document is received by the reading sensor 36 via the imaging lens 35, so that the document is formed. It is read and image information of black, yellow, magenta and cyan is obtained.

The image information of each color is transmitted to the image forming unit 120 of each color, and a toner image of each color is formed. As shown in FIG. 4, the image forming unit 120 of each color includes the photoconductor drum 10, the charging roller 160 that uniformly charges the photoconductor drum 10, and the photoconductor drum 10 based on the image information of each color. The toner image is intermediate between an exposure device that exposes the exposure light L to form an electrostatic latent image of each color and 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 each color formed by the image forming unit 120 of each color are sequentially transferred (primary transfer) onto the intermediate transfer body 50 which is stretched and moved by the rollers 14, 15 and 16, and superposed 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, and the recording paper is fed out from one of the paper feed cassettes 144 provided in the paper bank 143 in multiple stages, and the separation rollers 145 are used one by one. It is separated and sent out to the paper feed path 146, conveyed by the transfer roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the resist roller 49 to be stopped. 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 resist roller 49 to stop. Although the resist roller 49 is generally grounded and used, it 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 resist roller 49 in time with the composite toner image formed on the intermediate transfer belt 50, the recording paper is sent out between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is formed. The toner image is transferred (secondary transfer) onto the recording paper. The toner remaining on the intermediate transfer belt 50 on which the composite toner image is transferred is removed by the cleaning device 17.

The recording paper on which the composite toner image is transferred is conveyed by the secondary transfer belt 24, and then the composite toner image is fixed by the fixing device 25. Next, the transport path of the recording paper is switched by the switching claw 55, and the recording paper is discharged onto the paper ejection tray 57 by the ejection roller 56. Alternatively, the transport path of the recording paper is switched by the switching claw 55, inverted by the sheet reversing device 28, an image is formed on the back surface in the same manner, and then the recording paper is ejected onto the output tray 57 by the ejection roller 56. ..

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples. In the description in the example, [%] indicates% by weight, and unless otherwise specified, when simply described as "part", it indicates "part by mass". Further, Examples 1 to 4 , 8, 9, 11 to 17 , 22 and 23 are Reference Examples 1 to 4, 8, 9, 11 to 17, 22 and 23 not included in the present invention.

(Synthesis Example A-1)
-Synthesis of binder resin A-1-
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 376 parts of bisphenol A propylene oxide 2 mol adduct and 109 parts of bisphenol A propylene oxide 3 mol adduct were placed in a molar ratio of 80/20. 116 parts of isophthalic acid and 44 parts of adipic acid were charged at a molar ratio of 70/30, charged at OH / COOH = 1.33, and reacted with 500 ppm titanium tetraisopropoxide at 230 ° C. for 10 hours at normal pressure. Next, 16 parts of benzoic acid was added to the reaction vessel, and the reaction was carried out under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours. Then, 11 parts of trimellitic anhydride was placed in the reaction vessel, and the reaction was carried out at 180 ° C. and normal pressure for 3 hours. A-1] was obtained.

-Synthesis of Dispersant A-
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 2300 parts by mass of deionized water, 25 parts by mass of methyl methacrylate and 75 parts by mass of 3-sodium sulfopropyl methacrylate are charged and nitrogen gas is charged. Was circulated for about 30 minutes. After raising the temperature to 60 ° C. while stirring the contents, 0.5 parts by mass of ammonium persulfate was added and the mixture was stirred for 3 hours to obtain [Dispersant A].

(Synthesis Example A-2)
-Synthesis of binder resin A-2-
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 376 parts of bisphenol A propylene oxide 2 mol adduct and 109 parts of bisphenol A propylene oxide 3 mol adduct were placed in a molar ratio of 80/20. 83 parts of isophthalic acid and 73 parts of adipic acid were charged at a molar ratio of 50/50, charged at OH / COOH = 1.33, and reacted with 500 ppm titanium tetraisopropoxide at 230 ° C. for 10 hours at normal pressure. Then, after reacting under reduced pressure of 10 mmHg to 15 mmHg for 5 hours, 11 parts of trimellitic anhydride was placed in a reaction vessel, and the reaction was carried out at 180 ° C. and normal pressure for 3 hours to obtain [binding resin A-2].

(Synthesis Example A-3)
-Synthesis of binder resin A-3-
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 376 parts of bisphenol A propylene oxide 2 mol adduct and 109 parts of bisphenol A propylene oxide 3 mol adduct were placed in a molar ratio of 80/20. 141 parts of terephthalic acid and 25 parts of isophthalic acid were charged at a molar ratio of 85/15, charged at OH / COOH = 1.35, and reacted with 500 ppm titanium tetraisopropoxide at 230 ° C. for 10 hours at normal pressure. Next, 26 parts of benzoic acid was added to the reaction vessel, and the reaction was carried out under a reduced pressure of 10 mmHg to 15 mmHg for 5 hours. Then, 11 parts of trimellitic anhydride was placed in the reaction vessel, and the reaction was carried out at 180 ° C. and normal pressure for 3 hours. A-3] was obtained.

