JP2013064886A - Toner manufacturing method and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner manufacturing method of good productivity capable of obtaining toner which has narrow particle size distribution, a small particle size, and low temperature fixability, and does not cause filming with good productivity.SOLUTION: The toner manufacturing method includes a droplet formation step for forming a standing wave of liquid column resonance by exerting vibration to a toner composition liquid in a liquid column resonance chamber in which at least one discharge port is formed, and discharging the toner composition liquid from the discharge port which is arranged at a region being an antinode of the standing wave. The toner composition liquid is formed by dissolving or dispersing a toner composition containing a binder resin and colorant in an organic solvent. When the liquid droplet is solidified, the droplet becomes a fine particle. The binder resin contains at least a crystalline polyester resin, and the crystalline polyester resin is dispersed in the toner composition liquid before changing into liquid droplets.

Description

  The present invention relates to a toner manufacturing method used for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, and a toner.

  In recent years, in the market, there is a demand for a toner having a small particle size for improving the quality of an output image and a low-temperature fixing property of the toner for energy saving. Further, from the viewpoint of reducing the environmental load, a toner manufacturing process that saves resources and energy is required.

Conventionally, as dry toners used for electrophotography, electrostatic recording, electrostatic printing, etc., so-called pulverized toners, in which a toner binder such as a styrene resin or a polyester resin is melt-kneaded together with a colorant and pulverized, are widely used. It is used.
However, in recent years, there has been a tendency for the toner to have a small particle size in order to obtain a high-quality image. In the above pulverization method, if the particle size is 6 μm or less, the pulverization efficiency is reduced and the loss due to classification is increased. This is a problem in that the cost is low.

In addition, a so-called polymerization type toner such as a suspension polymerization method and an emulsion polymerization aggregation method, and a method involving volume shrinkage called a polymer dissolution suspension method have been proposed and put into practical use (see Patent Document 1). These toners are excellent in terms of producing a toner having a small particle diameter.
However, since it is assumed that the dispersant is used in an aqueous medium, the dispersant that impairs the charging characteristics of the toner remains on the surface of the toner, causing problems such as loss of environmental stability and removal of this. It is known that a very large amount of washing water is required to achieve this, and this is a problem in that it is not always satisfactory as a production method.

As an alternative method for producing toner, a method has been proposed in which fine droplets are formed from fine nozzles using piezoelectric pulses, and then dried and solidified to form toner (see Patent Document 2).
In addition, a method has been proposed in which fine droplets are formed by utilizing thermal expansion in the nozzle, and this is dried and solidified into a toner (see Patent Document 3). Furthermore, a method has been proposed in which minute droplets are formed using an acoustic lens and dried to solidify into toner (see Patent Document 4).
However, with these methods, it is easy to reduce the particle size of the toner, but there is a problem in that the number of droplets that can be ejected from one nozzle per unit time is small and productivity is low. This is a problem in that the spread of the particle size distribution due to coalescence cannot be avoided and a toner having a uniform particle diameter cannot be obtained, and there is a case where loss due to classification may occur.

In order to save energy, toner that melts at a low temperature is used to reduce energy generated in the fixing process. Therefore, it has been proposed to use a crystalline resin that can be melted at a low temperature for the toner (see Patent Documents 5 to 8).
In Patent Documents 9 and 10, crystalline polyester is introduced into the polymerization method in order to improve low-temperature fixability, but a dispersion having a small particle size cannot be stably obtained, and the particle size distribution of the toner deteriorates. cause. Another problem is that filming is caused by exposure of the crystalline resin to the toner surface.
Similarly, in order to improve the low-temperature fixability, when crystalline polyester is introduced into the toner manufacturing method by forming fine droplets, there is a problem in that the crystalline resin is clogged at the discharge port and the productivity is low.

  Therefore, the present situation is that there is a need to provide a toner manufacturing method capable of obtaining a toner having a narrow particle size distribution, a small particle size, a low-temperature fixability, and no filming with high productivity.

An object of the present invention is to solve the above-described problems and achieve the following objects.
That is, an object of the present invention is to provide a toner manufacturing method capable of obtaining a toner having a narrow particle size distribution, a small particle size, a low temperature fixability, and no filming with high productivity.

The above-mentioned problems are solved by the present invention including “toner production method”, “toner” and “developer using the toner” described in the following items (1) to (9).
(1) “A standing wave due to liquid column resonance is formed by applying vibration to the toner composition liquid in the liquid column resonance liquid chamber in which at least one discharge port is formed, and becomes an antinode of the standing wave. A droplet forming step of discharging the toner composition liquid from the discharge port disposed in a region, wherein the toner composition liquid is obtained by dissolving or dispersing a toner composition containing a binder resin and a colorant in an organic solvent. The droplets become fine particles when solidified, and the binder resin contains at least a crystalline polyester resin, and the crystalline polyester resin is dispersed in the toner composition liquid before the droplets are formed. A method for producing toner, ”
(2) “The crystalline polyester resin contains at least a divalent alcohol component and a divalent acid component, and at least one of the divalent alcohol component and the divalent acid component is at least two kinds. The method for producing a toner according to item (1), which comprises a monomer.
(3) “The ratio of the dispersion diameter (volume average particle diameter) of the crystalline polyester resin in the toner composition liquid to the opening diameter of the discharge port is 1% or more and 30% or less (1) Or the method for producing the toner according to the item (2)).
(4) “Production of toner according to any one of (1) to (3) above, wherein the binder resin contains 3% by mass to 50% by mass of a crystalline polyester resin. Method".
(5) As described in any one of (1) to (4) above, the solubility of the crystalline polyester resin at 70 ° C. with respect to 100 parts by mass of the organic solvent is 10 parts by mass or more. Toner manufacturing method ".
(6) “The toner manufacturing method according to any one of (1) to (5) above, wherein the crystalline polyester resin has a melting point of 65 ° C. or higher and lower than 75 ° C.”.
(7) “In the crystalline polyester resin, the molecular weight distribution by GPC of the soluble part of orthodichlorobenzene is 3000 to 30000 in weight average molecular weight (Mw), 1000 to 10,000 in number average molecular weight (Mn), Mw / Mn. The toner production method according to any one of items (1) to (6), wherein is 1 to 10.
(8) “obtained by the method for producing a toner according to any one of (1) to (7), having a weight average particle size of 1 μm to 10 μm, and a particle size distribution (weight average particle size / number average particle size). Toner) having a diameter in the range of 1 to 1.10.
(9) “Developer comprising at least the toner according to the above item (8) and a carrier”.

  According to the present invention, it is possible to provide a toner manufacturing method capable of obtaining a toner having a narrow particle size distribution, a small particle size, a low-temperature fixability, and no filming with high productivity.

It is sectional drawing which shows the structure of a liquid column resonance droplet formation means. It is sectional drawing which shows the structure of a liquid column resonance droplet unit. It is sectional drawing of a discharge outlet. It is the schematic which shows the standing wave of the speed and pressure fluctuation in the case of N = 1,2,3. It is the schematic which shows the standing wave of the speed and pressure fluctuation in the case of N = 4 and 5. It is the schematic which shows the mode of the liquid column resonance phenomenon which arises in the liquid column resonance flow path of a liquid column resonance droplet formation means. It is sectional drawing which shows another structure of a liquid column resonance droplet formation means. 1 is a schematic view of a toner manufacturing apparatus.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings. However, these descriptions are intended to facilitate understanding of the present invention and to limit the present invention. is not. According to the following detailed description including each form example for fully understanding, so-called persons skilled in the art can make other embodiments within the scope of the claims by changing or modifying the disclosed form example. Therefore, it should be understood that these changes and modifications can depart from the technical scope of the present invention.

  An example of the toner manufacturing means of the present invention will be described below with reference to FIGS. The toner production means of the present invention includes toner particle preparation means divided into droplet discharge means and droplet solidification collection means. Each is explained below.

[Droplet discharge means]
The droplet discharge means used in the present invention is not particularly limited as long as the particle size distribution of the discharged droplets is narrow, and a known one can be used. Examples of the droplet discharge means include one-fluid nozzle, two-fluid nozzle, membrane vibration type discharge means, Rayleigh split type discharge means, liquid vibration type discharge means, liquid column resonance type discharge means, and the like. JP 2008-292976, Rayleigh splitting type is described in Japanese Patent No. 4647506, and liquid vibration type is described in JP 2010-102195A.
In order to ensure the productivity of the toner with a narrow droplet size distribution, vibration is imparted to the liquid in the liquid column resonance liquid chamber in which a plurality of ejection openings are formed to form a standing wave by liquid column resonance. However, there is a liquid droplet resonance that discharges liquid from the discharge port formed in the region that becomes the antinode of the standing wave, and any of these is preferably used.

[Liquid column resonance ejection means]
The liquid column resonance type discharge means that discharges using the resonance of the liquid column will be described.
FIG. 1 shows a liquid column resonance droplet discharge means (11). The liquid common supply path (17) and the liquid column resonance liquid chamber (18) are included. The liquid column resonance liquid chamber (18) communicates with a liquid common supply path (17) provided on one of the wall surfaces at both ends in the longitudinal direction. Further, the liquid column resonance liquid chamber (18) is formed on the wall surface facing the discharge port (19) and the discharge port (19) for discharging the droplet (21) to one wall surface among the wall surfaces connected to both ends. And a vibration generating means (20) for generating high-frequency vibration to form a liquid column resonance standing wave. Note that a high-frequency power source (not shown) is connected to the vibration generating means (20).

