JP2015114466A - Image formation device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image formation device that has low temperature fixability and heat-resistant storageability, and uses toner allowing an in-page image glossiness variation to be minimized.SOLUTION: An image formation device comprises a toner image fixation device that includes; a fixation member; a pressure member that forms a fixation nip part between the fixation member and the pressure member; heating means for heating the fixation member; and heating control means for controlling the heating means. In the image formation device in which the heating means is configured to include an exothermic area having the exothermic area plurally divided, and the heating control means is configured to independently control a temperature of the fixation member and control a heating temperature of a non-image area lower than that of an image area, when a temperature reaching a storage modulus G'=3.0×10[Pa] is T1, and a temperature reaching a storage modulus G'=1.0×10[Pa] is T2, the toner satisfies T2-T1≥20°C, and a glass transition temperature (Tg1st) at a first temperature rising in a differential scanning calorimetry (DSC) is 30°C to 50°C.

Description

  The present invention relates to an electrophotographic image forming apparatus.

In an image forming apparatus such as a copying machine, a printer, or a facsimile, a toner image is formed on an image carrier based on image information, the toner image is transferred onto a recording material such as paper or an OHP sheet, and the toner image is carried. The recorded material is passed through a fixing device, and the toner image is fixed on the recording material by heat and pressure.
In recent years, fixing devices have been reduced in heat capacity to save energy, and belt and film systems are often used. Heat insulation rollers are heated from the outside, and only image areas are selectively heated based on image information. Techniques to do this have been proposed.
For example, Patent Document 1 discloses an invention in which the temperature of each element of the heating element of the thermal head is measured and the appropriate heat is supplied, thereby taking into consideration the influence of the ambient temperature and applying heat only to the toner portion on the paper surface. Is disclosed.
Further, in Patent Document 2, by heating the roller from the outside, the toner is melted by the heat stored in the vicinity of the surface of the fixing roller, and the rise time is shortened compared to the internal heating method in which the entire fixing roller is heated. Is reduced. Similarly to Patent Document 1, a configuration is disclosed in which only the image area is selectively heated and the second set temperature is lower than the fixing set temperature.

An image forming apparatus of a type in which a heating member in a fixing device is divided into a large number in the axial direction and each heating unit is independently controlled based on image information is known. However, in this apparatus, if the image portion and the non-image portion are alternately repeated in continuous printing, it is difficult to maintain the temperature of the image portion constant because the temperature rise and cooling are repeated. For this reason, in a color image having many photographs and drawings, the gloss fluctuation in the page tends to be large.
SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an image forming apparatus using toner that has low-temperature fixability and heat-resistant storage stability, and that can suppress fluctuations in image gloss within a page even when used in the above-described image forming apparatus. To do.

  As a result of diligent investigations to solve the above-described conventional problems, the inventors have reduced the sensitivity to temperature unevenness of the fixing device by reducing the change rate of the storage elastic modulus of the toner in the temperature control range of the fixing device. As a result, the present inventors have found out that it can be achieved.

That is, the above problem is solved by the following invention 1).
1) An electrostatic latent image is formed on a photoconductor based on image data, a toner image obtained by developing the electrostatic latent image with toner is transferred to a sheet-like recording material, and rotated in contact with the toner image. A fixing member; a pressure member that forms a fixing nip portion between the fixing member; a heating unit that heats the fixing member; and a heating control unit that controls the heating unit, and carries a toner image. A fixing device configured to fix the recording material through the fixing nip portion, wherein the heating unit includes a heating region divided into a plurality of longitudinal directions orthogonal to the recording material conveyance direction, and the heating control unit includes unfixed toner In an image forming apparatus that independently controls the temperature of a fixing member corresponding to each heating area according to position information on which an image is formed on the recording material, and controls the heating temperature of a non-image area to be lower than that of the image area ,
The toner is
The temperature at which the storage elastic modulus G ′ = 3.0 × 10 ⁴ [Pa] is T1,
The temperature at which the storage elastic modulus G ′ = 1.0 × 10 ⁴ [Pa] is T2,
And when
T2-T1 ≧ 20 ° C. is satisfied, and
An image forming apparatus having a glass transition temperature (Tg1st) of 30 ° C. to 50 ° C. in a first temperature increase of differential scanning calorimetry (DSC).

  According to the present invention, it is possible to provide an image forming apparatus using toner that has low-temperature fixability and heat-resistant storage stability and can suppress fluctuations in the image glossiness within a page even when used in the image forming apparatus of the above-described type.

1 is a cross-sectional view (schematic diagram) illustrating an example of an image forming apparatus of the present invention. FIG. 4 is a diagram illustrating an example in which the fixing device 12 is an external heating method. FIG. 4 is a diagram illustrating an example in which the fixing device 12 is an external heating method. The figure for demonstrating an example of control operation | movement (A and B show the case where an image area | region and a non-image area | region differ). FIG. 5 is another diagram for explaining an example of a control operation (A and B show a case where an image region and a non-image region are different). The figure which shows the structure heated from the inside of a belt. Another figure which shows the structure heated from the inside of a belt. The figure which shows the structure arrange | positioned in the location of a nip part, since a plate-shaped heating means functions as a press member. The figure for demonstrating 1st target temperature and 2nd target temperature. The figure which shows the image pattern for investigating the glossiness variation (DELTA) in a page.

Hereinafter, the present invention 1) will be described in detail, but the following 2) to 7) are also included in the embodiment of the present invention, and these will be described together.
2) The image forming apparatus according to 1), wherein the toner satisfies T2−T1 ≧ 30 ° C.
3) The image forming apparatus according to 1) or 2), wherein the toner contains at least a non-linear amorphous polyester resin and another amorphous polyester resin.
4) The image forming apparatus according to any one of 1) to 3), wherein the toner satisfies the following requirements (1) and (2).
(1) The glass transition temperature (Tg2nd: THF insoluble matter) at the second temperature increase in differential scanning calorimetry (DSC) of the THF insoluble matter is −40 ° C. to 30 ° C.
(2) The THF-insoluble matter satisfies G ′ (100) = 1 × 10 ⁵ to 1 × 10 ⁷ [Pa] and satisfies G ′ (40) / G ′ (100) ≦ 3.50 × 10. Here, G ′ (40) and G ′ (100) are storage elastic moduli at 40 ° C. and 100 ° C., respectively.
5) The toner further contains a crystalline polyester resin, and the glass transition temperature (Tg2nd: THF soluble content) at the second temperature increase in the differential scanning calorimetry (DSC) of the THF soluble content is 20 ° C to 35 ° C. The image forming apparatus according to any one of 1) to 4), wherein:
6) The image forming apparatus according to any one of 1) to 5), wherein the toner has a THF-insoluble content of 20 to 35% by mass.
7) The image forming apparatus according to any one of 1) to 6), wherein a surface pressure of the fixing device is 1.5 kg / cm ² or more.

  The storage elastic modulus G ′ is a sinusoidal strain (a strain having the same phase as the stress), where γ0 is the shear strain measured by dynamic viscoelasticity measurement, σ0 is the shear stress, and δ is the phase difference between the shear strain and the shear stress. ) And a stress amplitude ratio σ0 / γ0 × cosδ, and represents a component stored in the object in the given energy. The higher the storage elastic modulus G ′, the smaller the strain with respect to the same stress. Therefore, when the toner image is passed through the fixing device and fixed, unevenness remains on the image surface and the glossiness becomes lower. On the contrary, if the storage elastic modulus G ′ is low, the strain is large for the same stress, and when the toner image is passed through the fixing device and fixed, the surface of the image becomes smooth and the glossiness becomes high.

As described above, in the first aspect of the present invention, a toner satisfying T2−T1 ≧ 20 ° C. is used, and the toner preferably satisfies T2−T1 ≧ 30 ° C. In this case, even if the temperature control of the fixing device overshoots, if the temperature control range is within 30 ° C., the glossiness fluctuation in the page is within the range where there is no problem, and the first target temperature shown in FIG. On the other hand, the second target temperature can be greatly lowered, and the energy saving property is more excellent. Moreover, the upper limit of T2-T1 is about 40 degreeC. In order to satisfy T2-T1> 40, it is necessary to broaden the molecular weight distribution or to increase the crosslink density. In this case, the gloss fluctuation of the image can be suppressed low, but the low-temperature fixability is significantly lowered. Note that it is not difficult to control the temperature so that the overshoot of the fixing device is suppressed to 40 ° C. or less.
Further, the toner used in the present invention preferably contains at least a non-linear amorphous polyester resin and another amorphous polyester resin.

  Furthermore, it is more preferable that the toner used in the present invention satisfies the requirement of the present invention 4). In the conventional toner, when Tg is about 50 ° C. or less, toner aggregation is likely to occur due to a temperature change in the storage environment and the toner transportation in the summer or the tropical region. As a result, solidification in the toner bottle and fixation of the toner in the developing machine occur. Also, replenishment failure due to toner clogging in the toner bottle and image abnormality due to toner fixation in the developing machine are likely to occur. On the other hand, for example, when a toner containing a non-linear amorphous polyester resin and another amorphous polyester resin is used, although the Tg is lower than that of the conventional toner, a low Tg component in the toner is used. The heat resistant storage stability can be maintained by the non-linear amorphous polyester resin.

The glass transition temperature [Tg2nd (THF insoluble content)] at the second temperature increase in differential scanning calorimetry (DSC) of the THF insoluble content of the toner is preferably −40 ° C. to 30 ° C. When the Tg2nd (THF insoluble content) is less than −40 ° C., the heat resistant storage stability is deteriorated, and when it exceeds 30 ° C., the low temperature fixability is deteriorated. The Tg2nd (THF-insoluble matter) corresponds to Tg2nd of a non-linear amorphous polyester resin, and lowers Tg2nd as compared with other amorphous polyester resins, and thus works favorably at low temperature fixability. Furthermore, when the non-linear amorphous polyester resin has a urethane bond or a urea bond having a high cohesive force, the effect of maintaining the heat resistant storage stability becomes more remarkable.
Further, when G ′ (100) of THF-insoluble matter is 1 × 10 ⁵ to 1 × 10 ⁷ [Pa] and G ′ (40) / G ′ (100) ≦ 3.50 × 10, high It promotes the compatibilization of other amorphous polyester resins that are Tg components and crystalline polyester resins that are included as required, and improves low-temperature fixability.

Further, in the toner used in the present invention, the Tg2nd is more preferably 0 ° C. to 30 ° C. When Tg2nd is less than 0 ° C., the blocking resistance of the fixed image (printed material) is lowered, and when it exceeds 30 ° C., sufficient low-temperature fixability and glossiness may not be obtained.
Furthermore, it is more preferable that the toner used in the present invention further contains a crystalline polyester resin, and Tg2nd of the THF-soluble component is 20 ° C. to 35 ° C. In this case, the THF-soluble component is composed of an amorphous polyester resin and a crystalline polyester resin, which are high Tg components. Since the crystalline polyester resin has crystallinity, it has a rapid viscosity around the fixing start temperature. Cause a drop. By using the crystalline polyester resin having such characteristics together with the amorphous polyester resin, the heat resistant storage stability due to crystallinity is good until just before the melting start temperature, and at the melting start temperature, the crystalline polyester resin is rapidly melted by melting. Therefore, the toner is compatible with the amorphous polyester resin, and suddenly drops in viscosity to be fixed, so that a toner having both good heat storage stability and low temperature fixability can be obtained. Tg2nd: When the THF soluble content is less than 5 ° C., the blocking resistance of the fixed image (printed material) is lowered, and when it is 35 ° C. or more, sufficient low-temperature fixability and glossiness may not be obtained. .

Furthermore, it is more preferable that the toner used in the present invention has a THF-insoluble content of 20 to 35% by mass. The THF-insoluble matter corresponds to the non-linear amorphous polyester resin. If the THF-insoluble content is less than 20% by mass, the Tg of the toner does not decrease, so that low-temperature fixability cannot be obtained. If it exceeds 35% by mass, the Tg of the toner decreases too much and the heat-resistant storage stability deteriorates.
Furthermore, it is more preferable that the toner used in the present invention has a G ′ (100) of THF insoluble content of 5 × 10 ^{5 to} 5 × 10 ⁶ [Pa]. Within this range, low temperature fixability, heat resistant storage stability, and hot offset resistance can be maintained.

