JP2014166628A - Method for producing grain, grain production device, and grain - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing particles, in the method of producing particles by an injection granulation method, capable of preventing the coalescence of droplets each other after spraying and stably achieving a narrower grain size distribution.SOLUTION: The method for producing grains comprises: a droplet discharge step of discharging a grain component liquid from at least one discharge hole and making the same into droplets; and a solidification step of solidifying the droplets, where a nozzle for droplet formation and an opening for an air flow addition are formed into the nozzle plate of a droplet discharging means used for the droplet discharge step.

Description

  The present invention relates to a particle production method, a particle production apparatus, and a particle production apparatus capable of producing a toner for developing an electrostatic image used for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like. This relates to the particles obtained.

Conventionally, toner for developing electrostatic images used in copying machines, printers, fax machines and their combined machines based on the electrophotographic recording method has been manufactured by a pulverization method.
However, in recent years, a production method called toner polymerization in which toner particles are formed in an aqueous medium has been widely adopted, and has surpassed the pulverization method. The toner produced by the polymerization method is called “polymerized toner” or “chemical toner” in some countries.
The polymerization method is referred to as such because it involves a polymerization reaction of the toner material at the time of toner particle formation or in the toner particle formation process. Various polymerization methods have been put to practical use in the polymerization method. Examples of the polymerization method include suspension polymerization, emulsion aggregation, polymer suspension (polymer aggregation), and ester elongation reaction.

  The toner obtained by the polymerization method generally has the characteristics that a small particle size is easily obtained, the particle size distribution is narrow, and the shape is almost spherical compared with the toner obtained by the pulverization method. For this reason, the use of the toner obtained by the polymerization method has an advantage that it is easy to obtain high image quality in an electrophotographic image. However, on the other hand, it takes a long time for the polymerization process, and after solidification, it is necessary to separate the solvent and toner particles, and then repeat washing and drying, which requires a lot of time and a large amount of water and energy. There is a problem.

  Therefore, a liquid in which a toner material is dissolved or dispersed in an organic solvent (hereinafter sometimes referred to as “toner component liquid”) is made into fine particles using various atomizers and then dried to obtain a powdery toner. An injection granulation method is known (see, for example, Patent Documents 1 to 3). According to this method, since it is not necessary to use water, steps such as washing and drying can be greatly reduced, so that problems in the polymerization method can be avoided.

  In the toner manufacturing methods disclosed in Patent Documents 1 to 3, droplets corresponding to the diameter of the discharge hole are discharged from the discharge hole. In such a manufacturing method, after spraying the toner component liquid, the droplets coalesce before the formed droplets are dried, and the solvent is dried in that state to obtain a toner. As a result, the spread of the particle size distribution of the obtained toner is inevitable, and the toner particle size distribution is not satisfactory.

  The present invention has been made in view of the above problems, and in the method of producing particles by the spray granulation method, the coalescence of droplets after spraying is prevented, and a narrower particle size distribution is stably realized. The object is to provide a process for the production of possible particles.

  The above problem is a method for producing particles according to the present invention, which includes a droplet discharge step of discharging a particle component liquid from at least one discharge hole to form droplets and a solidifying step of solidifying the droplets. The particle manufacturing method is characterized in that a droplet forming nozzle and an airflow adding opening are formed in a nozzle plate of a droplet discharging means used in the droplet discharging step. Can do.

  According to the manufacturing method of the present invention, the droplets can be miniaturized as quickly as possible, so that the interval between the droplets is maintained and the size of the particles themselves is miniaturized. That is, the coalescence probability of the droplets is lowered, and the generation of coarse particles due to the coalescence can be suppressed, and as a result, more uniform particles can be stably obtained. Further, the toner obtained by the production method of the present invention has a very uniform particle size distribution, can use raw materials without waste, and can obtain a higher-definition image at low cost.

It is sectional drawing which shows the structure of a liquid column resonance droplet discharge means. It is sectional drawing which shows the structure of a droplet discharge part. It is the schematic which shows the shape of the standing wave of the speed and pressure fluctuation in the case of N = 1, 2, 3. It is the schematic which shows the shape of 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 discharge means. It is a figure which shows the mode of the actual droplet discharge in a liquid column resonance droplet discharge means. It is a characteristic view which shows a drive frequency and a droplet discharge speed frequency characteristic. It is the figure which showed the coalescence prevention effect by the droplet position immediately after nozzle discharge, and lateral airflow addition. It is the figure which showed the operation | movement of the droplet immediately after discharge by an additional airflow. It is a figure which shows two examples of arrangement | positioning of the nozzle for droplet formation and the opening part for airflow addition which are arrange | positioned on the nozzle plate plane. FIG. 10A illustrates an example in which the airflow adding opening is formed of a slit, and FIG. 10B illustrates an example in which the airflow adding opening is formed of a plurality of nozzles. It is the sectional view on the aa line in FIG. 1 is a schematic diagram illustrating an entire toner manufacturing apparatus. 6 is a graph showing the particle size distribution of toner collected for about 10 minutes at an additional air flow pressure of 0.5 atm and collected through a dry air flow path. It is the graph which showed the particle size distribution of the toner which carried out about 10 minutes by making additional airflow pressure into 1.0 atmosphere, and was collected through the dry air flow path.

EMBODIMENT OF THE INVENTION Below, the form for implementing this invention is demonstrated based on drawing.
Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. . The following description is an example of an embodiment of the present invention, and does not limit the scope of the claims.

The method for producing particles according to the present invention is a method for producing particles comprising: a droplet discharge step for discharging a particle component liquid from at least one discharge hole to form droplets; and a solidification step for solidifying the droplets. is there. A droplet forming nozzle and an airflow adding opening are formed in a nozzle plate of a droplet discharge means used in the droplet discharge step.
In the present invention, a liquid containing a component that forms the particles to be obtained is discharged from the droplet discharge means. In the present invention, a liquid containing a component that forms the particles is referred to as a particle component liquid. The particle component liquid may be a liquid under the conditions for discharging. Therefore, the particle component liquid may be in a state where the particle components are dissolved or dispersed in a solvent, or may be in a state where the particle component is melted without containing the solvent.

  As described above, the droplet forming nozzle and the airflow adding opening are integrally formed on the nozzle plate of the droplet discharge means, so that the droplet forming nozzle and the airflow adding opening are arranged at high density. In addition, the discharge nozzle surface can be easily cleaned. Further, since the airflow adding opening is formed in the nozzle plate, the liquid droplets formed by discharging from the droplet forming nozzle are united by the airflow supplied from the airflow adding opening. This can be suppressed.

  The particle manufacturing apparatus of the present invention is a particle manufacturing apparatus having a droplet discharge means for discharging a particle component liquid from at least one discharge hole into droplets and a solidifying means for solidifying the droplets. . A droplet forming nozzle and an airflow adding opening are formed in the nozzle plate of the droplet discharge means. According to the particle production apparatus of the present invention, particles with good uniformity can be collected stably and with high efficiency.

In the particle production method of the present invention and the particle production apparatus of the present invention, toner particles can be produced by using a toner component liquid as the particle component liquid. Since the toner thus obtained can be stably manufactured without being united, it can be made inexpensive and highly uniform in particle size.
Hereinafter, the method for producing particles and the apparatus for producing particles will be described by taking a toner production method and a toner production apparatus applied to toner as an example. In this case, the particle component liquid is referred to as a toner component liquid.

  An example of a manufacturing apparatus capable of carrying out the toner manufacturing method of the present invention will be described below with reference to FIGS. The toner manufacturing apparatus according to the present invention is divided into a droplet discharge unit and a droplet drying / collecting unit (solidification unit). Each will be described 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, and liquid column resonance type discharge means.
Among them, the liquid in the liquid column resonance liquid chamber in which a plurality of discharge holes are formed is vibrated to form a standing wave by liquid column resonance, and the discharge hole formed in the region that becomes the antinode of this standing wave. The liquid droplet resonance which ejects liquid is excellent in mass productivity from the aspect of high frequency and multi-nozzle arrangement.

