JP2011212668A - Production method of fine particle, fine particle production apparatus, and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of fine particles and a fine particle production apparatus, each of which enables achieving continuous ejection of a liquid owing to its ability of continuous driving, thereby which assures extremely high productivity and enables uniformly and stably producing extremely fine particles.SOLUTION: An ejection hole 19 for ejecting the liquid is formed by opening a part of a member constituting a liquid column resonance-generating liquid chamber 18 to which the liquid containing a resin at the least is supplied. A vibration generating means 20 for applying a vibration to the liquid is arranged in the liquid column resonance-generating liquid chamber 18. The vibration is applied to the liquid in the liquid column resonance-generating liquid chamber 18 to form a standing wave through liquid column resonance in the liquid column resonance-generating liquid chamber and the liquid is ejected from the ejection hole 19 formed in a region corresponding to an antinode of the standing wave. Thereafter, the liquid is formed into liquid droplets and the liquid droplets are solidified to produce fine particles.

Description

  The present invention relates to a method and apparatus for producing fine particles having a uniform particle diameter by spray granulation. The present invention also relates to a toner produced by a fine particle production method or a fine particle production apparatus.

  First, as an example of conventional resin fine particles, a pulverization method which is one of toner production methods will be described. The pulverization method is a conventional method for producing toner, and the toner composition is melt-kneaded with a two-roll or twin-screw extruder, etc., cooled, and then coarsely pulverized, finely pulverized, and classified. And, if necessary, mixing treatment of external additives such as a fluidizing agent with a Henschel mixer or the like. A rotoplex or pulverizer can be used for the coarse pulverization treatment, and a jet mill or a turbo mill can be used for the fine pulverization treatment. In the classification process, a known manufacturing apparatus such as an elbow jet or various air classifiers can be used.

  As another conventional toner manufacturing method other than the pulverization method, there is a spray method. This spraying method uses a one-fluid discharge hole (pressure discharge hole) sprayer that pressurizes liquid and sprays from the discharge hole, a multi-fluid spray discharge hole sprayer that mixes and sprays liquid and compressed gas, and a rotating disk. In this method, a toner composition liquid is formed into droplets in a gas phase using a rotating disk type sprayer or the like that forms liquid droplets by centrifugal force. In this spraying method, a commercially available device can be used as a spray drying system that performs spraying and drying at the same time, but if sufficient drying is not possible, secondary drying such as fluidized bed drying is performed, and if necessary, a Henschel mixer, etc. In this method, external additives such as a fluidizing agent are mixed.

  As another conventional toner production method other than the above pulverization method, there is an injection granulation method. This spray granulation method is a method for ejecting droplets from ejection holes having the same diameter as that of toner using vibration generating means, although the liquid droplets are solidified by the same method as the spraying method. It is. Several spray granulation methods have been conventionally proposed. As one of them, in Patent Document 1, a pressure column is pressurized to generate a liquid column from a nozzle, the liquid column is divided by weak ultrasonic vibrations to form droplets, which are dried and solidified to become toner. A toner manufacturing method and an apparatus therefor have been proposed. Such a toner manufacturing apparatus includes a toner composition liquid container that contains a toner composition liquid to be supplied to the pressure chamber of the droplet ejecting unit, and the toner composition liquid that is contained in the toner composition liquid container is agitated. In general, a configuration in which a stirring member for generating a flow is arranged. In the toner composition container, the flow is generated by the stirring member, so that each material can be kept uniformly dispersed in the toner composition liquid, and each material is dispersed unevenly in the toner composition liquid. It can suppress that it becomes a material non-uniform dispersion state. Pressurize the toner composition liquid to form a liquid column from the through-hole, give minute vibrations to the liquid column by vibration generating means to induce Rayleigh splitting, form uniform droplets, solidify the droplets A toner manufacturing apparatus for manufacturing toner base particles is disclosed. The Rayleigh splitting method has an advantage that the vibration generating means only needs to generate a weak vibration in order to pressurize and discharge the liquid, and can be particleized at a low voltage.

  Moreover, in the head part in Patent Document 2 as another conventional example using the spray granulation method, pressurization is performed by uniformly pressurizing and discharging the entire raw material stored in the raw material storage part for storing the toner raw material. A pulse operation is performed to discharge the toner material from the discharge hole. The principle of droplet discharge disclosed in Patent Document 2 will be outlined below with reference to FIG. In FIG. 24, the pressure value in the raw material reservoir is also shown. The droplet discharge method in Patent Document 2 is a method of intermittently forming droplets by repeatedly operating the following three states. The head portion is in the first state, and no discharge signal is input. That is, as shown in FIG. 24A, the piezoelectric body is not deformed, the volume of the raw material reservoir is not changed, and the discharge hole Thus, the raw material liquid is not discharged. Next, as a second state, a discharge signal is input, and as shown in FIGS. 24B and 24C, the piezoelectric body is displaced to the inside of the raw material reservoir, and the volume of the raw material reservoir is reduced. . At this time, the pressure in the entire raw material reservoir is uniformly and instantaneously increased, and droplets are ejected from the ejection holes. At this time, a flow of the raw material is generated from the raw material storage unit to the raw material storage unit (not shown) side. Next, as a third state, after the discharge of one raw material is completed, as shown in FIGS. 24D and 24E, the application of voltage is stopped, and the piezoelectric element has almost the original shape. Return. At this time, a negative pressure acts on the raw material liquid, and an amount of the raw material liquid corresponding to the discharge amount is supplied to the raw material storage unit from a raw material storage unit called a feeder that stores the raw material.

  However, in Patent Document 1 described above, in order to use Rayleigh splitting, droplets having a particle size that is about twice the inner diameter of the discharge hole are formed. Further, there is a problem that the liquid is unidirectionally pressurized in the storage portion and the toner component is clogged inside the nozzle due to the toner composition.

  Moreover, in the said patent document 2, since it is the method of pressurizing and discharging the raw material liquid collected intermittently in the raw material storage part, the raw material in the raw material storage part decreased by the amount discharged | emitted in the 3rd state mentioned above It is necessary to supply the liquid and return to the first state where the raw material liquid is stored again. Therefore, there is a problem that a time loss occurs in view of the entire time for the third state and the entire manufacturing process time, and the toner production efficiency corresponding to the time loss is reduced. It was. Furthermore, in the method disclosed in Patent Document 2, generally large droplets are formed. Therefore, in order to obtain dry toner particles, it has been necessary to use a discharge portion with a small diameter or to dilute the raw material. However, if the size of the discharge part is reduced, the probability of clogging solid dispersions such as pigments that are indispensable as toner constituents and release agents that are added as necessary is dramatically increased. There was a problem. Moreover, when the raw material is diluted, the energy for drying and solidifying the diluted liquid becomes large, which also causes a problem of greatly reducing the production efficiency. In addition, the reduction in production efficiency means that the time for storing the raw material liquid in the raw material storage part becomes long, the stagnation of the raw material liquid occurs, and sticking of the toner raw material occurs in long-term production. There was also.

  The present invention has been made in view of the above-described problems, and the object thereof is to enable continuous driving, so that continuous discharge of liquid can be realized, so that very high productivity can be expected, and extremely small liquid can be expected. It is an object to provide a fine particle production method, a fine particle production apparatus, and a toner capable of producing droplets uniformly and stably.