The liquid ejected from the ejection means in the present invention is a "fine particle component-containing liquid" in which the fine particle components to be obtained are dissolved or dispersed, or a solvent if it is liquid under the conditions of ejection. It is a “fine particle component melt” in which the fine particle component is melted. (Hereinafter, these will be described as “toner component liquid” for the description of the case where toner is manufactured.) The toner component liquid (14) is passed through a liquid supply pipe by a liquid circulation pump not shown in FIG. Flows into the liquid common supply path (17) of the liquid column resonance droplet forming unit (10) shown, and is supplied to the liquid column resonance liquid chamber (18) of the liquid column resonance droplet discharge means (11) shown in FIG. The
In the liquid column resonance liquid chamber (18) filled with the toner component liquid (14), a pressure distribution is formed by the liquid column resonance standing wave generated by the vibration generating means (20). Then, the droplet (21) is ejected from the ejection port (19) arranged in the region where the amplitude of the liquid column resonance standing wave is large and the pressure fluctuation is large and which is the antinode of the standing wave. The region that becomes the antinode of the standing wave due to the liquid column resonance means a region other than the node of the standing wave. Preferably, it is a region where the pressure fluctuation of the standing wave has an amplitude large enough to discharge the liquid, and more preferably a position where the amplitude of the pressure standing wave becomes a maximum (a section as a velocity standing wave). ) To a minimum position in a range of ± 1/4 wavelength. If the region is an antinode of a standing wave, even if a plurality of discharge ports are opened, it is possible to form substantially uniform droplets from each of them, and more efficiently to discharge droplets. And clogging of the discharge port is less likely to occur. The toner component liquid (14) that has passed through the common liquid supply path (17) flows through a liquid return pipe (not shown) and is returned to the raw material container. When the amount of the toner component liquid (14) in the liquid column resonance liquid chamber (18) decreases due to the discharge of the liquid droplet (21), suction by the action of the liquid column resonance standing wave in the liquid column resonance liquid chamber (18). The force acts, the flow rate of the toner component liquid (14) supplied from the liquid common supply path (17) increases, and the toner component liquid (14) is replenished into the liquid column resonance liquid chamber (18). When the toner component liquid (14) is replenished in the liquid column resonance liquid chamber (18), the flow rate of the toner component liquid (14) passing through the liquid common supply path (17) is restored.

The liquid column resonance liquid chamber (18) in the liquid column resonance droplet discharge means (11) is formed of a material having such a high rigidity that does not affect the resonance frequency of the liquid at a driving frequency such as metal, ceramics, or silicon. The frames are joined to each other. Further, as shown in FIG. 1, the length (L) between the wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber (18) is determined based on the liquid column resonance principle as described later. Further, the width (W) of the liquid column resonance liquid chamber (18) shown in FIG. 2 is 2 of the length (L) of the liquid column resonance liquid chamber (18) so as not to give an extra frequency to the liquid column resonance. It is desirable to be less than a fraction. Furthermore, it is preferable that a plurality of liquid column resonance liquid chambers (18) are arranged for one droplet forming unit (10) in order to dramatically improve productivity. The range is not limited, but one droplet forming unit provided with 100 to 2000 liquid column resonance liquid chambers (18) is most preferable because both operability and productivity can be achieved.
In addition, for each liquid column resonance liquid chamber, a flow path for supplying liquid is connected in communication from the liquid common supply path (17), and the liquid common supply path (17) includes a plurality of liquid column resonance liquid chambers (18). Communicated with.

  Further, the vibration generating means (20) in the liquid column resonant droplet discharging means (11) is not particularly limited as long as it can be driven at a predetermined frequency, but the piezoelectric body is bonded to the elastic plate (9). Is desirable. The elastic plate constitutes a part of the wall of the liquid column resonance liquid chamber so that the piezoelectric body does not come into contact with the liquid. Examples of the piezoelectric body include piezoelectric ceramics such as lead zirconate titanate (PZT). However, since the amount of displacement is generally small, the piezoelectric body is often used by being laminated. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), and single crystals such as quartz, LiNbO3, LiTaO3, and KNbO3 can be used. Furthermore, it is desirable that the vibration generating means (20) is arranged so that it can be controlled individually for each liquid column resonance liquid chamber. In addition, the block-shaped vibrating member made of one material is partially cut in accordance with the arrangement of the liquid column resonance liquid chambers, and each liquid column resonance liquid chamber can be individually controlled via an elastic plate. desirable.

  Furthermore, the diameter of the opening of the discharge port (19) is desirably in the range of 1 [μm] to 40 [μm]. If the particle size is smaller than 1 [μm], the formed droplets may be very small, so that the toner may not be obtained. In the case of a configuration in which solid fine particles such as a pigment are contained as a component of the toner, the discharge port ( In 19), there is a possibility that productivity is reduced due to frequent occurrence of blockages. When the particle diameter is larger than 40 [μm], the droplet diameter is large, and when this is dried and solidified to obtain a desired toner particle diameter of 3 to 6 μm, the toner composition is diluted with an organic solvent into a very dilute liquid. In some cases, a large amount of drying energy is required to obtain a certain amount of toner, which is inconvenient. Further, as can be seen from FIG. 2, adopting a configuration in which the discharge port (19) is provided in the width direction in the liquid column resonance liquid chamber (18) can provide a large number of openings of the discharge port (19). Therefore, it is preferable because production efficiency is increased. Further, since the liquid column resonance frequency varies depending on the opening arrangement of the discharge port (19), it is desirable that the liquid column resonance frequency is appropriately determined by confirming the discharge of the droplet.

The cross-sectional shape of the discharge port (19) is described as a tapered shape in which the diameter of the opening is reduced in FIG. 1 and the like, but the cross-sectional shape can be appropriately selected.
FIG. 3 shows the possible cross-sectional shapes of the discharge port (19). (A) has a shape in which the opening diameter becomes narrow while having a round shape from the liquid contact surface of the discharge port (19) toward the discharge port. When the thin film (41) vibrates, the discharge port ( 19) Since the pressure applied to the liquid is maximized in the vicinity of the outlet, this is the most preferable shape for stabilizing the discharge.
(B) has such a shape that the opening diameter becomes narrower with a certain angle from the liquid contact surface of the discharge port (19) toward the discharge port, and the nozzle angle (44) is appropriately changed. Can do. The pressure applied to the liquid can be increased in the vicinity of the outlet of the discharge port (19) when the thin film (41) vibrates by this nozzle angle similar to (a), but the range of 60 to 90 ° is preferable. If it is less than 60 °, it is difficult to apply pressure to the liquid, and it is difficult to process the thin film (41), which is not preferable. When the nozzle angle 44 exceeds 90 °, (c) corresponds, but it is difficult to apply pressure to the outlet, so 90 ° is the maximum value. If the angle exceeds 90 °, no pressure is applied to the outlet of the hole (12), so that the droplet discharge becomes very unstable.
(D) is a shape combining (a) and (b). In this way, the shape may be changed step by step.

Next, the mechanism of droplet formation by the droplet formation unit in liquid column resonance will be described.
First, the principle of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber (18) in the liquid column resonance droplet discharge means (11) of FIG. 1 will be described. c), and the drive frequency given to the toner component liquid as a medium from the vibration generating means (20) is (f), the wavelength (λ) at which the liquid resonance occurs is
λ = c / f Formula (1)
Are in a relationship.

Further, in the liquid column resonance liquid chamber (18) of FIG. 1, the length from the end of the frame on the fixed end side to the end on the liquid common supply path (17) side is (L), and further the liquid common supply path ( 17) The height of the end of the frame on the side (h1 (= about 80 [μm])) is about twice the height of the communication port (h2 (= about 40 [μm])) and the end is closed In the case of the fixed ends on both sides that are equivalent to the fixed ends, the resonance is formed most efficiently when the length (L) matches an even multiple of one-fourth of the wavelength (λ). That is, it is expressed by the following calculation formula (2).
L = (N / 4) λ ... Formula (2)
(However, N is an even number.)

Furthermore, the above formula (2) is also established in the case of both open ends where both ends are completely open.
Similarly, when one side is equivalent to an open end with a pressure relief portion and the other side is closed (fixed end), that is, one side fixed end or one side open end, the length (L) is the wavelength. Resonance is most efficiently formed when it coincides with an odd multiple of one quarter of (λ). That is, N in the calculation formula (2) is expressed as an odd number.

The most efficient drive frequency (f) is calculated from the above formula (1) and the above formula (2).
f = N × c / (4L) Formula (3)
It is guided. However, in reality, since the liquid has a viscosity that attenuates resonance, vibration is not infinitely amplified, and has a Q value, as shown in calculation formulas (4) and (5) described later. Resonance also occurs at a frequency in the vicinity of the most efficient drive frequency (f) shown in the calculation formula (3).