[Liquid column resonance droplet discharge means]
Hereinafter, a liquid column resonance type droplet discharge unit that discharges a droplet using resonance of the liquid column will be described.
FIG. 1 is a cross-sectional view showing the configuration of the liquid column resonance droplet discharge means. The liquid column resonance droplet discharge means 11 shown in FIG. 1 includes a liquid common supply path 17 and a liquid column resonance liquid chamber 18. 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 provided on a wall surface facing the discharge hole 19 and a discharge hole 19 for discharging the droplet 21 to one wall surface of the wall surfaces connected to both ends. Vibration generating means 20 for generating high-frequency vibrations to form standing waves. The vibration generating means 20 is connected to a high frequency power source (not shown).

  The toner component liquid 14 flows into the liquid common supply path 17 of the liquid column resonance droplet forming unit 10 shown in FIG. 2 through the liquid supply pipe by the liquid circulation pump 15 shown in FIG. It is supplied to the liquid column resonance liquid chamber 18 of the liquid column resonance droplet discharge means 11 shown. A pressure distribution is formed in the liquid column resonance liquid chamber 18 filled with the toner component liquid 14 by the liquid column resonance standing wave generated by the vibration generating means 20. Then, the droplet 21 is ejected from the ejection hole 19 arranged in a region where the amplitude of the liquid column resonance standing wave is large and the pressure fluctuation is large and which is an 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 there are a plurality of discharge holes, substantially uniform droplets can be formed from each, and moreover, the droplets can be discharged efficiently. And clogging of the discharge holes is less likely to occur.

  The toner component liquid 14 that has passed through the liquid common supply path 17 flows through a liquid return pipe (not shown) and is returned to the raw material container 13 shown in FIG. 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 droplets 21, a suction force due to the action of the liquid column resonance standing wave in the liquid column resonance liquid chamber 18 acts, and the liquid common supply The flow rate of the toner component liquid 14 supplied from the path 17 increases. As a result, 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 has a frame formed of a material having such a high rigidity that does not affect the resonance frequency of the liquid at the driving frequency, such as metal, ceramics, and silicon. Each is formed by bonding. 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.
FIG. 2 is a cross-sectional view (liquid chamber layer) of the configuration example of the liquid column resonance droplet forming unit as viewed from the ejection surface side. An airflow is supplied from the upper part in the figure, and the airflow is discharged from an airflow nozzle at a position indicated by 12. Ink liquid is supplied from the lower liquid common supply path 17 in the figure, and droplets are ejected from a nozzle disposed at a position indicated by 19. (In addition, 12 and 19 show a nozzle position and are joined in alignment on this liquid chamber.)
Further, it is desirable that the width W of the liquid column resonance liquid chamber 18 is smaller than a half 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.

  Furthermore, it is preferable that a plurality of liquid column resonance liquid chambers 18 are arranged for one liquid column resonance droplet forming unit 10 in order to dramatically improve productivity. The range is not limited, but one liquid column resonance droplet forming unit provided with 100 to 2000 liquid column resonance liquid chambers 18 is more 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 from the common liquid supply path 17, and the common liquid supply path 17 communicates with a plurality of liquid column resonance liquid chambers 18. .

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 a form in which a piezoelectric body is bonded to an elastic plate 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), and are generally used in a stacked manner because the displacement is small. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO _3, and KNbO ₃ can be used. Furthermore, it is desirable that the vibration generating means 20 is arranged so that it can be individually controlled 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 hole 19 is desirably in the range of 1 to 40 μm. When the diameter of the opening is 1 μm or more, it is possible to prevent the droplets from becoming too small and obtain an appropriately sized toner. Even in the case where the toner contains a solid fine particle such as a pigment as a constituent component of the toner, the discharge hole 19 is not clogged, and the productivity can be improved. Moreover, it can prevent that the diameter of a droplet becomes large too much because it is 40 micrometers or less. As a result, the toner component liquid can be dried and solidified without significantly diluting to obtain a toner having a desired particle diameter of 3 to 6 μm. Since it is not necessary to dilute the toner component liquid significantly with an organic solvent to make a very dilute liquid, the amount of the organic solvent used for dilution can be reduced. Furthermore, the drying energy required to obtain a certain amount of toner can be reduced. Further, as can be seen from FIG. 2, by adopting a configuration in which the discharge holes 19 are provided in the width direction in the liquid column resonance liquid chamber 18, a large number of openings of the discharge holes 19 can be provided, thereby increasing the production efficiency. Therefore, it is preferable. Further, since the liquid column resonance frequency varies depending on the arrangement of the discharge holes 19, it is desirable to appropriately determine the liquid column resonance frequency after confirming the discharge of the droplet.

Next, the mechanism of droplet formation by the liquid column resonance droplet forming unit in the toner manufacturing apparatus of the present invention will be described.
First, the principle of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber 18 in the liquid column resonance droplet discharge means 11 of FIG. 1 will be described. Wavelength λ at which liquid resonance occurs, where c is the speed of sound of the toner component liquid 14 in the liquid column resonance liquid chamber 18 and f is the drive frequency applied from the vibration generating means 20 to the toner component liquid 14 as a medium. Is
λ = c / f (Formula 1)
Are in a relationship.

Further, in the liquid column resonance liquid chamber 18 shown in 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 end of the frame on the liquid common supply path 17 side. The height h1 (= about 80 μm) of the part is about twice the height h2 (= about 40 μm) of the communication port, and the end is equivalent to the closed fixed end. The resonance is most efficiently formed when the length L matches an even multiple of a quarter of the wavelength λ. That is, it is expressed by the following formula 2.
L = (N / 4) λ (Expression 2)
(However, N is an even number.)

Furthermore, the above formula 2 is also established in the case of a double-sided open end 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 4 of the wavelength λ. A resonance is most efficiently formed when it matches an odd multiple of a fraction. That is, this is a case where N in Equation 2 is an odd number.

The most efficient drive frequency f is obtained 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, the vibration is not amplified infinitely. It has a Q value, and as shown in equations 4 and 5 described later, Resonance also occurs at frequencies near the highly efficient drive frequency f.

  FIG. 3 is a schematic diagram showing the shape of the standing wave of the velocity and pressure fluctuation (resonance mode) when N = 1, 2, and 3. FIG. 4 shows the velocity and pressure when N = 4 and 5. It is the schematic which shows the shape (resonance mode) of the standing wave of a fluctuation | variation. The standing wave is originally a sparse / dense wave (longitudinal wave), but is generally expressed as shown in FIGS. 3 and 4, 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 one-side fixed end with N = 1, the velocity distribution has an amplitude of zero at the closed end and a maximum amplitude at the open end, which is intuitively easy to understand. . When the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 is L, the wavelength at which the liquid resonates is λ, and the standing wave is generated most efficiently when the integer N is 1 to 5. To do. Further, since the standing wave pattern varies depending on the open / closed state of both ends, they are also shown in FIGS. 3 and 4. As will be described later, the condition of the end is determined by the state of the opening of the discharge hole and the opening on the supply side.

  In acoustics, the open end is an end where the moving speed of the medium (liquid) in the longitudinal direction becomes maximum, and conversely, the pressure becomes minimum. 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 resonance standing wave having a form as shown in FIGS. 3 and 4 is generated by superposition of waves. However, the standing wave pattern varies depending on the number of ejection holes and the opening position of the ejection holes, and the resonance frequency appears at a position deviated from the position obtained from the above Equation 3. However, the stable ejection condition can be adjusted by appropriately adjusting the driving frequency. Can produce.

  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, and N = 2 resonance that is completely equivalent to the fixed ends on both sides. When the mode is used, the resonance frequency with the highest efficiency is derived as 324 kHz from Equation 2 above. In another 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, the same conditions as described above, wall surfaces are present at both ends, and equivalent to both fixed ends. When N = 4 resonance mode is used, the most efficient resonance frequency is derived as 648 kHz from Equation 2 above. Thus, higher-order resonance can be used even in a liquid column resonance liquid chamber having the same configuration.