In order to achieve the above object, a first aspect of the present invention provides a fine particle having a droplet discharge step of discharging a liquid from at least one discharge hole to form a droplet and a solidifying step of solidifying the droplet. In the manufacturing method, the liquid is obtained by dissolving or dispersing the finely divided component in a solvent, or by melting the finely divided component, and the droplet discharging step is a liquid in which the discharge hole is formed. A vibration is applied to the liquid in the column resonance liquid chamber to form a standing wave due to the liquid column resonance, and the liquid is discharged from the discharge hole formed in the region that becomes the antinode of the standing wave to form a droplet. This is a method for producing fine particles.
According to a second aspect of the present invention, in the method for producing fine particles according to the first aspect, the finely divided component is a resin or a resin composition.
Furthermore, the invention of claim 3 is the method for producing fine particles according to claim 1 or 2, wherein a plurality of the discharge holes are formed in at least one of the regions that become the antinodes of the standing wave. It is characterized by this.
The invention of claim 4 is the method for producing fine particles according to any one of claims 1 to 3, wherein a plurality of the discharge holes are provided in one liquid column resonance liquid chamber. To do.
Furthermore, the invention of claim 5 is the method for producing fine particles according to any one of claims 1 to 4, wherein at least a part of the reflection wall surface is provided at both ends in the longitudinal direction of the liquid column resonance liquid chamber. It is characterized by being.
The invention of claim 6 is the method for producing fine particles according to any one of claims 1 to 5, wherein the vibration is f = N × c / (4L) (L: the liquid column resonance liquid chamber). The vibration of the frequency f which establishes the length in the longitudinal direction, c: velocity of the sound wave of the liquid, N: integer) is applied.
Furthermore, the invention of claim 7 is the method for producing fine particles according to any one of claims 1 to 5, wherein the vibration is N × c / (4L) ≦ f ≦ N × c / (4Le) ( L: length in the longitudinal direction of the liquid column resonance liquid chamber, Le: distance to the discharge hole closest to the end on the liquid supply path side, c: velocity of the sound wave of the liquid, N: integer) The vibration of f is imparted.
The invention according to claim 8 is the method for producing fine particles according to claim 7, wherein Le / L> 0.6.
Furthermore, the invention of claim 9 is the method for producing fine particles according to any one of claims 1 to 5, wherein the vibration is N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le. ) (L: length in the longitudinal direction of the liquid column resonance liquid chamber, Le: distance to the discharge hole closest to the end on the liquid supply path side, c: velocity of liquid acoustic wave, N: integer) The vibration having the frequency f is applied.
According to a tenth aspect of the present invention, in the method for producing fine particles according to the first aspect, the frequency of the vibration is a high-frequency vibration of 300 kHz or more.
Furthermore, the invention of claim 11 is the method for producing fine particles according to any one of claims 1 to 10, wherein the gas for forming an air current that does not contract the distance between the discharged droplets is the solidifying step. It is characterized by providing a flow channel that flows to a region where the above is performed.
According to a twelfth aspect of the present invention, in the method for producing fine particles according to the eleventh aspect, the initial discharge speed of the discharged liquid droplets is smaller than the speed of the air flow.
Furthermore, the invention of claim 13 is the method for producing fine particles according to claim 1, wherein the liquid contains an organic solvent, and in the solidification step, the organic solvent is removed to dry and solidify the droplets. It is characterized by this.
The invention of claim 14 is a fine particle manufacturing apparatus comprising: a droplet discharge unit that discharges a liquid from at least one discharge hole to form a droplet; and a solidification unit that solidifies the droplet. The liquid is obtained by dissolving or dispersing the micronized component in a solvent, or by melting the micronized component, and a liquid column resonance liquid chamber in which the discharge hole is opened, and the liquid column resonance liquid chamber Vibration generating means for applying vibration to the liquid, and by applying vibration to the liquid in the liquid column resonance liquid chamber by the vibration generating means to form a standing wave by liquid column resonance, the standing wave The fine particle manufacturing apparatus is characterized in that the liquid is ejected from the ejection holes formed in the region of the antinodes to form droplets.
Furthermore, a fifteenth aspect of the invention is a toner produced by the fine particle production method according to any one of the first to thirteenth aspects or the fine particle production apparatus according to the fourteenth aspect.
According to a sixteenth aspect of the present invention, in the toner according to the fifteenth aspect, the toner has a particle size of 3.0 [μm] to 6.0 [μm].

  In the present invention, a discharge hole for discharging the composition liquid is formed in a part of the liquid column resonance liquid chamber to which the composition liquid containing fine particles is supplied. The liquid column resonance liquid chamber is provided with vibration generating means for applying vibration to the composition liquid. When a high frequency that meets the resonance condition is applied, a standing wave due to liquid column resonance is formed in the liquid column resonance liquid chamber. A pressure distribution is formed in the liquid column resonance liquid chamber by the standing wave due to the liquid column resonance. The standing wave generated by the liquid column resonance generated in the liquid column resonance chamber has a pressure distribution region where a high pressure is generated, which is called an antinode. By providing the discharge holes in a pressure distribution region corresponding to the antinode, a high pressure is applied to the composition liquid in the vicinity of the discharge holes, and the composition liquid is continuously discharged. Thereafter, the toner particles are produced by solidifying the droplets of toner droplets. As a result, continuous toner droplet ejection can be realized, and extremely high productivity can be expected.

  As described above, according to the present invention, there is an excellent effect that continuous liquid droplet ejection at a high frequency can be realized, and extremely high productivity can be expected.

1 is a cross-sectional view illustrating an overall configuration of a toner manufacturing apparatus according to an embodiment of the present invention. FIG. 2 is a cross-sectional view illustrating a configuration of a droplet discharge head in the droplet formation unit of FIG. 1. FIG. 2 is a cross-sectional view taken along line A-A ′ showing the configuration of the droplet forming unit in FIG. 1. It is the schematic which shows the standing wave of the speed and pressure fluctuation in the case of N = 1,2,3. It is the schematic which shows the standing wave of the speed and pressure fluctuation in the case of N = 4 and 5. FIG. 5 is a schematic diagram illustrating a liquid column resonance phenomenon that occurs in a liquid column resonance liquid chamber in a droplet discharge head in a droplet forming unit. It is a figure which shows the mode of actual droplet discharge. It is a characteristic view which shows a drive frequency and a droplet discharge speed frequency characteristic. It is a characteristic view which shows the relationship between the applied voltage and discharge speed in each nozzle. It is a characteristic view which shows the relationship between the applied voltage and droplet diameter in each nozzle. It is a figure which shows the Example of a droplet discharge head. It is a figure which shows the other Example of a droplet discharge head. It is a figure which shows the other Example of a droplet discharge head. It is a figure which shows the other Example of a droplet discharge head. It is a figure which shows the other Example of a droplet discharge head. It is a figure which shows the other Example of a droplet discharge head. It is a figure which shows the other Example of a droplet discharge head. It is a figure which shows the other Example of a droplet discharge head. It is a figure which shows the other Example of a droplet discharge head. It is a figure which shows the other Example of a droplet discharge head. It is sectional drawing which shows another structure of the droplet discharge head in a droplet formation unit. It is sectional drawing which shows another structure of the droplet discharge head in a droplet formation unit. It is the schematic which shows the mode of the liquid column resonance phenomenon in the liquid column resonance chamber of a droplet discharge head. It is sectional drawing which shows the mode of the droplet operation | movement in the toner droplet head in the conventional toner manufacturing apparatus.

  FIG. 1 is a cross-sectional view showing the overall configuration of a toner manufacturing apparatus according to an embodiment of the present invention. FIG. 2 is a cross-sectional view showing a configuration of a droplet discharge head in the droplet formation unit of FIG. FIG. 3 is a cross-sectional view taken along line A-A ′ showing the configuration of the droplet forming unit of FIG. 1. A toner manufacturing apparatus 1 according to the present embodiment shown in FIG. 1 mainly includes a droplet forming unit 10 and a dry collection unit 30. The droplet forming unit 10 is a liquid chamber having a liquid ejection region that communicates with the outside through an ejection hole, and generates a liquid column resonance standing wave under the conditions described later. A plurality of droplet discharge heads 11 as droplet forming means for ejecting the droplets as droplets from the discharge holes are arranged. Airflow generated by airflow generation means (not shown) passes through both sides of each droplet discharge head 11 so that the droplets of the toner composition liquid discharged from the droplet discharge head 11 flow out to the dry collection unit 30 side. An airflow passage 12 is provided. Further, the droplet forming unit 10 includes a raw material container 13 that stores a toner composition liquid 14 that is a toner raw material, and a liquid droplet discharge head 11 that passes the toner composition liquid 14 stored in the raw material container 13 through a liquid supply pipe 16. And a liquid circulation pump 15 that pumps the toner composition liquid 14 in the liquid supply pipe 16 to be supplied to the liquid common supply path 17 (described later) and then returned to the raw material container 13 through the liquid return pipe 22. It is configured. Furthermore, as shown in FIG. 2, the droplet discharge head 11 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. The liquid column resonance liquid chamber 18 is provided on the wall surface facing the toner discharge hole 19 and the toner discharge hole 19 for discharging the toner droplet 21 to one wall surface among the wall surfaces connected to both ends. In order to form a columnar resonance standing wave, vibration generating means 20 that generates high-frequency vibration is included. The vibration generating means 20 is connected to a high frequency power source (not shown).