(Synthesis Example A-4)
-Synthesis of binder resin A-4-
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 376 parts of bisphenol A propylene oxide 2 mol adduct and 109 parts of bisphenol A propylene oxide 3 mol adduct were placed in a molar ratio of 80/20. 116 parts of isophthalic acid and 44 parts of adipic acid were charged at a molar ratio of 70/30, charged at OH / COOH = 1.33, and reacted with 500 ppm titanium tetraisopropoxide at 230 ° C. for 10 hours at normal pressure. Then, after reacting under reduced pressure of 10 mmHg to 15 mmHg for 5 hours, 11 parts of trimellitic anhydride was placed in a reaction vessel, and the reaction was carried out at 180 ° C. and normal pressure for 3 hours to obtain [binding resin A-4].

(Synthesis Example B-1)
-Synthesis of binder resin B-1-
Sebacic acid, adipic acid and 1,4-butanediol were charged at a molar ratio of 40/9/51 in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and titanium dihydroxybis (triethanol) was charged as a condensation catalyst. 0.25 part of aminate) was added to 100 parts of the monomer component, and the reaction was carried out under a nitrogen stream for 4 hours while distilling off water produced at 180 ° C. Then, while gradually raising the temperature to 225 ° C., the reaction was carried out for two and a half hours while distilling off the generated water and 1,4-butanediol under a nitrogen stream, and then the weight average molecular weight was further reduced to 5 to 20 mmHg. The reaction was carried out until Mw reached about 1000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and 250 parts of ethyl acetate, 40 parts of hexamethylene diisocyanate (HDI) and 25 parts of maleic anhydride were added. The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Then, ethyl acetate was distilled off under reduced pressure to obtain a binder resin B-1.

(Synthesis Example B-2)
-Synthesis of binder resin B-2-
Crystalline polylactic acid "N-3000" (manufactured by Nature Works) was placed in a 35 x 25 cm vat and allowed to stand in an environment of a temperature of 80 ° C. and a humidity of 95% for 48 hours. Obtained.

(Synthesis Example B-3)
-Synthesis of binder resin B-3-
Sebacic acid, adipic acid and 1,4-butanediol were charged at a molar ratio of 40/9/51 in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and titanium dihydroxybis (triethanol) was charged as a condensation catalyst. 0.25 part of aminate) was added to 100 parts of the monomer component, and the reaction was carried out under a nitrogen stream for 4 hours while distilling off water produced at 180 ° C. Then, while gradually raising the temperature to 225 ° C., the reaction was carried out for 3 hours while distilling off the generated water and 1,4-butanediol under a nitrogen stream, and then under a reduced pressure of 5 to 20 mmHg, the weight average molecular weight Mw. Was reacted until it reached about 1200.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and 250 parts of ethyl acetate, 40 parts of hexamethylene diisocyanate (HDI) and 25 parts of maleic anhydride were added. The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Then, ethyl acetate was distilled off under reduced pressure to obtain [binding resin B-3].

(Preparation of masterbatch (MB))
Add 1,200 parts of water, 540 parts of carbon black (manufactured by Printex 35 Dexa, DBP oil absorption = 42 mL / 100 mg, pH = 9.5), and 1,200 parts of [binding resin A-1], and add a Henschel mixer (Mitsui). The mixture was mixed in (manufactured by Mining Co., Ltd.), and the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a palperizer to obtain [Master Batch 1].

(Adjustment of wax dispersant)
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 600 parts of xylene and 300 parts of low molecular weight polyethylene (Sunwax LEL-400, softening point 128 ° C., manufactured by Sanyo Kasei Kogyo Co., Ltd.) were placed and sufficiently dissolved. After substitution with nitrogen, a mixed solution of 2,310 parts of styrene, 270 parts of acrylonitrile, 150 parts of butyl acrylate, 78 parts of di-t-butylperoxyhexahydroterephthalate, and 455 parts of xylene was added dropwise at 175 ° C. over 3 hours. And polymerized, and kept at this temperature for 30 minutes. Then, the solvent was removed to synthesize [Wax Dispersant 1].

(Preparation of toner base)
[Toner bases 1 to 10] were prepared using the binder resin, masterbatch, etc. prepared in the above synthesis example. As shown in Table 1 below, the production of the [toner bases 1 to 10] is only a change in the binding resin 1 and the binding resin 2 and the number of copies thereof, and other than that, a production example of the [toner base 1] described later. It is created in the same way as.