  The liquid column resonance liquid chamber 18 in the liquid column resonance droplet discharge means 11 shown in FIG. 1 can be described as an acoustically soft wall because both ends are equivalent to the closed end state or due to the influence of the opening of the discharge hole. The end portion is preferable for increasing the frequency, but is not limited thereto, and may be an open end. The influence of the opening of the discharge hole here means that the acoustic impedance is reduced, and in particular, the compliance component is increased. Therefore, the structure in which the wall surfaces are formed at both ends in the longitudinal direction of the liquid column resonance liquid chamber as shown in FIG. 3B and FIG. 4A is the resonance mode at both fixed ends, and one side where the discharge hole side is regarded as an opening. This is a preferred configuration because all resonance modes at the open end can be used.

  Further, the numerical aperture of the discharge holes, the opening arrangement position, and the cross-sectional shape of the discharge holes are also factors that determine the drive frequency, and the drive frequency can be appropriately determined according to this factor. For example, when the number of ejection holes is increased, the restriction at the tip of the liquid column resonance liquid chamber that was the fixed end gradually becomes loose, a resonance standing wave that is almost close to the opening end is generated, and the drive frequency increases. Furthermore, it becomes a loose constraint condition starting from the opening arrangement position of the discharge hole existing on the most liquid supply path side, and the discharge hole volume varies depending on the round shape of the discharge hole or the thickness of the frame, The actual 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 hole closest to the end on the liquid supply side is Le, the following formula is obtained by the length of both L and Le. It is possible to eject the liquid droplets from the ejection holes by oscillating the vibration generating means using a driving waveform whose main component is the driving frequency f in the range determined by Equations 4 and 5 to induce liquid column resonance. .

N × c / (4L) ≦ f ≦ N × c / (4Le) (Formula 4)
N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le) (Formula 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 hole closest to the end on the liquid supply side is preferably Le / L ≧ 0.6. .

  A liquid column resonance pressure standing wave is formed in the liquid column resonance liquid chamber 18 of FIG. 1 using the principle of the liquid column resonance phenomenon described above, and the discharge holes 19 arranged in a part of the liquid column resonance liquid chamber 18. In this case, droplet discharge occurs continuously. Note that it is preferable to dispose the discharge hole 19 at a position where the pressure of the standing wave fluctuates the most, since the discharge efficiency is increased and the driving can be performed with a low voltage. Further, one discharge hole 19 may be provided for one liquid column resonance liquid chamber 18, but it is preferable to arrange a plurality of discharge holes 19 from the viewpoint of productivity. Specifically, it is preferable that 2 to 100 are formed in one liquid column resonance liquid chamber 18.

  When the number of discharge holes is 100 or less, the voltage applied to the vibration generating means 20 when a desired droplet is formed from the discharge holes 19 can be kept low, and the piezoelectric body as the vibration generating means 20 can be suppressed. The behavior can be stabilized. Further, when the plurality of discharge holes 19 are opened, the pitch between the discharge holes 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 holes is 20 μm or more and not more than the length of the liquid column resonance liquid chamber, it is possible to reduce the probability that the droplets discharged from the adjacent discharge holes collide with each other to form large droplets. The particle size distribution of the toner can be improved.

  Next, the state of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber in the droplet discharge head in the liquid column resonance droplet forming unit will be described with reference to FIG. FIG. 5 is a schematic view showing a liquid column resonance phenomenon occurring in the liquid column resonance flow path of the liquid column resonance droplet discharge means. In FIG. 5, the solid line written in the liquid column resonance liquid chamber 18 plots the velocity at each arbitrary measurement position from the fixed end side to the end on the liquid common supply path side in the liquid column resonance liquid chamber 18. The velocity distribution is shown, and the direction from the liquid common supply path side to the liquid column resonance liquid chamber is +, and the opposite direction is-. The dotted line in the liquid column resonance liquid chamber 18 indicates a pressure distribution in which pressure values are plotted at arbitrary measurement positions from the fixed end side to the liquid common supply path side end in the liquid column resonance liquid chamber. The positive pressure is + with respect to 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 FIG. 5, as described above, the liquid common supply path side of the liquid column resonance liquid chamber 18 is opened, but the height of the opening through which the liquid common supply path 17 and the liquid column resonance liquid chamber 18 communicate (see FIG. 5). The height of the frame serving as the fixed end (height h1 shown in FIG. 1) is about twice or more than the height h2 shown in FIG. For this reason, each change of the velocity distribution and the pressure distribution in time is shown under the approximate condition that the liquid column resonance liquid chamber 18 is substantially fixed on both sides.

  FIG. 5A shows a pressure waveform (dotted line) and a velocity waveform (solid line) in the liquid column resonance liquid chamber 18 during droplet discharge. FIG. 5B shows that the meniscus pressure increases again after the liquid is drawn immediately after the droplet is discharged. As shown in FIGS. 5A and 5B, the pressure in the flow path in the liquid column resonance liquid chamber 18 provided with the discharge hole 19 is maximum. Thereafter, as shown in FIG. 5C, the positive pressure in the vicinity of the ejection hole 19 decreases, and the liquid droplet 21 is ejected in a negative pressure direction.

  And as shown in FIG.5 (d), the pressure of the discharge hole 19 vicinity becomes 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. 5E, the negative pressure in the vicinity of the discharge hole 19 becomes smaller and shifts to the positive pressure direction. At this time, the filling of the toner component liquid 14 is completed. Then, as shown in FIG. 5A again, 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 hole 19. As described above, 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. Further, since the discharge hole 19 is disposed in the droplet discharge region corresponding to the antinode of the standing wave due to the liquid column resonance at the position where the pressure fluctuates the most, the droplet 21 corresponds to the antinode period. The ink is continuously discharged from the discharge hole 19.

  Next, an example of a configuration in which droplets are actually ejected by the liquid column resonance phenomenon will be described. FIG. 6 is a diagram showing a state of actual droplet discharge by the liquid column resonance droplet discharge means. 6 shows a resonance mode in which the length L between the longitudinal ends of the liquid column resonance liquid chamber 18 in FIG. 1 is 1.85 mm and N = 2, and the first to fourth discharge holes are N = A state is shown in which a laser shadowgraphy method is used to image ejection performed using a sine wave having a driving frequency of 340 kHz, which is arranged at the antinode of the two-mode pressure standing wave. As can be seen from FIG. 6, the discharge of droplets having a uniform diameter and a substantially uniform speed is realized.

  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 to 395 kHz. As can be seen from FIG. 7, in the first to fourth discharge holes, the discharge speed from each discharge hole is uniform and the maximum discharge speed when the drive frequency is around 340 kHz. From the characteristic results shown in FIG. 7, it can be seen that uniform discharge is realized at the antinode of the liquid column resonance standing wave at 340 kHz which is the second mode of the liquid column resonance frequency. Further, from the characteristic results shown in FIG. 7, it is said that no droplets are ejected between the droplet ejection speed peak at 130 kHz which is the first mode and the droplet ejection speed peak at 340 kHz which is the second mode. I understand that. This is because the characteristic liquid column resonance standing wave frequency characteristic of the liquid column resonance is generated in the liquid column resonance liquid chamber.

[Droplet drying collection means]
The toner of the present invention can be obtained by drying and collecting the droplets of the toner component liquid discharged into the gas from the droplet discharge means described above. Here, the means for drying and collecting will be described.
FIG. 12 is a schematic view showing an example of a toner manufacturing 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. As the droplet discharge means 2, several types of droplet discharge means can be appropriately used as described above. A raw material container 13 for storing the toner component liquid 14 and a liquid circulation pump 15 are connected to the droplet discharge means 2, and the toner component liquid 14 can be supplied to the droplet discharge means 2 at any time. . The liquid circulation pump 15 supplies the toner component liquid stored in the raw material container 13 to the droplet discharge means 2 through the liquid supply pipe 16 and further returns to the raw material container 13 through the liquid return rod 22. The toner component liquid 14 in the liquid supply pipe 16 can be pumped. The liquid supply pipe 16 is provided with a liquid pressure gauge P1, and the dry collection unit 60 is provided with an in-chamber pressure gauge P2. The pressure for feeding liquid to the droplet discharge means 2 and the pressure in the dry collection unit are pressure Managed by totals P1 and P2. At this time, if P1> P2, the toner component liquid 14 may ooze out from the discharge hole provided in the droplet discharge means 2, and if P1 <P2, the droplet discharge means 2 may Therefore, it is desirable that P1≈P2 exists.