  The dry collection unit 30 shown in FIG. 1 includes a chamber 31 and a toner collection unit 32. In the chamber 31, a large descending airflow is formed by combining the airflow generated by the airflow generating means (not shown) and the descending airflow 33. Since the toner droplet 21 ejected from the droplet ejection head 11 of the droplet ejecting unit 10 is conveyed downward not only by gravity but also by a descending airflow 33, the ejected toner droplet 21 is air. It can suppress decelerating by resistance. Thereby, when the toner droplet 21 is continuously ejected, the toner droplet 21 ejected before is decelerated by the air resistance, and the toner droplet 21 ejected later is the toner droplet 21 ejected before. By catching up with the toner droplets 21, it is possible to prevent the toner droplets 21 from being joined and integrated to increase the particle size of the toner droplets 21. As the air flow generation means, either a method of providing a blower in the upstream portion and pressurizing, or a method of suctioning from the toner collecting unit 32 and reducing the pressure can be employed. In addition, a rotating airflow generator (not shown) that generates a rotating airflow that rotates around an axis parallel to the vertical direction is disposed in the toner collecting unit 32. Further, the toner collecting unit 32 has a toner storing unit 35 that stores dried and solidified toner particles that have passed through a toner collecting tube 34 that communicates with the chamber 31.

Next, an outline of the toner manufacturing process in the toner manufacturing apparatus of the present embodiment will be described.
The toner composition liquid 14 accommodated in the raw material container 13 shown in FIG. 1 is passed through the liquid supply pipe 16 by a liquid circulation pump 15 for circulating the toner composition liquid 14, and then the droplet forming unit shown in FIG. The liquid common supply path 17 flows into the liquid column resonance liquid chamber 18 of the droplet discharge head 11 shown in FIG. A pressure distribution is formed in the liquid column resonance liquid chamber 18 filled with the toner composition liquid 14 by the liquid column resonance standing wave generated by the vibration generating means 20. Then, the toner droplet 21 is discharged from the toner discharge hole 19 disposed in a region where the amplitude of the liquid column resonance standing wave has a large amplitude 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, which is within a range of ± 1/4 wavelength (see FIG. 23 described later). 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 composition liquid 14 that has passed through the common liquid supply path 17 flows through the liquid return pipe 22 and is returned to the raw material container 13. When the amount of the toner composition liquid 14 in the liquid column resonance liquid chamber 18 decreases due to the ejection of the toner 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 The flow rate of the toner composition liquid 14 supplied from the supply path 17 increases, and the toner composition liquid 14 is replenished into the liquid column resonance liquid chamber 18. Then, when the toner composition liquid 14 is replenished in the liquid column resonance liquid chamber 18, the flow rate of the toner composition liquid 14 passing through the liquid common supply path 17 is restored to the original, and the liquid supply pipe 16 and the liquid return pipe 22 are supplied. The flow of the toner composition liquid 14 circulating in the apparatus is again formed. On the other hand, the toner droplets 21 ejected from the droplet ejection head 11 of the droplet ejecting unit 10 are not only caused by gravity but also an air flow generated by an air flow generating means (not shown) as shown in FIG. 12 is conveyed downward by a descending airflow 33 formed through 12. Next, a spiral airflow is formed along the conical inner wall surface of the toner collecting portion 32 by the rotating airflow and the descending airflow 33 generated by a rotating airflow generator (not shown) in the toner collecting portion 32, The toner particles are dried and solidified in a laminar flow state on the spiral airflow. The dried and solidified toner particles are stored in the toner storage unit 35 through the toner collecting tube 34.

  The liquid column resonance liquid chamber 18 in the droplet discharge head 11 is joined to a frame formed of a material having such a high rigidity that does not affect the resonance frequency of the liquid at a driving frequency such as metal, ceramics, or silicon. Has been formed. Further, as shown in FIG. 2, the length L between the wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 is determined based on the liquid column resonance principle as described later. Further, the width W of the liquid column resonance liquid chamber 18 shown in FIG. 3 is desirably smaller than one 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 droplet forming unit 10 in order to dramatically improve productivity. The range is not limited, but one droplet forming unit provided with 100 to 2000 liquid column resonance liquid chambers 18 is most preferable because both operability and productivity can be achieved. In addition, for each liquid column resonance liquid chamber, a flow path for supplying liquid is connected 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. .

The vibration generating means 20 in the droplet discharge head 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). However, since the amount of displacement is generally small, the piezoelectric body is often used by being laminated. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO _{3, and the} like can be given. 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.

  Further, the diameter of the opening of the toner discharge hole 19 is desirably in the range of 1 [μm] to 40 [μm]. If the particle size is smaller than 1 [μm], the formed droplets may be very small, and thus the toner may not be obtained. In 19, there is a possibility that the blockage is frequently generated and the productivity is lowered. When the particle size is larger than 40 [μm], the diameter of the toner droplet is large, and when this is dried and solidified to obtain a desired toner particle diameter of 3 to 6 μm, the toner composition is diluted with an organic solvent into a very dilute liquid. In order to obtain a certain amount of toner, a large amount of drying energy is required, which is inconvenient. Also, as can be seen from FIG. 3, adopting a configuration in which the toner discharge holes 19 are provided in the width direction in the liquid column resonance liquid chamber 18 can provide a large number of openings of the toner discharge holes 19, thereby improving the production efficiency. It is preferable because it becomes high. Further, since the liquid column resonance frequency varies depending on the arrangement of the toner discharge holes 19, it is desirable that the liquid column resonance frequency is appropriately determined by confirming the discharge of the droplets.

Next, the mechanism of droplet formation by the droplet formation unit in the toner manufacturing apparatus of the present invention will be described.
First, the principle of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber 18 in the liquid droplet ejection head 11 of FIG. 2 will be described. The sound velocity of the toner composition liquid in the liquid column resonance liquid chamber is c, and the vibration generating means 20 When the driving frequency applied to the toner composition liquid as a medium is f, the wavelength λ at which the liquid resonance occurs is
λ = c / f (Formula 1)
Are in a relationship.

Further, in the liquid column resonance liquid chamber 18 of FIG. 2, 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]) is about twice the height h2 (= about 40 [μm]) of the communication port, and the fixed ends on both sides are assumed to be equivalent to the fixed end closed. In this case, resonance is formed most efficiently when the length L coincides with 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 having a pressure relief portion and the other side is closed (fixed end), that is, one side fixed end or one side open end, the length L is the wavelength λ. Resonance is most efficiently formed when it matches an odd multiple of a quarter. That is, N in Expression 2 is expressed as 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 the resonance, the vibration is not amplified infinitely, and has a Q value. As shown in equations 4 and 5, which will be described later, Resonance also occurs at frequencies near the highly efficient drive frequency f.

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

  Note that the liquid column resonance liquid chamber in the liquid droplet ejection head of the liquid droplet formation unit of the present embodiment shown in FIGS. 1 and 2 is equivalent to the closed end state or the influence of the opening of the toner ejection hole. An end portion that can be described as an acoustically soft wall 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 configuration in which the wall surfaces are formed at both ends in the longitudinal direction of the liquid column resonance liquid chamber as shown in FIG. 4B and FIG. 5A is the resonance mode at both fixed ends, and the toner discharge hole side is open. This is a preferable configuration because all the resonance modes of the one-side open end to be considered can be used.

  Further, the numerical aperture of the toner discharge hole, the opening arrangement position, and the cross-sectional shape of the toner discharge hole are factors that determine the drive frequency, and the drive frequency can be appropriately determined according to this. For example, when the number of toner discharge holes is increased, the restriction at the tip of the liquid column resonance liquid chamber, which has been the fixed end, gradually loosens, a resonance standing wave that is almost close to the opening end is generated, and the drive frequency increases. Furthermore, the opening position of the toner discharge hole that is closest to the liquid supply path is a starting point, and the loose restriction condition is used. The cross-sectional shape of the toner discharge hole is round, or the volume of the discharge hole varies depending on 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 toner discharge hole closest to the end on the liquid supply side is Le, both the lengths of L and Le are used. Then, the vibration generating means is vibrated using a driving waveform whose main component is the driving frequency f in the range determined by the following formulas 4 and 5, and a liquid column resonance is induced to eject a droplet from the toner ejection hole. Is possible.