FIG. 4 shows the shape of the standing wave of velocity and pressure fluctuation (resonance mode) when N = 1, 2, and 3. FIG. 5 shows the standing wave of velocity and pressure fluctuation when N = 4, 5. The shape (resonance mode) is shown.
Originally, it is a dense wave (longitudinal wave), but it is generally expressed as shown in FIGS.
The solid line is the velocity standing wave, and the dotted line is the pressure standing wave. For example, as can be seen from FIG. 3A showing the case of a fixed end with N = 1, in the case of velocity distribution, the amplitude of the velocity distribution is zero at the closed end, and the amplitude is maximum at the open end. Easy to understand. When the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is (L), the wavelength at which the liquid resonates is (λ), and the standing wave is the most when the integer N is 1 to 5. It occurs efficiently. In addition, since the standing wave pattern varies depending on the open / closed state of both ends, they are also shown. As will be described later, the condition of the end is determined by the state of the opening of the discharge port and the opening of the supply side. In acoustics, the open end is an end at which the moving speed of the medium (liquid) in the longitudinal direction becomes zero, and conversely, the pressure becomes maximum. Conversely, the closed end is defined as an end where the moving speed of the medium becomes zero. The closed end is considered as an acoustically hard wall and wave reflection occurs. When ideally completely closed or open, a resonant standing wave of the form shown in FIGS. 4 and 5 is generated by superposition of the waves, but it also stands depending on the number of discharge ports and the opening position of the discharge ports. The wave pattern fluctuates and a resonance frequency appears at a position deviated from the position obtained from the above equation 3. However, a stable ejection condition can be created by appropriately adjusting the driving frequency. For example, the sound velocity (c) of the liquid is 1,200 [m / s], the length (L) of the liquid column resonance liquid chamber is 1.85 [mm], wall surfaces exist at both ends, When the resonance mode of N = 2 that is completely equivalent to the above is used, the most efficient resonance frequency is derived as 324 kHz from the calculation formula (2). In another example, the sound velocity (c) of the liquid is 1,200 [m / s], the length of the liquid column resonance liquid chamber (L) is 1.85 [mm], and the same condition as above is used. When N = 4 resonance mode equivalent to the fixed ends on both sides exists and a wall surface exists, the most efficient resonance frequency is derived from the above formula (2) as 648 kHz. Higher order resonances can also be used in the chamber.

The liquid column resonance liquid chamber in the liquid column resonance droplet discharge means (11) shown in FIG. 1 can be described as an acoustically soft wall due to whether the both ends are equivalent to the closed end state or the influence of the opening of the discharge port. Although it is preferable for the frequency to increase, it is not limited to this, but it may be an open end.
The influence of the opening of the discharge port here means that the acoustic impedance is reduced, and in particular, the compliance component is increased. Therefore, the configuration in which the wall surfaces are formed at both ends in the longitudinal direction of the liquid column resonance liquid chamber as shown in FIGS. 4B and 5A is regarded as the resonance mode at both fixed ends, and the outlet side is an opening. This is a preferred configuration because all resonance modes at one open end can be used.

In addition, the numerical aperture of the discharge port, the opening arrangement position, and the cross-sectional shape of the discharge port are factors that determine the drive frequency, and the drive frequency can be appropriately determined according to this. For example, when the number of discharge ports is increased, the restriction at the tip of the liquid column resonance liquid chamber, which has been the fixed end, gradually loosens, a resonant standing wave that is almost close to the open end is generated, and the drive frequency increases. In addition, the opening position of the discharge port that is closest to the liquid supply channel is a starting point, and the loose restriction condition is applied.The cross-sectional shape of the discharge port is round or the volume of the discharge port varies depending on the frame thickness. The upper standing wave has a short wavelength and is higher than the driving frequency. When a voltage is applied to the vibration generating means at the drive frequency determined in this way, the vibration generating means is deformed, and a resonant standing wave is generated most efficiently at the drive frequency. Further, the liquid column resonance standing wave is generated even at a frequency in the vicinity of the drive frequency at which the resonance standing wave is generated most efficiently. That is, when the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is (L) and the distance to the discharge port closest to the end on the liquid supply side is (Le), (L) and (Le) The vibration generating means is vibrated using a drive waveform mainly composed of a drive frequency (f) in a range determined by the following calculation formula (4) and calculation formula (5) using both lengths of It is possible to eject the droplet from the ejection port by inducing resonance.
N × c / (4L) ≦ f ≦ N × c / (4Le) (Formula 4)
N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le) (5)

  The ratio of the length (L) between both ends in the longitudinal direction of the liquid column resonance liquid chamber to the distance (Le) to the discharge port closest to the end on the liquid supply side is Le / L> 0.6. It is preferable.

Using the principle of the liquid column resonance phenomenon described above, a liquid column resonance pressure standing wave is formed in the liquid column resonance liquid chamber (18) of FIG. 1, and is disposed in a part of the liquid column resonance liquid chamber (18). Thus, droplet discharge continuously occurs at the discharge port (19). Note that it is preferable to dispose the discharge port (19) at a position where the pressure of the standing wave fluctuates the most, because the discharge efficiency becomes high and the drive can be performed with a low voltage. Further, although one discharge column (19) may be provided for one liquid column resonance liquid chamber (18), it is preferable to arrange a plurality of discharge ports from the viewpoint of productivity. Specifically, it is preferably between 2 and 100.
When the number exceeds 100, if a desired droplet is to be formed from 100 ejection ports (19), it is necessary to set a high voltage to the vibration generating means (20), and the vibration generating means (20). As a result, the behavior of the piezoelectric body becomes unstable. When the plurality of discharge ports (19) are opened, the pitch between the discharge ports is preferably 20 [μm] or more and not more than the length of the liquid column resonance liquid chamber.
When the pitch between the discharge ports is smaller than 20 [μm], there is a high probability that droplets discharged from adjacent discharge ports collide with each other to form large droplets, leading to a deterioration in the toner particle size distribution.

Next, the state of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber in the droplet discharge head in the droplet forming unit will be described with reference to FIG. In the figure, the solid line drawn in the liquid column resonance liquid chamber represents the velocity distribution plotting the velocity at any measurement position from the fixed end side to the liquid common supply path side end in the liquid column resonance liquid chamber. The direction from the common liquid supply path to the liquid column resonance liquid chamber is +, and the opposite direction is −. In addition, the dotted line marked in the liquid column resonance liquid chamber indicates a pressure distribution in which the pressure value at each arbitrary measurement position between the fixed end side and the liquid common supply path side end in the liquid column resonance liquid chamber is plotted. The positive pressure is + with respect to the atmospheric pressure, and the negative pressure is-.
Moreover, if it is a positive pressure, a pressure will be applied to the downward direction in the figure, and if it is a negative pressure, a pressure will be applied to the upward direction in the figure. Further, in the same figure, as described above, the liquid common supply path side is open, but the height of the opening (the height shown in FIG. 1) where the liquid common supply path (17) communicates with the liquid column resonance liquid chamber (18). The height of the frame that is the fixed end (height (h1) shown in FIG. 1) is about twice or more than that of (h2)), so that the liquid column resonance liquid chamber (18) is substantially fixed on both side fixed ends. These graphs show changes in the velocity distribution and the pressure distribution over time under the approximate condition of.

FIG. 6A shows a pressure waveform and a velocity waveform in the liquid column resonance liquid chamber (18) when droplets are discharged.
In FIG. 6B, the meniscus pressure increases again after the liquid is drawn immediately after the droplet is discharged. As shown in (a) and (b) of these figures, the pressure in the flow path provided with the discharge port (19) in the liquid column resonance liquid chamber (18) is maximum. Thereafter, as shown in FIG. 6C, the positive pressure in the vicinity of the discharge port (19) is reduced, and the liquid droplet (21) is discharged in a negative pressure direction.

  And as shown in (d) of Drawing 6, the pressure near discharge mouth (19) becomes the minimum. From this time, filling of the liquid component resonance liquid chamber (18) with the toner component liquid (14) starts. Thereafter, as shown in FIG. 6E, the negative pressure in the vicinity of the discharge port (19) becomes smaller and shifts to the positive pressure direction. At this point, the filling of the toner component liquid (14) is completed. Then, again, as shown in FIG. 6A, the positive pressure in the droplet discharge region of the liquid column resonance liquid chamber (18) becomes maximum, and the droplet (21) is discharged from the discharge port (19). Discharged. In this way, a standing wave due to liquid column resonance is generated in the liquid column resonance liquid chamber by high-frequency driving of the vibration generating means, and corresponds to an antinode of standing wave due to liquid column resonance where the pressure changes most. Since the discharge port (19) is arranged in the droplet discharge region to be discharged, the droplet (21) is continuously discharged from the discharge port (19) according to the antinode period.

