JP5920653B2 - Fine particle production apparatus and fine particle production method - Google Patents

Description

The present invention, electrophotography, electrostatic recording, production of fine particles production equipment and fine particles for the production of fine particles such as toner for developing electrostatic images used for developing an electrostatic charge image in electrostatic printing and the like It is about the method .

  As a method for producing toner for developing electrostatic images used in image forming apparatuses such as copying machines, printers, facsimiles, and composite machines based on the electrophotographic recording method, the pulverization method has been the mainstream in the past. Then, the polymerization method is increasingly employed. The polymerization method is a method of forming toner particles in an aqueous medium, and is referred to as such because it involves a polymerization reaction of the toner raw material at the time of toner particle formation or in the process. Various polymerization methods have been put into practical use, and those utilizing suspension polymerization, emulsion aggregation, polymer suspension (polymer aggregation), ester elongation reaction, and the like are known. The toner manufactured by the polymerization method is called a polymerization toner or a chemical toner.

  The toner obtained by the polymerization method generally has the characteristics that it is easy to obtain a small particle size, the particle size distribution is narrow, and the shape is almost spherical compared to the toner obtained by the pulverization method. These characteristics bring about an effect that it is easy to obtain high image quality as an image formed by an electrophotographic method. However, in the polymerization method, the emulsion-polymerized resin particles are dispersed in an aqueous medium, followed by heat treatment and agglomeration to a predetermined particle size by a method such as addition of a flocculant. After agglomeration, a cleaning process is required to remove a solvent such as ethyl acetate contained in the toner particles when dispersed in an aqueous medium. In this solvent cleaning, a solvent such as ethyl acetate has a high solvent resistance, so that the cleaning effect is not sufficient with only one cleaning with water. For this purpose, the toner particles are once dried, and the water and solvent used for cleaning are evaporated from the toner particles, and then the cleaning is performed again. By repeating such washing and drying several times, the solvent can be removed from the toner particles. Such operations of repeating washing and drying are required, and there is a disadvantage that a lot of time, a large amount of water, and a lot of energy are required.

  Also, a liquid (toner component liquid) in which the raw material components of the toner are dissolved or dispersed in an organic solvent is discharged into fine droplets using a sprayer (atomizer), etc., and dried to form a fine particle toner As a toner production method called a jet granulation method for obtaining the above, those described in Patent Documents 1 to 4 are known. According to this toner manufacturing method, since it is not necessary to use water, the time and energy required for washing and drying can be greatly reduced, and the disadvantages of the polymerization method can be avoided.

  When manufacturing fine particles such as toner by the jet granulation method, the discharge operation of discharging the liquid droplets of the fine particle component liquid such as the toner component liquid from a plurality of discharge holes opened on the discharge surface of the droplet discharge device is continued. Fine particles are produced by solidifying the discharged droplets. The fine particle component-containing liquid may be a liquid in which raw material components of fine particles are dissolved or dispersed in a solvent, or may be free of a solvent as long as the liquid is discharged under the condition that it is discharged. It is mixed and presents a liquid state. And by using the technology of the existing ink jet recording method, the size of the droplets discharged from the discharge holes of the droplet discharge device can be controlled with high accuracy, so the particle size of the fine particles can be set with high accuracy. It becomes possible to control.

  However, in the case of producing fine particles by discharging droplets of a liquid containing a fine particle component from a plurality of discharge holes opened on the discharge surface of a droplet discharge device, the droplets discharged from each discharge hole are directed in the target flight direction. If you do not fly properly at the target flight speed, the following problems will occur. For example, there is a case in which a phenomenon called coalescence occurs in which droplets after ejection are brought into contact with other droplets before solidifying. When such coalescence occurs, the particle size of the coalesced fine particles becomes larger than the desired particle size. In addition, for example, when the ejected droplets collide with other droplets vigorously before solidifying, a phenomenon may occur in which the droplets break and split into smaller droplets. In this case, the particle size of the fine particles obtained by solidifying the divided microdroplets is smaller than the desired particle size. When these phenomena occur, there arises a problem that the particle size distribution of the produced fine particles is widened.