  The dry collection unit 60 shown in FIG. 12 includes a chamber 61, a toner collection unit 62, and a toner storage unit 63. The mechanism of the drying process will be described below. The droplet 21 composed of the toner component liquid 14 is in a liquid state immediately after being ejected from the droplet ejection means 2, but the volatile solvent contained in the toner component liquid is volatilized while being transported through the chamber 61. As the drying progresses, the liquid changes to a solid. In such a solid state, even if the particles are brought into contact with each other, coalescence does not occur any more. Therefore, the toner can be collected as toner powder by the toner collecting means 62 and can be stored in the toner reservoir 63. The toner stored in the toner storage unit 63 is further dried in another process as necessary.

  In the chamber 61, a carrier airflow 101 is formed by the airflow introduced from the carrier airflow inlet 64. Since the droplet 21 ejected from the droplet ejection means 2 is transported downward not only by gravity but also by the transport airflow 101, it is possible to prevent the ejected droplet 21 from being decelerated by air resistance. can do. Thereby, it can suppress that the droplets 21 unite | combine and unite and the particle size of the droplet 21 becomes large. That is, when droplets 21 are continuously ejected, the previously ejected droplets 21 are decelerated by air resistance before drying, and the later ejected droplets 21 are ejected before. Keeping up with can be suppressed.

  In FIG. 12, the droplet discharge means 2 discharges the droplet 21 in the direction of gravity, but this is not always necessary, and the discharge angle can be selected as appropriate. As the air flow generation means, either a method in which a blower is provided at the transport air flow inlet 64 at the top of the chamber 61 and pressurization, or a method of suction from the transport air flow outlet 65 can be adopted. As the toner collecting means 62, a known collecting device can be used, and a cyclone collecting machine, a back filter, or the like can be used.

  The carrier airflow 101 is not particularly limited as a state of the airflow as long as the coalescence of the droplets 21 can be suppressed, and may be a laminar flow, a swirl flow, or a turbulent flow. There is no particular limitation on the type of gas constituting the carrier airflow 101, and air or a nonflammable gas such as nitrogen may be used. As described above, it is preferable that the droplet 21 has a condition that can promote drying of the droplet 21 because the droplet 21 has a property of not being united by drying. Therefore, it is desirable that the droplet 21 does not contain the solvent vapor contained in the toner component liquid 14. Moreover, the temperature of the conveyance airflow 101 can be adjusted as appropriate, and it is desirable that there is no fluctuation during production. Further, a 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 droplets 21 from being united but also to prevent the droplets 21 from adhering to the chamber 61.

[Unity prevention measures]
In the droplet drying and collecting means described above, the coalescence of the droplets is suppressed by the air flow, but if the droplet drying and collecting means alone is not sufficient to prevent the droplets from being coalesced, further coalescence prevention means Can also be incorporated.
Examples of the coalescence prevention means include introduction of an auxiliary transport air current in the vicinity of the droplet discharge means 2, charging of the same polarity to the droplets, electric field control, and the like, which can be used as appropriate.

  FIG. 8 shows an outline of conventional coalescence prevention using a transverse airflow. Usually, the droplet discharged from the nozzle is subjected to the resistance of the surrounding gas, and its velocity is rapidly reduced. At this time, in the ejection in which the interval between the droplets as shown in the drawing is not sufficiently obtained, the droplets cross each other and become a large droplet (see FIG. 8-31). For this reason, conventionally, as shown in FIG. 8-32, an air flow is applied from the side to maintain the interval between the droplets and prevent coalescence. However, when a plurality of nozzles are arranged for one liquid chamber in order to increase the production efficiency of toner, unification cannot be prevented by only the transverse airflow (FIG. 8-33-A part). .

  FIG. 9 shows the discharge of droplets when the airflow of the present invention is added. Since the nozzle plate used in the present invention is provided with a droplet forming nozzle and an opening for adding airflow, the interval between the droplets is sufficiently maintained by the airflow applied parallel to the discharge direction of the droplet. . For this reason, it is possible to dry and collect particles having a uniform size without causing the droplets to merge.

FIG. 10 shows two examples of arrangements of droplet forming nozzles and airflow adding openings in the nozzle plate.
The toner component liquid is supplied through a liquid chamber extending from the lower part in the figure. From the upper part of the figure, an airflow is provided to prevent the droplets from coalescing. Thereby, the droplet discharged from the nozzle is conveyed to the drying tower in a state surrounded by the air current, and solidified and collected.
The shape of the opening may be any shape as long as the airflow can be blown out so as to prevent the droplets from being coalesced. For example, as shown in FIG. Alternatively, as shown in FIG. 10B, the opening may be composed of a plurality of nozzles. The slit may be a single continuous slit or a plurality of slits arranged in a line.
In the arrangement example shown in FIG. 10A, the air flow path is arranged so as to sandwich the liquid chamber in which the droplet forming nozzle (droplet discharge 5 nozzles / ch) is formed. Although 10 nozzles for adding airflow are arranged in one row at the tip of the air flow path on the nozzle plate, the layout is not limited to this. In other words, it is sufficient that the airflow adding nozzle is disposed in the vicinity of the droplet forming nozzle. FIG. 11 is an end view taken along line aa in FIG.
The diameter of the nozzle (ejection hole) provided in the nozzle plate is φ5 μm to 30 μm, and the thickness of the nozzle plate is several tens of μm. The material of the nozzle plate is not particularly limited. For example, nickel, SUS, silicon, polyimide, or the like can be used, and the nozzle plate can be manufactured by electrodeposition processing, punching processing, laser processing, or the like.

  It is preferable that the flow velocity of the airflow discharged from the airflow adding opening is at least half of the initial velocity of the droplet discharged from the droplet forming nozzle. The flow velocity of the air flow discharged from the opening for adding air flow is more than half of the initial velocity of the liquid droplets, so that the liquid droplets can be collected as particles without proceeding. it can. The flow rate of the airflow is preferably 0.5 times or more, more preferably 1.0 times or more than the initial velocity of the droplets. In addition, depending on the configuration of the apparatus, the flow velocity of the air current is about 5 times the initial velocity of the droplet, but the structural limit is used.

  Moreover, the kind of gas supplied from the opening part for airflow addition is not specifically limited, The thing similar to the said conveyance airflow can be used. That is, the airflow may be air or an incombustible gas such as nitrogen. Moreover, since it is preferable that it can accelerate | stimulate drying of a droplet, it is preferable that it is a thing which does not contain the vapor | steam of the solvent contained in the liquid which comprises the droplet. The temperature of the airflow can be adjusted as appropriate, and it is preferable that there is no fluctuation during production.

  Further, it is preferable that a mechanism capable of discharging the cleaning liquid from the airflow adding opening and / or the droplet forming nozzle is provided. By providing a mechanism capable of discharging the cleaning liquid from the airflow adding opening and / or the droplet forming nozzle, cleaning of the nozzle surface and cleaning of the flow path inside the air flow path can be easily performed. . For example, at the time of cleaning, the space including the nozzle surface is isolated by the shutter mechanism, the solvent is filled from the air flow path to the sealed space, and a signal is given to the PZT of the head to perform ultrasonic cleaning of the nozzle surface and the inside of the head. As the cleaning solution, for example, water, ethanol, IPA, ethyl acetate, toluene, acetone, methanol, or the like can be used.

  It is preferable that the inside of the opening for adding air current is subjected to a liquid repellent treatment with a fluorine-based coating agent, Teflon coating or the like (Teflon: registered trademark). Examples of the coating method include a method in which a solution containing a water repellent agent is passed through an air channel and then dried. Due to the liquid repellent treatment inside the airflow addition opening, the solution containing the toner composition does not enter the airflow addition opening and the occurrence of defects such as nozzle clogging is suppressed. be able to. As the water repellent treatment agent, for example, a fluorine-based coating agent, a Teflon coating agent, or the like can be used.