  Next, an example of a configuration in which droplets are actually ejected by the liquid column resonance phenomenon will be described. This example is a resonance mode in which the length (L) between both ends in the longitudinal direction of the liquid column resonance liquid chamber (18) in FIG. 1 is 1.85 [mm] and N = 2. FIG. 7 shows a state in which the discharge port is arranged at the antinode of the N = 2 mode pressure standing wave and the discharge performed with a sine wave with a drive frequency of 340 [kHz] is photographed by the laser shadowgraphy method. Shown in As can be seen from the figure, it was possible to discharge droplets with very uniform diameters and almost uniform speeds. FIG. 7 is a characteristic diagram showing droplet velocity frequency characteristics when driven by the same amplitude sine wave with a drive frequency of 290 [kHz] to 395 [kHz]. As can be seen from the figure, the discharge speed from each nozzle is uniform and the maximum discharge speed when the drive frequency is around 340 [kHz] in the first to fourth nozzles. From this result, it can be seen that, in the second mode of the liquid column resonance frequency, 340 [kHz], uniform ejection is realized at the antinode position of the liquid column resonance standing wave. Further, from the characteristic results of FIG. 7, the droplet is between the droplet discharge speed peak at 130 [kHz] which is the first mode and the droplet discharge speed peak at 340 [kHz] which is the second mode. It can be seen that the characteristic frequency characteristic of the liquid column resonance standing wave of the liquid column resonance that does not discharge is generated in the liquid column resonance liquid chamber.

[Droplet solidification]
The toner of the present invention can be obtained by solidifying and then collecting the droplets of the toner component liquid discharged into the gas from the droplet discharge means described above.

[Droplet solidification means]
To solidify, although the way of thinking differs depending on the properties of the toner component liquid, basically any means can be used as long as the toner component liquid can be brought into a solid state.
For example, if the toner component liquid is obtained by dissolving or dispersing a solid raw material in a solvent capable of volatilization, it can be achieved by drying the droplets in the conveying airflow after droplet ejection, that is, volatilizing the solvent. In drying the solvent, the drying state can be adjusted by appropriately selecting the temperature, vapor pressure, gas type, and the like of the gas to be injected. Further, even if the particles are not completely dried, they may be additionally dried in a separate step after the collection as long as the collected particles maintain a solid state.
Even if it does not follow the said example, you may achieve by application of a temperature change, a chemical reaction, etc.

[Solidification particle collection means]
The solidified particles can be recovered from the air by a known powder collecting means such as a cyclone collecting or a back filter.

FIG. 7 is a cross-sectional view of an example of an apparatus for carrying out the toner manufacturing method of the present invention. The toner manufacturing apparatus (1) mainly includes a droplet discharge means 2 and a dry collection unit (60).
In the droplet discharge means (2), a raw material container (13) for storing the toner component liquid (14) and a toner component liquid (14) stored in the raw material container (13) are supplied to the liquid supply pipe (16). ) To the droplet discharge means (2), and further, the toner component liquid (14) in the liquid supply pipe (16) is pumped to return to the raw material container (13) through the liquid return pipe (22). A liquid circulation pump (15) is connected, and the toner component liquid (14) can be supplied to the droplet discharge means (2) at any time. The liquid supply pipe (16) is provided with a pressure measuring device of (P1) and the dry collection unit (P2), and the liquid feeding pressure to the droplet discharge means (2) and the inside of the dry collection unit are provided. Is controlled by pressure gauges (P1) and (P2). At this time, if P1> P2, the toner component liquid (1) may ooze out from the hole (12), and if P1 <P2, gas may enter the discharge means and discharge may stop. Therefore, it is desirable that P1≈P2.
In the chamber (61), a descending airflow (101) created from the carrier airflow inlet (64) is formed. The droplet (21) discharged from the droplet discharge means 2 is transported downward not only by gravity but also by the transport airflow (101), and is collected by the solidified particle collecting means (62).

[Conveyance airflow]
When the ejected droplets come into contact with each other before drying, the droplets coalesce and become one particle (hereinafter, this phenomenon is called coalescence). In order to obtain solidified particles having a uniform particle size distribution, it is necessary to maintain the distance between the ejected droplets. However, the ejected droplets have a constant initial velocity, but eventually become stalled due to air resistance. The jetted droplets catch up with the stalled particles and coalesce as a result. Since this phenomenon occurs constantly, the particle size distribution is greatly deteriorated when the particles are collected. In order to prevent coalescence, it is necessary to transport the liquid droplets while solidifying the liquid droplets while preventing the liquid droplets from decreasing in speed and preventing the liquid droplets from contacting each other. The solidified particles are transported to the solidified particle collecting means.
For example, as shown in FIG. 1, a part of the transport airflow (101) is disposed as a first airflow in the vicinity of the droplet discharge means in the same direction as the droplet discharge direction. Speed reduction can be prevented and coalescence can be prevented. Alternatively, as shown in FIG. 8, the direction may be transverse to the ejection direction. Alternatively, although not shown, it may have an angle, and it is desirable to have an angle at which the droplets are separated from the droplet discharge means. As shown in FIG. 8, when the anti-adhesion airflow is applied from the lateral direction to the droplet discharge, it is desirable that the trajectories do not overlap when the droplets are conveyed by the anti-adhesion airflow from the discharge port. .
After preventing coalescence by the first air stream as described above, the solidified particles may be carried to the solidified particle collecting means by the second air stream.
It is desirable that the velocity of the first air flow is equal to or higher than the droplet jet velocity. If the speed of the anti-adhesion airflow is lower than the droplet ejection speed, it is difficult to exert the function of preventing the droplet particles, which is the original purpose of the anti-adhesion airflow, from contacting.
The property of the first air stream can be added with a condition such that the droplets do not coalesce with each other, and may not necessarily be the same as the second air stream. Further, a chemical substance that promotes solidification of the particle surface may be mixed in the anti-adhesion airflow, or may be imparted in anticipation of physical action.
The carrier airflow (101) is not particularly limited as a state of the airflow, and may be a laminar flow, a swirl flow or a turbulent flow. There are no particular limitations on the type of gas constituting the carrier airflow (101), and it may be air or an incombustible gas such as nitrogen. Further, the temperature of the conveying airflow (101) can be adjusted as appropriate, and it is desirable that there is no fluctuation during production. Also, means for changing the airflow state of the carrier airflow (101) in the chamber (61) may be taken. The carrier airflow (101) may be used not only to prevent the adhesion of the droplets (21) but also to prevent them from adhering to the chamber (61).

[Secondary drying]
When the amount of residual solvent contained in the toner particles obtained by the dry collecting means shown in FIG. 7 is large, secondary drying is performed as necessary to reduce this. As the secondary drying, general known drying means such as fluidized bed drying or vacuum drying can be used. If the organic solvent remains in the toner, not only the toner characteristics such as heat-resistant storage stability, fixing properties, and charging characteristics will change over time. Since the organic solvent volatilizes during fixing by heating, the possibility of adverse effects on the user and peripheral equipment is increased. Therefore, sufficient drying is performed.

[toner]
The toner of the present invention contains at least a binder resin, a colorant and a release agent, and optionally contains a charge adjusting agent, an additive and other components.

The “toner composition liquid” used in the present invention will be described. The toner composition liquid is in a liquid state in which the above toner components are dissolved or dispersed in a solvent, or may be free from a solvent as long as it is liquid under the conditions of ejection, and a part or all of the toner components are melted. In a liquid state.
As the toner material, if the above toner composition liquid can be adjusted, the same material as that of a conventional electrophotographic toner can be used. As described above, the droplets are made into fine droplets by the droplet discharge means, and the target toner particles can be produced by the droplet solidification collecting means.

(Organic solvent)
As the organic solvent, a solvent in which the crystalline polyester resin is completely dissolved at a high temperature to form a uniform solution, and on the other hand, when it is cooled to a low temperature, it is phase-separated from the crystalline polyester resin to form a heterogeneous solution. In other words, the organic solvent is preferably a solution in which the crystalline polyester resin is completely dissolved at a high temperature, and at a low temperature, at least a part of the crystalline polyester resin is precipitated from the solution to be in a solid-liquid mixed state.
As specific examples, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more.

(Binder resin)
The binder resin contains at least a crystalline polyester resin, and further contains other components such as a binder resin other than the crystalline polyester resin as necessary.

(Crystalline polyester resin)
-Effect of crystalline polyester resin-
Since the crystalline polyester resin in the toner according to the present invention has high crystallinity, it exhibits a heat-melting characteristic showing a rapid viscosity decrease near the fixing start temperature. In other words, by using such a crystalline polyester resin, the present inventors have good heat-resistant storage stability due to crystallinity until immediately before the melting start temperature, and at the melting start temperature, a sharp viscosity drop (sharp melt property) is caused to fix. Thus, it was found that a toner having both good heat storage stability and low-temperature fixability can be obtained. It was also found that the release width (difference between the fixing lower limit temperature and the hot offset occurrence temperature) also showed good results.

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

  Among them, the crystalline polyester resin has a small peak half width and high crystallinity, and in particular, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, , 12 dodecanediol alcohol component, fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, It is preferably composed of only one type of dicarboxylic acid component of 1,12-dodecanedioic acid.

  In addition, as a method for controlling the crystallinity and softening point of the crystalline polyester resin, a trivalent or higher polyhydric alcohol such as glycerin as an alcohol component or a trivalent or higher valency such as trimellitic anhydride as an acid component at the time of polyester resin synthesis. Examples thereof include a method of designing and using a non-linear polyester resin that has been subjected to condensation polymerization by adding a polyvalent carboxylic acid.

The molecular structure of the crystalline polyester resin in the present invention can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. As an example, a method for detecting, as an example of a crystalline polyester resin, an infrared absorption spectrum having absorption based on δCH (out-of-plane variable vibration) of olefin at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ is given. Can do.