  As a result of intensive investigations on this problem, the present inventors are one of the main causes of the above-described coalescence and splitting due to dirt adhering to the ejection surface where the ejection holes for ejecting droplets are opened. I found out. In detail, the contamination of the liquid containing the fine particle component generated during the previous droplet discharge accumulates on the discharge surface of the conventional droplet discharge device, and the droplet discharged from the discharge hole comes into contact with the stain and the liquid is discharged. A phenomenon occurs in which the droplet flight direction deviates from the target flight direction. As a result, the liquid droplet comes into contact with a liquid droplet ejected from an adjacent or adjacent ejection hole, thereby causing the liquid droplet to coalesce or break up.

  The cause of the contamination of the discharge surface that causes the coalescence and splitting of the droplets is due to the fine particle-containing liquid oozing out from the discharge hole onto the discharge surface. Specifically, when the fine particle-containing liquid oozes out, the discharged liquid droplets come into contact with the dirt on the discharge surface due to the fine particle-containing liquid, and the discharge direction of the liquid drops from the target discharge direction. It will come off and normal discharge will not be possible. In this case, as described above, the coalescence and breakup of the droplets are caused, and the particle size distribution of the manufactured fine particles is widened.

  In addition, when such a fine particle-containing liquid oozes out and grows until the stain of the exuded fine particle-containing liquid gradually spreads and entrains the peripheral discharge holes, the peripheral discharge holes are blocked and the discharge is stopped. In some cases. In this case, since the number of produced fine particles is reduced, the production efficiency of the fine particles is lowered. Further, in this case, since the pressure in the liquid chamber where the closed discharge hole communicates changes, the discharge state of the other discharge holes communicated with this liquid chamber, particularly the discharge speed, is affected. When the discharge speed changes, the discharge operation becomes unstable, and the uniformity of the droplet size and the droplet discharge directionality are lost. As described above, when the uniformity of the droplet size is lost, or when the droplet discharge directionality is lost and coalescence or division occurs, the particle size distribution of the produced fine particles is widened and narrow. Fine particles with a particle size distribution cannot be produced.

  As described above, when a phenomenon in which the fine particle-containing liquid oozes out from the discharge hole, due to this, the coalescence or breakage of the droplet occurs, or the peripheral discharge hole is blocked and the pressure fluctuation in the liquid chamber is changed. This causes a problem that the uniformity of the size of the droplets and the direction in which the droplets are ejected are lost, and the particle size distribution of the produced fine particles is widened.

  Therefore, the present inventors have intensively studied the cause of the occurrence of the fine particle-containing liquid, and the occurrence of the fine particle-containing liquid is greatly influenced by the turbulence that can occur around the outlet of the discharge hole. I found. Hereinafter, this point will be described in detail.

  When droplets are continuously ejected from each of the plurality of ejection holes at short time intervals, an air flow is generated along the row of droplets ejected from each ejection hole. On the other hand, when such an air flow is generated, inflow of gas from the lateral direction with respect to the row of droplets occurs around the outlet of the discharge hole. The airflow generated by such gas inflow generates turbulent airflow including a spiral airflow and the like around the row of droplets. When such a turbulent air flow occurs, due to the influence, droplets that have lost their directionality or mist that may be generated during droplet discharge move (reversely move) on a reverse air flow in the direction opposite to the discharge direction. This was confirmed by a droplet observation experiment.

  Some of the liquid droplets and mist that move backward in this way reach the discharge surface and adhere to the discharge surface. When the reversely moved droplet or mist adheres to the discharge hole outlet or the vicinity of the discharge hole outlet on the discharge surface, the droplet or mist comes into contact with the fine particle-containing liquid filled in the discharge hole. This causes a phenomenon that the liquid containing fine particles exudes from the discharge hole. This causes a problem that the fine particle-containing liquid oozes out and the particle size distribution of the produced fine particles is widened.