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 toner discharge hole closest to the end on the liquid supply side is preferably Le / L> 0.6. .

  The liquid column resonance pressure standing wave is formed in the liquid column resonance liquid chamber 18 of FIG. 2 using the principle of the liquid column resonance phenomenon described above, and the toner discharge holes disposed in a part of the liquid column resonance liquid chamber 18. In 19, droplet discharge continuously occurs. Note that it is preferable to dispose the toner discharge hole 19 at a position where the standing wave pressure fluctuates the most, because the discharge efficiency is increased and the toner can be driven at a low voltage. Further, one toner discharge hole 19 may be provided for one liquid column resonance liquid chamber 18, but it is preferable to arrange a plurality of toner discharge holes 19 from the viewpoint of productivity. Specifically, it is preferably between 2 and 100. When the number exceeds 100, if a desired toner droplet is formed from the 100 toner discharge holes 19, it is necessary to set a high voltage to the vibration generating means 20, and the piezoelectric body as the vibration generating means 20 is required. The behavior of becomes unstable. Further, when the plurality of toner discharge holes 19 are opened, the pitch between the toner 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 toner discharge holes is larger than 20 [μm], there is a high probability that the droplets discharged from the adjacent toner discharge holes collide with each other to form large droplets, leading to deterioration of the toner particle size distribution. .

  Next, the state of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber in the droplet discharge head in the droplet forming unit will be described with reference to FIG. In the figure, the solid line drawn in the liquid column resonance liquid chamber represents the velocity distribution plotting the velocity at any measurement position from the fixed end side to the liquid common supply path side end in the liquid column resonance liquid chamber. The direction from the common liquid supply path to the liquid column resonance liquid chamber is +, and the opposite direction is −. In addition, the dotted line marked in the liquid column resonance liquid chamber indicates a pressure distribution in which the pressure value at each arbitrary measurement position between the fixed end side and the liquid common supply path side end in the liquid column resonance liquid chamber is plotted. The positive pressure is + with respect to the atmospheric pressure, and the negative pressure is-. Moreover, if it is a positive pressure, a pressure will be applied to the downward direction in the figure, and if it is a negative pressure, a pressure will be applied to the upward direction in the figure. Furthermore, in the same figure, the liquid common supply path side is opened as described above, but the height of the opening where the liquid common supply path 17 and the liquid column resonance liquid chamber 18 communicate with each other (height h2 shown in FIG. 2). On the other hand, since the height of the frame serving as the fixed end (height h1 shown in FIG. 2) is about twice or more, the approximate condition is that the liquid column resonance liquid chamber 18 is substantially fixed on both sides. The change in the velocity distribution and the pressure distribution over time is shown.

  (A) of the figure shows a pressure waveform and a velocity waveform in the liquid column resonance liquid chamber 18 when droplets are discharged. Moreover, (b) of the figure shows a pressure waveform and a velocity waveform in the liquid column resonance liquid chamber 18 when the liquid is drawn immediately after the droplet is discharged. As shown in FIGS. 4A and 4B, the pressure in the flow path provided with the toner discharge hole 19 in the liquid column resonance liquid chamber 18 is maximum. The flow of the toner composition liquid in the liquid column resonance liquid chamber 18 is in the direction of flowing toward the liquid common supply path 17 and the speed is small. Thereafter, as shown in FIG. 5C, the positive pressure in the vicinity of the toner discharge hole 19 becomes small and shifts to the negative pressure direction. The flow of the toner composition liquid in the liquid column resonance flow path 18 does not change depending on the flow direction toward the liquid common supply path 17 and (a), (b) in the figure, but the speed becomes maximum.

  As shown in (d) of the figure, the pressure in the vicinity of the toner discharge hole 19 is minimized. From this time, the filling of the toner composition liquid 14 into the liquid column resonance liquid chamber 18 starts. Thereafter, as shown in (e) of the figure, the negative pressure near the toner discharge hole 19 becomes smaller and shifts to the positive pressure direction. At this time, the filling of the toner composition liquid 14 is completed. Then, again, as shown in FIG. 5A, 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 toner discharge hole 19. In this way, a standing wave due to liquid column resonance is generated in the liquid column resonance liquid chamber by high-frequency driving of the vibration generating means, and corresponds to an antinode of standing wave due to liquid column resonance where the pressure changes most. Since the toner discharge hole 19 is disposed in the droplet discharge region to be discharged, the toner droplet 21 is continuously discharged from the toner discharge hole 19 in accordance with the antinode period.

  Next, an example of a configuration in which droplets are actually ejected by the liquid column resonance phenomenon will be described. This example is a resonance mode in which the length L between both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 in FIG. 2 is 1.85 [mm] and N = 2, and the first to fourth toner discharge holes. FIG. 7 shows a state in which a toner discharge hole is arranged at the antinode of the N = 2 mode pressure standing wave, and a discharge performed with a sine wave with a drive frequency of 340 [kHz] is photographed by a laser shadowgraphy method. . As can be seen from the figure, it is possible to discharge droplets having a uniform diameter and a substantially uniform speed. FIG. 8 is a characteristic diagram showing droplet velocity frequency characteristics when driven by the same amplitude sine wave with a drive frequency of 290 [kHz] to 395 [kHz]. As can be seen from the figure, in the first to fourth nozzles, the discharge speed from each nozzle is uniform and the maximum discharge speed when the drive frequency is around 340 [kHz]. From this characteristic result, it can be seen that, in the second mode of the liquid column resonance frequency, 340 [kHz], uniform discharge is realized at the antinode position of the liquid column resonance standing wave. Further, from the characteristic results of FIG. 8, the droplet is between the droplet discharge speed peak at 130 [kHz] which is the first mode and the droplet discharge speed peak at 340 [kHz] which is the second mode. It can be seen that the characteristic frequency characteristic of the liquid column resonance standing wave of the liquid column resonance that does not discharge is generated in the liquid column resonance liquid chamber.

  FIG. 9 is a characteristic diagram showing the relationship between the applied voltage and the discharge speed at each nozzle, and FIG. 10 is a characteristic diagram showing the relationship between the applied voltage and the droplet diameter at each nozzle. As can be seen from both figures, the ejection speed and the droplet diameter tended to monotonously increase with respect to the applied voltage. Therefore, since the ejection speed and the droplet diameter depend on the applied voltage, the droplet diameter corresponding to the desired ejection speed or the desired toner particle diameter can be adjusted by adjusting the applied voltage.

  The following shows an example of the relationship between the standing wave and the number and pattern of the ejection holes of the droplet ejection head in the toner manufacturing apparatus of this embodiment. The present invention is not limited to these examples. In each of the following embodiments, the resonance frequency can be known by experimentally searching for the discharge frequency. In addition, the results of the evaluation of the toner obtained by discharging the toner composition liquid under each condition to obtain toner base particles and then performing the external addition treatment are also shown.

Example 1
FIG. 11 is a diagram showing an embodiment of a droplet discharge head. As shown in FIG. 5A in the first embodiment, in the first embodiment, two toner discharge holes 19 are opened on the fixed end side in the liquid column resonance liquid chamber 18 and the liquid column resonance liquid chamber is formed. It is an example of the standing wave at the time of providing a reflecting wall in the 18 liquid common supply path side end. Both ends can be regarded as standing waves in a resonance mode of N = 2, which are substantially fixed ends. The driving frequency was 328 [kHz]. Example 1 shows the result of driving at the resonance peak frequency. The resonance peak is a node of the velocity resonance standing wave in the resonance state, which is the antinode of the liquid column resonance standing wave, that is, a state in which the pressure is highest, and a droplet is experimentally ejected, as shown in FIG. The frequency at which the speed becomes maximum can be determined.

-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
17 parts by mass of carbon black (Regal 400; manufactured by Cabot) and 3 parts by mass of a pigment dispersant were primarily dispersed in 80 parts by mass of ethyl acetate using a mixer having stirring blades. As the pigment dispersant, Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion in which aggregates of 5 μm or more were completely removed.