-Example of manufacturing toner base 1-
[Raw material composition]
Binder resin 1: Binder resin A-1 94 parts Binder resin 2: None 0 part Colorant: Masterbatch 17 parts Charge control agent: Bontron E-84 (manufactured by Orient Chemical Industry Co., Ltd.) 1 part Release agent: Carnauba wax (WA-05, manufactured by Ceralica Noda) 6 parts Wax dispersant: None 0 parts

The toner powder raw material was sufficiently mixed with a super mixer (SMV-200, manufactured by Kawata Co., Ltd.) to obtain a toner powder raw material mixture. This toner powder raw material mixture was supplied to a raw material supply hopper of a Busconider (TCS-100, manufactured by Buss), and kneaded at a supply amount of 120 kg / h. After rolling and cooling the obtained kneaded product with a double belt cooler, it is roughly crushed with a hammer mill and finely crushed with a jet stream type crusher (I-20 jet mill, manufactured by Nippon Pneumatic Co., Ltd.), and then a wind power classifier. (DS-20 / DS-10 classifier, manufactured by Nippon Pneumatic Co., Ltd.) was used to classify fine powder to prepare [Toner base 1].

The formulations of [Toner Mothers 1-10] are shown in Table 1 below.

(Example of manufacturing inorganic fine particles)
-Preparation of external additive 1-
600 parts by mass of methanol and 90 parts by mass of 10% aqueous ammonia were placed in a glass reaction vessel having a volume of 2 L and equipped with a stirring blade, a dropping nozzle and a thermometer, and the mixture was stirred and mixed to obtain an alkaline catalyst solution (1). At this time, the amount of ammonia catalyst in the alkaline catalyst solution (1): NH ₃ amount (NH ₃ [mol] / (NH ₃ + methanol + water) [L]) was 0.62 mol / L.
Next, the temperature of the alkaline catalyst solution (1) was adjusted to 25 ° C., and the alkaline catalyst solution (1) was replaced with nitrogen. Then, while stirring the alkaline catalyst solution (1) at 120 rpm, 420 parts by mass of tetramethoxysilane (TMS) and _{300 parts by mass of aqueous ammonia having a catalyst (NH 3} ) concentration of 4.4% by mass were supplied in the following amounts. Then, the dropping was started at the same time, and the dropping was carried out over 20 minutes to obtain a suspension of the inorganic fine particles.
Here, the amount of tetramethoxysilane (TMS) supplied was 7 g / min with respect to the total number of moles of methanol in the alkaline catalyst solution (1). The supply amount of 4.4% ammonia water was 5.0 g / min with respect to the total supply amount of tetraalkoxysilane per minute.
Then, 250 parts by mass of the solvent of the obtained suspension of the inorganic fine particles was distilled off by heating distillation, 250 parts by mass of pure water was added, and then the mixture was dried by a freeze dryer to obtain a deformed [inorganic fine particles 1]. '] Was obtained.
Further, 20 parts by mass of trimethylsilane was added to 100 parts by mass of [inorganic fine particles 1'], and the mixture was reacted at 150 ° C. for 2 hours to obtain an irregularly shaped hydrophobic inorganic fine particles having a hydrophobic treatment on the surface of the inorganic technical particles. Obtained. The obtained irregularly shaped inorganic fine particles were designated as [inorganic fine particles 1]. In order to obtain a sharp particle size distribution, the obtained [inorganic fine particles 1] were classified by a classifying device to adjust the particle size distribution to obtain [Appendix 1].

-Preparation of external additive 2-
In the preparation of the [inorganic fine particles 1], 260 parts by mass of tetramethoxysilane (TMS) and 200 parts by mass of 4.4% aqueous ammonia were used, and the amount of tetramethoxysilane (TMS) supplied was adjusted to the alkali catalyst solution (1). 8 g / min with respect to the total number of mols of methanol in the medium, and the supply amount of 4.4% ammonia water is 6 g / min with respect to the total supply amount of tetraalkoxysilane per minute. [Inorganic fine particles 2] were obtained in the same manner as in the production of [Inorganic fine particles 1] except for the above. In order to obtain a sharp particle size distribution, the obtained [inorganic fine particles 2] were classified by a classifying device, and the particle size distribution was adjusted to obtain [external agent 2].

-Preparation of external additive 3-
In the preparation of the [inorganic fine particles 1], 150 parts by mass of tetramethoxysilane (TMS) was used, 60 parts by mass of 4.4% aqueous ammonia was used, and the amount of tetramethoxysilane (TMS) supplied was adjusted to the alkali catalyst solution (1). The supply amount of 4.4% ammonia water is 6 g / min with respect to the total supply amount of tetraalkoxysilane per minute with respect to the total number of mols of methanol in the medium. [Inorganic fine particles 3] were obtained in the same manner as in the production of [Inorganic fine particles 1] except for the above. In order to obtain a sharp particle size distribution, the obtained [inorganic fine particles 3] were classified by a classifying device, and the particle size distribution was adjusted to obtain [Appendix 3].