Furthermore, in the present invention, the fixing member of the fixing device is a flexible endless fixing belt, and the pressure from the pressure member is applied by a support member disposed on the inner peripheral surface side of the fixing belt. More preferably, the heating source is disposed inside the fixing belt, and the fixing belt is heated by radiant heat.
Since the fixing device having the above configuration has a lower heat capacity than conventional ones, it is possible to further shorten the warm-up time and improve energy saving by combining with a toner having excellent low-temperature fixing property. However, due to the low heat capacity, temperature control becomes difficult and overshoot tends to occur.

On the other hand, by combining the toner used in the present invention with the fixing device having the above-described configuration, even when overshoot occurs, the fluctuation in glossiness within the page can be suppressed to a small level, and the fixing device and toner are excellent in energy saving. The energy saving property is further improved by the combination.
Furthermore, in the image forming apparatus of the present invention, the surface pressure of the fixing device is more preferably 1.5 kg / cm ² or more. By setting the surface pressure high, an image fixed near the fixing lower limit temperature becomes smooth by crushing the toner layer, and the image glossiness can be increased. On the other hand, the image glossiness fixed at a temperature with a sufficient amount of heat is such that the toner is sufficiently melted and the surface is smooth, so that the image glossiness does not increase even if the surface pressure is increased. Therefore, when the surface pressure is increased, the in-page glossiness fluctuation can be further reduced.
The upper limit of the surface pressure is about 2.0 kg / cm ² . If it exceeds 2.0 kg / cm ² , it is necessary to increase the base of the fixing roller and the core metal of the pressure roller in order to maintain the durability. This increases the heat capacity of the fixing device and reduces the energy saving performance.

(Image forming device)
FIG. 1 shows a cross-sectional view (schematic diagram) of an example of the image forming apparatus of the present invention.
The image forming apparatus includes a paper feeding unit 4, a registration roller pair 6, a photosensitive drum 8 as an image carrier, a transfer unit 10, a fixing device 12, and the like.
The paper feeding means 4 feeds the paper Pa as recording material stored in a stacked state and the paper Pa stored in the paper feeding tray 14 one by one in order from the top. It has a roller 16 and the like. The paper Pa sent out by the paper feed roller 16 is temporarily stopped by the registration roller pair 6 and corrected for posture deviation, and then formed at the timing synchronized with the rotation of the photosensitive drum 8, that is, on the photosensitive drum 8. The toner image is sent to the transfer portion N by the registration roller pair 6 at a timing when the leading end of the toner image coincides with a predetermined position at the leading end of the paper Pa in the transport direction.
Around the photosensitive drum 8, in the rotation direction indicated by the arrows, a charging roller 18 as a charging unit, a mirror 20 constituting a part of an exposure unit (not shown), a developing unit 22 including a developing roller 22a, A transfer unit 10 and a cleaning unit 24 including a cleaning blade 24a are disposed.
Between the charging roller 18 and the developing means 22, exposure light Lb is irradiated to the exposure unit 26 on the photosensitive drum 8 via the mirror 20 and scanned.

The image forming operation in the image forming apparatus is performed in the same manner as in the past.
That is, when the photosensitive drum 8 starts to rotate, the surface of the photosensitive drum 8 is uniformly charged by the charging roller 18, and the exposure light 26 is irradiated and scanned on the exposure unit 26 based on the image information to create an image to be created. An electrostatic latent image corresponding to is formed. The electrostatic latent image is moved to the developing means 22 by the rotation of the photosensitive drum 8, where toner is supplied to be visualized to form a toner image. The toner image formed on the photosensitive drum 8 is transferred onto the paper Pa that has entered the transfer portion N at a predetermined timing by applying a transfer bias by the transfer means 10.
The paper Pa carrying the toner image is conveyed toward the fixing device 12, fixed by the fixing device 12, and then discharged and stacked on a paper discharge tray (not shown).
Residual toner remaining on the photosensitive drum 8 without being transferred at the transfer portion N reaches the cleaning means 24 as the photosensitive drum 8 rotates, and is scraped off by the cleaning blade 24 a while passing through the cleaning means 24. To be cleaned.
Thereafter, the residual potential on the photosensitive drum 8 is removed by a neutralizing unit (not shown), and is prepared for the next image forming process.

[Fixing device]
2 and 3 show an example in which the fixing device 12 is an external heating method. In this example, the image forming apparatus includes a fixing roller 28, a pressure roller 30 as a pressure member that forms a fixing nip portion SN between the fixing roller 28, and a thermal heater 56 as a heating unit. The heater 56 and the power source 40 constitute external heating means. The thermal heater 56 has a heating region composed of a plurality of (seven in this example) heaters arranged in the width direction of the paper Pa, and each heater can independently heat the fixing roller. A thermistor 34 as a temperature detecting means for detecting the surface temperature, a thermistor 36 as a heating member temperature detecting means for detecting the temperature of the heating means 56, and a heating means downstream of the nip SN of the fixing roller 28 and upstream of the heating means 56. A power source 40 that supplies power to 56 and an external heating control means 42 that controls the power source 40 based on detection information of the thermistors 34 and 36 are provided. The external heating control means 42 means a microcomputer including a CPU, ROM, RAM, I / O interface and the like.

  The fixing roller 28 has an aluminum cored bar 28a having an outer diameter of 40 mm and a thickness of 1 mm, and a heat insulating layer 28b coated on the surface of the cored bar 28a. The heat insulation layer 28b is made of silicon rubber and has a thickness of 3 mm. The heat insulating layer 28b may be formed of foamed silicon rubber with less heat escape in order to further enhance its heat insulating function. A good heat conductive layer 28c made of nickel is formed on the heat insulating layer 28b of the fixing roller 28. The good heat conductive layer 28c is not limited to nickel, but is an iron-based alloy such as stainless steel, aluminum, copper, or the like. It is only necessary that the thermal conductivity of the metal system, graphite sheet, etc. is at least higher than that of the heat insulating layer 28b. By forming the good heat conductive layer 28 c on the fixing roller 28, local temperature unevenness of the surface temperature of the fixing roller 28 due to uneven heat generation of the thermal heater 56 is reduced. In addition, the temperature of the region slightly wider than the region heated by the thermal heater 56 is raised by the function of the good heat conductive layer 28c, so that there is an advantage that a slight deviation from the image can be compensated. In other words, there is an advantage that the degree of freedom in design is large in setting the size and interval of each heater constituting the thermal heater 56. Further, in order to enhance the durability of the fixing roller 28 and ensure the releasability, a release layer having a thickness of 5 to 30 μm made of fluorine resin such as PFA or PTFE may be formed on the surface of the heat insulating layer 28b. The pressure roller 30 has an iron cored bar 30a having an outer diameter of 40 mm and a thickness of 2 mm, and an elastic layer 30b coated on the surface of the cored bar 30a. The elastic layer 30b is made of silicon rubber and has a thickness of 5 mm. It is desirable to form a fluororesin layer having a thickness of about 40 μm on the surface of the elastic layer 30b in order to improve the releasability. The pressure roller 30 is pressed against the fixing roller 28 by an urging means (not shown). The heating means 56 is pressed against the surface of the fixing roller 28 by an urging means (not shown).

〔control〕
As described below, energy saving can be realized by controlling each heater according to image information. In this example, the heating member 56 is brought into contact with the surface of the fixing roller 28 for heating, but the external heating means may be constituted by a coil and an inverter and may be a non-contact heating method by the IH method. In the IH system, a configuration in which a large number of heating coils are arranged or a configuration in which a large number of members that cancel magnetic flux are arranged to control the heating region and the heating amount may be used.
The external heating control means 42 changes the heating rate of the heating member 56 based on image information for forming an image on the paper Pa. An example of this control operation is shown in FIGS.

  FIG. 4A shows an image forming pattern in which an image area a, a non-image area b, and an image area a ′ exist on the paper Pa in order from the leading end side in the transport direction. Fixing is required in the image area a and the image area a ′, but there is no need for fixing in the non-image area b because there is no toner to be fixed. When image information of the above pattern is input to the external heating control unit 42 from an image processing apparatus (not shown), the external heating control unit 42 determines that the temperature of the part of the fixing roller 28 corresponding to the non-image region b is the image region a, The heating roller 32 is controlled so as to be lower than the temperature of the fixing roller 28 corresponding to a ′. Here, “corresponding to an image region or a non-image region” means a position where the fixing roller 28 is in close contact, and is hereinafter also expressed as close contact as appropriate. That is, the power corresponding to the fixing temperature is supplied to the entire area of the heating member 56 at the part corresponding to the image area a, and the supplied power is reduced at the part corresponding to the non-image area b. In the portion corresponding to the paper rear end image area a ′, the electric power for obtaining the fixing temperature is supplied again. At this time, the actual supplied power is input so as to preliminarily heat the part before the image area enters the nip as shown by the shaded area in the figure, and this preheating area is mainly heated. This is a region to be prepared because the heating length in the circumferential direction of the member and the heating element itself also require a heating time. It is desirable that the preheating area is as small as possible from the viewpoint of energy saving.

FIG. 5A shows an image forming pattern in which an image region c and a non-image region d exist on the paper Pa in the longitudinal direction of the fixing member perpendicular to the transport direction. Similarly, in this case, the external heating control means 42 heats so that the temperature of the part of the fixing roller 28 corresponding to the non-image area d is lower than the temperature of the part of the fixing roller 28 corresponding to the image area c. The roller 32 is controlled. In other words, the power corresponding to the fixing temperature is supplied to the heating member 56 at the portion corresponding to the image region c, and the supplied power is reduced at the portion corresponding to the non-image region d. This also requires a preheated area in the shaded area as described above. As a control, the power supply may be completely stopped (off) at a portion corresponding to the non-image area d. However, when the temperature is extremely lowered, the rise to the fixing temperature in the next image area is not in time. Sometimes. For this reason, as shown in FIG. 9, it is desirable to perform control so that the fixing member temperature is maintained at a second target temperature that is lower than the first target temperature corresponding to the image region but higher than the room temperature by a predetermined temperature or more. .
In this way, power is also supplied to the portion corresponding to the non-image area d, but the power supply is reduced. That is, since the power supplied in the region P ′ is smaller than the power supplied in the region P of FIG. 9, energy saving can be achieved.

[Belt configuration]
The present invention is not limited to the roller configuration of FIG. 2, and may be configured to heat from the inside of the belt as shown in FIGS. In the fixing device of this example, the heating means 56 is a thermal head or a ceramic heater in which a resistance heating element is formed on a plate-like substrate, and is placed inside the film to raise the temperature of the film or belt with the heat. Thus, the fixed image conveyed to the nip portion SN is heated and fixed. The plate-like heating means 56 has a heating region divided into a plurality of lengths in the direction perpendicular to the paper transport direction, and each heating member can be controlled independently. The fixing belt 38 has a SUS base 38a having an outer diameter of 40 mm and a thickness of 40 μm, and an elastic layer 38b coated on the surface of the base 38a. The elastic layer 38b is made of silicon rubber and has a thickness of 100 μm. On the surface of the fixing belt 38, a release layer 38 c having a thickness of 5 to 50 μm is formed with a fluorine-based resin such as PFA or PTFE in order to enhance durability and secure release properties. The fixing belt base 38a may be made of polyimide. A fixing member 61 is provided inside the fixing belt, and a pressing member 60 and a pressing member 56 are installed at the nip portion SN, and are connected to an external member (not shown) to support the fixing member.
In addition, as shown in FIG. 8, since the said plate-shaped heating means 56 functions as a pressing member, the structure arrange | positioned in the location of the nip part SN may be sufficient. Although not shown, the belt or film configuration of FIG. 6 may be heated by the external heating member of FIG.
As described above, each heating region of the heating member is independently heated, and the heating is controlled according to the image information as described above.