  In view of this, the inventors of the present invention, in Japanese Patent Application No. 2011-205129 (hereinafter referred to as the prior application), regulates the generation of a reverse air flow that reversely moves the discharged liquid droplets toward the discharge surface, and seeps out the liquid containing fine particles. Proposed a fine particle production apparatus capable of suppressing the spread of the particle size distribution of fine particles generated due to the above. A specific configuration will be described below with reference to the drawings. FIG. 28 is a schematic view showing a partial configuration of the fine particle manufacturing apparatus of the prior application. In the fine particle manufacturing apparatus of the prior application shown in the same figure, the carrier airflow generated by the blower 801 flows through the air flow path 802, and a droplet discharge head 803 is provided in a part of the wall portion constituting the air flow path 802. A rectifying plate 804 is provided in order to suppress the leakage of the toner component liquid from the ejection holes of the droplet ejection head 803. The rectifying plate 804 regulates the generation of a reverse airflow that reversely moves the droplets discharged from the discharge holes of the droplet discharge head 803 toward the discharge surface. As shown in FIG. 29, the rectifying plate 804 includes an opening 805 through which liquid droplets discharged from the respective discharge holes pass, and is disposed opposite to the discharge surface where the outlet of the discharge hole is opened. By providing such a rectifying plate 804, a reverse airflow is generated vertically below the rectifying plate 804 that raises the liquid droplets discharged from the discharge holes and the minute liquid droplets generated at the time of discharge toward the discharge surface. However, the reverse airflow is blocked by the rectifying plate 804. As a result, the momentum of the reverse airflow generated around the outlet of the discharge hole is reduced, and it is possible to reduce the number of liquid droplets and the like that adhere to the discharge surface by riding the reverse airflow. In addition, when the rectifying plate 804 is disposed, an airflow flowing along the horizontal direction in the air flow path 802 flows in the gap between the rectifying plate 804 and the discharge surface, thereby forming a flow path. This flow path separates the air flow along the horizontal direction and the air flow toward the discharge direction having a predetermined angle with the direction of the air flow, and vortices are less likely to be generated around the discharge holes. Therefore, it is difficult to generate a reverse airflow caused by such a vortex, and it is possible to reduce the number of liquid droplets and the like that are attached to the discharge surface due to the reverse airflow.

  However, in the fine particle manufacturing apparatus of the prior application, as shown in FIG. 30 which is a partial cross-sectional view, the gas flowing through the air flow path 802 passes through the rectifying plate 804, so that the flow velocity of the air flow path 802 depends on the magnitude. It was found that the space (portion surrounded by the dotted line in FIG. 30) extending downstream of the current plate 804 is in a negative pressure state. And it turned out that the return airflow which goes to the negative pressure space from the periphery of the space generate | occur | produces, and the return airflow may approach into the clearance gap between the rectifying plate 804 and a discharge surface. Due to this return air flow, the flow in the discharge direction of the droplet after discharge is disturbed, and the discharge direction of the droplet deviates from the target discharge direction, and the discharge is adjacent or close at the portion indicated by the broken line in FIG. It was in contact with the droplet discharged from the hole 806. It is conceivable that the plate portion on the downstream side of the rectifying plate 802 is widened in the flow velocity direction so that the return airflow does not reach the discharge surface. However, there are structural problems that increase the number of mounting screws 806 to support the widened current plate and increase the strength of the air flow path 802 that supports the current plate. For this reason, there was a limit in making the current plate 802 wider in the flow velocity direction. As a result, the return airflow that causes the coalescence and breakup of the droplets cannot be suppressed, and the particle size distribution may be widened.

The present invention has been made in view of the above problems, and an object of the present invention is to reduce the coalescence and breakage of ejected droplets and to produce fine particles having a narrow particle size distribution and fine particles. It is to provide a manufacturing method .