  The solubility of the crystalline polyester resin at 20 ° C. with respect to 100 parts by mass of the organic solvent is preferably less than 3.0 parts by mass. In the case of 3.0 parts by mass or more, the crystalline polyester resin dissolved in the organic solvent is easily compatible with the non-crystalline polyester resin, resulting in deterioration of heat-resistant storage stability, contamination of the developing device, and image deterioration. May occur.

  The solubility of the crystalline polyester resin at 70 ° C. with respect to 100 parts by mass of the organic solvent is preferably 10 parts by mass or more. When the amount is less than 10 parts by mass, since the affinity between the organic solvent and the crystalline polyester resin is poor, it is difficult to disperse the crystalline polyester resin to a submicron size in the organic solvent.

As for the molecular weight, as a result of earnest examination from the viewpoint that the molecular weight distribution is sharp and the low molecular weight is excellent in low-temperature fixability, and the heat resistant storage stability is deteriorated when there are many components having low molecular weight, the soluble content of o-dichlorobenzene In the molecular weight distribution by GPC, the peak position of the molecular weight distribution diagram in which the horizontal axis is log (M) and the vertical axis is expressed by weight% is in the range of 3.5 to 4.0, and the half width of the peak is 1.5. It is preferable that the weight average molecular weight (Mw) is 3000 to 30000, the number average molecular weight (Mn) is 1000 to 10000, and Mw / Mn is 1 to 10.
Furthermore, it is preferable that the weight average molecular weight (Mw) is 5000 to 15000, the number average molecular weight (Mn) is 2000 to 10000, and Mw / Mn is 1 to 5.

  The acid value of the crystalline polyester resin is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more in order to achieve the desired low-temperature fixability from the viewpoint of the affinity between the paper and the resin. On the other hand, in order to improve hot offset property, it is preferable that it is 45 mgKOH / g or less. Further, the hydroxyl value of the crystalline polyester resin is 0 to 50 mgKOH / g, more preferably 5 to 50 mgKOH / g, in order to achieve a predetermined low-temperature fixability and to achieve good charging characteristics. preferable.

(Binder resin other than crystalline polyester resin)
The binder resin other than the crystalline polyester resin (hereinafter sometimes referred to as “other binder resin”) is not particularly limited and may be appropriately selected depending on the intended purpose. Monomers, vinyl monomers such as acrylic monomers, methacrylic monomers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins , Polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, terpene resin, coumarone indene resin, polycarbonate resin, petroleum resin, and the like.

  As other properties of the binder resin, it is desirable that the binder resin be dissolved in a solvent, and it is desirable to have a conventionally known performance except for this feature.

(Molecular weight distribution of binder resin)
The molecular weight distribution of the binder resin by GPC (gel permeation chromatography) preferably has at least one peak in the region of molecular weight of 3,000 to 50,000 from the viewpoint of toner fixing property and offset resistance. As the THF soluble component, a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100 [%] is also preferable, and the binder resin has at least one peak in a molecular weight region of 5,000 to 20,000. Is more preferable.

(Binder resin acid value)
What has 60 [mass%] or more of resin whose acid value of binder resin has 0.1-50 [mgKOH / g] is preferable.
In the present invention, the acid value of the binder resin component of the toner composition is measured according to JIS K-0070.

  As the magnetic material that can be used in the present invention, known magnetic materials conventionally used for electrophotographic toners can be used. For example, (1) magnetic iron oxide such as magnetite, maghemite, ferrite, and iron oxide containing other metal oxides, (2) metals such as iron, cobalt, nickel, or these metals and aluminum, cobalt, copper Alloys with metals such as lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium. (3) and mixtures thereof are used. The magnetic material can also be used as a colorant. As the usage-amount of the said magnetic body, 10-200 mass parts of magnetic bodies are preferable with respect to 100 mass parts of binder resin, and 20-150 mass parts is more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 [μm], more preferably 0.1 to 0.5 [μm]. The number average diameter can be obtained by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.

[Colorant]
The colorant is not particularly limited, and a commonly used resin can be appropriately selected and used.

  The content of the colorant is preferably 1 to 15 [% by mass] and more preferably 3 to 10 [% by mass] based on the toner.

  The colorant used in the toner according to the present invention can also be used as a master batch combined with a resin. The master batch is for dispersing the pigment in advance, and may not be used if sufficient dispersion of the pigment is obtained. In general, a master batch is obtained by dispersing a pigment in hardness in a resin by applying high shear to the pigment and the resin. A conventionally well-known thing can be used as binder resin knead | mixed with manufacture of a masterbatch or a masterbatch. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.

  A dispersant may be used to increase the dispersibility of the pigment during the production of the masterbatch. From the viewpoint of pigment dispersibility, it is preferable that the compatibility with the binder resin is high, and conventionally known ones can be used. Specific examples of commercially available products include “Ajisper PB821”, “Azisper PB822” (Ajinomoto Fine). Techno), “Disperbyk-2001” (by Big Chemie), “EFKA-4010” (by EFKA), and the like.

  The dispersant is preferably blended in the toner at a ratio of 0.1 to 10 [mass%] with respect to the colorant. When the blending ratio is less than 0.1 [% by mass], the pigment dispersibility may be insufficient, and when more than 10 [% by mass], the chargeability under high humidity may be deteriorated.

  The addition amount of the dispersant is preferably 1 to 200 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 1 part by mass, the dispersibility may be lowered, and if it exceeds 200 parts by mass, the chargeability may be lowered.

(Release agent)
The toner component liquid used in the present invention contains a release agent together with a binder resin and a colorant.
There are no particular limitations on the release agent, and those that are usually used can be appropriately selected and used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin release agent, microcrystalline release agent, paraffin release agent. Aliphatic hydrocarbon release agents such as mold agents, sazol release agents, oxides of aliphatic hydrocarbon release agents such as oxidized polyethylene release agents, or block copolymers thereof, candelilla release agents, carnauba Release agents, plant release agents such as wood wax, jojoba wax, animal release agents such as beeswax, lanolin, and whale wax, mineral release agents such as ozokerite, ceresin, and petrolatum, and montanate release agents Mold release agents mainly composed of fatty acid esters such as caster mold release agents. Deoxidized carnauba mold release agents and the like are partially or wholly deoxidized fatty acid esters.

  The melting point of the release agent is preferably 70 to 140 [° C.] and more preferably 70 to 120 [° C.] in order to balance the fixing property and the offset resistance. If it is less than 70 [° C.], the blocking resistance may be lowered, and if it exceeds 140 [° C.], the offset resistance effect may be difficult to be exhibited.

  The total content of the release agent is preferably 0.2 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

  In the present invention, the temperature of the peak top of the endothermic peak of the release agent measured by DSC (differential scanning calorimetry) is defined as the melting point of the release agent.

  As the DSC measuring device for the release agent or toner, it is preferable to perform measurement with a highly accurate internal heat input compensation type differential scanning calorimeter. As a measuring method, it carries out according to ASTM D3418-82. The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 [° C./min] after raising and lowering the temperature once and taking a previous history.

  In the toner according to the present invention, as other additives, protection of the electrostatic latent image carrier / carrier, improvement of cleaning properties, adjustment of thermal characteristics / electrical characteristics / physical characteristics, resistance adjustment, softening point adjustment, fixing rate For the purpose of improvement, various metal soaps, fluorosurfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, and inorganic such as titanium oxide, aluminum oxide, alumina A fine powder or the like can be added as necessary. These inorganic fine powders may be hydrophobized as necessary. In addition, lubricants such as polytetrafluoroethylene, zinc stearate, and polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, and strontium titanate, anti-caking agents, and white and black fine particles having opposite polarity to the toner particles Can also be used in small amounts as a developability improver.

  These additives have a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicons for the purpose of charge control and the like. It is also preferable to treat with a treating agent such as a compound or various treating agents.

  As the additive, inorganic fine particles can be preferably used. As said inorganic fine particle, well-known things, such as a silica, an alumina, a titanium oxide, can be used, for example.

  In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, thermosetting resin And polymer particles.

  Such an external additive can be made hydrophobic by the surface treatment agent and prevent deterioration of the external additive itself even under high humidity. Examples of the surface treatment agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, a modified silicone oil, Etc. are preferable.

  The primary particle diameter of the external additive is preferably 5 [nm] to 2 [μm], and more preferably 5 [nm] to 500 [nm]. Moreover, as a specific surface area by BET method, it is preferable that it is 20-500 [m2 / g]. The use ratio of the inorganic fine particles is preferably 0.01 to 5 [% by weight] of the toner, and more preferably 0.01 to 2.0 [% by weight].

  Examples of the cleaning property improver for removing the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymethyl methacrylate. There may be mentioned polymer fine particles produced by soap-free emulsion polymerization such as fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 [μm].

  Hereinafter, the present invention will be described more specifically with reference to examples.

[Synthesis of binder resin]
(Production Example 1: Synthesis of crystalline polyester resin A)
Into a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 2320 g of 1,10-decanedioic acid, 1430 g of 1,8-octanediol, and 4.9 g of hydroquinone were added, and the temperature was 200 ° C. Then, the temperature was raised to 230 ° C. and reacted for 3 hours, and further reacted at 8.3 kPa for 4 hours to obtain a crystalline polyester resin A. Table 1 shows the melting point, solubility in organic solvent, and molecular weight measurement results.
The molecular weight is measured by GPC measurement using a soluble component of o-dichlorobenzene. The same applies to the crystalline polyester resins B to H shown below.