By providing an appropriate space between the droplet forming nozzle and the airflow adding opening, the droplets can be accelerated in a short time, and the coalescence of the droplets can be more efficiently suppressed. be able to. The distance between the droplet forming nozzle and the airflow adding opening is preferably 0.5 mm or less. When the distance between the droplet forming nozzle and the airflow adding opening is 0.5 mm or less, the speed of the discharged droplets is accelerated without being reduced, and the droplets are aligned in the discharge direction. There is nothing to do. Further, as the density of the droplet forming nozzles increases, in the conventional apparatus, the droplets are collected in the direction of the airflow before the droplets get on the transverse airflow. Since the droplets are separated from each other by the air flow immediately after the droplets are discharged, coalescence can be prevented. In addition, the closer the distance between the droplet forming nozzle and the airflow adding opening, the easier the effect is obtained.
The distance between the droplet forming nozzle and the airflow adding opening means the distance between a certain droplet discharge hole and the airflow discharge hole located closest to the droplet discharge hole.

It is preferable that a plurality of the droplet forming nozzles are arranged for one liquid chamber. This increases the particle production efficiency and makes it possible to produce a cheaper toner.
Moreover, the air flow path is formed as shown in FIG. 2, for example. At this time, it is preferable that a plurality of the airflow adding openings are also arranged for one airflow chamber. This makes it possible to accelerate the droplet velocity to the velocity of the airflow in a shorter time.

[Dry]
If necessary, secondary drying such as fluidized bed drying or vacuum drying is further performed. When the organic solvent remains in the toner, not only the toner characteristics such as heat-resistant storage stability, fixing property, and charging characteristics change with time. Since the organic solvent volatilizes at the time of fixing by heating, the possibility of adverse effects on the user and peripheral equipment is increased. Therefore, sufficient drying is performed.

Next, the toner according to the present invention will be described as an example of particles.
The toner according to the present invention is a toner manufactured by a toner manufacturing method to which the present invention is applied as in the toner manufacturing apparatus according to the above-described embodiment. Is obtained.

Next, toner materials that can be used in the present invention will be described. First, a toner component liquid in which the above-described toner material is dispersed or dissolved in a solvent will be described.
As the toner material, the same toner material as that used in the conventional electrophotographic toner can be used. The toner particles are prepared by dissolving the binder resin in various organic solvents, dispersing the colorant, and dispersing or dissolving the release agent, and drying and solidifying the particles as fine droplets by the toner manufacturing method. Can do.

[Toner material]
The toner material contains at least a resin, a colorant and a wax, and optionally contains a charge adjusting agent, an additive and other components.

〔resin〕
Examples of the resin include at least a binder resin.
The binder resin is not particularly limited, and a commonly used resin can be appropriately selected and used. Examples of the binder resin include vinyl polymers such as styrene monomers, acrylic monomers, and methacrylic monomers, copolymers of these monomers or two or more types, polyester resins, Examples include polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins, coumarone indene resins, polycarbonate resins, and petroleum resins.

  Examples of the styrene monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-amyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, Examples thereof include styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof. Examples of the styrene copolymer include styrene acrylic resins.

  Examples of acrylic monomers include acrylic acid, or methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic acid. Examples include 2-ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid such as phenyl acrylate, and esters thereof.

  Examples of the methacrylic monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid 2 -Methacrylic acid such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, or esters thereof.

Examples of other monomers that form the vinyl polymer or vinyl copolymer include the following (1) to (18).
(1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylden chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; (8), vinyl naphthalenes; (9) acrylonitrile, Methacrylonitrile and a Acrylic acid derivatives and methacrylic acid derivatives such as rilamide; (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; (11) maleic anhydride, citraconic acid Unsaturated dibasic acid anhydrides such as anhydride, itaconic anhydride and alkenyl succinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid Monoesters of unsaturated dibasic acids such as monoethyl ester, citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester and mesaconic acid monomethyl ester; (13) dimethylmaleic acid Unsaturated dibasic acid esters such as dimethyl fumaric acid; (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; and (15) α, β-unsaturated such as crotonic acid anhydride and cinnamic anhydride. (16) Carboxyl groups such as anhydrides of the above α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides thereof and monoesters thereof (17) acrylic acid hydroxyalkyl esters and methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy- 1-methylbutyl) styrene and 4- (1-hydroxy-1-methylhexyl) E) Monomers having a hydroxy group such as styrene.

  In the toner according to the present invention, the vinyl polymer or copolymer as the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6. Examples include xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing the acrylate of these compounds with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.

  Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of these compounds replaced with methacrylate. Examples include lucyanurate and triallyl trimellitate.

  The amount of these crosslinking agents used is preferably 0.01 to 10 parts by mass and more preferably 0.03 to 5 parts by mass with respect to 100 parts by mass of the other monomer components. Among these crosslinkable monomers, diacrylates bonded to a toner resin by a bond chain containing one aromatic divinyl compound (especially divinylbenzene), one aromatic group and an ether bond from the viewpoint of fixability and offset resistance. Preferred examples include compounds. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

  Examples of the polymerization initiator used in the production of the vinyl polymer or copolymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1 , 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2 ′ , 4′-dimethyl-4′-methoxyvaleronitrile, 2,2′-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, Ketone peroxides such as rohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, Lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxide Xidicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclo Hexylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaurate, tert-butyl-oxybenzoate, tert -Butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di- Such as tert- butyl to peroxy hexa hydro terephthalate and tert- butylperoxy azelate, and the like.

  When the binder resin is a styrene acrylic resin, there is at least one peak in the region of molecular weight 3000 to 50,000 (in terms of number average molecular weight) in the molecular weight distribution by GPC of the soluble component in the resin component tetrahydrofuran (THF). A resin having at least one peak in a region having a molecular weight of 100,000 or more is preferable in terms of fixing property, offset property and storage property. Moreover, as the THF-soluble component, a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50 to 90% is preferable, and a binder resin having a main peak in a molecular weight region of 5000 to 30,000 is more preferable. A binder resin having a main peak in the region of 5,000 to 20,000 is more preferable.

  The acid value when the binder resin is a vinyl polymer such as a styrene acrylic resin is preferably 0.1 to 100 mgKOH / g, more preferably 0.1 to 70 mgKOH / g, and More preferably, it is 1-50 mgKOH / g.

The following are mentioned as a monomer which comprises a polyester-type polymer.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, Examples include 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerization of bisphenol A with a cyclic ether such as ethylene oxide and propylene oxide. It is done.

In order to crosslink the polyester resin, it is preferable to use a trivalent or higher alcohol together.
Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and 1,3,5-trihydroxybenzene Etc.

  Examples of the acid component forming the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid; Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride And unsaturated dibasic acid anhydrides.

  Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, anhydrides thereof, partial lower alkyl esters and the like.

When the binder resin is a polyester resin, the molecular weight distribution of the THF-soluble component of the resin component having at least one peak in the molecular weight region of 3000 to 50,000 is good for toner fixability and offset resistance. This is preferable. Further, 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 preferable, and a binder resin having at least one peak in a region having a molecular weight of 5,000 to 20,000 is more preferable. preferable.
When the binder resin is a polyester resin, the acid value is preferably 0.1 to 100 mgKOH / g, more preferably 0.1 to 70 mgKOH / g, and 0.1 to 50 mgKOH / g. More preferably it is.
In the present invention, the molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.

As the binder resin that can be used in the toner according to the present invention, a resin containing a monomer component capable of reacting with both of the vinyl polymer component and the polyester resin component can be used. . Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. As a monomer which comprises a vinyl polymer component, the monomer which has a carboxyl group, the monomer which has a hydroxyl group, acrylic acid esters, and methacrylic acid esters are mentioned.
Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what contains 60 mass% or more of resin whose acid value of the whole binder resin is 0.1-50 mgKOH / g is preferable. .