To achieve the above object, a first aspect of the invention, a droplet discharge means for discharging liquid droplets of the fine particle component-containing liquid comprising the liquid droplets are solidified particles from a plurality of discharge holes opened in the ejection surface, wherein a gas flow path in which a plurality droplets discharged from the discharge hole of are introduced, the particle production apparatus and a stream generating means for generating an air flow in the gas flow path, of the air flow path two by a droplet discharge direction is divided into air flow path, the air flow direction upstream of or one prior Symbol droplet discharging means comprises a partition wall for connection communicates to the air flow direction downstream of the droplet discharge means, in the partition, the liquid droplet ejection A through-hole communicating with the two air flow paths is provided at a position facing the discharge surface of the means, and a droplet discharged by the droplet discharge means is the droplet discharge means of the two air flow paths. before passing through the through hole from one of the gas flow path on the side It is characterized in that which is introduced into the other air flow path of the two air flow paths.

  According to the present invention, the air flow path for discharging liquid droplets from the plurality of discharge holes opened on the discharge surface of the liquid droplet discharge means is divided into two air flow paths by the partition wall. This partition wall is continuous with at least the downstream side of the droplet ejecting means with respect to the outer wall forming the other air flow path. As a result, there is no space extending downstream of the partition wall, and no conventional return airflow is generated. The droplets discharged from the discharge holes of the droplet discharge means are conveyed to the other air flow path through one air flow path and the opening provided in the partition wall at a discharge speed. When the liquid droplets are conveyed while pushing the gas in one air flow path and the opening, a gas flow is generated from one air flow path to the other air flow path through the opening. And since each air flow path is divided by the partition, the air flow in the other air flow path does not interfere with the air flow passing through the opening from one air flow path. For this reason, in the vicinity of the discharge hole of the droplet discharge means provided on one air flow path side, the return air flow is also eliminated, and there is only an air flow passing through the opening from one air flow path. The airflow around the discharge hole and the airflow to the opening are stabilized. Thereby, coalescence and division of the discharged droplets can be reduced. Therefore, an excellent effect that fine particles having a narrow particle size distribution can be produced can be obtained.

It is the schematic diagram which expanded and showed a part of droplet discharge part of the liquid column resonance type droplet discharge apparatus used by embodiment. It is sectional drawing which showed typically a part of liquid column resonance droplet formation unit which is the droplet discharge device. It is explanatory drawing for demonstrating the mode of the standing wave of the velocity distribution and pressure distribution which arise in the liquid in the liquid column resonance liquid chamber of the liquid column resonance droplet formation unit in case of N = 1, 2, 3. It is explanatory drawing for demonstrating the mode of the standing wave of the velocity distribution and pressure distribution which arise in the liquid in the liquid column resonance liquid chamber of the liquid column resonance droplet formation unit in the case of N = 4 and 5. It is explanatory drawing which represented typically the mode of the liquid column resonance phenomenon which arises in the liquid column resonance liquid chamber. It is a figure which shows the mode of the actual droplet discharge in the droplet discharge part of a liquid column resonance type droplet discharge apparatus. It is a characteristic view which shows a drive frequency and a droplet discharge speed frequency characteristic. It is the schematic which shows the structure of an indirect vibration type droplet discharge means. It is the schematic which shows the structure which looked at the indirect vibration type droplet discharge means shown in FIG. 8 from the discharge surface. It is a characteristic view which shows the relationship between the radial direction coordinate of a thin film, and vibration displacement. It is the schematic which shows the structure of a direct vibration type droplet discharge means. It is the schematic which shows the structure which looked at the direct vibration type droplet discharge means shown in FIG. 11 from the discharge surface. It is the schematic which shows the cross section of the thin film of a membrane vibration type discharge means. FIG. 2 is a schematic diagram illustrating an example of a toner manufacturing apparatus that performs the toner manufacturing method of the present invention. It is the schematic which shows an example of the coalescence prevention means using auxiliary conveyance airflow. 6 is a graph showing an example of a toner particle size distribution when coalescence can be prevented. 6 is a graph illustrating an example of a toner particle size distribution when coalescence cannot be prevented. It is the schematic which shows the whole fine particle manufacturing apparatus of this embodiment. It is a perspective view which shows the structure of a part of this microparticle manufacturing apparatus. It is a fragmentary sectional view of this fine particle manufacturing apparatus. It is a fragmentary sectional view which shows the modification 1 of the microparticle manufacturing apparatus of this embodiment. (A) is a schematic diagram of the head, (b) and (c) are schematic diagrams showing the ejection of droplets, and (d) is a schematic diagram showing the ejection of droplets when the coalescence prevention means is used. It is the schematic which shows an example of a coalescence prevention means. It is the schematic and detailed figure which show an example at the time of providing the channel | path for liquid collection | recovery in the throttle part of the coalescence prevention means. It is a fragmentary perspective view which shows the modification 2 of the microparticle manufacturing apparatus of this embodiment. It is a fragmentary sectional view of FIG. It is a figure which shows the measurement result of the ratio based on the number based on circle | round | yen equivalent diameter distribution, and the particle | grains which have the prescribed | regulated equivalent circle diameter. It is the schematic which shows the structure of a part of fine particle manufacturing apparatus of a prior application. It is a top view which shows a baffle plate. It is a fragmentary sectional view of the fine particle manufacturing apparatus of a prior application.