-Preparation of external additive 4-
In response to the preparation of the [inorganic fine particles 1], the 10% aqueous ammonia placed in a glass reaction vessel having a volume of 2 L equipped with a stirring blade, a dropping nozzle, and a thermometer was changed to 95 parts by mass, and tetramethoxysilane (TMS) was added. 300 parts by mass, 4.4% aqueous ammonia was 180 parts by mass, and the amount of tetramethoxysilane (TMS) supplied was 15 g / min with respect to the total number of mol of methanol in the alkaline catalyst solution (1). The supply amount of 4.4% ammonia water was 9 g / min with respect to the total supply amount of tetraalkoxysilane per minute, in the same manner as in the production of [Inorganic Fine Particles 1]. [Inorganic fine particles 4] were obtained. In order to obtain a sharp particle size distribution, the obtained [inorganic fine particles 4] were classified by a classifying device, and the particle size distribution was adjusted to obtain [external agent 4].

-Preparation of external additive 5-
In the preparation of the [inorganic fine particles 3], the amount of tetramethoxysilane (TMS) supplied was 16 g with respect to the total number of mols of methanol in the alkaline catalyst solution (1), with 4.5% aqueous ammonia as 55 parts by mass. [Inorganic fine particles 5] were obtained in the same manner as in the production of [Inorganic fine particles 3] except that / min was set. In order to obtain a sharp particle size distribution, the obtained [inorganic fine particles 5] were classified by a classifying device, and the particle size distribution was adjusted to obtain [external agent 5].

(Example 1)
− Mixing −
The above-mentioned [Toner base 1] is used as the toner base, the above-mentioned [Outside agent 1] is used as the external additive, and 1.5 parts of [External additive 1] is added to 100 parts of [Toner base 1]. , 20L Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) was mixed 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].

(Example 2)
[Toner 2] was produced in the same manner as in Example 1 except that TG5110 (manufactured by Cabot Corporation) was used instead of [External agent 1] in Example 1.

(Example 3)
[Toner 3] was produced in the same manner as in Example 1 except that [Toner base 2] was used as the toner base and [Outer agent 4] was used as the external additive in Example 1.

(Example 4)
[Toner 4] was produced in the same manner as in Example 1 except that [External additive 4] was used as the external additive in Example 1.

(Example 5)
[Toner 5] was produced in the same manner as in Example 1 except that [Toner base 3] was used as the toner base and [Outer agent 4] was used as the external additive in Example 1.

(Example 6)
[Toner 6] was produced in the same manner as in Example 1 except that [Toner base 4] was used as the toner base and [Outer agent 4] was used as the external additive in Example 1.

(Example 7)
[Toner 7] was produced in the same manner as in Example 1 except that [Toner base 5] was used as the toner base and [Outer agent 4] was used as the external additive in Example 1.

(Example 8)
[Toner 8] was prepared in the same manner as in Example 1 except that [External agent 3] was used as the external additive in Example 1.

(Example 9)
In Example 1, 0.3 part of [External Additive 3] was added to 100 parts of [Toner Base 1] as an external additive, and 0.3 part of [External Additive 4] was added to 100 parts of [Toner Base 1]. [Toner 9] was prepared in the same manner as in Example 1 except that 1.2 parts were added.

(Example 10)
[Toner 10] was produced in the same manner as in Example 1 except that [Toner base 5] was used as the toner base and [Outer agent 3] was used as the external additive in Example 1.

(Example 11)
[Toner 11] was prepared in the same manner as in Example 1 except that [External agent 5] was used as the external additive in Example 1.

(Comparative Example 1)
In Example 1, [Toner 12] was prepared in the same manner as in Example 1 except that [Toner base 6] was used as the toner base and [Outer agent 4] was used as the external additive.

(Comparative Example 2)
[Toner 13] was prepared in the same manner as in Example 1 except that HDK2000 (manufactured by Wacker Chemie) was used as an external additive in Example 1.

(Comparative Example 3)
[Toner 14] was produced in the same manner as in Example 1 except that [External additive 2] was used as the external additive in Example 1.

(Example 12)
In Example 1, [Toner 15] was prepared in the same manner as in Example 1 except that [External agent 3] was used as an external additive and the mixing time was set to 10 minutes.

(Example 13)
In Example 1, [Toner 16] was prepared in the same manner as in Example 1 except that [External agent 3] was used as an external additive and the mixing time was set to 3 minutes.

(Example 14)
[Toner 17] was produced in the same manner as in Example 1 except that [Toner base 7] was used as the toner base and [Outer agent 3] was used as the external additive in Example 1.

(Example 15)
In Example 1, [Toner 18] was prepared in the same manner as in Example 1 except that [External agent 3] was used as an external additive and the mixing time was set to 15 minutes.

(Example 16)
In Example 1, [Toner 19] was prepared in the same manner as in Example 1 except that [External agent 3] was used as an external additive and the mixing time was set to 2 minutes.

(Example 17)
[Toner 20] was produced in the same manner as in Example 1 except that [Toner base 8] was used as the toner base and [Outer agent 3] was used as the external additive in Example 1.