(toner)
In the present invention, a toner having the characteristics defined in the present invention 1) is used. However, the toner preferably contains at least a non-linear amorphous polyester resin A and an amorphous polyester resin B. Further, a crystalline polyester resin C may be contained. Further, if necessary, other components known as toner additives may be contained.
The non-linear amorphous polyester resin A preferably has a Tg of −60 ° C. to 0 ° C. The amorphous polyester resin B preferably has a Tg of 40 ° C to 80 ° C. Further, the glass transition temperature (Tg1st) of the toner at the first temperature increase in differential scanning calorimetry (DSC) is 30 ° C. to 50 ° C.
In order to further improve the low-temperature fixability, a method of lowering the Tg or a method of reducing the molecular weight is conceivable so that the amorphous polyester resin is eutectic with the crystalline polyester resin. However, simply lowering the Tg of the amorphous polyester resin or reducing the molecular weight to lower the melt viscosity deteriorates the heat-resistant storage stability of the toner and the high-temperature offset property during fixing, and controls the temperature of the fixing device. Since the rate of change of the storage elastic modulus in the width also increases, it is easily imagined that the in-page image gloss fluctuation also increases.

  On the other hand, since the non-linear amorphous polyester resin A has a very low Tg, it has a property of being deformed at a low temperature, and is deformed by heating and pressurizing at the time of fixing. It has a property that it is easy to adhere to a recording material such as. The non-linear amorphous polyester resin A has a branched structure in the molecular skeleton because the reactive precursor is non-linear, and the molecular chain has a three-dimensional network structure. It has a rubbery property of deforming at low temperatures but not flowing. Therefore, it is possible to maintain the heat resistant storage stability and high temperature offset resistance of the toner. Further, since the rate of change of the storage elastic modulus in the temperature control range of the fixing device is also reduced, the in-page image gloss fluctuation can be suppressed to be small. In addition, when the non-linear amorphous polyester resin A has a urethane bond or a urea bond having high cohesive energy, adhesion to a recording material such as paper is further improved. In addition, since the urethane bond or urea bond behaves like a pseudo-crosslinking point, the rubber property becomes stronger, and as a result, the heat resistant storage stability and high temperature offset resistance of the toner are further improved, and the fixing Since the change rate of the storage elastic modulus in the temperature control range of the apparatus is also reduced, the in-page image gloss fluctuation can be suppressed to be small.

  That is, the toner used in the present invention has a Tg in an ultra-low temperature range, but has a high melt viscosity and is difficult to flow, the non-linear amorphous polyester resin A, the amorphous polyester resin B, and in some cases. By using in combination with the crystalline polyester resin C, it is possible to maintain heat-resistant storage stability and high-temperature offset resistance even when the Tg of the toner is set lower than before, and to lower the Tg of the toner. Excellent low temperature fixability. Further, since the rate of change of the storage elastic modulus in the temperature control range of the fixing device is also reduced, the in-page image gloss fluctuation can be suppressed to be small.

<Nonlinear Amorphous Polyester Resin A>
The non-linear amorphous polyester resin A is obtained by a reaction between a non-linear reactive precursor and a curing agent.
-Non-linear reactive precursor-
The non-linear reactive precursor is not particularly limited as long as it is a polyester resin having a group capable of reacting with a curing agent (hereinafter sometimes referred to as “prepolymer”). You can choose.
Examples of the group capable of reacting with the curing agent in the prepolymer include a group capable of reacting with an active hydrogen group. Examples thereof include an isocyanate group, an epoxy group, a carboxylic acid group, and an acid chloride group. Among these, an isocyanate group is preferable because a urethane bond and / or a urea bond can be introduced into the non-linear amorphous polyester resin A. Moreover, as said prepolymer, the polyester resin which has an isocyanate group is preferable. In addition, the said non-linear means having a branched structure provided by at least one of a trivalent or higher alcohol and a trivalent or higher carboxylic acid.

--Polyester resin having isocyanate group--
There is no restriction | limiting in particular as the polyester resin which has the said isocyanate group, According to the objective, it can select suitably, For example, the reaction product etc. of the polyester resin and polyisocyanate which have an active hydrogen group are mentioned.
The polyester resin having an active hydrogen group can be obtained, for example, by polycondensing a diol, a dicarboxylic acid, a trivalent or higher alcohol and / or a trivalent or higher carboxylic acid. The trivalent or higher alcohol and the trivalent or higher carboxylic acid impart a branched structure to the polyester resin having an isocyanate group.

--- Diol ---
There is no restriction | limiting in particular as said diol, According to the objective, it can select suitably. Examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8 -Aliphatic diols such as octanediol, 1,10-decanediol, 1,12-dodecanediol; having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Diols: 1,4-cyclohexanedimethanol, alicyclic diols such as hydrogenated bisphenol A; alicyclic diols added with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide; Nord A, bisphenol F, bisphenol such as bisphenol S; the bisphenols include ethylene oxide, propylene oxide, and alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide. Among these, an aliphatic diol having 4 to 12 carbon atoms is preferable.
These diols may be used alone or in combination of two or more.

--- Dicarboxylic acid ---
There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably. Examples thereof include aliphatic dicarboxylic acids and aromatic dicarboxylic acids. Moreover, you may use these anhydrides, a lower (C1-C3) alkylesterification thing, a halide, etc.
Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid.
The aromatic dicarboxylic acid is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid and the like.
Of these, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferred.
These dicarboxylic acids may be used individually by 1 type, and may use 2 or more types together.

--Alcohol having a valence of 3 or more ---
There is no restriction | limiting in particular as said trihydric or more alcohol, According to the objective, it can select suitably, For example, alkylene oxide of trihydric or more aliphatic alcohol, trihydric or more polyphenols, trihydric or more polyphenols Examples include adducts.
Examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like.
Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like.
Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to trihydric or higher polyphenols.

--Carboxylic acid having a valence of 3 or more ---
There is no restriction | limiting in particular as said trivalent or more carboxylic acid, According to the objective, it can select suitably, For example, trivalent or more aromatic carboxylic acid etc. are mentioned. Moreover, you may use these anhydrides, a lower (C1-C3) alkylesterification thing, a halide, etc.
The trivalent or higher aromatic carboxylic acid is preferably a trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms. Examples thereof include trimellitic acid and pyromellitic acid.

--- Polyisocyanate ---
There is no restriction | limiting in particular as said polyisocyanate, According to the objective, it can select suitably, For example, diisocyanate, trivalent or more isocyanate etc. are mentioned.
Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetra And methyl hexane diisocyanate.
Examples of the alicyclic diisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate.

Examples of the aromatic diisocyanate include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanatodiphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl. 4,4'-diisocyanato-3-methyldiphenylmethane, 4,4'-diisocyanato-diphenyl ether, and the like.
Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate.
Examples of the isocyanurates include tris (isocyanatoalkyl) isocyanurate and tris (isocyanatocycloalkyl) isocyanurate.
These polyisocyanates may be used alone or in combination of two or more.

-Curing agent-
The curing agent is not particularly limited as long as it is a curing agent that reacts with the non-linear reactive precursor and generates the non-linear amorphous polyester resin A, and is appropriately selected according to the purpose. Examples thereof include active hydrogen group-containing compounds.

-Active hydrogen group-containing compound-
There is no restriction | limiting in particular as an active hydrogen group in the said active hydrogen group containing compound, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as said active hydrogen group containing compound, Although it can select suitably according to the objective, Amines are preferable at the point which can form a urea bond.
Examples of the amines include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. These may be used individually by 1 type and may use 2 or more types together.
Among these, diamine and a mixture of diamine and a small amount of trivalent or higher amine are preferable.

Examples of the diamine include aromatic diamines, alicyclic diamines, and aliphatic diamines.
Examples of the aromatic diamine include phenylene diamine, diethyl toluene diamine, and 4,4′-diaminodiphenyl methane.
Examples of the alicyclic diamine include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane, and isophorone diamine.
Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.

Examples of the trivalent or higher amine include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid include aminopropionic acid and aminocaproic acid.
Examples of the blocked amino group include ketimine compounds and oxazoline compounds obtained by blocking amino groups with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

The non-linear amorphous polyester resin A preferably satisfies any of the following (a) to (c) in order to lower the Tg and to easily impart the property of being deformed at a low temperature.
(A) A diol component is included as a constituent component, and the diol component contains 50% by mass or more of an aliphatic diol having 4 to 12 carbon atoms.
(B) 50% by mass or more of an aliphatic diol having 4 to 12 carbon atoms is contained in all alcohol components.
(C) A dicarboxylic acid component is included as a constituent component, and the dicarboxylic acid component contains 50% by mass or more of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms.

The non-linear amorphous polyester resin A has a Tg of -60 ° C to 0 ° C, more preferably -40 ° C to -20 ° C. When the Tg is less than −60 ° C., the flow of toner at a low temperature cannot be suppressed, heat resistance storage stability is deteriorated, and filming resistance is deteriorated. If the Tg exceeds 0 ° C., the toner is not sufficiently deformed by heating and pressing during fixing, and the low-temperature fixability becomes insufficient.
The weight average molecular weight of the non-linear amorphous polyester resin A is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 20,000 to 100,000 in GPC (gel permeation chromatography) measurement. When the weight average molecular weight is less than 20,000, the toner tends to flow at a low temperature and may have poor heat-resistant storage stability, and the viscosity at the time of melting may be low, and the high temperature offset property may be reduced. On the other hand, if it exceeds 100,000, the low-temperature fixability deteriorates.

The molecular structure of the non-linear amorphous polyester resin A can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. At a convenient infrared absorption spectrum, and a method of detecting the 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 and having no absorption based on olefin? Ch (out-of-plane deformation vibration) as an amorphous polyester resin .
The content of the non-linear amorphous polyester resin A is not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferably 5 to 25 parts by mass with respect to 100 parts by mass of the toner, and 10 to 20 Part by mass is more preferable. When the content is less than 5 parts by mass, the low-temperature fixability and the high-temperature offset resistance may be deteriorated. When the content exceeds 25 parts by mass, the heat-resistant storage stability is deteriorated and the glossiness of an image obtained after fixing may be reduced. . When the content is in the more preferable range, it is advantageous in that it is excellent in all of low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability.

<Amorphous polyester resin B>
The amorphous polyester resin B is not particularly limited as long as Tg is 40 ° C. to 80 ° C., and can be appropriately selected according to the purpose.
The amorphous polyester resin B is preferably a linear polyester resin. An unmodified polyester resin is preferred. The unmodified polyester resin here is a polyester resin obtained by using a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or a derivative thereof. It is a polyester resin that is not modified with an isocyanate compound or the like.

Examples of the polyhydric alcohol include diols.
Examples of the diol include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. Bisphenol A alkylene (2 to 3 carbon atoms) oxide (average addition mole number 1 to 10) adduct; ethylene glycol, propylene glycol; hydrogenated bisphenol A, hydrogenated bisphenol A alkylene (2 to 3 carbon atoms) Examples include oxide (average added mole number 1 to 10) adducts.
These may be used individually by 1 type and may use 2 or more types together.

Examples of the polyvalent carboxylic acid include dicarboxylic acid.
Examples of the dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, dodecenyl succinic acid, octyl succinic acid and the like, or an alkyl group having 1 to 20 carbon atoms or 2 to 20 carbon atoms. And succinic acid substituted with an alkenyl group.
These may be used individually by 1 type and may use 2 or more types together.

Further, the amorphous polyester resin B may contain a trivalent or higher carboxylic acid and / or a trivalent or higher alcohol at the end of the resin chain in order to adjust the acid value or the hydroxyl value.
Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, or acid anhydrides thereof.
Examples of the trivalent or higher alcohol include glycerin, pentaerythritol, and trimethylolpropane.

The molecular weight of the amorphous polyester resin B is not particularly limited and may be appropriately selected depending on the purpose. However, if the molecular weight is too low, the toner may be inferior in heat resistance and durability against stress such as stirring in the developing machine. May be inferior. Therefore, the weight average molecular weight (Mw) in GPC measurement is preferably 3000 to 10,000, and more preferably 4000 to 7000. Moreover, 1000-4000 are preferable and, as for a number average molecular weight (Mn), 1500-3000 are more preferable. Further, Mw / Mn is preferably 1.0 to 4.0, and more preferably 1.0 to 3.5.
However, in the present invention, in order to satisfy the requirement (2), if necessary, the amorphous polyester resin B is extracted with methanol, and a part of the components having a molecular weight of 600 or less is removed and purified.