Hereinafter, an embodiment in which a fine particle production apparatus according to the present invention is applied to production of toner will be described with reference to the drawings.
The toner manufacturing apparatus according to the present embodiment allows toner component liquid (particulate component-containing liquid), which becomes toner particles (fine particles) when the liquid droplets are solidified, to be discharged from a plurality of discharge holes opened on the discharge surface of the liquid droplet discharge apparatus. The toner particles are obtained by continuously performing the discharging operation of discharging the droplets and solidifying the discharged droplets.

  The droplet discharge device that can be used in the toner manufacturing method of the present embodiment preferably has a narrow particle size distribution of discharged droplets, but is not particularly limited, and a known one can be used. Examples of the droplet discharge device include a one-fluid nozzle, a two-fluid nozzle, a membrane vibration type discharge unit, a Rayleigh split type discharge unit, a liquid vibration type discharge unit, and a liquid column resonance type discharge unit. An example of a membrane vibration type discharge means is disclosed in Japanese Patent Application Laid-Open No. 2008-292976. Further, as a Rayleigh splitting type discharge means, there is one disclosed in Japanese Patent No. 4647506. Moreover, as a liquid vibration type discharge means, there is one disclosed in Japanese Patent Application Laid-Open No. 2010-102195.

  In order to ensure the productivity of the toner with a narrow droplet size distribution, vibration is imparted to the liquid in the liquid column resonance liquid chamber in which a plurality of ejection holes are formed to form a standing wave by liquid column resonance. In addition, a liquid column resonance type liquid droplet ejection device that ejects liquid from the ejection holes formed in the region that becomes the antinode of the standing wave is suitable. In the present embodiment, an example in which toner is manufactured using a liquid column resonance type droplet discharge device will be described.

FIG. 1 is an enlarged schematic view showing a part of a droplet discharge portion of a liquid column resonance type droplet discharge apparatus used in this embodiment.
The liquid droplet ejection unit 11 of the present embodiment includes a liquid column resonance liquid chamber 18, and this liquid column resonance liquid chamber 18 has one side wall portion (opening) among the side wall portions at both ends in the longitudinal direction (left-right direction in the drawing). It communicates with the liquid common supply path 17 via a communication path provided in the side wall portion. Further, the liquid column resonance liquid chamber 18 has a plurality of discharge holes 19 for discharging the droplets 21 to one wall portion (the bottom wall portion on the lower side in the drawing) of the wall portions connecting the side wall portions at both ends in the longitudinal direction. It has. Further, vibration generating means 20 for generating high-frequency vibration is provided on the upper wall portion side facing the discharge hole 19 in the liquid column resonance liquid chamber 18 in order to generate a liquid column resonance standing wave. The vibration generating means 20 is connected to a high frequency power source (not shown).