(Example 18)
In Example 1, [Toner 21] was used in the same manner as in Example 1 except that [Toner base 5] was used as the toner base and [Outer agent 3] was used as the external additive and the mixing time was set to 10 minutes. ] Was prepared.

(Example 19)
In Example 1, [Toner 22] was used in the same manner as in Example 1 except that [Toner base 5] was used as the toner base and [Outer agent 3] was used as the external additive and the mixing time was set to 3 minutes. ] Was prepared.

(Example 20)
[Toner 23] was produced in the same manner as in Example 1 except that [Toner base 9] was used as the toner base and [Outer agent 3] was used as the external additive in Example 1.

(Example 21)
In Example 1, [Toner 24] was used in the same manner as in Example 1 except that [Toner Base 5] was used as the toner base and [Outer Addendum 3] was used as the external additive and the mixing time was set to 15 minutes. ] Was prepared.

(Example 22)
In Example 1, [Toner 25] was used as the toner base and [Toner 3] was used as the external additive, and the mixing time was set to 2 minutes in the same manner as in Example 1. ] Was prepared.

(Example 23)
[Toner 26] was produced in the same manner as in Example 1 except that [Toner base 10] was used as the toner base and [Outer agent 3] was used as the external additive in Example 1.

Table 2 shows the characteristics of the toner obtained as described above.

(Measurement)
The following measurements were performed on the toners obtained in the above Examples and Comparative Examples.

<GPC measurement>
The GPC measurement was performed as follows.
Gel permeation chromatography (GPC) measuring device: GPC-8220 GPC (manufactured by Tosoh Corporation)
Columns: TSK-GEL SUPER HZ2000, TSK-GEL SUPER HZ2500, TSK-GEL SUPER HZ3000
Temperature: 40 ° C
Solvent: tetrahydrofuran (THF)
Flow velocity: 0.35 ml / min
Sample: THF sample solution adjusted to 0.15 wt% Sample pretreatment: Dissolve the toner in tetrahydrofuran THF (containing stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) at 0.15 wt%, filter with a 0.45 μm filter, and filter the filtrate. Was used as a sample.
The measurement was carried out by injecting 10 μL to 200 μL of the THF sample solution. In measuring 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, Pressure Chemical co., Ltd. ^{Molecular weight of 6 × 10 2} , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3 manufactured by Toyo Soda Industries, Ltd. ^{.9 × 10 5, 8.6 × 10} 5, 2 × 10 6, used as a 4.48 × 10 ^6, the detector using a RI (refractive index) detector.

For the GPC measurement results, plot the molecular weight distribution curve with the vertical axis as the peak intensity and the horizontal axis as the molecular weight, and set the point where the maximum peak intensity is in the range of 20000 or less as 100, and the peak of the entire molecular weight distribution curve. The intensity was corrected. Next, with respect to the range of the molecular weight of 300 to 5000, the difference between the maximum value and the minimum value of the peak intensity was determined in the range of the molecular weight M ± 300. The GPC peak intensity difference in Table 1 below is the maximum value of the obtained difference values.

<SEM observation>
The volume average particle size of the inorganic fine particles is 50% of the cumulative frequency of the equivalent circle diameter obtained by observing 100 inorganic fine particles at a magnification of 40,000 times using a SEM (Scanning Electron Microscope) device. It was calculated as the diameter (D50v).
As the method of image analysis, the following method was performed using the image solution software LMeye for OPTELICSC130 of Lasertec Co., Ltd. as the image analysis software.
(1) The image observed by the SEM at 5.0 kV is captured.
(2) Adjust the calibration (scale).
(3) Perform automatic contrast.
(4) Invert.
(5) Edge extraction (sobel) is performed.
(6) Perform edge extraction (sobel) again.
(7) Perform binarization processing (discriminant analysis mode).
(8) The shape features (circularity, absolute maximum length, diagonal width) are calculated by measurement.

<DSC measurement>
For DSC measurement, use DSC-6220R (manufactured by Seiko Instruments Inc.), heat from room temperature to 150 ° C. at a heating rate of 10 ° C./min (first temperature rise), leave at 150 ° C. for 10 minutes, and reach room temperature. The sample was cooled, left for 10 minutes, and heated again to 150 ° C. at a heating rate of 10 ° C./min (second temperature rise). The glass transition point Tg (° C.) was determined from the curved portion where the height of the baseline below the glass transition point and the height of the baseline above the glass transition point corresponded to 1/2.