-Preparation of wax dispersion-
Next, a wax dispersion was prepared.
18 parts by mass of carnauba wax and 2 parts by mass of a wax dispersant were primarily dispersed in 80 parts by mass of ethyl acetate using a mixer having stirring blades. The primary dispersion was heated to 80 ° C. with stirring to dissolve the carnauba wax, and then the temperature of the liquid was lowered to room temperature to precipitate wax particles so that the maximum diameter was 3 μm or less. As the wax dispersant, a polyethylene wax grafted with a styrene-butyl acrylate copolymer was used. The obtained dispersion was further finely dispersed by a strong shearing force using a dyno mill and adjusted so that the maximum diameter was 1 μm or less.

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

-Preparation of toner-
The obtained toner composition liquid was used in the toner manufacturing apparatus shown in FIG. 1 having the droplet discharge head shown in FIG. Further, an air flow was generated from the air flow passage 12 in the same direction as the droplet traveling direction. After the dispersion was prepared, the droplets were discharged under the following conditions, and the droplets were dried and solidified to produce toner base particles.

[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.888 [g / cm ³ ]
Dry air flow rate: 30.0 [L / min]
In-apparatus temperature: 27-28 [° C]
Drive frequency: 328 [kHz]
Applied voltage sine wave peak value: 10.0 [V]
The formed droplet diameter was 11.8 [μm].

  The dried and solidified toner particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 [μm] pores. Particle size of collected particles The particle size distribution of the collected particles was measured under the following measurement conditions using a flow particle image analyzer (FPIA-2000). The weight average particle size (D4) was 5.5 [μm]. Further, toner base particles having a number average particle diameter (Dn) of 5.2 [μm] and D4 / Dn of 1.06 were obtained.

  A measurement method using a flow particle image analyzer (Flow Particle Image Analyzer) will be described below. The measurement of toner, toner particles and external additives using a flow particle image analyzer can be performed using, for example, a flow particle image analyzer FPIA-2000 manufactured by Toa Medical Electronics Co., Ltd.

The measurement removes fine dust through a filter, and as a result, the number of particles in a measurement range (for example, an equivalent circle diameter of 0.60 [μm] or more and less than 159.21 [μm]) in 10 −3 cm 3 water is 20 or less. A few drops of a nonionic surfactant (preferably Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.) is added to 10 [ml] of water, and 5 [mg] of a measurement sample is further added thereto, and UH-50 manufactured by an ultrasonic dispersing device STM. Dispersion treatment is performed for 1 minute under the conditions of 20 [kHz], 50 [W] / 10 [cm ³ ], and dispersion treatment is further performed for a total of 5 minutes, so that the particle concentration of the measurement sample is 4000 to 8000 [pieces] / 10 ^−3. Using a sample dispersion of [cm ³ ] (for particles in the measurement equivalent circle diameter range), the particle size distribution of particles having an equivalent circle diameter of 0.60 [μm] or more and less than 159.21 [μm] is measured. To do.

  The sample dispersion is passed through a flat and flat transparent flow cell (thickness: about 200 [μm]) flow path (spread along the flow direction). 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 is in a certain range parallel to the flow cell. Is taken 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 is calculated as the equivalent circle diameter.

  In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, 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 0.06-400 [μm] into 226 channels (divided into 30 channels for one octave). In actual measurement, particles are measured in a range where the equivalent circle diameter is 0.60 [μm] or more and less than 159.21 [μm].

(External processing)
After drying and solidifying the toner base particles, a cyclone is collected, and then hydrophobic silica (H2000, manufactured by Clariant Japan) 1.0 [mass%] is externally added using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). To produce a toner.

(Creation of carrier)
A silicone resin as a coating layer material is dispersed in toluene to prepare a coating layer dispersion, and then spray-coated and fired on a core material (spherical ferrite particles having an average particle size of 50 [μm]) in a heated state. After cooling, a carrier having an average thickness of the coating layer of 0.2 [μm] was produced.

-Production of developer-
96 parts by mass of the carrier was mixed with 4 parts by mass of the obtained toner to prepare a two-component developer.

<Thin wire reproducibility>
The prepared developer is put into a modified machine with an improved developer part of a commercially available copying machine (Imagiono 271 manufactured by Ricoh Co., Ltd.), and 6000 paper manufactured by Ricoh Co., Ltd. is used with a printing ratio of 7%. And run. Compare the original 10th image and the 30,000th image thin line with the original, and observe it at 100x magnification using an optical microscope. , ◯, Δ, × evaluated in four stages. Note that the image quality is high in the order of ◎>○>Δ> ×, and in particular, the evaluation of “x” is a level that cannot be adopted as a product. In Table 1 below, evaluation results of fine line reproducibility of Examples 2 to 13 after Example 1 are also listed.

(Example 2)
FIG. 12 is a diagram showing another embodiment of the droplet discharge head. In the second embodiment shown in the figure, ten toner discharge holes 19 are opened on the fixed end side in the liquid column resonance liquid chamber 18 and a reflection wall is provided on the liquid common supply path side of the liquid column resonance liquid chamber 18. It is an example of a standing wave. The drive frequency was 377 [kHz]. Therefore, the fixed end side is a loosely fixed end compared to the first embodiment of FIG.

(Example 3)
FIG. 13 is a diagram showing another embodiment of the droplet discharge head. In the third embodiment shown in the figure, 24 toner discharge holes 19 are opened on the fixed end side in the liquid column resonance liquid chamber 18 and a reflection wall is provided on the liquid common supply path side of the liquid column resonance liquid chamber 18. It is an example of a standing wave. The drive frequency was 417 [kHz]. Therefore, as compared with the first embodiment of FIG. 11, the tip side regarded as the fixed end in the liquid column resonance liquid chamber 18 is a standing wave of N = 3 resonance mode close to the open end.

Example 4
FIG. 14 is a diagram showing another embodiment of the droplet discharge head. In the fourth embodiment shown in the figure, four toner discharge holes 19 are opened on the fixed end side in the liquid column resonance liquid chamber 18 and a reflection wall is provided on the liquid common supply path side of the liquid column resonance liquid chamber 18. It is an example of a standing wave. The driving frequency was 344 [kHz]. Therefore, the fixed end side is somewhat looser than the first embodiment of FIG. 11 due to the influence of the opening of the discharge hole, but is a fixed end with the standing wave of the resonance mode of N = 2.

(Example 5)
FIG. 15 is a diagram showing another embodiment of the droplet discharge head. In the fifth embodiment shown in the figure, when the number of the toner discharge holes is locally increased, the toner discharge hole 19 approaches the liquid common supply path side, and the other end is a closed end. A region having a toner discharge hole arranged closer to the fixed end than a pressure distribution in a region where the toner discharge hole arranged closer to the liquid common supply path is generated and a standing wave of resonance mode of N = 1 is generated The pressure distribution is flat. The driving frequency was 160 [kHz].

(Example 6)
FIG. 16 is a diagram showing another embodiment of the droplet discharge head. In the sixth embodiment shown in the same figure, 36 toner discharge holes 19 are opened on the fixed end side in the liquid column resonance liquid chamber 18, so that the toner discharge to a range of about one third of the length of the liquid column resonance liquid chamber. A hole is provided. In Example 6, the resonance mode standing wave of N = 2 is obtained, but the fixed end side is a loosely fixed end. The driving frequency was 468 [kHz].

(Example 7)
FIG. 17 is a diagram showing another embodiment of the droplet discharge head. Example 7 shown in the figure is an example of a liquid resonance flow path and an opening pattern of toner ejection holes having the same form as Example 6, but the frequency is slightly lowered. The drive frequency was 395 [kHz]. In this case, the resonance standing wave pattern is as shown in the figure, and the pressure distribution is further uniformized in a densely confined region of the toner discharge holes, which is loosely constrained. Compared to Example 6, D4 / DN was smaller, that is, the particle size distribution was more uniform. Thus, even in the same form, the particle size distribution can be optimized by appropriately determining the drive frequency within the region where resonance occurs.

(Example 8)
FIG. 18 is a diagram showing another embodiment of the droplet discharge head. The eighth embodiment shown in the figure is an example in which four toner discharge holes are arranged on the fixed end side and the liquid common supply path side. As in the first embodiment, the resonance mode standing wave of N = 2 is obtained. Even with such an arrangement of toner discharge holes, it was possible to discharge uniformly from all the toner discharge holes. The driving frequency was 344 [kHz].