There is no restriction | limiting in particular in the acid value of the said amorphous polyester resin B, Although it can select suitably according to the objective, 1-50 mgKOH / g is preferable and 5-30 mgKOH / g is more preferable. When the acid value is 1 mgKOH / g or more, the toner is likely to be negatively charged, and further, the affinity between the paper and the toner is improved during fixing on the paper, and the low-temperature fixability can be improved. On the other hand, when the acid value exceeds 50 mgKOH / g, the charging stability, particularly the charging stability against environmental fluctuations may be lowered.
There is no restriction | limiting in particular in the hydroxyl value of the said amorphous polyester resin B, Although it can select suitably according to the objective, It is preferable that it is 5 mgKOH / g or more.

The amorphous polyester resin B has a Tg of preferably 40 ° C to 80 ° C, more preferably 50 ° C to 70 ° C. When the Tg is less than 40 ° C., the heat resistant storage stability of the toner and the durability against stress such as stirring in the developing machine are inferior, and the filming resistance is deteriorated. On the other hand, if Tg exceeds 80 ° C., the deformation due to heating and pressurization at the time of fixing the toner is not sufficient, and the low-temperature fixability becomes insufficient.
The molecular structure of the amorphous polyester resin B can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement by solution or solid. At a convenient infrared absorption spectrum, and a method of detecting the 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 and having no absorption based on olefin? Ch (out-of-plane deformation vibration) as an amorphous polyester resin .

  The content of the amorphous polyester resin B is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 to 90 parts by weight, more preferably 60 to 80 parts by weight with respect to 100 parts by weight of the toner. preferable. When the content is less than 50 parts by mass, the dispersibility of the pigment and the release agent in the toner is deteriorated and the image may be easily fogged or disturbed. On the other hand, when the amount exceeds 90 parts by mass, the content of the crystalline polyester resin C and the non-linear amorphous polyester resin A is decreased, so that the low-temperature fixability may be inferior. When the content is in the more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

<Crystalline polyester resin C>
Since the crystalline polyester resin C has high crystallinity, the crystalline polyester resin C exhibits a heat-melting characteristic showing a rapid viscosity decrease near the fixing start temperature. By using the crystalline polyester resin C having such characteristics together with the amorphous polyester resin B, the heat-resistant storage stability due to crystallinity is good until just before the melting start temperature, and at the melting start temperature, the crystalline polyester resin C is melted. Causes a drastic drop in viscosity (sharp melt), which is compatible with the amorphous polyester resin B, and fixes with a sudden drop in viscosity. A combined toner is obtained. Also, good results are shown for the release width (difference between the fixing lower limit temperature and the high temperature resistant offset occurrence temperature).
The crystalline polyester resin C refers to one obtained from a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or a derivative thereof. Accordingly, the crystalline polyester resin C does not include a modified polyester resin, for example, the prepolymer and a resin obtained by crosslinking and / or elongation reaction of the prepolymer.

-Polyhydric alcohol-
There is no restriction | limiting in particular as said polyhydric alcohol, According to the objective, it can select suitably, For example, diol and trihydric or more alcohol are mentioned.
Examples of the diol include saturated aliphatic diol. Examples thereof include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated aliphatic diols having 2 to 12 carbon atoms are more preferable. . When the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin C may be lowered, and the melting point may be lowered. Further, when the saturated aliphatic diol has more than 12 carbon atoms, it is difficult to obtain a practical material.

Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, Examples thereof include 18-octadecanediol and 1,14-eicosandecanediol. Among these, the crystalline polyester resin C has high crystallinity and is excellent in sharp melt properties, so that ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1, 10-decanediol and 1,12-dodecanediol are preferred.
Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.
These may be used individually by 1 type and may use 2 or more types together.

-Multivalent carboxylic acid-
There is no restriction | limiting in particular as said polyvalent carboxylic acid, According to the objective, it can select suitably, For example, bivalent carboxylic acid and trivalent or more carboxylic acid are mentioned.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid; and the like, and anhydrides and lower (C1 to C3) alkyl esters thereof.
Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. Lower (carbon number 1 to 3) alkyl ester and the like.
In addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the polyvalent carboxylic acid may include a dicarboxylic acid having a sulfonic acid group. Furthermore, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid having a double bond may be contained. These may be used individually by 1 type and may use 2 or more types together.

The crystalline polyester resin C is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, it is preferable to have a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. As a result, the crystallinity becomes high and the sharp melt property is excellent, so that excellent low-temperature fixability can be exhibited.
There is no restriction | limiting in particular in the melting | fusing point of the said crystalline polyester resin C, Although it can select suitably according to the objective, 60 to 80 degreeC is preferable. If the melting point is less than 60 ° C., the crystalline polyester resin C is likely to melt at low temperatures and the heat-resistant storage stability of the toner may be reduced. Insufficient, low-temperature fixability may decrease.

  The molecular weight of the crystalline polyester resin C is not particularly limited and may be appropriately selected depending on the purpose. However, those with sharp molecular weight distribution and low molecular weight are excellent in low-temperature fixability, and when there are many components with low molecular weight, the heat-resistant storage stability is lowered. Therefore, the soluble content of orthodichlorobenzene in crystalline polyester resin C is GPC. In measurement, it is preferable that they are weight average molecular weight (Mw) 3000-30000, number average molecular weight (Mn) 1000-10000, and Mw / Mn = 1.0-10. More preferably, it is weight average molecular weight (Mw) 5000-15000, number average molecular weight (Mn) 2000-10000, Mw / Mn = 1.0-5.0.

The acid value of the crystalline polyester resin C is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of affinity between paper and resin, in order to achieve desired low-temperature fixability, 5 mgKOH / g or more is preferable, and 10 mgKOH / g or more is more preferable. On the other hand, 45 mgKOH / g or less is preferable in order to improve the high temperature offset resistance.
The hydroxyl value of the crystalline polyester resin C is not particularly limited and may be appropriately selected according to the purpose. However, in order to achieve a desired temperature fixability and to achieve good charging characteristics, 0 to 50 mgKOH / g is preferable, and 5-50 mgKOH / g is more preferable.
The molecular structure of the crystalline polyester resin C can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement by solution or solid. For example, in the infrared absorption spectrum, a method of detecting, as crystalline polyester resin C, those having absorption at 965 ± 10 cm ⁻¹ and 990 ± 10 cm ⁻¹ based on δCH (out-of-plane variable angular vibration) of olefin can be mentioned.

  There is no restriction | limiting in particular in content of the said crystalline polyester resin C, Although it can select suitably according to the objective, 3-20 mass parts is preferable with respect to 100 mass parts of toner, and 5-15 mass parts is more preferable. . If the content is less than 3 parts by mass, the low-temperature fixability may be inferior due to insufficient sharp-melting with the crystalline polyester resin C. If the content exceeds 20 parts by mass, the heat-resistant storage stability may be reduced, or the image may be fogged. May occur easily. When the content is within the more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

<Other ingredients>
In addition to the components described above, the toner used in the present invention may contain additives such as a release agent, a colorant, a charge control agent, an external additive, a fluidity improver, a cleaning property improver, and a magnetic material as necessary. It can be included.

-Release agent-
There is no restriction | limiting in particular as said mold release agent, It can select suitably from well-known things, For example, the following are mentioned.
Examples of waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin and microcrystalline And natural waxes such as petroleum waxes such as Petrolatum;
In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene, and polypropylene; synthetic waxes such as esters, ketones, and ethers;
Furthermore, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon; low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n -Polyacrylate homopolymer or copolymer such as lauryl methacrylate (eg, n-stearyl acrylate-ethyl methacrylate copolymer); crystalline polymer having a long alkyl group in the side chain, etc. Good.
Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax are preferable.

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 80 ° C. When the melting point is less than 60 ° C., the release agent tends to melt at low temperatures, and the heat resistant storage stability may be inferior. When the melting point exceeds 80 ° C., even when the resin is melted and is in the fixing temperature region, the release agent may not be sufficiently melted to cause a fixing offset and cause an image defect.
There is no restriction | limiting in particular in content of a mold release agent, Although it can select suitably according to the objective, 2-10 mass parts is preferable with respect to 100 mass parts of toner, and 3-8 mass parts is more preferable. If the content is less than 2 parts by mass, the high temperature offset resistance and the low temperature fixability at the time of fixing may be inferior. is there. When the content is in the more preferable range, it is advantageous in terms of improving the image quality and improving the fixing stability.

-Colorant-
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably.
There is no restriction | limiting in particular in content of a coloring agent, Although it can select suitably according to the objective, 1-15 mass parts is preferable with respect to 100 mass parts of toner, and 3-10 mass parts is more preferable.

  Examples of colorants include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthra Zan Yellow BGL, Isoindolinone Yellow, Bengala, Red Plum, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, ben Gin orange, Perinone orange, Oil orange, Cobalt blue, Cerulean blue, Alkaline blue rake, Peacock blue rake, Victoria blue rake, Metal-free phthalocyanine blue, phthalocyanine blue, Fast sky blue, Indanthrene blue (RS, BC), Indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B , Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium oxide, zinc white, ritbon, etc. are mentioned.

  The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded together with the production of the master batch or the master batch include, in addition to the amorphous polyester resin B, styrene such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene, or a polymer of a substituted product thereof; styrene -P-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloro Methyl methacrylate copolymer, styrene-acrylic Nitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Examples thereof include resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. These may be used individually by 1 type and may use 2 or more types together.

  The masterbatch can be obtained by mixing and kneading the masterbatch resin and the colorant under high shearing force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called an aqueous paste of a colorant is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed. This is preferable because it can be dried. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

-Charge control agent-
There is no restriction | limiting in particular in the said charge control agent, According to the objective, it can select suitably. Examples include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkyls. Examples include amide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, and metal salt of salicylic acid derivative. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), LRA-901, LR-147 (manufactured by Nippon Carlit) which is a boron complex, copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. It is done.

  The content of the charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 to 10 parts by weight, and preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the toner. Is more preferable. When the content exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, the flowability of the developer is reduced, and the image The concentration may decrease. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, or may be added when directly dissolving and dispersing in an organic solvent, or after toner particles are produced on the toner surface. It may be fixed.

-External additive-
An external additive can be added to the toner of the present invention in order to adjust fluidity, charge amount, and electrical characteristics. There is no restriction | limiting in particular as an external additive, According to the objective, it can select suitably. Examples thereof include silica fine particles, hydrophobized silica fine particles, fatty acid metal salts such as zinc stearate, metal oxides such as titania and alumina, or their hydrophobized products, fluoropolymers, and the like.
The content of the external additive is not particularly limited and may be appropriately selected depending on the intended purpose. preferable.
The primary particle diameter of the external additive fine particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 100 nm or less, more preferably 3 to 70 nm. If the thickness is smaller than 3 nm, the fine particles of the external additive are buried in the toner, and the function is difficult to be effectively exhibited. On the other hand, if it is larger than 70 nm, the surface of the photoreceptor is not uniformly damaged, which is not preferable.

-Fluidity improver-
The fluidity improver is not particularly limited as long as it can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity, and can be appropriately selected according to the purpose. it can. Examples thereof include silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. It is particularly preferable that the external additive silica or titanium oxide is surface-treated with such a fluidity improver and used as hydrophobic silica or hydrophobic titanium oxide.

-Cleaning improver-
The cleaning property improving agent is not particularly limited as long as it is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium, and can be appropriately selected according to the purpose. it can. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles.
The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.

-Magnetic material-
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone.

As described above, the toner used in the present invention has a glass transition temperature (Tg1st) of 30 ° C. to 50 ° C. at the first temperature increase in differential scanning calorimetry (DSC). When the temperature is lower than 30 ° C., the heat resistant storage stability is deteriorated, blocking in the developing machine and filming to the photoconductor occur, and when the temperature is higher than 50 ° C., the low temperature fixability of the toner is decreased.
When the Tg is about 50 ° C. or less, the conventional toner is likely to aggregate due to a temperature change in the storage environment and during the transportation of the toner in the summer or the tropical region. As a result, solidification in the toner bottle and fixation of the toner in the developing machine occur. Also, replenishment failure due to toner clogging in the toner bottle and image abnormality due to toner fixation in the developing machine are likely to occur. In contrast, the toner used in the present invention has a Tg lower than that of the conventional toner, but can retain heat-resistant storage stability because it contains the non-linear amorphous polyester resin A, which is a low Tg component. .