<Dynamic viscoelasticity measurement>
For dynamic viscoelasticity measurement, ARES (manufactured by TA Instruments) was used to mold pellets with a diameter of 8 mm and a thickness of 1 to 2 mm, fixed to a parallel plate with a diameter of 8 mm, and then stabilized at 40 ° C. Measured by raising the temperature to 200 ° C. at a heating rate of 2.0 ° C./min at a frequency of 1 Hz (6.28 rad / s) and a strain amount of 0.1% (strain amount control mode), and a storage elastic modulus at 150 ° C. The value of the ratio tan δ (G'' / G') between G'(Pa) and the loss viscoelasticity G'(Pa) was determined.
Further, the value of the ratio tan δ (G ″ / G ′) of the storage elastic modulus G ′ (Pa) and the loss viscosity G ″ (Pa) at 150 ° C. is tan δA, and all the attached inorganic particles are used. The tan δ of the toner from which the fine particles had been peeled off at 150 ° C. was defined as tan δB, and the difference tan δA-tan δB was determined (see above for the measurement method). Further, using a multipurpose mixer manufactured by Nippon Coke Industries Co., Ltd., the toner (toner base) before adding the inorganic fine particles and the inorganic fine particles in each example are mixed under the above conditions, and the toner is tan δ at 150 ° C. Was tanδC, and the difference tanδA-tanδC was obtained.

<Amount of inorganic fine particles released>
The amount of inorganic fine particles released in the obtained toner was determined under the above conditions.

(Evaluation method and evaluation result)
The obtained toner was evaluated as follows. The evaluation results are shown in Table 3.

<Storage stability (idle fluidity)>
8 parts by weight of each toner obtained as shown in Table 2 and 92 parts by weight of the carrier obtained in the manufacturing example of the carrier are stirred at 100 rpm for 1 hour using a type of tabler mixer in which the container is rotated and stirred. A developer was prepared by stirring at a rotation speed. Then, 15 g of the obtained developer was placed in a screw vial and stored in a constant temperature bath at 45 ° C. for 3 hours. After storage, the screw vial was taken out from the constant temperature layer, allowed to stand at room temperature for 1 hour, and cooled. After standing, the storage agent was dropped from a height of about 15 cm, and the fluidity was confirmed.
Storage stability was evaluated in the following four stages.
〔Evaluation criteria〕
⊚: Level at which the vial falls from the mouth without any trouble.
◯: It falls without any trouble, but it takes some time. No problem at all.
△: Level at which the bottle needs to be tapped from the back. There is no problem in practical use.
×: A level at which the agent does not run off even if the bottle is tapped from the back. There is a problem as a high quality toner.

<Photoreceptor contamination and photoconductor scraping>
An image was formed under the following conditions using a device modified so that the linear velocity 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 specified, the agent volume was 110 g, and the linear velocity of the developing roller in the developing machine was 266 mm / sec.
From 0 to less than 10,000 sheets at 23 ° C, 50% RH, from 10,000 sheets to less than 20,000 sheets at 28 ° C, 85% RH, from 20,000 sheets to less than 30,000 sheets at 15 ° C. Under the condition of 30% RH, an image having an image area ratio of 5% and an image having an image area ratio of 20% were alternately output every 1,000 images. This actual machine image was carried out up to 90,000 sheets in 3 sets. After the formation of the 90,000 images was completed, the observation of the photoconductor and the occurrence of abnormal images in the dot images were confirmed and evaluated according to the following criteria. Photoreceptor scraping means a state in which the photoconductor is scratched by toner or the like, and in severe cases, the circumferential direction of the photoconductor is scraped.
〔Evaluation criteria〕
⊚: No scraping of the photoconductor and no contamination of the photoconductor.
◯: Photoreceptor contamination is slightly observed, but it is not detected in the dot image.
Δ: Although the photoconductor was scraped, no difference was detected in the dot image.
X: The photoconductor is scratched, and a difference is clearly detected in the dot image.

<Bosotsuki>
Using the image forming apparatus, a test image having a printing rate of 6 [%] was continuously output on 50,000 sheets of A3 size paper. After that, as a sample image, a halftone image was output on three sheets of A3 size paper, and the unevenness in each was visually evaluated. The evaluation was performed by a sensory evaluation method in which a pre-made halftone image for a rank sample and a sample image were visually compared.
⊚: No roughness is seen in the image, and there is no problem at all.
◯: A part of the image (about 5% of all images as a guide) is slightly rough, but there is no problem at all.
Δ: Some roughness is seen in a part of the image (about 10 to 25% of all images as a guide), but there is no problem in practical use.
X: Roughness is seen in the image (25% or more of all images as a guide), which is a problematic level for high-quality toner.