Example 9
FIG. 19 is a diagram showing another embodiment of the droplet discharge head. In the ninth embodiment shown in the figure, when the cross-sectional area of the liquid common supply path is larger than the cross-sectional area of the liquid column resonance liquid chamber, the liquid common supply path side is an open end. In this case, N = 1 resonance mode standing wave. The drive frequency was 261 [kHz].

(Example 10)
FIG. 20 is a diagram showing another embodiment of the droplet discharge head. The tenth embodiment shown in the figure has the same form as the ninth embodiment, but is an example in which the drive frequency is changed. The driving frequency was 516 [kHz]. In the case of the tenth embodiment, N = 4 resonance mode standing wave.

(Example 11)
FIG. 21 is a diagram showing another embodiment of the droplet discharge head. Example 11 shown in the figure is an example in which the configuration of the airflow passage 12 through which the airflow generated by the airflow generating means in Example 1 passes is different. Although the direction of the airflow path 12 of Example 1 was the same direction as the droplet discharge direction, the airflow path 12 of Example 11 was the first airflow path 12-1 and the first airflow path 12-1. And a second airflow passage 12-2 connected to the gas phase of the chamber 31 in the dry collection unit 30. The direction of the first airflow passage 12-1 is substantially perpendicular to the droplet discharge direction, and the second airflow passage 12-1 is substantially orthogonal to the direction of the first airflow passage 12-1. And the same direction as the droplet discharge direction. The air velocity was 20 [m / s] in the vicinity of the toner discharge hole. The number average particle diameter was 4.6 [μm] and D4 / DN = 1.05.

(Example 12)
FIG. 22 is a diagram showing another embodiment of the droplet discharge head. The twelfth embodiment shown in the figure is an example in which the configuration of the airflow passage 12 through which the airflow generated by the airflow generating means in the first embodiment passes is different. The direction of the airflow passage 12 in Example 1 was the same direction as the droplet discharge direction, but the direction of the airflow passage 12 in Example 12 was a direction substantially orthogonal to the droplet discharge direction, and this direction Is the direction to the gas phase of the chamber 31 in the dry collection unit 30. The air velocity was 20 [m / s] in the vicinity of the toner discharge hole. The number average particle diameter was 4.8 [μm] and D4 / DN = 1.09.

(Example 13)
The air flow in Example 12 shown in FIG. 22 was an air flow generated by pressurization by the air flow generation means, but the air flow in Example 13 was obtained by suction using a suction means provided on the dry collection unit 30 side, for example. It is the generated air current. Other than that is the same as Example 12. The air velocity was 16 [m / s] in the vicinity of the toner discharge hole. The number average particle diameter was 4.8 [μm] and D4 / DN = 1.09.

Next, the toner according to the present invention will be described as an example of fine 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 above-described toner manufacturing apparatus according to the present embodiment. can get.

  Specifically, the particle size distribution (weight average particle diameter / number average particle diameter) of the toner is preferably in the range of 1.00 to 1.15. More preferably, it is 1.00 to 1.05. Moreover, as a weight average particle diameter, it is preferable to exist in the range of 1-20 [micrometer], More preferably, it is 3-10 [micrometer].

Next, toner materials that can be used in the present invention will be described. First, a toner composition liquid in which a toner composition is dispersed and dissolved in a solvent as described above will be described.
As the toner material, the same material as that of a conventional electrophotographic toner can be used. That is, a toner binder such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin is dissolved in various organic solvents, a colorant is dispersed, and a release agent is dispersed or dissolved. The target toner particles can be produced by drying and solidifying into fine droplets by the toner production method.

[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. For example, a styrene monomer, an acrylic monomer, a methacrylic monomer, etc. Vinyl polymers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins , Coumarone indene resin, polycarbonate resin, petroleum resin, and the like.

  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 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, or 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 -Ethylhexyl, stearyl methacrylate, phenyl methacrylate, methacrylic acid such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate or esters thereof, and the like.

  The following (1)-(18) is mentioned as an example of the other monomer which forms the said vinyl polymer or a copolymer. (1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene 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, N-vinyl pyrrolidone; (8), vinyl naphthalenes; (9) acrylonitrile, Such as methacrylonitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as 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 monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; 16) Monomers having a carboxyl group such as anhydrides of the α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof; ) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1 -Hydroxy-1-methylhexyl) monomers having a hydroxy group such as styrene.

  In the toner according to the present invention, the vinyl polymer or copolymer of 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 vinyl vinyl 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. And xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates 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 the above compounds in place of methacrylate, triallyl cyanide. Examples include nurate and triallyl trimellitate.

  These crosslinking agents are preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, with respect to 100 parts by mass of 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, cyclohexanone Ketone peroxides such as oxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di -Tert-butyl peroxide, tert-butyl cumyl 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-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexyl Sulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexarate, tert-butyl peroxylaurate, tert-butyl-oxybenzoate, tert-butyl Peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-tert-butyl Kisa Hydro terephthalate to Rupaokishi, tert- butylperoxy azelate, and the like.

  When the binder resin is a styrene-acrylic resin, the molecular weight distribution by GPC soluble in the resin component tetrahydrofuran (THF) has at least one peak in the region of molecular weight 3,000 to 50,000 (in terms of number average molecular weight). A resin which is present and has 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. Further, 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 5,000 to 30,000 is more preferable. A binder resin having a main peak in the region of 5,000 to 20,000 is most preferable.

  The acid value when the binder resin is a vinyl polymer such as styrene-acrylic resin is preferably 0.1 [mg KOH / g] to 100 [mg KOH / g], and preferably 0.1 [mg KOH / g]. ] To 70 [mgKOH / g], more preferably 0.1 [mgKOH / g] to 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, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned.

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, such as dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene , Etc.

  Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic 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, or anhydrides thereof, partial lower alkyl esters, and the like.

  When the binder resin is a polyester resin, the toner has fixability and offset resistance because at least one peak exists in the molecular weight range of 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component. In addition, as the THF-soluble component, a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100 [%] is also preferable, and at least one peak is in a region having a molecular weight of 5,000 to 20,000. A binder resin in which is present is more preferred.

  When the binder resin is a polyester resin, the acid value is preferably 0.1 [mgKOH / g] to 100 [mgKOH / g], and preferably 0.1 [mgKOH / g] to 70 [mgKOH / g]. It is more preferable that it is 0.1 [mg KOH / g] to 50 [mg KOH / g].

  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, it is also possible to use a resin containing a monomer component capable of reacting with both of these resin components in at least one of the vinyl polymer component and the polyester resin component. it can. 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. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  Moreover, when using together a polyester polymer, a vinyl polymer, and other binder resin, the resin whose acid value of the whole binder resin is 0.1-50 [mgKOH / g] is 60 [mass%] or more. What has is preferable.

In the present invention, the acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation conforms to JIS K-0070.
(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. . The pulverized product 0.5 to 2.0 [g] is precisely weighed, and the weight of the polymer component is defined as W [g]. For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant or 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 usage amount of the KOH solution at this time is set to S [ml], the blank is measured at the same time, and the usage amount of the KOH solution at this time is set to B [ml], and the following formula is calculated. However, f is a factor of KOH.
Acid value [mgKOH / g] = [(SB) × f × 5.61] / W

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

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

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 ₂ O ₄ , _{PbFe 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, nickel powder, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of triiron tetroxide and γ-iron trioxide are particularly preferable.

  Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used. Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, And gallium. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or 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 precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grains production | generation, or adding salt of each element and adjusting pH.

  As the usage-amount of the said magnetic body, 10-200 mass parts of magnetic bodies are preferable with respect to 100 mass parts of binder resin, and 20-150 mass parts is more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 [μm], more preferably 0.1 to 0.5 [μm]. The number average diameter can be obtained by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.

In addition, as magnetic characteristics of the magnetic material, the magnetic characteristics when applied with 10K oersted are coercive force 20 to 150 oersted, saturation magnetization 50 to 200 [emu / g], and residual magnetization 2 to 20 [emu / g], respectively. Is preferred.
The magnetic material can also be used as a colorant.