There is no particular limitation on the difference (Tg1st−Tg2nd) between the Tg1st and the glass transition temperature (Tg2nd) of the second temperature increase in differential scanning calorimetry (DSC) of the toner used in the present invention. It is preferable that it is 10 degreeC or more at a point. That the difference is 10 ° C. or more is that the crystalline polyester resin C, which was in an incompatible state before heating (before the first temperature increase), the non-linear amorphous polyester resin A, and It means that the amorphous polyester resin B is in a compatible state after heating (after the first temperature increase). In addition, the compatible state after a heating does not need to be a complete compatible state. The upper limit of the difference is not particularly limited and can be appropriately selected according to the purpose, but is preferably 50 ° C. or lower.
The melting point of the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 60 ° C to 80 ° C.
The volume average particle diameter of the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 to 7 μm. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Moreover, it is preferable to contain 1-10 number% of components with a volume average particle diameter of 2 micrometers or less.

<Calculation method and analysis method of various characteristics of toner and toner component>
Various physical properties of the non-linear amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and the release agent may be measured on their own. Each component may be separated by GPC or the like, and for these, physical properties such as Tg, molecular weight, melting point, etc. may be measured or the mass ratio of the constituent components may be obtained by an analysis method described later.

Separation of each component by GPC can be performed, for example, by the following method.
In GPC measurement using THF as a mobile phase, the eluate is fractionated by a fraction collector or the like, and fractions corresponding to a desired molecular weight portion of the entire integral of the elution curve are collected. The concentrated eluate is concentrated and dried by an evaporator or the like, and then the solid content is dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, and 1H-NMR measurement is performed. The constituent monomer ratio is calculated.
As another method, after concentrating the eluate, it is hydrolyzed with sodium hydroxide or the like, and the decomposition product is subjected to qualitative quantitative analysis by high performance liquid chromatography (HPLC) to calculate the constituent monomer ratio.

  The toner manufacturing method forms toner base particles while generating a non-linear amorphous polyester resin A by an extension reaction and / or a cross-linking reaction between the non-linear reactive precursor and the curing agent. In this case, the non-linear amorphous polyester resin A may be obtained from the actual toner by GPC or the like, and the Tg thereof may be obtained separately. Alternatively, the non-linear reactive precursor and the curing agent may be separately obtained. A non-linear amorphous polyester resin A may be synthesized by an extension reaction and / or a cross-linking reaction, and Tg and the like may be measured from the synthesized non-linear amorphous polyester resin A.

<< Toner component separation means >>
An example of a separation unit for each component when analyzing toner will be described.
First, 1 g of toner is put into 100 mL of THF to obtain a solution in which the soluble component is dissolved while stirring for 30 minutes at 25 ° C.
This is filtered through a membrane filter having an opening of 0.2 μm to obtain a THF soluble component in the toner.
Subsequently, this is melt | dissolved in THF, it is set as the sample for GPC measurement, and it inject | pours into GPC used for the molecular weight measurement of each above-mentioned resin.

On the other hand, a fraction collector is placed at the eluate outlet of GPC, and the eluate is collected every predetermined count, and the eluate is eluted every 5% in area ratio from the elution curve elution start (curve rise). Get.
Next, for each elution, 30 mg of sample is dissolved in 1 mL of deuterated chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance.
The solution is filled in a glass tube for NMR measurement having a diameter of 5 mm, and a spectrum is obtained by performing integration 128 times at a temperature of 23 ° C. to 25 ° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.).
The monomer composition and composition ratio of the non-linear amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin C contained in the toner are determined from the peak integration ratio of the obtained spectrum. be able to.

For example, peak assignment is performed as follows, and the component ratio of the constituent monomer is determined from each integral ratio.
The assignment of the peak can be performed, for example, as follows.
-Near 8.25 ppm: derived from benzene ring of trimellitic acid (for one hydrogen)
-8.07-8.10 ppm vicinity: Derived from the benzene ring of terephthalic acid (for 4 hydrogen)
・ 7.1 to 7.25 ppm vicinity: derived from benzene ring of bisphenol A (for 4 hydrogens)
・ Approximately 6.8 ppm: Derived from the benzene ring of bisphenol A (for 4 hydrogens) and from the double bond of fumaric acid (for 2 hydrogens)
・ 5.2 to 5.4 ppm vicinity: bisphenol A propylene oxide adduct derived from methine (one hydrogen)
3.7-4.7 ppm vicinity: derived from methylene of bisphenol A propylene oxide adduct (for 2 hydrogens) and derived from methylene of bisphenol A ethylene oxide adduct (for 4 hydrogens)
-Around 1.6 ppm: derived from methyl group of bisphenol A (for 6 hydrogens)

From these results, for example, the extract recovered in the fraction in which the non-linear amorphous polyester resin A accounts for 90% by mass or more can be treated as the non-linear amorphous polyester resin A. . Similarly, the extract recovered in the fraction in which the amorphous polyester resin B occupies 90% by mass or more is regarded as the amorphous polyester resin B, and the crystalline polyester resin C is recovered in the fraction in which 90% by mass or more. The extracted products can be handled as the crystalline polyester resin C, respectively.

<< Measurement Method of Storage Elastic Modulus (G ') >>
The storage elastic modulus (G ′) under various conditions can be measured using, for example, a dynamic viscoelasticity measuring device (ARES, manufactured by TA Instruments). The frequency at the time of measurement is 1 Hz.
Specifically, a measurement sample was molded into a pellet having a diameter of 8 mm and a thickness of 1 to 2 mm, fixed to a parallel plate having a diameter of 8 mm, stabilized at 40 ° C., a frequency of 1 Hz (6.28 rad / s), and a distortion amount. Measurement is performed by increasing the temperature to 200 ° C. at a rate of 0.1% (strain amount control mode) and a temperature increase rate of 2.0 ° C./min.

<< Measurement Method of Melting Point and Glass Transition Temperature (Tg) >>
The melting point and Tg in the present invention can be measured, for example, using a DSC system (differential scanning calorimeter, Q-200: manufactured by TA Instruments).
Specifically, it can be measured by the following procedure.
First, about 5.0 mg of a target sample is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, heating is performed from −80 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere (first temperature increase). Thereafter, the temperature is lowered from 150 ° C. to −80 ° C. at a temperature drop rate of 10 ° C./min, and further heated to 150 ° C. at a temperature rise rate of 10 ° C./min (second temperature rise). At each of the first temperature increase and the second temperature increase, a DSC curve is measured using a differential scanning calorimeter (Q-200: manufactured by TA Instruments).
From the obtained DSC curve, the DSC curve at the first temperature rise can be selected using the analysis program in the Q-200 system, and the Tg at the first temperature rise of the target sample can be obtained. Similarly, the DSC curve at the second temperature increase can be selected, and the Tg of the target sample at the second temperature increase can be obtained.
Further, from the obtained DSC curve, using the analysis program in the Q-200 system, the DSC curve at the first temperature rise is selected, and the endothermic peak top temperature at the first temperature rise of the target sample is obtained as the melting point. Can do. Similarly, the DSC curve at the second temperature increase can be selected, and the endothermic peak top temperature at the second temperature increase of the target sample can be obtained as the melting point.

In the present invention, when toner is used as the target sample, the glass transition temperature at the first temperature rise is Tg1st, and the glass transition temperature at the second temperature rise is Tg2nd.
In the present invention, the non-linear amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and the Tg and melting point of other components such as the release agent As for, unless otherwise specified, the endothermic peak top temperature and Tg at the second temperature rise are defined as the melting point and Tg of each target sample.

<< Measurement Method of Particle Size Distribution >>
The volume average particle diameter (D4), the number average particle diameter (Dn), and the ratio (D4 / Dn) of the toner are determined using, for example, Coulter Counter TA-II, Coulter Multisizer II (both manufactured by Coulter). Can be measured. In the present invention, Coulter Multisizer II is used. The measurement method is as follows.
First, 0.1 to 5 mL of a surfactant [preferably polyoxyethylene alkyl ether (nonionic surfactant)] as a dispersant is added to 100 to 150 mL of the electrolytic aqueous solution. Here, the electrolytic aqueous solution is a 1 mass% NaCl aqueous solution prepared using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Next, 2 to 20 mg of a measurement sample is added. The electrolytic aqueous solution in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toner particles or toner are measured with the measuring device using a 100 μm aperture as the aperture, and the volume distribution is measured. And calculate the number distribution. From the obtained distribution, the volume average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained.
As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

<< Method for measuring molecular weight >>
The molecular weight of each component of the toner can be measured, for example, by the following method.
・ Permeation chromatography (GPC) measuring device
: GPC-8220GPC (manufactured by Tosoh Corporation)
・ Column: TSKgel SuperHZM-H 15cm triple (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
・ Solvent: THF
・ Flow rate: 0.35 mL / min
Sample: 0.4 mL of 0.15% by mass sample was injected. Sample pretreatment: Toner was dissolved in THF (stabilized Wako Pure Chemical Industries, Ltd.) at a concentration of 0.15% by mass. Filter through a 2 μm filter and use the filtrate as a sample. 100 μL of the THF sample solution is injected and measured.

When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Showd STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580 are used. An RI (refractive index) detector is used as the detector.

<Toner production method>
A method for producing the toner is not particularly limited and may be appropriately selected depending on the intended purpose. The non-linear amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin C may be selected. In addition, if necessary, it is preferably granulated by dispersing an oil phase containing the release agent, the colorant and the like in an aqueous medium.
Further, the toner includes the non-linear reactive precursor, the amorphous polyester resin B, and the crystalline polyester resin C. If necessary, the toner further includes the curing agent, the release agent, and the coloring agent. It is preferable to granulate by dispersing an oil phase containing an agent in an aqueous medium.
An example of such a method for producing the toner is a known dissolution suspension method.
As an example of a toner manufacturing method, toner base particles are formed while generating a non-linear amorphous polyester resin A by an extension reaction and / or a cross-linking reaction between the non-linear reactive precursor and the curing agent. The method to do is shown below. In this method, the aqueous medium is prepared, the oil phase containing the toner material is prepared, the toner material is emulsified or dispersed, and the organic solvent is removed.

-Preparation of aqueous medium (aqueous phase)-
The aqueous medium can be prepared, for example, by dispersing resin particles in an aqueous medium. There is no restriction | limiting in particular in the addition amount in the aqueous medium of the said resin particle, Although it can select suitably according to the objective, 0.5-10 mass parts is preferable with respect to 100 mass parts of said aqueous media.
There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water, the solvent miscible with water, these mixtures etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, water is preferable.
The solvent miscible with water is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. Examples of the alcohol include methanol, isopropanol, and ethylene glycol. Examples of the lower ketones include acetone and methyl ethyl ketone.

-Preparation of oil phase-
The preparation of the oil phase containing the toner material includes at least the non-linear reactive precursor, the amorphous polyester resin B, and the crystalline polyester resin C, and if necessary, the curing A toner material containing an agent, the release agent, the colorant, and the like can be dissolved or dispersed in an organic solvent.
There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, The organic solvent whose boiling point is less than 150 degreeC is preferable at the point which is easy to remove.
Examples of the organic solvent having a boiling point of less than 150 ° C. include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, Examples thereof include methyl acetate, ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. These may be used individually by 1 type and may use 2 or more types together.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is more preferable.

-Emulsification or dispersion-
The emulsification or dispersion of the toner material can be performed by dispersing the oil phase containing the toner material in the aqueous medium. Then, when emulsifying or dispersing the toner material, the nonlinear amorphous polyester resin A is obtained by subjecting the curing agent and the nonlinear reactive precursor to an extension reaction and / or a crosslinking reaction. Generate.

The non-linear amorphous polyester resin A can be produced, for example, by the following methods (1) to (3).
(1) An oil phase containing the non-linear reactive precursor and the curing agent is emulsified or dispersed in an aqueous medium, and the curing agent and the non-linear reactive precursor in the aqueous medium Is produced by subjecting to elongation reaction and / or crosslinking reaction.
(2) The oil phase containing the non-linear reactive precursor is emulsified or dispersed in an aqueous medium to which the curing agent is added in advance, and the curing agent and the non-linear reactive precursor are added in the aqueous medium. A method of producing a body by an extension reaction and / or a crosslinking reaction.
(3) After emulsifying or dispersing the oil phase containing the non-linear reactive precursor in an aqueous medium, the curing agent is added to the aqueous medium, and the curing agent is added from the particle interface in the aqueous medium. And a non-linear reactive precursor by an extension reaction and / or a crosslinking reaction.
When the curing agent and the nonlinear reactive precursor are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, the nonlinear amorphous polyester is preferentially formed on the surface of the toner to be produced. Since the resin A is formed, a concentration gradient of the non-linear amorphous polyester resin A can be provided in the toner.