(Production Example 2: Synthesis of crystalline polyester resin B)
Into a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 2,300 g of 1,10-decanedioic acid, 1430 g of 1,8-octanediol and 4.9 g of hydroquinone were added, and 190 ° C. Then, the temperature was raised to 220 ° C. and reacted for 3 hours, and further reacted at 7.8 kPa for 1 hour to obtain a crystalline polyester resin B. Table 1 shows the melting point, solubility in organic solvent, and molecular weight measurement results.

(Production Example 3; Synthesis of crystalline polyester resin C)
2,400 g of 1,10-decanedioic acid, 620 g of ethylene glycol and 4.9 g of hydroquinone were placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, and reacted at 200 ° C. for 10 hours. Then, the temperature was raised to 220 ° C. and reacted for 3 hours, and further reacted at 8.3 kPa for 2 hours to obtain crystalline polyester resin C. Table 1 shows the melting point, solubility in organic solvent, and molecular weight measurement results.

(Production Example 4: Synthesis of crystalline polyester resin D)
Into a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 2,400 g of 1,10-decanedioic acid, 1330 g of 1,6-hexanediol, and 4.9 g of hydroquinone were added, and 200 ° C. Then, the temperature was raised to 200 ° C. and reacted for 3 hours, and further reacted at 8.3 kPa for 2 hours to obtain a crystalline polyester resin D. Table 1 shows the melting point, solubility in organic solvent, and molecular weight measurement results.

(Production Example 4: Synthesis of crystalline polyester resin E)
Into a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 2,300 g of 1,10-dodecanedioic acid, 2030 g of 1,10-dodecanediol, and 4.9 g of hydroquinone were added, and 180 ° C. Then, the temperature was raised to 200 ° C. and reacted for 3 hours, and further reacted at 8.3 kPa for 2 hours to obtain a crystalline polyester resin E. Table 1 shows the melting point, solubility in organic solvent, and molecular weight measurement results.

(Production Example 6; Synthesis of crystalline polyester resin F)
Into a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 2520 g of 1,10-terephthalic acid, 2880 g of 1,6-hexanediol, and 4.9 g of hydroquinone were added at 180 ° C. After making it react for 10 hours, it heated up at 200 degreeC, made it react for 3 hours, and also made it react at 8.3 kPa for 2 hours, and obtained the crystalline polyester resin F. Table 1 shows the melting point, solubility in organic solvent, and molecular weight measurement results.

(Production Example 7; Synthesis of crystalline polyester resin G)
Into a 5 liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple, 1920 g of fumaric acid, 2480 g of 1,6-hexanediol and 4.9 g of hydroquinone were added and reacted at 180 ° C. for 10 hours. Then, the temperature was raised to 200 ° C. and reacted for 3 hours, and further reacted at 8.3 kPa for 2 hours to obtain a crystalline polyester resin G. Table 1 shows the melting point, solubility in organic solvent, and molecular weight measurement results.

[Other binder resin synthesis]
(Production Example 8; Synthesis of polyester resin H)
In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 0.5 mol of bisphenol A propylene oxide adduct and bisphenol A ethylene oxide adduct 0. 5 mol was added as a carboxylic acid component, 0.9 mol of terephthalic acid, and tin octylate was added as an esterification catalyst, and subjected to a condensation polymerization reaction at 180 ° C. for 4 hours in a nitrogen atmosphere. Thereafter, 0.07 mol of trimellitic acid was added, the temperature was raised to 210 ° C., the mixture was reacted for 1 hour, and further reacted at 8 KPa for 1 hour to synthesize polyester resin H. Table 1 shows the melting point, solubility in organic solvent, and molecular weight measurement results.

(Confirmation of physical properties of binder resin)
Crystalline polyester resin A, crystalline polyester resin B, crystalline polyester resin C, crystalline polyester resin D, crystalline polyester resin E, crystalline polyester resin F, crystalline polyester resin G synthesized in Production Examples 1 to 8, The melting point and solubility of the polyester resin H were measured by the following methods and are summarized in Table 1.

(Evaluation of melting point of binder resin)
In addition, melting | fusing point of resin was calculated | required by measuring the maximum endothermic peak using TG-DSC system TAS-100 (made by Rigaku Corporation) which is a differential scanning calorimeter.

(Evaluation of solubility of crystalline polyester resin in organic solvents)
The solubility of the crystalline polyester resin in the organic solvent is determined by the following method.
First, 20 g of the crystalline polyester resin and 80 g of the organic solvent are stirred at a predetermined temperature for 1 hour.
Next, Kiriyama funnel (manufactured by Kiriyama Mfg. Co., Ltd.) was used. 4 (manufactured by Kiriyama Seisakusho) is set, and the solution after stirring using this is suction filtered at a predetermined temperature with an aspirator to separate the organic solvent and the crystalline polyester resin.
Furthermore, the separated organic solvent was heated for 1 hour at the boiling point of the organic solvent + 50 ° C. to evaporate the organic solvent, and the crystalline polyester resin dissolved in the organic solvent from the weight change before and after heating. The dissolution amount of is calculated.

[Preparation of dispersion of crystalline polyester resins A to G]
(Preparation of crystalline polyester dispersion A)
100 g of [Crystalline Polyester Resin A] and 400 g of ethyl acetate were placed in a metal 2 L container, heated and dissolved at 75 ° C., and then rapidly cooled in an ice water bath at a rate of 27 ° C./min. To this, 500 ml of glass beads (3 mmφ) was added, and pulverized for 10 hours with a batch-type sand mill apparatus (manufactured by Campehapio) to obtain [Crystalline Polyester Dispersion A]. The volume average particle size of the crystalline polyester resin A in the obtained crystalline polyester dispersion A was measured using a laser diffraction / scattering particle size distribution analyzer (LA-950, manufactured by Horiba Seisakusho). It was 56 μm.

(Preparation of crystalline polyester dispersion B)
[Crystalline Polyester Resin B] was obtained by changing [Crystalline Polyester Resin A] to [Crystalline Polyester Resin B] in the same manner as in the preparation of Crystalline Polyester Dispersion A. The volume average particle diameter of the crystalline polyester resin B measured by the same method as that for the crystalline polyester resin A was 0.52 μm.

(Preparation of crystalline polyester dispersion C)
[Crystalline Polyester Resin A] was obtained by changing [Crystalline Polyester Resin A] to [Crystalline Polyester Resin C] in the same manner as in the preparation of Crystalline Polyester Dispersion A. The volume average particle diameter of the crystalline polyester resin C measured by the same method as that for the crystalline polyester resin A was 0.59 μm.

(Preparation of crystalline polyester dispersion D)
[Crystalline Polyester Resin A] was obtained by changing [Crystalline Polyester Resin A] to [Crystalline Polyester Resin D] in the same manner as in the preparation of Crystalline Polyester Dispersion A. The volume average particle diameter of the crystalline polyester resin D measured by the same method as that for the crystalline polyester resin A was 0.60 μm.

(Preparation of crystalline polyester dispersion E)
[Crystalline Polyester Resin A] was obtained by changing [Crystalline Polyester Resin A] to [Crystalline Polyester Resin E] in the same manner as in preparation of Crystalline Polyester Dispersion A. The volume average particle diameter of the crystalline polyester resin E measured by the same method as that for the crystalline polyester resin A was 2.70 μm.

(Preparation of crystalline polyester dispersion F)
[Crystalline Polyester Resin A] was obtained by changing [Crystalline Polyester Resin A] to [Crystalline Polyester Resin F] in the same manner as in preparation of Crystalline Polyester Dispersion A. The volume average particle diameter of the crystalline polyester resin F measured by the same method as that for the crystalline polyester resin A was 0.53 μm.

(Preparation of crystalline polyester dispersion G)
[Crystalline Polyester Resin G] was obtained by changing [Crystalline Polyester Resin A] to [Crystalline Polyester Resin G] in the same manner as in preparation of Crystalline Polyester Dispersion A. The volume average particle diameter of the crystalline polyester resin G measured by the same method as that for the crystalline polyester resin A was 0.58 μm.

(Preparation of crystalline polyester dispersion A-1)
[Crystalline Polyester Dispersion A] is pulverized for 5 hours in a batch type sand mill apparatus (manufactured by Campehapio) in the same manner as in the preparation of Crystalline Polyester Dispersion A. Dispersion A-1], and the volume average particle diameter of the crystalline polyester resin A in the obtained crystalline polyester dispersion A-1 was 2.98 μm.

(Preparation of colorant dispersion)
First, a carbon black dispersion as a colorant was prepared.
17 parts by mass of carbon black (Rega L400; manufactured by Cabot) and 3 parts by mass of a pigment dispersant were primarily dispersed in 80 parts by mass of ethyl acetate using a mixer having stirring blades.
As the pigment dispersant, Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The obtained primary dispersion is finely dispersed by a strong shearing force using a bead mill (LMZ type manufactured by Ashizawa Finetech Co., Ltd., zirconia bead diameter 0.3 mm), and the secondary dispersion in which aggregates of 5 μm or more are completely removed. A liquid was prepared.