<Low temperature fixability>
The image is a thick paper ("copy printing paper <135>"; manufactured by NBS Ricoh Co., Ltd.) using an evaluation machine tuned by modifying the image forming device ("IPSIO Color 8100"; manufactured by Ricoh Co., Ltd.) to an oilless fixing method. ) Was set, and the solid image was adjusted so that 1.0 ± 0.1 mg / cm ² of toner was developed. The fixing roll temperature at which the residual rate of the image density after rubbing the obtained fixing image with a pad is 70% or more was defined as the fixing lower limit temperature.
〔Evaluation criteria〕
⊚: Lower limit of fixing is less than 110 ° C ○: Lower limit of fixing is 110 ° C or more and less than 125 ° C Δ: Lower limit of fixing is 125 ° C or more and less than 150 ° C ×: Lower limit of fixing is 150 ° C or more

<Charging stability>
Using each developer, a durability test was carried out in which 300,000 sheets were continuously output using a character image pattern having an image area ratio of 12%, and the change in the amount of charge at that time was evaluated. A small amount of the developer was collected from the sleeve, the change in the amount of charge was determined by the blow-off method, and the evaluation was made according to the following criteria.
〔Evaluation criteria〕
⊚: The change in the amount of charge is less than 2.0 μC / g.
◯: The change in the amount of charge is 2.0 μC / g or more and less than 5.0 μC / g.
Δ: The change in the amount of charge is 5.0 μC / g or more and less than 8.0 μC / g.
X: The change in the amount of charge is 8.0 μC / g or more.

<Maximum glossiness>
A copying test was performed on POD gloss coated paper (basis weight: 128 g / m ^{2) manufactured by Oji Paper Co., Ltd. using an image forming apparatus.} The glossiness evaluation image is a 3 cm x 10 cm solid image with an adhesion amount of 0.40 ± 0.02 mg / cm ^{2 on} Oji Paper's POD gloss coated paper (basis weight: 128 g / m ^{2), left and right 3 cm from the top.} It was formed in the center of the direction. This image was fixed in the range of paper feed linear velocity: 280 mm / sec, surface pressure: 1.2 kgf / cm ² , nip width: 11 mm, fixing temperature: 160 ° C to 180 ° C in 5 ° C increments, and glossy. It was used as an evaluation image of the degree. For the evaluation of glossiness, a glossiness meter VG-7000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used to measure 60-degree glossiness at arbitrary 10 points, and an average value was calculated to obtain glossiness. Among the evaluation images of each fixing temperature, the value having the maximum glossiness was defined as the maximum glossiness and evaluated according to the following criteria. "◎" is very good, "○" is good, "△" is an acceptable level, and "×" is a level that cannot be used practically.

〔Evaluation criteria〕
⊚: Maximum glossiness is 30% or more ○: Maximum glossiness is 25% or more and less than 30% Δ: Maximum glossiness is 20% or more and less than 25% ×: Maximum glossiness is less than 20%

<Gloss unevenness>
Using an image forming apparatus, first, on a Mondi Color Copy 300 (basis weight: 300 g / m ² ) manufactured by Mondi, with an adhesion amount of 1.00 ± 0.03 mg / cm ² , an evaluation chart (FIG. 5) was used. The first image and the second full solid image are formed in succession, and the fixing temperature is changed with the linear velocity of the paper feed: 400 mm / sec, the surface pressure: 1.6 kgf / cm ² , and the nip width: 15 mm. The second fixed image at each fixing temperature was used as an evaluation image of gloss unevenness. For the evaluation of the glossy afterimage, the glossiness meter VG-7000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) is used to measure the 60-degree glossiness at any three points (1) and (2) of the evaluation image. Then, the average glossiness of each was determined, and the fixing temperature at which the difference in glossiness was 20% or more was investigated. The case where the fixing temperature at which the glossiness difference is 20% or more is 190 ° C. or higher or the glossiness difference is not 20% or more is ⊚, the case where the glossiness difference is 180 ° C. or more and less than 190 ° C. is ○, and the case where the glossiness difference is 170 ° C. or more and 180 ° C. When it was less than 170 ° C., it was judged as Δ, and when it was less than 170 ° C., it was judged as ×.

〔Evaluation criteria〕
⊚: The fixing temperature at which the glossiness difference is 20% or more is 190 ° C. or higher, or the glossiness difference is not 20% or more. ◯: The fixing temperature at which the glossiness difference is 20% or more is 180 ° C. or higher and less than 190 ° C. Δ: Fixing temperature with a gloss difference of 20% or more is 170 ° C or more and less than 180 ° C ×: Fixing temperature with a gloss difference of 20% or more is less than 170 ° C

As is clear from the evaluation results in Table 3, the results of Examples 1 to 11 produced by the method of the present invention are sufficiently excellent in storage stability, low temperature fixability, and charge stability, and in particular, Examples 8 to 8 to As for 10, the result is better. On the other hand, the toners of Comparative Examples 1 to 3 have practically problematic results as high-quality toners in terms of storage stability and image stability.

Further, from Table 4, the results of Examples 12 to 23 produced by the method of the present invention were sufficiently excellent in storage stability, low temperature fixability, and charge stability, and in particular, Examples 12, 14, 18, and 20. As for, the result is better.