There are no particular limitations on the reaction conditions (reaction time, reaction temperature) for producing the non-linear amorphous polyester resin A, and the combination of the curing agent and the non-linear reactive precursor is not limited. Depending on the situation, it can be appropriately selected.
The reaction time is preferably 10 minutes to 40 hours, more preferably 2 to 24 hours.
The reaction temperature is preferably 0 ° C to 150 ° C, more preferably 40 ° C to 98 ° C.

The method for stably forming the dispersion containing the non-linear reactive precursor in the aqueous medium is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a method in which an oil phase prepared by dissolving or dispersing a toner material in a solvent is added to an aqueous medium phase and dispersed by shearing force.
The disperser for the dispersion is not particularly limited and can be appropriately selected depending on the purpose. For example, a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, Examples include an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion (oil droplets) can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the number of rotations, the dispersion time, and the dispersion temperature can be appropriately selected according to the purpose. The rotational speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch method, the dispersion time is preferably 0.1 to 5 minutes. The dispersion temperature is preferably 0 ° C to 150 ° C, more preferably 40 ° C to 98 ° C under pressure. In general, dispersion is easier when the dispersion temperature is higher.

  The amount of the aqueous medium used when emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 50 to 2000 parts by mass with respect to 100 parts by mass of the toner material. -1000 mass parts is more preferable. When the amount of the aqueous medium used is less than 50 parts by mass, the dispersion state of the toner material is deteriorated, and toner base particles having a predetermined particle diameter may not be obtained. When the amount exceeds 2000 parts by mass, the production cost is high. May be.

When emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets to obtain a desired shape and sharpening the particle size distribution. .
There is no restriction | limiting in particular in the said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.
As said surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant etc. can be used, for example.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, and phosphate esters. Among these, those having a fluoroalkyl group are preferable.

A catalyst can be used for the elongation reaction and / or the crosslinking reaction in producing the non-linear amorphous polyester resin A.
There is no restriction | limiting in particular as said catalyst, According to the objective, it can select suitably, For example, a dibutyltin laurate, a dioctyltin laurate, etc. are mentioned.

-Removal of organic solvent-
The method for removing the organic solvent from the dispersion such as the emulsified slurry is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature of the entire reaction system is gradually raised, and the organic in the oil droplets Examples include a method of evaporating the solvent, and a method of removing the organic solvent in the oil droplets by spraying the dispersion liquid in a dry atmosphere.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. The classification may be performed by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, or may be performed after drying.

The obtained toner base particles may be mixed with particles such as the external additive and the charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent the particles such as the external additive from detaching from the surface of the toner base particles.
The method for applying the mechanical impact force is not particularly limited and may be appropriately selected depending on the purpose.For example, a method for applying an impact force to a mixture using a blade rotating at high speed, Examples include a method in which a mixture is charged and accelerated to cause particles or particles to collide with an appropriate collision plate.
The apparatus used in the above method is not particularly limited, and can be appropriately selected according to the purpose. For example, an ang mill (manufactured by Hosokawa Micron Co., Ltd.) and an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) are modified to lower the pulverization air pressure. Examples thereof include a device, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries Ltd.), and an automatic mortar.

(Developer)
The developer of the present invention contains at least the toner of the present invention and, if necessary, other components such as a carrier that are appropriately selected.
For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably.
The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. Agents are preferred.
When the developer is used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, the blade for thinning the toner, etc. The toner is less fused to the member, and good and stable developability and images can be obtained even with long-term stirring in the developing device.
When the developer is used as a two-component developer, there is little fluctuation in the particle diameter of the toner even if the toner balance for a long period of time is performed, and good and stable developability and long-term agitation in the developing device. An image is obtained.

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

−Core material−
There is no restriction | limiting in particular as a material of the said core material, According to the objective, it can select suitably, For example, 50-90 emu / g manganese-strontium type material, 50-90 emu / g manganese-magnesium type material etc. Can be mentioned. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 to 120 emu / g. In addition, it is preferable to use a low-magnetization material such as 30-80 emu / g of copper-zinc system because it can reduce the impact of the developer in a spiked state on the photoconductor and is advantageous for high image quality. .
These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular in the volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10-150 micrometers is preferable and 40-100 micrometers is more preferable. If the volume average particle diameter is less than 10 μm, fine particles are increased in the carrier, and the magnetization per particle may be reduced to cause carrier scattering. On the other hand, if the thickness exceeds 150 μm, the specific surface area may be reduced and toner scattering may occur, and in the case of a full color having many solid portions, the reproduction of the solid portions may be particularly poor.

  When toner is used as a two-component developer, it is mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and can be appropriately selected according to the purpose, but is preferably 90 to 98 parts by mass with respect to 100 parts by mass of the two-component developer. 93-97 mass parts is more preferable.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples. Unless otherwise specified, “part” and “%” refer to “part by mass” and “% by mass”.
Each measured value was measured by the method described above. Moreover, Tg, melting | fusing point, molecular weight, etc. of non-linear amorphous polyester resin A, amorphous polyester resin B, crystalline polyester resin C, etc. are the measured values of each resin obtained by the manufacture example.

(Production Example 1)
<Synthesis of ketimine>
170 parts of isophorone diamine and 75 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

(Production Example A1)
<Synthesis of Non-Linear Amorphous Polyester Resin A1>
-Synthesis of prepolymer A1-
3-methyl-1,5-pentanediol, isophthalic acid, adipic acid, and trimethylolpropane were mixed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube with a molar ratio of hydroxyl group to carboxyl group “OH / COOH. Was added to 1.1. The diol component is 3-methyl-1,5-pentanediol 100 mol%, the dicarboxylic acid component is 45 mol% isophthalic acid and 55 mol% adipic acid, and trimethylolpropane is 1.5 mol based on the total amount of monomers. % And was added together with titanium tetraisopropoxide (1000 ppm based on all resin components). Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours until the effluent water disappeared. Then, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and intermediate body polyester A1 was obtained.
Next, the intermediate polyester A1 and isophorone diisocyanate (IPDI) are mixed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe at a molar ratio (isocyanate group of IPDI / hydroxyl group of intermediate polyester A1) of 2.0. And diluted with ethyl acetate to a 50% ethyl acetate solution and reacted at 100 ° C. for 5 hours to obtain Prepolymer A1.

-Synthesis of non-linear amorphous polyester resin A1-
The obtained prepolymer A1 was stirred in a reaction vessel equipped with a heating apparatus, a stirrer, and a nitrogen introduction tube, and the amine amount of [ketimine compound 1] was equimolar with respect to the isocyanate amount in the prepolymer A1. An amount of [ketimine compound 1] was dropped into the reaction vessel and stirred at 45 ° C. for 10 hours, and then the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a nonlinear amorphous polyester resin A1.

(Production Example A2)
<Synthesis of Non-Linear Amorphous Polyester Resin A2>
-Synthesis of prepolymer A2-
3-Methyl-1,5-pentanediol, adipic acid and trimethylolpropane were mixed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and the molar ratio of hydroxyl group to carboxyl group “OH / COOH” was 1. .1 was added. Trimethylolpropane was added together with titanium tetraisopropoxide (1000 ppm with respect to all resin components) so that the amount of trimethylolpropane was 1.5 mol% with respect to the total monomer amount. Thereafter, the temperature was raised to 200 ° C. in about 4 hours, then heated to 230 ° C. over 2 hours, and reacted until there was no effluent water. Then, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and intermediate polyester A2 was obtained.
Next, the intermediate polyester A2 and isophorone diisocyanate (IPDI) are mixed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe at a molar ratio (IPDI isocyanate group / intermediate polyester A2 hydroxyl group) of 2.0. And diluted with ethyl acetate to a 50% ethyl acetate solution and reacted at 100 ° C. for 5 hours to obtain prepolymer A2.

-Synthesis of non-linear amorphous polyester resin A2-
The obtained prepolymer A2 was stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the amount of amine of [ketimine compound 1] was equimolar with respect to the amount of isocyanate in prepolymer A2. An amount of [ketimine compound 1] was dropped into the reaction vessel and stirred at 45 ° C. for 10 hours, and then the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a nonlinear amorphous polyester resin A2.

(Production Example A3)
<Synthesis of Nonlinear Amorphous Polyester Resin A3>
-Synthesis of prepolymer A3-
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 2-mole adduct, terephthalic acid, and trimellitic anhydride, hydroxyl group and carboxyl group The molar ratio of “OH / COOH” was 1.3. The diol component is 90 mol% of bisphenol A ethylene oxide 2 mol adduct, 10 mol% of bisphenol A propylene oxide 2 mol adduct, the carboxylic acid component is 90 mol% of terephthalic acid, and 10 mol% of trimellitic anhydride. It was added together with propoxide (1000 ppm with respect to the resin component). Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours until the effluent water disappeared. Then, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and intermediate body polyester A3 was obtained.
Next, the intermediate polyester A3 and isophorone diisocyanate (IPDI) were mixed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe at a molar ratio (isocyanate group of IPDI / hydroxyl group of intermediate polyester A3) 2.0. And diluted with ethyl acetate to a 50% ethyl acetate solution, followed by reaction at 100 ° C. for 5 hours to obtain prepolymer A3.

-Synthesis of non-linear amorphous polyester resin A3-
The obtained prepolymer A3 was stirred in a reaction vessel equipped with a heating apparatus, a stirrer and a nitrogen introduction tube, and the amine amount of [ketimine compound 1] was equimolar with respect to the isocyanate amount in the prepolymer A3. An amount of [ketimine compound 1] was dropped into the reaction vessel and stirred at 45 ° C. for 10 hours, and then the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less, to obtain a nonlinear amorphous polyester resin A3.

(Production Example A4)
<Synthesis of Non-Linear Amorphous Polyester Resin A4>
-Synthesis of prepolymer A4-
1,2-propylene glycol, terephthalic acid, adipic acid, and trimellitic anhydride are mixed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and the molar ratio of hydroxyl group to carboxyl group is “OH / COOH”. Was set to 1.3. The dicarboxylic acid component is 80 mol% terephthalic acid and 20 mol% adipic acid, and trimellitic anhydride is 2.5 mol% with respect to the total amount of monomers. For 1000 ppm). Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours until the effluent water disappeared. Then, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and intermediate polyester A4 was obtained.
Next, the intermediate polyester A4 and isophorone diisocyanate are charged at a molar ratio (IPDI isocyanate group / intermediate polyester A4 hydroxyl group) of 2.0 into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. After dilution with ethyl acetate to a 50% ethyl acetate solution, the mixture was reacted at 100 ° C. for 5 hours to obtain prepolymer A4.

-Synthesis of non-linear amorphous polyester resin A4-
The obtained prepolymer A4 was stirred in a reaction vessel equipped with a heating device, a stirrer, and a nitrogen introduction tube, and the amount of amine of [ketimine compound 1] was equimolar with respect to the amount of isocyanate in the prepolymer A4. An amount of [ketimine compound 1] was dropped into the reaction vessel and stirred at 45 ° C. for 10 hours, and then the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a nonlinear amorphous polyester resin A4.

(Production Example A5)
<Synthesis of Non-Linear Amorphous Polyester Resin A5>
-Synthesis of prepolymer A5-
3-Methyl-1,5-pentanediol, isophthalic acid, adipic acid, and trimellitic anhydride in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and a molar ratio of hydroxyl group to carboxyl group Was added so that OH / COOH was 1.5. The dicarboxylic acid component is 40 mol% isophthalic acid and 60 mol% adipic acid, and trimellitic anhydride is 1 mol% based on the total amount of monomers, and titanium tetraisopropoxide (based on all resin components). 1000 ppm). Thereafter, the temperature was raised to 200 ° C. in about 4 hours, then heated to 230 ° C. over 2 hours, and reacted until there was no effluent water. Then, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and intermediate polyester A5 was obtained.
Next, the intermediate polyester A5 and isophorone diisocyanate are charged at a molar ratio (IPDI isocyanate group / intermediate polyester A5 hydroxyl group) of 2.0 in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. After dilution with ethyl acetate to a 50% ethyl acetate solution, the mixture was reacted at 100 ° C. for 5 hours to obtain Prepolymer A5.