[Colorant]
The colorant is not particularly limited and may be appropriately selected from commonly used resins. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fu Issey Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor 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, Nacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine 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 Blue, Bitumen, 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 , Malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.

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

  The colorant used in the toner according to the present invention can also be used as a master batch combined with a resin. As the binder resin kneaded together with the production of the master batch or the master batch, in addition to the above-mentioned modified and unmodified polyester resins, for example, polystyrene, poly p-chlorostyrene, polyvinyltoluene and other styrene and its substitutes Polymer: 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-Chloromethyl methacrylate Polymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, Styrene copolymers such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl Examples include butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or 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 master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, there is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. 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 [mg KOH / g] or less, an amine value of 1 to 100 and a colorant dispersed therein, and an acid value of 20 [mg KOH / g]. Hereinafter, it is more preferable that the amine value is 10 to 50 and the colorant is dispersed and used. When the acid value exceeds 30 [mgKOH / g], the chargeability under high humidity may be lowered and the pigment dispersibility may be insufficient. Also, 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 examples of commercially available products include “Ajisper PB821” and “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.). , “Disperbyk-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like.

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

  The weight average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene conversion weight in gel permeation chromatography, preferably 500 to 100,000, and more preferably 3000 to 100,000 from the viewpoint of pigment dispersibility. In particular, 5000 to 50000 is preferable, and 5000 to 30000 is most preferable. When the molecular weight is less than 500, the polarity becomes high and the dispersibility of the colorant may be lowered. When the molecular weight exceeds 100,000, the affinity with the solvent is increased and the dispersibility of the colorant is lowered. There is.

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

<Wax>
The toner composition liquid used in the present invention contains a wax together with a binder resin and a colorant.
The wax is not particularly limited and can be appropriately selected from those usually used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sazol wax, etc. Of aliphatic hydrocarbon waxes, oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof, plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax, beeswax, Waxes mainly composed of animal waxes such as lanolin and whale wax, mineral waxes such as ozokerite, ceresin, and petrolatum, and fatty acid esters such as montanic acid ester wax and castor wax. Deoxidized carnauba wax and other fatty acid esters that have been partially or wholly deoxidized are included.

  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, prandidic acid, eleostearic acid, and valinal acid. Unsaturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnupyl alcohol, seryl alcohol, mesyl alcohol, or long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acids Fatty acid amides such as amide and lauric acid amide, methylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide and other saturated fatty acid bisamides, ethylene bis oleic acid amide, hexamethylene bis Unsaturated fatty acid amides such as oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasinic acid amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Grafted onto aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate, and aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid. Examples thereof include waxes, partial ester compounds of polyhydric alcohols such as behenic acid monoglycerides, and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  More preferable examples 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 polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure. Polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method, age method, etc. Hydrocarbon wax synthesized by the above, synthetic wax using a compound having one carbon atom as a monomer, hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group, hydrocarbon wax and hydrocarbon having a functional group Mixture of system wax, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.

  In addition, these waxes have a sharp molecular weight distribution using a press perspiration 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. If it is less than 70 [° C.], the blocking resistance may be lowered, and if it exceeds 140 [° C.], the offset resistance effect may be difficult to be exhibited.

  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 [° C.] 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 the same 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. If it is less than 10 [° C.], the function separation effect may be difficult to appear, and if it exceeds 100 [° C.], the function may not be emphasized by interaction. At this time, since the function separation effect tends to be exhibited, the melting point of at least one of the waxes is preferably 70 to 120 [° C.], and more preferably 70 to 100 [° C.].

  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 end temperature of the maximum peak is in the region of 70 to 110 [° C.] in the endothermic peak observed in the DSC measurement of the toner. It is preferable that it has a maximum peak in the region of 70 to 110 [° C.].

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

  In the present invention, the 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, for example, carbon black, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder unoxidized titanium, Fine powder non-alumina, treated silica obtained by subjecting them to surface treatment with a silane coupling agent, titanium coupling agent or silicone oil, treated titanium oxide, treated alumina, and the like can be mentioned. Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these 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] as an 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 preferably shows a value of 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 preferable method, a method of treating a silica fine powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferable.

  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, Examples include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to Si. 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].

The specific surface area by nitrogen adsorption measured by the BET method is preferably 30 [m ² / g] or more, and more preferably 60 to 400 [m ² / g]. The surface-treated fine powder is preferably 20 [m ² / g] or more, more preferably 40 to 300 [m ² / g].

  The application amount of these fine powders 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 / carrier, improvement of cleaning properties, adjustment of thermal characteristics / electrical characteristics / physical characteristics, resistance adjustment, softening point adjustment, fixing rate For the purpose of improvement, various metal soaps, fluorosurfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, and inorganic such as titanium oxide, aluminum oxide, alumina A fine powder or the like can be added as necessary. These inorganic fine powders may be hydrophobized as necessary. In addition, lubricants such as polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, strontium titanate, anti-caking agents, white particles and black 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 rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. The load may then be given a relatively weak load 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, a Henschel mixer, and the like.

  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 composed of a binder resin and a colorant is melt-kneaded and then finely pulverized. Using a hybridizer, mechano-fusion, etc., the resulting material is mechanically adjusted, or the so-called spray-drying method is used to dissolve and disperse the toner material in a solvent in which the toner binder is soluble, and then using a spray-drying device. Examples thereof include a method of removing a solvent to obtain a spherical toner and a method of forming a spherical toner by heating in an aqueous medium.

  As the external additive, inorganic fine particles can be preferably used. Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like. The primary particle diameter of the inorganic fine particles is preferably 5 [mμ] to 2 [μm], and more preferably 5 [mμ] to 500 [mμ].

The specific surface area according to the BET method is preferably ^{20 to} 500 [m ² / g]. The use ratio of the inorganic fine particles is preferably 0.01 to 5 [mass%] of the toner, and more preferably 0.01 to 2.0 [mass%].

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

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

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

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

  The developing method using the toner according to the present invention can use all of the electrostatic latent image carriers used in the conventional electrophotography. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image, and the like. A carrier, a selenium electrostatic latent image carrier, a zinc oxide electrostatic latent image carrier, and the like can be suitably used.

  According to the toner manufacturing method of the present embodiment described above, the toner for discharging the toner composition liquid 14 to a part of the liquid column resonance liquid chamber 18 to which the toner composition liquid 14 containing at least resin is supplied. A discharge hole 19 is opened. The liquid column resonance liquid chamber 18 is provided with vibration generating means 20 for applying vibration to the toner composition liquid. When a frequency that meets the resonance condition is applied, a standing wave is formed in the liquid column resonance liquid chamber 18 due to liquid column resonance. A pressure distribution is formed in the liquid column resonance liquid chamber 18 by a standing wave due to liquid column resonance. The standing wave generated by the liquid column resonance generated in the liquid column resonance liquid chamber has a pressure distribution region where a high pressure is generated, which is called an antinode. By providing the toner discharge hole 19 in the pressure distribution region corresponding to the antinode, the toner composition liquid is continuously discharged from the toner discharge hole 19. Thereafter, the toner particles are produced by solidifying the droplets of toner droplets. A plurality of toner ejection holes 19 are formed in at least one of the regions that become antinodes of the standing wave due to the liquid column resonance. Therefore, continuous toner droplet ejection can be realized, and high productivity can be expected. In addition, a plurality of toner discharge holes are formed in at least one of the regions where the standing wave becomes antinode, and furthermore, a plurality of toner discharge holes are provided in one liquid column resonance liquid chamber. The property is further improved.

  Further, when the length of the liquid column resonance liquid chamber in the longitudinal direction is L, the frequency of the high frequency vibration generated by the vibration generating means is f, the speed of the sound wave of the toner composition liquid is c, and N is an integer, The vibration generating means is vibrated using a drive waveform whose main component is frequency f when f = N × c / (4L) is established, and liquid column resonance is induced in the liquid column resonance liquid chamber to thereby generate the toner. The composition liquid is continuously discharged from the toner discharge hole. Therefore, the toner composition liquid can be discharged continuously and stably from the toner discharge hole.