10 Electrostatic latent image carrier (photoreceptor drum)
10K Electrostatic image carrier for black 10Y Electrostatic image carrier for yellow 10M Electrostatic image carrier for magenta 10C Electrostatic image carrier for cyan 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer cleaning device 18 Image forming means 20 Charging roller 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressurizing roller 28 Sheet reversing device 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Developer 41 Developer belt 42K Developer storage 42Y Developer housing 42M Developer housing 42C Developer housing 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer Supply roller 44K Development roller 44Y Development roller 44M Development roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Resist roller 50 Intermediate transfer belt 51 Roller 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Corona charging device 60 Cleaning device 61 Developing device 62 Transfer roller 63 Photoreceptor cleaning device 64 Static elimination lamp 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 stand 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transfer roller 148 Paper feed path 150 Copying device main body 160 Charging device 200 Paper feed table 300 Scanner 400 Document automatic transfer device (ADF)

Japanese Unexamined Patent Publication No. 2006-047743 Japanese Unexamined Patent Publication No. 2012-189960 Japanese Unexamined Patent Publication No. 08-054750

Claims (9)

A toner in which inorganic fine particles are externally added to a toner base containing at least a binder resin and a mold release agent.
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 or more and 5000 or less is selected, all the molecular weights M in the range of 300 or more and 5000 or less are used. The difference between the maximum value and the minimum value of the peak intensity defined below in the range of ± 300 of the molecular weight M is 30 or less.
The volume average particle diameter of the inorganic fine particles is 40 nm or more and 300 nm or less.
The binding resin contains a polyester resin and contains
The value of the ratio tan δ (G ″ / G ′) of the storage elastic modulus G ′ (Pa) and the loss viscosity G ″ (Pa) in the viscoelasticity measurement of the toner is 120 ° C. or higher and 150 ° C. or lower at the measurement temperature. in a temperature range state, and it is 0.40 to 1.10,
In the differential scanning calorimetry (DSC) of the toner, a glass transition point was observed at 40 to 70 ° C. at the first temperature rise, and when the glass transition point was set to X ° C., the glass transition point at the second temperature rise. Is not found in the range of X to X-20 ° C.
However, the molecular weight distribution measured by GPC was determined by using TSK-GEL SUPER HZ2000, TSK-GEL SUPER HZ2500, and TSK-GEL SUPER HZ3000 as columns.
Peak intensity: Relative value when the vertical axis is the intensity and the horizontal axis is the molecular weight distribution curve of the molecular weight, and the maximum intensity value in the range of 20000 or less is set to 100 by GPC measurement. The toner according to claim 1, wherein the toner contains a crystalline resin in the binder resin, the melting point of the crystalline resin in said toner being in the range of below 65 ° C. or higher 50 ° C.. The value of the ratio tan δ (G ″ / G ′) of the storage elastic modulus G ′ (Pa) and the loss viscosity G ″ (Pa) in the measurement of the viscoelasticity of the toner is tan δA, and the following (measurement method 1) is used. The invention according to claim 1 or 2 , wherein when the tan δB is determined, the difference tan δA-tan δB at the same temperature is 0.05 or more and 0.25 or less in the region of 120 ° C. or more and 150 ° C. or less. toner.
(Measurement method 1)
Let tan δ of the toner from which all the inorganic fine particles externally attached to the toner base have been peeled off be tan δB. The value of the ratio tan δ (G ″ / G ′) of the storage elastic modulus G ′ (Pa) and the loss viscosity G ″ (Pa) in the measurement of the viscoelasticity of the toner is tan δA, and the following (measurement method 2) is used. The invention according to claim 1 or 2 , wherein when the tan δC is determined, the difference tan δA-tan δC at the same temperature is 0.05 or more and 0.25 or less in the region of 120 ° C. or more and 150 ° C. or less. toner.
(Measurement method 2)
Using a multi-purpose mixer, the toner base and the inorganic fine particles are mixed at 5425 rpm for 10 minutes, and the tan δ of the obtained toner is tan δC. The toner according to any one of claims 1 to 4 , wherein the free amount [mass%] of the inorganic fine particles determined by the following measurement formula is 0.3 or more and 0.7 or less.
Measurement formula: Free amount [mass%] = ((mass of inorganic fine particles of toner)-(mass of residual inorganic fine particles after irradiation with a calibration curve of 2400J with a fluorescent X-ray analyzer)) / (mass of inorganic fine particles of toner) The toner according to any one of claims 1 to 5 , wherein the average circularity of the inorganic fine particles is 0.4 or more and 0.8 or less. The toner according to any one of claims 1 to 6 , wherein the toner contains a wax dispersant. A toner accommodating unit comprising accommodating the toner according to any one of claims 1 to 7. Electrostatic latent image carrier and
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier,
A developing means for developing a visible image by developing the electrostatic latent image with toner, and
A transfer means for transferring the visible image onto a recording medium,
It has at least a fixing means for fixing the transferred image transferred on the recording medium.
An image forming apparatus according to any one of claims 1 to 7 , wherein the developer is the toner.