In the present invention, the acid value of the binder resin component of the toner composition can be determined by the following method in accordance with JIS K-0070 for basic operation.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. To use. 0.5 to 2.0 g of the pulverized sample is precisely weighed, and the weight of the polymer component is defined as W [g]. For example, when the acid value of the binder resin is measured from the toner, the acid value and content of the colorant and magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 ml beaker, and 150 ml of a mixed solution of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / L KOH.
(4) The amount of KOH solution used at this time is set to S [ml], a blank is measured at the same time, the amount of KOH solution used at this time is set to B [ml], and the acid value is calculated by the following formula. However, f is a factor of KOH.
Acid value [mgKOH / g] = [(SB) × f × 5.61] / W

  The toner binder resin and the toner composition containing the binder resin preferably have a glass transition temperature (Tg) of 35 to 80 ° C., more preferably 40 to 75 ° C., from the viewpoint of toner storage stability. . If the Tg is lower than 35 ° C., the toner is likely to deteriorate in a high temperature atmosphere, and offset may easily occur during fixing. On the other hand, when Tg exceeds 80 ° C., fixability may be deteriorated.

Examples of the magnetic material that can be used in the present invention include the following (1) to (3).
(1) Magnetic iron oxides such as magnetite, maghemite, ferrite, and iron oxides containing other metal oxides (2) Metals such as iron, cobalt, nickel, or these metals and aluminum, cobalt, copper, lead, magnesium , Tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and other alloys (3) mixtures of (1) and (2) above

Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₁₂ O ₄ and PbFe. Examples thereof include ₁₂ O, NiFe ₂ O ₄ , NdFe ₂ O, BaFe ₁₂ O ₁₉ , MgFe ₂ O ₄ , MnFe ₂ O ₄ , LaFeO ₃ , iron powder, cobalt powder and nickel powder. These may be used individually by 1 type and may be used in combination of 2 or more type. Of these, fine powders of Fe ₃ O ₄ (triiron tetroxide) and γ-Fe ₂ O ₃ (γ-iron sesquioxide) are particularly preferred.

  Also, magnetic iron oxides such as magnetite, maghemite and ferrite containing different elements, or a mixture thereof can be used. Examples of the different elements include lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, and gallium. Etc. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus and zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may be present on the surface as an oxide or hydroxide. Is preferably contained as an oxide.

  The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can be made to deposit on the particle | grain surface by adjusting pH after magnetic body particle | grain production | generation, or adding salt of each element and adjusting pH.

  10-200 mass parts is preferable with respect to 100 mass parts of binder resin, and, as for the usage-amount of the said magnetic body, 20-150 mass parts is more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 μm, and 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.

As the magnetic properties of the magnetic material, each magnetic properties at 10k oersted applied coercive force from 20 to 150 oersted, saturation magnetization 50~200A · m ² / kg, that of the residual magnetization 2~20A · m ² / kg Is preferred.
The magnetic material can also be used as a colorant.

[Colorant]
The colorant is not particularly limited, and a commonly used resin can be appropriately selected and used. Examples of the colorant include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, and oil. Yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthra Zan Yellow BGL, Isoindolinone Yellow, Bengala, Red Plum, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scar G, Brilliant Fast Scarlet, Brilliant Carmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B , Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B , Thioindigo maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, Njidin Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC) , Indigo, Ultramarine, Bituminous, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green , Titanium oxide, zinc white, lithobon, and mixtures thereof.
The content of the colorant is preferably 1 to 15% by mass in the toner, and more preferably 3 to 10% by mass.

  The colorant used in the toner according to the present invention can also be used as a master batch combined with a resin. As the resin to be kneaded with the production of the master batch or with the master batch, in addition to the modified polyester and the unmodified polyester resin, for example, polystyrene, poly-p-chlorostyrene, polyvinyltoluene and other styrene and substituted polymers thereof; styrene -P-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloro Methyl methacrylate copolymer Styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, and styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Examples thereof include acrylic resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant with a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. In addition, the so-called flushing method can be preferably used because it can use the wet cake of the colorant as it is, and does not need to be dried. The flushing method is a method in which an aqueous paste containing colorant water is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.
As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.

  The resin for the masterbatch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and a colorant dispersed therein. The acid value is 20 mgKOH / g or less and the amine value is 10 It is more preferable that the colorant is dispersed and used at ˜50. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered, and the pigment dispersibility may be insufficient. Further, when the amine value is less than 1 and when the amine value exceeds 100, the pigment dispersibility may be insufficient. The acid value can be measured by the method described in JIS K0070, and the amine value can be measured by the method described in JIS K7237.

  The dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific commercially available products include “Azisper PB821”, “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.), “Disperbyk-2001” (manufactured by BYK Chemie), “EFKA-4010” (manufactured by EFKA), and the like. .

  The weight average molecular weight of the dispersant is preferably 500 to 100,000 in terms of the maximum molecular weight of the main peak in terms of styrene conversion weight in gel permeation chromatography. From the viewpoint of pigment dispersibility, 3000 to 10%. Ten thousand is more preferable. Furthermore, 5000-50,000 are preferable and 5000-30,000 are especially preferable. When the weight average molecular weight of the dispersant is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the molecular weight exceeds 100,000, the affinity with the solvent increases, Dispersibility may decrease.

  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. Sufficient dispersibility can be obtained when the amount of the dispersant added is 1 part by mass or more. Moreover, when the addition amount of the dispersant is 200 parts by mass or less, it is possible to prevent a decrease in chargeability.

<Wax>
The toner component liquid used in the present invention contains a wax together with a binder resin and a colorant.
There is no restriction | limiting in particular as wax, What is normally used can be selected suitably and can be used. For example, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax and sazol wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or blocks thereof Copolymers; plant waxes such as candelilla wax, carnauba wax, wax and jojoba wax; animal waxes such as beeswax, lanolin and whale wax; mineral waxes such as ozokerite, ceresin and petrolatum; montanic acid ester wax And waxes mainly composed of fatty acid esters such as castor wax; those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax.

  Examples of the wax further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group; plandic acid, eleostearic acid and valinal acid Unsaturated fatty acids such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesyl alcohol, or long-chain alkyl alcohol; polyhydric alcohols such as sorbitol; linoleic acid amide, olefinic acid Fatty acid amides such as amides and lauric acid amides; saturated fatty acid bisamides such as methylene biscapric acid amide, ethylene bislauric acid amides and hexamethylene bisstearic acid amides; ethylene bisoleic acid amides, hexamethyle Unsaturated fatty acid amides such as bisoleic acid amide, N, N′-dioleyl adipic acid amide and N, N′-dioleyl sepasic acid amide; m-xylene bisstearic acid amide and N, N-distearyl isophthalate Aromatic bisamides such as acid amides; Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate; grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid And wax; partial ester compounds of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and the like.

More preferred examples of the wax include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, and catalysts such as Ziegler catalysts and metallocene catalysts under low pressure. Polymerized polyolefins, polyolefins polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefins obtained by thermal decomposition of high molecular weight polyolefins, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method and age Synthetic hydrocarbon waxes synthesized by the method, synthetic waxes having a compound having one carbon atom as monomers, hydrocarbon waxes having functional groups such as hydroxyl groups or carboxyl groups, hydrocarbon waxes and functional groups Mixture of hydrocarbon wax, styrene these waxes as a matrix, maleic acid esters, acrylates, and graft modified wax in such a vinyl monomer methacrylate and maleic anhydride.
In addition, these waxes have a sharp molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.

  The melting point of the wax is preferably 70 to 140 ° C., and more preferably 70 to 120 ° C., in order to balance the fixability and the offset resistance. When the melting point of the wax is 70 ° C. or higher, sufficient blocking resistance can be obtained. Moreover, when the melting point of the wax is 140 ° C. or less, a good offset resistance effect is exhibited.

  Further, by using two or more different types of waxes in combination, the plasticizing action and the releasing action which are the actions of the wax can be expressed simultaneously. Examples of the type of wax having a plasticizing action include waxes having a low melting point, those having a branched structure on the molecular structure, and those having a polar group. Examples of the wax having a releasing action include a wax having a high melting point, and the molecular structure includes a linear structure and a non-polar one having no functional group. Examples of use include a combination of two or more different waxes having a difference in melting point of 10 to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.