  The length of the liquid column resonance liquid chamber in the longitudinal direction is L, the distance to the toner discharge hole closest to the end on the liquid supply path side is Le, and the frequency of the high frequency vibration generated by the vibration generating means is f. When the velocity of the sound wave of the toner composition liquid is c and N is an integer, L and Le are used to determine a range determined by N × c / (4L) ≦ f ≦ N × c / (4Le). The vibration generating means is vibrated using a drive waveform having frequency f as a main component, and liquid column resonance is induced in the liquid column resonance liquid chamber, so that the toner composition liquid can be continuously discharged from the toner discharge hole. In addition, it is preferable that Le / L> 0.6.

  Further, the length in the longitudinal direction of the liquid column resonance liquid chamber is L, the distance to the toner discharge hole closest to the end on the liquid supply path side is Le, and the frequency of the high frequency vibration generated by the vibration generating means is f. When the velocity of the sound wave of the toner composition liquid is c and N is an integer, L and Le are used to determine N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le). The vibration generating means is vibrated using a driving waveform having a frequency f in the range as a main component, and liquid column resonance is induced in the liquid column resonance liquid chamber to continuously discharge the toner composition liquid from the toner discharge hole. it can.

  In addition, when only droplets are ejected by the droplet forming means, the flow velocity of the toner droplets is reduced due to the viscous resistance of the toner droplets due to air, and the toner droplets coalesce when continuously ejected. There was a risk of occurrence. Therefore, a flow path through which a gas forming an air flow for transporting the toner droplets formed by the droplet forming means to the solidifying means flows is provided in the vicinity of the toner discharge hole, and a further flow velocity is applied to the discharged toner droplets. To prevent the following toner droplets from coalescing with the preceding toner droplets. Therefore, a toner having a uniform particle diameter can be stably produced.

  Furthermore, since it is possible to control the speed of the toner droplets by the gas flow rate, it is preferable that the initial discharge speed of the toner droplets discharged from the droplet forming means is smaller than the gas speed. If the speed control of the toner droplets becomes possible, the discharged toner droplets do not coalesce and the continuous discharge can be stably performed. Further, an organic solvent is contained in the toner composition liquid. Then, the solidifying means removes the organic solvent contained in the toner composition liquid, and dries and solidifies the toner droplets. Being able to contain an organic solvent prevents it from sticking inside the head. Therefore, the efficiency of toner production is improved.

  The toner manufacturing apparatus of the present invention mainly includes droplet forming means 10 and solidifying means 30. The droplet forming means 10 discharges a toner composition liquid containing at least a resin from a toner discharge hole 19 provided in a part of a surface connected to both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 shown in FIG. To form droplets. Further, in the liquid column resonance liquid chamber, a liquid supply path 17 through which the toner composition liquid is supplied into the flow path is provided on a part of one of the wall surfaces at both ends in the longitudinal direction in the flow path. . Further, the liquid column resonance liquid chamber is provided with vibration generating means 20 for applying vibration to the toner composition liquid. Then, when high frequency vibration generated by the vibration applying means 20 is applied to the toner composition liquid supplied into the liquid column resonance liquid chamber, the longitudinal direction in the liquid column resonance liquid chamber as shown in FIGS. A standing wave is generated by liquid column resonance due to the liquid column resonance phenomenon in accordance with the resonance condition formed between the wall surfaces at both ends. The vibration frequency generated by the vibration generating means is preferably high-frequency vibration of 300 kHz or more. A standing wave due to the liquid column resonance is generated in the liquid column resonance liquid chamber, whereby a pressure distribution is formed in the liquid column resonance liquid chamber. According to the pressure distribution, toner discharge and liquid supply are continuously performed. The discharged toner droplets are solidified by a solidifying means to generate toner particles. Therefore, continuous toner droplet ejection can be realized, and high productivity can be expected.

  The present invention is not limited to the above-described embodiment, and various modifications, substitutions, and applications are possible as long as they are described within the scope of the claims.

DESCRIPTION OF SYMBOLS 1; Toner manufacturing apparatus, 10; Droplet formation unit, 11: Droplet discharge head,
12; Airflow passage, 12-1; First airflow passage, 12-2; Second airflow passage,
13; Raw material container, 14; Toner composition 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; toner droplet, 22; liquid return pipe,
30; Dry collection unit, 31; Chamber, 32; Toner collection unit,
33; Downstream air flow; 34; Toner collecting tube; 35; Toner reservoir.

JP 2007-199463 A Japanese Patent No. 3786034

Claims (16)

A method for producing fine particles, comprising: a droplet discharge step of discharging liquid from at least one discharge hole to form droplets; and a solidification step of solidifying the droplets,
The liquid is a liquid obtained by dissolving or dispersing a fine particle component in a solvent, or a melt of the fine particle component,
The droplet discharge step is formed in a region that forms an antinode of the standing wave by applying a vibration to the liquid in the liquid column resonance liquid chamber in which the discharge hole is formed to form a standing wave by the liquid column resonance. A method for producing fine particles, wherein the liquid is discharged from the discharge holes into droplets. In the manufacturing method of the microparticles according to claim 1,
A method for producing fine particles, wherein the fine particle component is a resin or a resin composition. The method for producing fine particles according to claim 1 or 2,
A method for producing fine particles, wherein a plurality of the discharge holes are formed in at least one of the regions that become the antinodes of the standing wave. In the manufacturing method of the microparticles according to any one of claims 1 to 3,
A method of producing fine particles, wherein a plurality of the discharge holes are provided in one liquid column resonance liquid chamber. In the manufacturing method of fine particles given in any 1 paragraph of Claims 1-4,
A method for producing fine particles, characterized in that reflection wall surfaces are provided at least partially at both ends in the longitudinal direction of the liquid column resonance liquid chamber. In the method for producing fine particles according to any one of claims 1 to 5,
As the above vibration
f = N × c / (4L)
(L: length of the liquid column resonance liquid chamber in the longitudinal direction, c: velocity of liquid acoustic wave, N: integer)
A method for producing fine particles, characterized by applying a vibration having a frequency f at which In the method for producing fine particles according to any one of claims 1 to 5,
As the above vibration
N × c / (4L) ≦ f ≦ N × c / (4Le)
(L: length in the longitudinal direction of the liquid column resonance liquid chamber, Le: distance to the discharge hole closest to the end on the liquid supply path side, c: velocity of liquid acoustic wave, N: integer)
A method for producing fine particles, characterized by applying a vibration having a frequency f at which The method for producing fine particles according to claim 7,
A method for producing fine particles, wherein Le / L> 0.6. In the method for producing fine particles according to any one of claims 1 to 5,
As the above vibration
N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le)
(L: length in the longitudinal direction of the liquid column resonance liquid chamber, Le: distance to the discharge hole closest to the end on the liquid supply path side, c: velocity of liquid acoustic wave, N: integer)
A method for producing fine particles, characterized by applying a vibration having a frequency f at which In the manufacturing method of the microparticles according to claim 1,
The method for producing fine particles, wherein the vibration frequency is high-frequency vibration of 300 kHz or more. In the manufacturing method of fine particles given in any 1 paragraph of Claims 1-10,
A method for producing fine particles, comprising providing a flow path for flowing a gas for forming an air flow that does not contract the distance between discharged droplets to a region where the solidification step is performed. The method for producing fine particles according to claim 11, wherein
A method for producing fine particles, wherein an initial discharge velocity of the discharged droplets is smaller than the velocity of the air flow. In the manufacturing method of the microparticles according to claim 1,
The liquid contains an organic solvent, and in the solidification step, the droplets are dried and solidified by removing the organic solvent. A fine particle manufacturing apparatus comprising: a droplet discharge unit that discharges liquid from at least one discharge hole to form droplets; and a solidification unit that solidifies the droplets.
The liquid is a liquid obtained by dissolving or dispersing a fine particle component in a solvent, or a melt of the fine particle component,
A liquid column resonance liquid chamber in which the discharge hole is opened;
Vibration generating means for applying vibration to the liquid in the liquid column resonance liquid chamber,
The vibration generating means imparts vibration to the liquid in the liquid column resonance liquid chamber to form a standing wave by liquid column resonance, and the liquid is discharged from the discharge hole formed in the region that becomes the antinode of the standing wave. An apparatus for producing fine particles, characterized by being discharged into droplets.   A toner produced by the method for producing fine particles according to any one of claims 1 to 13, or the fine particle production apparatus according to claim 14. The toner according to claim 15.
A toner having a particle size of 3.0 [μm] to 6.0 [μm].