-Synthesis of non-linear amorphous polyester resin A5-
The obtained prepolymer A5 was stirred in a reaction vessel equipped with a heating device, a stirrer, and a nitrogen introduction tube, and the amount of amine of [ketimine compound 1] was equimolar with respect to the amount of isocyanate in the prepolymer A5. An amount of [ketimine compound 1] was dropped into the reaction vessel and stirred at 45 ° C. for 10 hours, and then the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a nonlinear amorphous polyester resin A5.

(Production Example A6)
<Synthesis of Non-Linear Amorphous Polyester Resin A6>
-Synthesis of prepolymer A6-
1,6-Hexanediol, isophthalic acid, adipic acid, and trimellitic anhydride are mixed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and OH / COOH, which is a molar ratio of hydroxyl group to carboxyl group. Was set to 1.5. The dicarboxylic acid component is 80 mol% isophthalic acid and 20 mol% adipic acid, and trimellitic anhydride is 1 mol% based on the total amount of monomers, and titanium tetraisopropoxide (based on all resin components). 1000 ppm). Thereafter, the temperature was raised to 200 ° C. in about 4 hours, and then the temperature was raised to 230 ° C. over 2 hours until the effluent water disappeared. Then, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and intermediate polyester A6 was obtained.
Next, the intermediate polyester A6 and isophorone diisocyanate are charged at a molar ratio (IPDI isocyanate group / intermediate polyester A6 hydroxyl group) of 2.0 in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. After dilution with ethyl acetate to a 50% ethyl acetate solution, the mixture was reacted at 100 ° C. for 5 hours to obtain Prepolymer A6.

-Synthesis of non-linear amorphous polyester resin A6-
The obtained prepolymer A6 was stirred in a reaction vessel equipped with a heating device, a stirrer and a nitrogen introduction tube, and the amount of amine of [ketimine compound 1] was equimolar with respect to the amount of isocyanate in the prepolymer A6. An amount of [ketimine compound 1] was dropped into the reaction vessel and stirred at 45 ° C. for 10 hours, and then the prepolymer extension product was taken out. The obtained prepolymer extension product was dried under reduced pressure at 50 ° C. until the amount of residual ethyl acetate was 100 ppm or less to obtain a nonlinear amorphous polyester resin A6.

(Production Example B1)
<Synthesis of Amorphous Polyester Resin B1>
To a four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, add bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 2-mole adduct, terephthalic acid, and adipic acid with a hydroxyl group. The molar ratio of the carboxyl groups “OH / COOH” was added to 1.3. The molar ratio of bisphenol A ethylene oxide 2 mol adduct and bisphenol A propylene oxide 3 mol adduct was 60/40, the molar ratio of terephthalic acid and adipic acid was 93/7, and titanium tetraisopropoxide (all resin components And 500 ppm) at 230 ° C. under normal pressure for 8 hours and further under reduced pressure of 10 to 15 mmHg for 4 hours, and then trimellitic anhydride is added to the reaction vessel in an amount of 1 mol% based on the total resin components. And reacted at 180 ° C. under normal pressure for 3 hours to obtain an amorphous polyester resin B1.

(Production Example B2)
<Synthesis of Amorphous Polyester Resin B2>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A propylene oxide 2-mol adduct, 1,3-propylene glycol, terephthalic acid, and adipic acid, hydroxyl group and carboxyl group The molar ratio of “OH / COOH” was 1.4. The molar ratio of bisphenol A propylene oxide 2 mol adduct and 1,3-propylene glycol was 90/10, the molar ratio of terephthalic acid and adipic acid was 80/20, and titanium tetraisopropoxide (based on the total resin components). 500 ppm) and normal pressure at 230 ° C. for 8 hours and further under reduced pressure of 10 to 15 mmHg for 4 hours, and then trimellitic anhydride is added to the reaction vessel to 1 mol% with respect to the total resin components. The mixture was reacted at 180 ° C. under normal pressure for 3 hours to obtain an amorphous polyester resin B2.

(Production Example B3)
<Synthesis of Amorphous Polyester Resin B3>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is combined with bisphenol A ethylene oxide side 2 mol adduct, bisphenol A propylene oxide 2 mol adduct, isophthalic acid, and adipic acid. And a carboxyl group molar ratio “OH / COOH” was 1.2. The molar ratio of bisphenol A ethylene oxide side 2 mol adduct and bisphenol A propylene oxide 2 mol adduct was 80/20, and the molar ratio of isophthalic acid and adipic acid was 80/20. Titanium tetraisopropoxide (all resins The reaction is carried out at 230 ° C. for 8 hours under normal pressure and further for 4 hours under reduced pressure of 10 to 15 mmHg, and then 1 mol of trimellitic anhydride is added to the reaction vessel in an amount of 1 mol with respect to all resin components. %, And reacted at 180 ° C. under normal pressure for 3 hours to obtain amorphous polyester resin B3.

(Production Example B4)
<Synthesis of Amorphous Polyester Resin B4>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is combined with bisphenol A ethylene oxide side 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, isophthalic acid, and adipic acid. And a carboxyl group molar ratio “OH / COOH” was 1.3. The molar ratio of bisphenol A ethylene oxide side 2 mol adduct and bisphenol A propylene oxide 3 mol adduct was 85/15, and the molar ratio of isophthalic acid to adipic acid was 80/20. And 500 ppm) under normal pressure at 230 ° C. for 8 hours and further under reduced pressure of 10 to 15 mmHg for 4 hours. Then, trimellitic anhydride is added to the reaction vessel in an amount of 1 mol% based on the total resin components. And reacted at 180 ° C. and normal pressure for 3 hours to obtain amorphous polyester resin B4.

(Production Example B5)
<Synthesis of Amorphous Polyester Resin B5>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple is combined with bisphenol A ethylene oxide side 2 mol adduct, bisphenol A propylene oxide 3 mol adduct, terephthalic acid, and adipic acid. And a carboxyl group molar ratio “OH / COOH” was 1.3. The molar ratio of bisphenol A ethylene oxide side 2 mol adduct and bisphenol A propylene oxide 3 mol adduct was 85/15, and the molar ratio of terephthalic acid and adipic acid was 80/20, and titanium tetraisopropoxide (all resins The reaction is carried out at 230 ° C. for 8 hours under normal pressure and further for 4 hours under reduced pressure of 10 to 15 mmHg, and then 1 mol of trimellitic anhydride is added to the reaction vessel in an amount of 1 mol with respect to all resin components. %, And reacted at 180 ° C. and normal pressure for 3 hours to obtain amorphous polyester resin B5.

(Production Example C1)
<Synthesis of crystalline polyester resin C>
In a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, sebacic acid and 1,6-hexanediol were mixed with a molar ratio of “OH / COOH” between a hydroxyl group and a carboxyl group. After charging to 0.9 and reacting with titanium tetraisopropoxide (500 ppm relative to all resin components) at 180 ° C. for 10 hours, the temperature was raised to 200 ° C. and reacted for 3 hours, and further 8. Reaction was performed under a pressure of 3 kPa for 2 hours to obtain a crystalline polyester resin C.

(Example 1)
<Synthesis of Masterbatch 1>
Add 1200 parts of water, 500 parts of carbon black (Printex 35, manufactured by Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5] and 500 parts of amorphous polyester resin B1, and add a Henschel mixer (made by Mitsui Mining Co., Ltd.). ) Was kneaded at 150 ° C. for 30 minutes using two rolls, and then cooled and pulverized with a pulverizer to obtain [Masterbatch 1].

<Preparation of WAX dispersion 1>
In a container in which a stir bar and a thermometer are set, 50 parts of paraffin wax (manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8) as release agent 1 and ethyl acetate 450 parts are charged, heated to 80 ° C. while stirring, held at 80 ° C. for 5 hours, cooled to 30 ° C. at 1 hour, and sent using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation). A liquid speed of 1 kg / hr, a disk peripheral speed of 6 m / second, 80% by volume of 0.5 mm zirconia beads, and dispersion were carried out under the conditions of 3 passes to obtain [WAX Dispersion 1].

<Preparation of crystalline polyester resin dispersion 1>
A container equipped with a stir bar and a thermometer was charged with 50 parts of crystalline polyester resin C and 450 parts of ethyl acetate, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, and then for 1 hour. At 30 ° C., and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / second, 80% by volume of 0.5 mm zirconia beads, 3 pass conditions To obtain [Crystalline polyester resin dispersion 1].

<Preparation of oil phase 1>
[WAX Dispersion 1] 50 parts, [Non-Linear Amorphous Polyester Resin A1] 150 parts, [Crystalline Polyester Resin Dispersion 1] 50 parts, [Amorphous Polyester Resin B1] 750 parts, [Masterbatch 1] 50 parts and 2 parts of [ketimine compound 1] were put in a container and mixed with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at 5000 rpm for 60 minutes to obtain [Oil Phase 1].

<Synthesis of fine particle dispersion 1 (organic fine particle emulsion)>
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 138 parts of styrene, 138 parts of methacrylic acid , And 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. This was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous dispersion of a vinyl resin (styrene salt copolymer of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate) [ A fine particle dispersion 1] was obtained.
The volume average particle size of [Fine Particle Dispersion 1] measured with LA-920 (manufactured by HORIBA) was 0.14 μm.

<Preparation of aqueous phase 1>
990 parts of water, 83 parts of [fine particle dispersion 1], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Kasei Kogyo Co., Ltd.) and 90 parts of ethyl acetate were mixed and stirred to give a milky white color Obtained liquid. This was designated as [Aqueous Phase 1].

<Emulsification / desolvation>
[Oil phase 1] 1200 parts of [Aqueous phase 1] were added to a container containing 1052 parts, and the mixture was mixed with a TK homomixer at 13,000 rpm for 20 minutes to obtain [Emulsion slurry 1].
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

<Washing and drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure, the following operations (1) to (4) were performed twice on the obtained filter cake to obtain [Filter Cake 1].
(1): Add 100 parts of ion-exchanged water to the filter cake, mix with a TK homomixer (10 minutes at 12,000 rpm), and then filter.
(2): Add 100 parts of a 10% aqueous sodium hydroxide solution to the filter cake of (1), mix with a TK homomixer (30 minutes at 12,000 rpm), and then filter under reduced pressure.
(3): 100 parts of 10% hydrochloric acid is added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12000 rpm for 10 minutes), and then filtered.
(4): Add 300 parts of ion-exchanged water to the filter cake of (3), mix with a TK homomixer (rotation speed 12000 rpm for 10 minutes), and then filter.

Next, [Filter cake 1] was dried with an air circulation dryer at 45 ° C. for 48 hours, and sieved with an opening of 75 μm mesh to obtain [Toner 1].
Table 1 shows the composition ratio of toner 1 obtained and Tg1st.

<Image forming apparatus>
The surface pressure of the nip SN is adjusted by adjusting the distance between the fixing roller 28 and the pressure roller 30 of the fixing device 12 shown in FIGS. ) Was adjusted so that the surface pressure at the central portion in the axial direction measured using) was 1.0 kg / cm ² . The adjusted fixing device 12 was incorporated in the image forming apparatus shown in FIG.

(Example 2)
An image forming apparatus having the same configuration as that of Example 1 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Example 3)
Except for changing the input amount of the non-linear amorphous polyester resin A1 to 120 parts and changing the input amount of the amorphous polyester resin B1 to 780 parts in <Preparation of oil phase> in Example 1.
[Toner 2] was obtained in the same manner as in Example 1.

Example 4
An image forming apparatus having the same configuration as that of Example 3 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Example 5)
Except that the input amount of the non-linear amorphous polyester resin A1 in Example 1 <Preparation of oil phase> was changed to 180 parts, and the input amount of the amorphous polyester resin B1 was changed to 720 parts,
[Toner 3] was obtained in the same manner as in Example 1.