(Adjustment of release agent dispersion)
Next, a release agent dispersion was prepared.
Carnauba release agent 18 parts by mass and release agent dispersant 2 parts by mass were primarily dispersed in 80 parts by mass of ethyl acetate using a mixer having stirring blades. The primary dispersion was heated to 80 ° C. while stirring to dissolve the carnauba release agent, and then the temperature of the solution was lowered to room temperature to precipitate release agent particles so that the maximum diameter was 3 μm or less. As the release agent dispersant, a polyethylene release agent obtained by grafting a styrene-butyl acrylate copolymer was used. The obtained dispersion was further finely dispersed by a strong shearing force using a bead mill (LMZ type manufactured by Ashizawa Finetech Co., Ltd., zirconia bead diameter 0.3 mm), and the maximum diameter was adjusted to 1 μm or less.

[Preparation of dispersion liquid (toner composition liquid)]
(Adjustment of toner composition liquid A)
Next, as shown in Table 2, 20 parts of the crystalline polyester resin A, 80 parts of the polyester resin H as another resin, 10 parts of a carbana wax release agent, the release agent dispersant Each dispersion liquid or solution was mixed so that the colorant (carbon crack) was 5 parts, and stirred for 10 minutes using a mixer having stirring blades to uniformly disperse. The crystalline polyester, pigment, and release agent particles were not aggregated by shock due to solvent dilution.

(Adjustment of toner composition liquid A-1)
Each dispersion or solution was mixed so that the crystalline polyester resin, polyester resin H, carbana wax release agent, release agent dispersant, and colorant as shown in Table 2 were in the proportions shown in the table. Thereafter, the same treatment as in the case of the toner composition liquid A was performed to prepare the toner composition liquid A-1.
The dispersibility of the crystalline polyester and other components (toner materials such as pigments and release agent particles) in the toner composition liquid was as follows.
That is, <Method for Confirming Dispersion State of Crystalline Polyester Resin in Prepared Toner Composition Liquid> Toner composition liquids A to H and A-1 are each placed in a 30 ml sample bottle and allowed to stand for a certain period of time to form crystalline polyester. The aggregation and sedimentation of the resin was visually observed.
[Evaluation criteria]
○: The aggregation and precipitation of the crystalline polyester resin cannot be confirmed even after 24 hours or more. Δ: The aggregation and precipitation of the crystalline polyester resin was confirmed within 5 hours. ×: The aggregation and precipitation of the crystalline polyester resin was confirmed within 1 hour. The results are shown in Table 2 (the same applies to other examples).

(Adjustment of toner composition liquid B)
Each dispersion or solution was mixed so that the crystalline polyester resin, polyester resin H, carbana wax release agent, release agent dispersant, and colorant as shown in Table 2 were in the proportions shown in the table. Thereafter, the same processing as in the case of the toner composition liquid A was performed to prepare the toner composition liquid B. The crystalline polyester, pigment, and release agent particles were not aggregated by shock due to solvent dilution.

(Adjustment of toner composition liquid C)
Each dispersion or solution was mixed so that the crystalline polyester resin, polyester resin H, carbana wax release agent, release agent dispersant, and colorant as shown in Table 2 were in the proportions shown in the table. Thereafter, the same processing as in the case of the toner composition liquid A was performed to prepare the toner composition liquid C. The crystalline polyester, pigment, and release agent particles were not aggregated by shock due to solvent dilution.

(Adjustment of toner composition liquid D)
Each dispersion or solution was mixed so that the crystalline polyester resin, polyester resin H, carbana wax release agent, release agent dispersant, and colorant as shown in Table 2 were in the proportions shown in the table. Thereafter, the same treatment as in the case of the toner composition liquid A was performed to prepare the toner composition liquid D. The crystalline polyester, pigment, and release agent particles were not aggregated by shock due to solvent dilution.

(Adjustment of toner composition liquid E)
Each dispersion or solution was mixed so that the crystalline polyester resin, polyester resin H, carbana wax release agent, release agent dispersant, and colorant as shown in Table 2 were in the proportions shown in the table. Thereafter, the same treatment as in the case of the toner composition liquid A was performed to prepare a toner composition liquid E. Table 2 shows the dispersibility of the crystalline polyester and other components (toner materials such as pigments and release agent particles) in the toner composition liquid.

(Adjustment of toner composition liquid F)
Each dispersion or solution was mixed so that the crystalline polyester resin, polyester resin H, carbana wax release agent, release agent dispersant, and colorant as shown in Table 2 were in the proportions shown in the table. Thereafter, the same processing as in the case of the toner composition liquid A was performed to prepare the toner composition liquid F. Table 2 shows the dispersibility of the crystalline polyester and other components (toner materials such as pigments and release agent particles) in the toner composition liquid.

(Adjustment of toner composition liquid G)
Each dispersion or solution was mixed so that the crystalline polyester resin, polyester resin H, carbana wax release agent, release agent dispersant, and colorant as shown in Table 2 were in the proportions shown in the table. Thereafter, the same treatment as in the case of the toner composition liquid A was performed to prepare the toner composition liquid G. Table 2 shows the dispersibility of the crystalline polyester and other components (toner materials such as pigments and release agent particles) in the toner composition liquid.

(Adjustment of toner composition liquid H)
After mixing each dispersion or solution such that the polyester resin H, carbana wax release agent, release agent dispersant, and colorant as shown in Table 2 are in the proportions shown in the table, the toner composition solution The same treatment as in the case of A was performed to prepare a toner composition liquid H. Table 2 shows the dispersibility of the crystalline polyester and other components (toner materials such as pigments and release agent particles) in the toner composition liquid.

Example 1 Production of Toner Base Particle A
Using the toner production apparatus shown in FIGS. 1 to 3, the toner composition liquid A was ejected with the droplets by the droplet ejection head using the liquid column resonance principle shown in FIG. 3 under the following conditions. Thereafter, the liquid droplets were dried and solidified, collected by a cyclone, and then secondarily dried at 35 ° C. for 48 hours to prepare toner base particles A.
[Liquid column resonance conditions]
Resonance mode: N = 2
Length between both ends in the longitudinal direction of the liquid column resonance liquid chamber: L = 1.8 mm
Height of end of frame on liquid common supply path side of liquid column resonance liquid chamber: h1 = 80 μm
The height of the communication port of the liquid column resonance liquid chamber: h2 = 40 μm
[Toner base particle preparation conditions]
Dispersion specific gravity: ρ = 1.1 g / cm 3
Discharge port shape: perfect circle Discharge port diameter: 7.5μm
Number of discharge ports: 4 per liquid column resonance liquid chamber Minimum distance between adjacent discharge ports: 130 μm (all at equal intervals)
Dry air temperature: 40 ° C
Applied voltage: 10.0V
Drive frequency: 395 kHz

[Preparation of Toner A]
To 100 parts by mass of the toner base particles 1-1, 1.0 part by mass of hydrophobic silica (H2000, manufactured by Clariant Japan Co.) as a fluidity improver and titanium oxide (SMT-150AI, manufactured by Teika Co., Ltd.) 1 0.0 part by mass was subjected to an external addition treatment using a Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) to obtain toner A. The nozzle clogging during the injection was observed, and the results are summarized in Table 3.

Example 2 Production of Toner Base Particle B
Toner base particle B was prepared by changing toner composition liquid A of Example 1 to toner composition liquid B, and toner B was obtained. The nozzle clogging during the injection was observed, and the results are summarized in Table 3.

Example 3 Production of Toner Base Particle C
Toner base particle C was prepared by changing toner composition liquid A of Example 1 to toner composition liquid C, and toner C was obtained. The nozzle clogging during the injection was observed, and the results are summarized in Table 3.

Example 4 Production of Toner Base Particle D
Toner D was obtained by changing toner composition liquid A of Example 1 to toner composition liquid D to produce toner base particles D. The nozzle clogging during the injection was observed, and the results are summarized in Table 3.

[Comparative Example 1; Preparation of toner base particles E]
Toner base particle E was produced by changing toner composition liquid A of Example 1 to toner composition liquid E, and toner E was obtained. The nozzle clogging during the injection was observed, and the results are summarized in Table 3.

[Comparative Example 2; Preparation of toner base particles F]
The toner composition liquid A of Example 1 was changed to the toner composition liquid F to produce toner base particles F, and toner F was obtained. The nozzle clogging during the injection was observed, and the results are summarized in Table 3.

[Comparative Example 3; Preparation of toner base particles G]
The toner composition liquid A of Example 1 was changed to the toner composition liquid G to produce toner base particles G, and a toner G was obtained. The nozzle clogging during the injection was observed, and the results are summarized in Table 3.

[Comparative Example 4; Preparation of toner base particles H]
The toner composition liquid A of Example 1 was changed to the toner composition liquid H to produce toner base particles H, and toner H was obtained. The nozzle clogging during the injection was observed, and the results are summarized in Table 3.

[Comparative Example 5; Preparation of toner base particle A-1]
Toner A-1 was obtained by changing toner composition liquid A of Example 1 to toner composition liquid A-1 to produce toner base particles A-1. The nozzle clogging during the injection was observed, and the results are summarized in Table 3.