  When selecting two types of wax, in the case of a wax having a similar structure, a wax having a relatively low melting point exhibits a plasticizing action, and a wax having a high melting point exhibits a releasing action. At this time, when the difference in melting point is 10 to 100 ° C., functional separation is effectively expressed. When the difference between the melting points of the two kinds of waxes is less than 10 ° C., the function separation effect may be difficult to appear, and when it exceeds 100 ° C., the function may not be emphasized by interaction. At this time, the melting point of at least one of the waxes is preferably 70 to 120 ° C, and more preferably 70 to 100 ° C, because the function separation effect tends to be easily exhibited.

  As for the wax, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exhibit a plastic action, and those having a more linear structure or functional group Nonpolar or non-denatured straight materials that do not have a mold exhibit a releasing action. Preferred combinations include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene, polyolefins and graft modified polyolefins, alcohol waxes, fatty acid waxes or ester waxes. And hydrocarbon wax combinations, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax combination, Fischer-Tropsch wax and polyolefin wax combination, paraffin wax and microcrystal wax combination, Carnauba Wax, Can Delila wax, rice wax or montan wax and hydrocarbon wax Combinations thereof.

In any case, since it becomes easy to balance the toner storage stability and the fixing property, the peak of the maximum peak in the region of 70 to 110 ° C. in the endothermic peak observed in the DSC measurement (differential scanning calorimetry) of the toner. It is preferable that there is a top temperature, and it is more preferable to have a maximum peak in the region of 70 to 110 ° C.
0.2-20 mass parts is preferable with respect to 100 mass parts of binder resin, and, as for the total content of the said wax, 0.5-10 mass parts is more preferable.

In the present invention, the peak top temperature of the endothermic peak of the wax measured by DSC is defined as the melting point of the wax.
The wax or toner DSC measuring device is preferably measured with a high-precision 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.

<Fluidity improver>
A fluidity improver may be added to the toner according to the present invention. The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface.
Examples of the fluidity improver include fluorocarbon resin powders such as carbon black, vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, fine powder silica such as wet process silica and dry process silica, fine powder titanium oxide, Examples thereof include finely powdered alumina, treated silica obtained by subjecting them to surface treatment with a silane coupling agent, a titanium coupling agent, or silicone oil, treated titanium oxide, and treated alumina. Among these, fine powder silica, fine powder titanium oxide and fine powder alumina are preferable, and treated silica subjected to surface treatment with a silane coupling agent or silicone oil is more preferable.
The particle size of the fluidity improver is preferably 0.001 to 2 μm, more preferably 0.002 to 0.2 μm in terms of average primary particle size.

The fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.
Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include, for example, AEROSIL (trade name of Nippon Aerosil Co., Ltd., hereinafter the same) -130, -300, -380, -TT600, -MOX170, -MOX80, -COK84; Ca-O-SiL (trade name of CABOT) -M-5, -MS-7, -MS-75, -HS-5, -EH-5; Wacker HDK (trade name of WACKER-CHEMIE)- N20 V15, -N20E, -T30, -T40; D-CFineSi1ica (trade name of Dow Corning); Franco1 (trade name of Franci1) and the like.

  Furthermore, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is more preferable. In the treated silica fine powder, it is particularly preferred to treat the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is preferably 30 to 80%. Hydrophobization is imparted by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, a method of treating fine silica powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound can be mentioned.

  Examples of the organosilicon compound include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, dimethylvinylchlorosilane, Divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α -Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane , Triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, each of which is located at the end Examples thereof include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The number average particle diameter of the fluidity improver is preferably 5 to 100 nm, more preferably 5 to 50 nm.
Flowability improver, the specific surface area by measuring nitrogen adsorption by the BET method, preferably at least ^{30m 2 / g, 60~400m 2 /} g is more preferable. The specific surface area of the surface-treated fine powder is preferably at least ^{20m 2 / g, 40~300m 2 /} g is more preferable.
The amount of the fine powder used is preferably 0.03 to 8 parts by mass with respect to 100 parts by mass of the toner particles.

  In the toner according to the present invention, as other additives, protection of the electrostatic latent image carrier and carrier, improvement of cleaning properties, adjustment of thermal characteristics, electrical characteristics and physical characteristics, resistance adjustment, softening point adjustment, fixing rate For the purpose of improvement, inorganic fine powders such as various metal soaps, fluorine surfactants and dioctyl phthalate, etc., tin oxide, zinc oxide, carbon black and antimony oxide as conductivity imparting agents, titanium oxide, aluminum oxide and alumina A body etc. can be added as needed. 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 include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control and the like. It is also preferable to treat with a treating agent or various treating agents.

  In preparing the developer, inorganic fine particles such as the hydrophobic silica fine powder mentioned above may be added and mixed in order to improve the fluidity, storage stability, developability and transferability of the developer. For mixing external additives, a general powder mixer can be appropriately selected and used. However, it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually, and the rotational speed, rolling speed, time, temperature, etc. of the mixer may be changed. A strong load and then a relatively weak load may be applied, and vice versa. Examples of the mixer that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, and a Henschel mixer.

  A method for further adjusting the shape of the obtained toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner material consisting of a binder resin and a colorant, melted and kneaded, and then finely pulverized and then mechanically adjusted using a hybridizer, mechanofusion, or the like, or a so-called spray dry method Examples thereof include a method in which the material is dissolved and dispersed in a solvent in which the binder resin is soluble and then desolvated using a spray dryer to obtain a spherical toner, and a method in which the material is made spherical by heating in an aqueous medium.

As the external additive, inorganic fine particles can be preferably used. Examples of inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
Other external additives include polymeric fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, and heavy polymers such as silicone, benzoguanamine and nylon. Examples thereof include polymer particles made of a condensation resin and a thermosetting resin.

  Such an external additive can be made hydrophobic by treatment with a surface treatment agent and can 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, and modified silicone oil. Are preferable.

The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 to 500 nm.
Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5 parts by mass, and more preferably 0.01 to 2.0 parts by mass with respect to 100 parts by mass of the toner.

  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. Examples thereof include 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.

Examples of the present invention will be described below, but the present invention is not limited to these examples.
Next, the formulation of the dissolution or dispersion used in the examples is shown.
The injection conditions are as follows.
<Injection conditions>
Drive voltage: 10V Drive waveform: Sine wave Frequency: 340kHz

-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
Carbon black (Rega L400; manufactured by Cabot) 17 parts by mass and pigment dispersant (Ajisper PB821; manufactured by Ajinomoto Fine-Techno Co., Ltd.) 3 parts by mass are mixed into 80 parts by mass of ethyl acetate using a mixer having stirring blades. I let you. The obtained primary dispersion is finely dispersed by a strong shearing force using a bead mill (LMZ type zirconia beads (diameter 0.3 mm); manufactured by Ashizawa Finetech Co., Ltd.) to completely remove aggregates having a diameter of 5 μm or more. A secondary dispersion was prepared.

-Preparation of wax dispersion-
Next, a wax dispersion was prepared.
Carnauba wax 18 parts by weight, wax dispersant (polyethylene wax grafted with styrene-butyl acrylate copolymer) 2 parts by weight, ethyl acetate 80 parts by weight using a mixer with stirring blades, primary dispersion I let you. The primary dispersion was heated to 80 ° C. with stirring to dissolve the carnauba wax, and then the liquid temperature was lowered to room temperature to precipitate wax particles so that the maximum diameter was 3 μm or less. The obtained dispersion was further finely dispersed by a strong shearing force using a bead mill (LMZ type zirconia beads (diameter 0.3 mm); manufactured by Ashizawa Finetech Co., Ltd.), and the maximum diameter was adjusted to 1 μm or less.