(Example 6)
An image forming apparatus having the same configuration as that of Example 5 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Example 7)
Example 1 except that the non-linear amorphous polyester resin A1 in Example 1 was changed to a non-linear amorphous polyester resin A2 and the amorphous polyester resin B1 was changed to an amorphous polyester resin B3. In the same manner as in Example 1, [Toner 4] was obtained.

(Example 8)
An image forming apparatus having the same configuration as that of Example 7 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

Example 9
In <Preparation of oil phase> in Example 1, the amount of non-linear amorphous polyester resin A1 was changed to 120 parts, the amount of amorphous polyester resin B1 was changed to 820 parts, and the crystalline polyester resin was changed. [Toner 5] was obtained in the same manner as in Example 1 except that the amount of C introduced was changed to 10 parts.

(Example 10)
An image forming apparatus having the same configuration as that of Example 9 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Example 11)
Example 1 except that the input amount of the non-linear amorphous polyester resin A1 in Example 1 <Preparation of oil phase> was changed to 180 parts and the input amount of the crystalline polyester resin C was changed to 20 parts. In the same manner as in Example 1, [Toner 6] was obtained.

(Example 12)
An image forming apparatus having the same configuration as that of Example 11 was produced except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Example 13)
In Example 1, the non-linear amorphous polyester resin A1 was changed to the non-linear amorphous polyester resin A2, and the input amount was 180 parts, and the amorphous polyester resin B1 was changed to the amorphous polyester resin B3. [Toner 7] was obtained in the same manner as in Example 1 except that the amount was changed and the amount was 720 parts.

(Example 14)
An image forming apparatus having the same configuration as that of Example 13 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Example 15)
In <Preparation of oil phase> in Example 1, the input amount of the non-linear amorphous polyester resin A1 was changed to 120 parts, the amorphous polyester resin B1 was changed to the amorphous polyester resin B2, and the input amount was changed. [Toner 8] was obtained in the same manner as in Example 1 except that the amount was 780 parts.

(Example 16)
An image forming apparatus having the same configuration as that of Example 15 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Example 17)
[Toner 9] was obtained in the same manner as in Example 1, except that the non-linear amorphous polyester resin A1 in Example 1 was changed to the non-linear amorphous polyester resin A2.

(Example 18)
An image forming apparatus having the same configuration as that of Example 17 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Example 19)
[Toner 10] was obtained in the same manner as in Example 1 except that the amorphous polyester resin B1 in Example 1 was changed to the amorphous polyester resin B2.

(Example 20)
An image forming apparatus having the same configuration as that of Example 19 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Example 21)
In Example 1, the amount of the non-linear amorphous polyester resin A1 was changed to 125 parts, the amount of the amorphous polyester resin B1 was changed to 825 parts, and the crystalline polyester resin C was not added. Except for the above, [Toner 11] was obtained in the same manner as in Example 1.

(Example 22)
An image forming apparatus having the same configuration as that of Example 21 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Example 23)
In Example 1, the non-linear amorphous polyester resin A1 was changed to the non-linear amorphous polyester resin A2, and the input amount was 180 parts, and the amorphous polyester resin B1 was changed to the amorphous polyester resin B3. [Toner 12] was obtained in the same manner as in Example 1 except that the amount was changed and the input amount was 720 parts.

(Example 24)
An image forming apparatus having the same configuration as that of Example 23 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Example 25)
Implementation was performed except that the non-linear amorphous polyester resin A1 in Example 1 was changed to a non-linear amorphous polyester resin A4 and the amorphous polyester resin B1 was changed to an amorphous polyester resin B3. [Toner 13] was obtained in the same manner as in Example 1.

(Example 26)
An image forming apparatus having the same configuration as that of Example 25 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Example 27)
Except that the input amount of the non-linear amorphous polyester resin A1 in Example 1 was changed to 80 parts and the input amount of the amorphous polyester resin B1 was changed to 820 parts, the same as in Example 1. [Toner 14] was obtained.

(Example 28)
An image forming apparatus having the same configuration as that of Example 27 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Comparative Example 1)
In <Preparation of oil phase> in Example 1, the non-linear amorphous polyester resin A1 was changed to a non-linear amorphous polyester resin A5, and the input amount was 180 parts. [Toner 15] was obtained in the same manner as in Example 1 except that the amount was changed to amorphous polyester resin B4 and the amount was 720 parts.

(Comparative Example 2)
An image forming apparatus having the same configuration as that of Comparative Example 1 was produced except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Comparative Example 3)
In <Preparation of oil phase> in Example 1, the non-linear amorphous polyester resin A1 was changed to a non-linear amorphous polyester resin A5, and the input amount was 180 parts. [Toner 16] was obtained in the same manner as in Example 1 except that the amount was changed to amorphous polyester resin B5 and the amount was 720 parts.

(Comparative Example 4)
An image forming apparatus having the same configuration as that of Comparative Example 3 was manufactured except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Comparative Example 5)
The non-linear amorphous polyester resin A1 in <Preparation of oil phase> in Example 1 is changed to a non-linear amorphous polyester resin A3, and the amorphous polyester resin B1 is changed to an amorphous polyester resin B2. Except for the changed points, [Toner 17] was obtained in the same manner as in Example 1.

(Comparative Example 6)
An image forming apparatus having the same configuration as that of Comparative Example 5 was produced except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

(Comparative Example 7)
The non-linear amorphous polyester resin A1 in <Preparation of oil phase> in Example 1 is changed to a non-linear amorphous polyester resin A4, and the amorphous polyester resin B1 is changed to an amorphous polyester resin B3. [Toner 18] was obtained in the same manner as in Example 1 except that the crystalline polyester resin C was not added.

(Comparative Example 8)
An image forming apparatus having the same configuration as that of Comparative Example 7 was produced except that the surface pressure of the fixing device 12 was changed to 1.5 kg / cm ² .

<Evaluation>
The above toners were measured as follows.
-Soxhlet extraction-
Using 100 parts of THF, 1 part of each toner was refluxed for 6 hours, and a THF-insoluble part and a soluble part were collected. The solid content obtained by removing the THF-soluble component of THF and the solid component of the THF-insoluble component were each dried at 40 ° C. for 20 hours. The THF-insoluble component was subjected to rheometer measurement, and the THF-soluble component was subjected to DSC measurement. . The measurement results are summarized in Table 1.

Using each of the above toners, each developer was prepared as follows, and the characteristics were evaluated using this developer. The results are summarized in Table 1.

<Production of developer>
-Production of carrier-
To 100 parts of toluene, 100 parts of silicone resin: 100 parts of organostraight silicone, 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black are added and dispersed for 20 minutes with a homomixer. A layer coating solution was prepared. Using a fluid bed type coating apparatus, the resin layer coating solution was applied to the surface of 1000 parts of spherical magnetite having an average particle size of 50 μm to prepare a carrier.

-Production of developer-
Using a ball mill, 5 parts of each toner and 95 parts of the carrier were mixed to prepare a developer.

<Low-temperature fixability (offset resistance)>
The carrier and the toner were mixed so that the toner concentration was 7% to obtain a developer.
After the developer is added to the developing unit 22 shown in FIG. 1, a rectangular solid image of 3 cm × 10 cm is formed on the PPC paper type 6000 <70W> A4T (manufactured by Ricoh), and the toner adhesion amount is 0.80 mg / It was formed to have a cm ^2. At this time, the surface temperature of the fixing roller is changed, and it is observed whether or not an offset occurs in which a solid development residual image is fixed at a place other than a desired place, and the fixing lower limit temperature is examined and evaluated according to the following criteria. did.
〔Evaluation criteria〕
◎: Less than 110 ° C ○: 110 ° C or more, less than 120 ° C △: 120 ° C or more, less than 130 ° C ×: 130 ° C or more

<Heat resistant storage stability>
A 50 mL glass container was filled with toner, left in a thermostatic bath at 50 ° C. for 24 hours, and then cooled to 24 ° C. Next, the penetration [mm] was measured by a penetration test (JISK 2235-1991), and the heat resistant storage stability was evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Needle penetration 20 mm or more ○: Needle penetration 15 mm or more and less than 20 mm △: Needle penetration 10 mm or more and less than 15 mm ×: Needle penetration less than 10 mm

<In-page glossiness variation Δ>
As shown in FIG. 10, an image pattern in which a rectangular solid portion of 5 cm × 4 cm and a blank with an adhesion amount of 0.8 mg / cm ² are alternately arranged is created and printed using each of the image forming apparatuses. PPC paper type 6000 <70W> (manufactured by Ricoh) was used as the transfer paper. About each solid part after printing, glossiness VG-7000 (manufactured by Nippon Denshoku Co., Ltd.) is used to measure 60-degree glossiness, and the in-page glossiness variation Δ is calculated as the maximum glossiness within the page and the minimum glossiness within the page. Difference value was used.
In-page glossiness variation Δ is less than 10.0.

Reference Signs List 4 Paper feeding means 6 Registration roller pair 8 Photosensitive drum 10 Transfer means 12 Fixing device 12
14 Paper feed tray 16 Paper feed roller 16
DESCRIPTION OF SYMBOLS 18 Charging roller 20 Mirror 22 Developing means 22a Developing roller 24 Cleaning means 24a Cleaning blade 26 Exposure part 28 Fixing roller 28a Core metal 28b Heat insulation layer 28c Heat-conductive layer 30 Pressure roller 30a Core metal 30b Heat insulation layer 32 Heating roller 34 Thermistor 36 Thermistor 38 Fixing belt 38a Substrate 38b Elastic layer 38c Release layer 40 Power source 42 External heating controller 56 Thermal heater 60 Press member 61 Support member 61
a image area a 'image area b non-image area c image area d non-image area Lb exposure light N transfer site P area P' area Pa paper SN fixing nip

JP 2005-181946 A JP 2001-343860 A

Claims (7)

A fixing member that forms an electrostatic latent image on a photoconductor based on image data, transfers a toner image obtained by developing the electrostatic latent image with toner onto a sheet-like recording material, and rotates in contact with the toner image And a pressure member that forms a fixing nip portion with the fixing member, a heating unit that heats the fixing member, and a heating control unit that controls the heating unit, and a recording material carrying a toner image A fixing device that fixes the toner through the fixing nip portion, the heating means has a heating area divided in a longitudinal direction perpendicular to the recording material conveyance direction, and the heating control means In the image forming apparatus that independently controls the temperature of the fixing member corresponding to each heating area according to the position information formed on the recording material, and controls the heating temperature of the non-image area to be lower than the image area.
The toner is
The temperature at which the storage elastic modulus G ′ = 3.0 × 10 ⁴ [Pa] is T1,
The temperature at which the storage elastic modulus G ′ = 1.0 × 10 ⁴ [Pa] is T2,
And when
T2-T1 ≧ 20 ° C. is satisfied, and
An image forming apparatus having a glass transition temperature (Tg1st) of 30 ° C. to 50 ° C. in a first temperature increase of differential scanning calorimetry (DSC).   The image forming apparatus according to claim 1, wherein the toner satisfies T2−T1 ≧ 30 ° C.   The image forming apparatus according to claim 1, wherein the toner contains at least a non-linear amorphous polyester resin and another amorphous polyester resin. The image forming apparatus according to claim 1, wherein the toner satisfies the following requirements (1) and (2).
(1) The glass transition temperature (Tg2nd: THF insoluble matter) at the second temperature increase in differential scanning calorimetry (DSC) of the THF insoluble matter is −40 ° C. to 30 ° C.
(2) The THF-insoluble matter satisfies G ′ (100) = 1 × 10 ⁵ to 1 × 10 ⁷ [Pa] and satisfies G ′ (40) / G ′ (100) ≦ 3.50 × 10. Here, G ′ (40) and G ′ (100) are storage elastic moduli at 40 ° C. and 100 ° C., respectively.   The toner further contains a crystalline polyester resin, and the glass transition temperature (Tg2nd: THF soluble content) at the second temperature increase in the differential scanning calorimetry (DSC) of the THF soluble content is 20 ° C. to 35 ° C. The image forming apparatus according to claim 1, wherein:   The image forming apparatus according to claim 1, wherein the toner has a THF insoluble content of 20 to 35% by mass. The image forming apparatus according to claim 1, wherein a surface pressure of the fixing device is 1.5 kg / cm ² or more.