(Creation of carrier)
The following composition was dispersed with a homomixer for 20 minutes to prepare a coating layer forming solution. This coating layer forming liquid was coated on the surface of 1,000 parts by mass of spherical magnetite having a particle diameter of 40 μm using a fluid bed type coating apparatus to obtain a magnetic carrier.
[composition]
Silicone resin (organostraight silicone) 100 parts by mass Toluene 100 parts by mass γ- (2-aminoethyl) aminopropyltrimethoxysilane 5 parts by mass Carbon black 10 parts by mass

(Development of developer)
For each of toner A to toner H and toner A-1, 4 parts by mass of black toner and 96 parts by mass of the magnetic carrier were mixed by a ball mill to prepare a two-component developer.
Each two-component developer was evaluated for the minimum fixing temperature, the maximum fixing temperature, the particle size distribution, and the clogging of the discharge ports by the following method.

(Evaluation of minimum fixing temperature)
Each of the produced two-component developers is put in a commercially available copying machine (Imagiono 455, manufactured by Ricoh Co., Ltd.), and the fixing temperature is increased every 100 degrees to 10 degrees, and the image is printed on paper (type 6000 paper, manufactured by Ricoh Co., Ltd.) Was output. The output image was rubbed by hand, and the temperature at which the toner could not be peeled was evaluated as the minimum fixing temperature.
[Evaluation criteria]
A: Fixing lower limit temperature is 125 ° C. or less ○: Fixing lower limit temperature is 130 ° C.
Δ: Fixing lower limit temperature is 135 ° C.
×: The minimum fixing temperature is 140 ° C. or higher.

(Evaluation of maximum fixing temperature)
Each of the produced two-component developers is put in a commercially available copying machine (Imagiono 455, manufactured by Ricoh Co., Ltd.), and an image is printed on paper (type 6000 paper, manufactured by Ricoh Co., Ltd.) while changing the fixing temperature from low temperature to high temperature. Output. Evaluation was made on the basis of the following evaluation criteria, with −5 ° C. being the fixing upper limit temperature from the temperature at which the glossiness of the output image was reduced or the temperature at which the offset image was observed in the image.
[Evaluation criteria]
A: Fixing upper limit temperature is 190 ° C. or higher. O: Fixing upper limit temperature is 185 ° C.
Δ: Fixing upper limit temperature is 180 ° C.
×: Fixing upper limit temperature is less than 180 ° C

(Evaluation of particle size distribution)
The volume average particle diameter (Dv) and number average particle diameter (Dn) of the toners A, B, C, D, E, F, G, H, and A-1 are measured by a particle size measuring device (Multisizer III, manufactured by Beckman Coulter, Inc.). ) Using an analysis software (Beckman Coulter Multisizer 3 Version 3.51).
Specifically, 0.5 mL of 10 mass% surfactant (alkylbenzene sulfonate Neogen SC-A, Daiichi Kogyo Seiyaku Co., Ltd.) was added to a glass beaker (100 mL volume). Next, 0.5 g of each toner was added, and after stirring with microspatel, 80 mL of ion-exchanged water was added. Subsequently, the dispersion process was performed for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.).
This dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner dispersion was dropped such that the concentration indicated by the Multisizer III was 8 ± 2%. The target particle size was 2.001 μm or more and 20.1874 μ or less.

  After measuring the volume and number of toner particles or toner, the volume distribution and number distribution were calculated. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner were determined. As an index of the particle size distribution, Dv / Dn obtained by dividing the volume average particle diameter (Dv) of the toner by the number average particle diameter (Dn) was used. If it is completely monodispersed, Dv / Dn = 1, and the larger this value, the wider the distribution.

(Evaluation of clogging of discharge port when each toner composition liquid is ejected)
When the toner base particles were produced, the droplet discharge head was observed with a CCD camera, and it was confirmed whether or not the discharged droplets were discharged from the discharge port, and the clogging of the discharge port was evaluated.
[Evaluation criteria]
○: Continuous droplet formation without clogging at the discharge port for 3 hours ×: Clogging occurred at 50% or more of the discharge ports in 1 hour

(Filming evaluation)
The image forming apparatus MF2800 (manufactured by Ricoh Co., Ltd.) was used to visually inspect the photoconductor after 10,000 images were formed, and the toner component, mainly the release agent, was fixed to the photoconductor. It was evaluated according to the following evaluation criteria.
[Filming evaluation criteria]
A: The toner component is not fixed to the photoconductor. A: The toner component is fixed to the photoconductor. However, this is not a practical problem. Δ: The toner component is fixed to the photoconductor. , Is a level that causes a problem in practical use. ×: The toner component can be firmly fixed to the photosensitive member, and is a level having a large problem in practical use.

In the toners A to D of Examples A to D, the toner could be suitably formed into droplets without clogging the discharge port in the continuous droplet formation for 3 hours.
On the other hand, in Comparative Examples E and A-1, some of the discharge ports were clogged when the toner droplets were formed, and the toner composition liquid could not be dropletized.
When the discharge ports where clogging of Comparative Examples E and A-1 occurred were analyzed, the crystalline polyester resin E and the crystalline polyester resin A were the main components, respectively. One reason is that the ratio of the dispersion diameter (volume average particle diameter) of the crystalline polyester resins E and A-1 in the toner composition liquid to the opening diameter of the discharge port was outside the range of 1% to 30%. There may be.

  The crystalline polyester resin at the discharge port was analyzed by a microscopic laser Raman spectroscope and identified by comparison with each toner component.

From the results of Table 3, in Examples A to D, a small particle diameter toner having a narrow particle size distribution with Dv / Dn of 1.10 or less was obtained, and low temperature fixing was possible.
On the other hand, in Comparative Examples F, G, and H, although the upper limit fixing temperature was good, the lower limit fixing temperature was relatively high, and a toner capable of low temperature fixing could not be obtained. In Comparative Examples E, F, G, and A-1, filming occurred.

  The toner production method of the present invention is excellent in toner productivity because it can discharge the toner composition liquid stably for a long time without clogging the discharge port when discharging the toner composition liquid. It can be seen that a toner having a diameter and excellent low-temperature fixability and having no filming can be obtained.

DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet discharge means 3 Nozzle plate 6 Toner component liquid supply port 7 Toner component liquid flow path 8 Toner component liquid discharge port 9 Elastic plate 10 Liquid column resonance droplet discharge unit 11 Liquid column resonance droplet discharge means 12 Airflow path 13 Raw material container 14 Toner component liquid 15 Liquid circulation pump 16 Liquid supply pipe 17 Liquid common supply path 18 Liquid column resonance flow path 19 Nozzle 20 Vibration generating means 21 Liquid droplet 22 Liquid return pipe 23 Merged liquid droplet 24 Nozzle angle 25 Jet Cleaning Means 60 Dry Collecting Means 61 Chamber 62 Toner Collecting Means 63 Toner Storage Unit 64 Conveying Air Flow Inlet 65 Conveying Air Flow Outlet P1 Liquid Pressure Gauge P2 In-Chamber Pressure Gauge

JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977 JP 05-045929 A JP 11-249339 A JP 2001-117268 A JP 2001-222138 A JP-A-8-176310 Japanese Patent Laid-Open No. 2005-15589

Claims (9)

  A standing wave by liquid column resonance is formed by applying vibration to the toner composition liquid in the liquid column resonance liquid chamber in which at least one or more discharge ports are formed, and the standing wave is disposed in an area that becomes an antinode of the standing wave. A droplet forming step of discharging the toner composition liquid from the discharge port, wherein the toner composition liquid is obtained by dissolving or dispersing a toner composition containing a binder resin and a colorant in an organic solvent. Is solidified, and the binder resin contains at least a crystalline polyester resin, and the crystalline polyester resin is dispersed in the toner composition liquid before droplet formation. A method for producing a toner.   The crystalline polyester resin contains at least a divalent alcohol component and a divalent acid component, and at least one of the divalent alcohol component and the divalent acid component contains at least two types of monomers. The method for producing a toner according to claim 1, wherein:   The ratio of the dispersed diameter (volume average particle diameter) of the crystalline polyester resin in the toner composition liquid to the opening diameter of the discharge port is 1% or more and 30% or less. Toner production method.   4. The toner production method according to claim 1, wherein the binder resin contains 3% by mass to 50% by mass of a crystalline polyester resin. 5.   5. The toner manufacturing method according to claim 1, wherein the solubility of the crystalline polyester resin at 70 ° C. with respect to 100 parts by mass of the organic solvent is 10 parts by mass or more.   6. The toner manufacturing method according to claim 1, wherein the crystalline polyester resin has a melting point of 65 ° C. or higher and lower than 75 ° C. 6.   The crystalline polyester resin has a GPC molecular weight distribution by GPC of 3000 to 30000 in weight average molecular weight (Mw), 1000 to 10000 in number average molecular weight (Mn), and 1 to 10 in Mw / Mn. The toner manufacturing method according to claim 1, wherein the toner manufacturing method is a toner.   A toner obtained by the method for producing a toner according to claim 1, having a weight average particle diameter of 1 μm to 10 μm and a particle size distribution (weight average particle diameter / number average particle diameter) of 1 to 1.10. A toner characterized by being in the range.   A developer comprising at least the toner according to claim 8 and a carrier.

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