-Preparation of dissolution or dispersion-
Next, a toner component liquid having the following composition to which a resin as a binder resin, the colorant dispersion, and the wax dispersion were added was prepared.
100 parts by mass of a polyester resin as a binder resin, 30 parts by mass of the colorant dispersion, and 30 parts by mass of the wax dispersion are stirred for 10 minutes in 840 parts by mass of ethyl acetate using a mixer having stirring blades. To make it evenly dispersed. Pigments and wax particles did not aggregate due to shock due to solvent dilution.

-Toner production equipment-
Using the toner production apparatus 1 having the configuration shown in FIG. 12, toner was produced using several ejection means as ejection means.
The size and conditions of each component are as follows.

--Liquid column resonance droplet discharge means--
The length L between both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 is 1.85 mm and the resonance mode is N = 2, and the first to fourth discharge holes are antinodes of the N = 2 mode pressure standing wave. The one in which the discharge holes are arranged at the position is used. A function generator WF 1973 manufactured by NF was used as the drive signal generation source 34 and connected to the vibration generating means with a polyethylene-coated lead wire. The driving frequency at this time is 340 kHz in accordance with the liquid resonance frequency.

-Toner collection part-
The chamber 61 has a cylindrical shape with an inner diameter of φ400 mm and a height of 2000 mm, and is vertically fixed. The upper end portion and the lower end portion are narrowed, the diameter of the carrier airflow inlet 64 is φ50 mm, and the diameter of the carrier airflow outlet 65 is φ50 mm. The droplet discharge means 2 is disposed at the center of the chamber 61 at a height of 300 mm from the upper end in the chamber 61. The carrier airflow was 10.0 m / s and 40 ° C. nitrogen.

Example 1
Toner particles were collected using the system configuration shown in FIG.
As the airflow adding opening, an opening made of a plurality of nozzles as shown in FIG. 10B was used.
At this time, as shown in FIG. 10, the droplet forming nozzle row is 5 nozzles / ch, the ch pitch is 0.28 mm, and is arranged over one head 400 ch. Nozzles for adding airflow are 10 nozzles / ch, and the ch pitch is also 0.28 mm, and one head is arranged for 401 ch. That is, the distance between the droplet forming nozzle and the airflow adding nozzle was 0.1 mm. The nozzle plate was made of nickel, the diameter of the droplet forming nozzle was φ10 μm, and the diameter of the airflow adding nozzle was φ20 μm. Further, the inside of the airflow addition nozzle was subjected to a liquid repellent treatment by applying about 0.1 μm of a fluorine coating agent.

The pressure of the added air flow was set to 0.5 atm, and the operation was performed for about 10 minutes. The initial velocity of the droplet was 12 m / s, and the flow velocity of the added air flow was 15 m / s.
The toner collected through the dry air flow path was taken out of the toner storage container to obtain a toner. The particle size distribution of the toner was measured with the following flow type particle image analyzer (FPIA-2000; Sysmex Corporation) under the following measurement conditions. When this was repeated three times, as shown in FIG. 13, the distribution was such that the average of the volume average particle diameter (Dv) was 5.0 μm, the average of the number average particle diameter (Dn) was 4.5 μm, and Dv / The average of Dn was 1.11.

  A measurement method using a flow particle image analyzer will be described below. Measurement of toner, toner particles and external additives by a flow type particle image analyzer can be performed using, for example, a flow type particle image analyzer FPIA-2000 manufactured by Toa Medical Electronics.

In the measurement, fine dust is first removed through a filter, and as a result, water with a particle size of 20 or less in a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) is placed in 10 ⁻³ cm ³ of water. Prepared. A few drops of nonionic surfactant (preferably Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.) is added to 10 ml of this water, and 5 mg of a measurement sample is further added, and an ultrasonic disperser (UH-50; manufactured by STM) is used. Dispersion treatment was performed for 1 minute under the conditions of 20 kHz and 50 W / 10 cm ³ . Further, a dispersion treatment was performed for a total of 5 minutes <0.60 μm using a sample dispersion liquid with a particle concentration of the measurement sample of 4000 to 8000 particles / 10 ⁻³ cm ³ (for particles in the equivalent circle diameter range). The particle size distribution of particles having an equivalent circle diameter of less than 159.21 μm was measured.

  The sample dispersion liquid is passed through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, the strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area was calculated as the equivalent circle diameter.

  The equivalent circle diameter of 1200 or more particles can be measured in about 1 minute, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. . As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 200 μm into 226 channels (divided into 30 channels for one octave). In actual measurement, particles were measured in a range where the equivalent circle diameter was 0.60 μm or more and less than 159.21 μm.

(Example 2)
Using the same toner manufacturing apparatus as in Example 1, a pressure of about 1 atm was applied to the airflow application nozzle, and while generating an airflow, droplets were discharged, dried, and collected to obtain a toner. The initial velocity of the droplet was 12 m / s, and the flow velocity of the added air flow was 15 m / s.
The particle size distribution of the toner was measured with a flow particle image analyzer (FPIA-2000; Sysmex Corporation) under the measurement conditions shown below. When this was repeated three times, the distribution was as shown in FIG. 14. The average of the volume average particle diameter (Dv) was 4.4 μm, the average of the number average particle diameter (Dn) was 4.2 μm, and Dv / The average Dn was 1.05.

(Comparative Example 1)
Using the same toner production apparatus as in Example 1, the toner was obtained by discharging, drying, and collecting droplets without applying pressure to the airflow application nozzle. The particle size distribution of the toner was measured with a flow particle image analyzer (FPIA-2000; Sysmex Corporation) under the measurement conditions shown below. When this was repeated three times, the average of the volume average particle diameter (Dv) was 5.8 μm, the average of the number average particle diameter (Dn) was 4.7 μm, and the average of Dv / Dn was 1.23. .

  As described above, the particle size distribution is dramatically improved by adding an air flow in the direction parallel to the droplet discharge direction. The air velocity may be appropriately selected and prepared according to the configuration of the apparatus, the condition of the toner component liquid, and the like.

1: Toner manufacturing device 2: Droplet discharge means 6: Toner component liquid supply port 10: Liquid column resonance droplet forming unit 11: Liquid column resonance droplet discharge means 12: Air flow passage 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 liquid chamber 19: Discharge hole 20: Vibration generating means 21: Liquid droplet 22: Liquid return pipe 34: Drive signal generation source 60: Drying Collection unit 61: Chamber 62: Toner collection means 63: Toner reservoir 64: Conveyance airflow inlet 65: Conveyance airflow outlet 101: Conveyance airflow

Japanese Patent No. 3786034 Japanese Patent No. 3786035 JP-A-57-201248

Claims (10)

A method for producing particles comprising: a droplet discharge step of discharging a particle component liquid from at least one discharge hole to form droplets; and a solidification step of solidifying the droplets,
A method for producing particles, wherein a droplet forming nozzle and an airflow adding opening are formed in a nozzle plate of a droplet discharging means used in the droplet discharging step.   2. The particle according to claim 1, wherein the flow velocity of the air flow discharged from the air flow addition opening is at least half of the initial velocity of the liquid droplet discharged from the droplet forming nozzle. Manufacturing method.   The method for producing particles according to claim 1, further comprising a mechanism capable of discharging a cleaning liquid from the airflow application opening and / or the droplet forming nozzle.   The method for producing particles according to any one of claims 1 to 3, wherein the inside of the airflow addition opening is liquid-repellent.   The method for producing particles according to any one of claims 1 to 4, wherein a distance between the droplet forming nozzle and the airflow adding opening is 0.5 mm or less.   The method for producing particles according to any one of claims 1 to 5, wherein a plurality of the droplet forming nozzles are arranged for one liquid chamber.   The method for producing particles according to any one of claims 1 to 6, wherein a plurality of openings for adding airflow are arranged for one airflow chamber.   The method for producing particles according to claim 1, wherein the particles are toner particles. A particle manufacturing apparatus comprising: a droplet discharge unit that discharges a particle component liquid from at least one discharge hole to form droplets; and a solidification unit that solidifies the droplets.
9. The method for producing particles according to claim 1, wherein a droplet forming nozzle and an airflow adding opening are formed in a nozzle plate of the droplet discharge means. Particle production equipment for.   A particle produced by the particle production apparatus according to claim 9.