FIG. 2 is a cross-sectional view schematically showing a part of the liquid column resonance droplet forming unit 10 which is the droplet discharge device of the present embodiment. 2 is viewed from above or below in FIG.
In the present embodiment, the liquid discharged from the droplet discharge unit 11 is a fine particle component-containing liquid in a state where the fine particle components to be manufactured are dissolved or dispersed. Since the present embodiment is an example of producing toner, this fine particle component-containing liquid will be described as a toner component liquid. The toner component liquid 14 flows into the liquid common supply path 17 of the liquid column resonance droplet forming unit 10 through a liquid supply pipe by a liquid circulation pump (not shown), and the liquid column resonance liquid chamber of each droplet discharge unit 11. 18 is replenished.

  In the toner component liquid 14 filled in the liquid column resonance liquid chamber 18, a pressure distribution is formed by the liquid column resonance standing wave generated by the vibration generating means 20. Then, the droplet 21 is discharged from the discharge hole 19 disposed in a region that is an antinode of the liquid column resonance standing wave (a region where the amplitude is large and the pressure fluctuation is large). 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 ± from the position where the amplitude of the standing wave is maximized to the position where the amplitude is minimized. The range is a quarter wavelength. If the region is an antinode of a standing wave, even if it has a configuration in which a plurality of discharge holes 19 are formed in one liquid column resonance liquid chamber 18 as in this embodiment, the size is almost uniform from each. Can be discharged. When the amount of liquid in the liquid column resonance liquid chamber 18 decreases due to the discharge of the liquid droplet 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 resonance supply chamber 17 The flow rate of the supplied liquid increases and the liquid is replenished in the liquid column resonance liquid chamber 18.

  The liquid column resonance liquid chamber 18 of the droplet discharge unit 11 is formed by joining frames formed of a material such as a metal, ceramics, or silicon having such a high rigidity that does not affect the liquid resonance frequency at the driving frequency. Is formed. Further, as shown in FIG. 1, the length L between the side wall portions 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, as shown in FIG. 2, the length (width) W between the side walls at both ends in the short direction of the liquid column resonance liquid chamber 18 is set so as not to give an extra frequency to the liquid column resonance. It is desirable to be less than half of the length L of 18.

  It is preferable that a plurality of liquid column resonance liquid chambers 18 are arranged with respect to one liquid column resonance droplet forming unit 10 in order to improve productivity. For this reason, the present embodiment employs a configuration in which a plurality of liquid column resonance liquid chambers 18 are arranged for one liquid column resonance droplet forming unit 10. The number of liquid column resonance liquid chambers 18 provided for one liquid column resonance droplet forming unit 10 is not particularly limited. However, one liquid column resonance liquid chamber having 100 to 2000 liquid column resonance liquid chambers 18 is provided. The droplet forming unit 10 is preferable because both operability and productivity can be realized. In the present embodiment, a plurality of liquid column resonance liquid chambers 18 communicate with one liquid common supply path 17.

The vibration generating means 20 in the droplet discharge section 11 is not particularly limited as long as it can be driven at a predetermined frequency, but has a structure in which an elastic plate 20B is attached to the piezoelectric body 20A as in this embodiment. Is preferred. The elastic plate 20B is provided so as to isolate the piezoelectric body 20A from the liquid column resonance liquid chamber 18 so that the piezoelectric body 20A does not come into contact with the liquid. Examples of the piezoelectric body 20A include piezoelectric ceramics such as lead zirconate titanate (PZT). Generally, the piezoelectric body 20A is often used by being laminated because of its small displacement. 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 18. For example, a configuration in which one piezoelectric material is divided into a plurality of piezoelectric bodies in accordance with the arrangement of the liquid column resonance liquid chambers, and each liquid column resonance liquid chamber can be individually controlled by each piezoelectric body is preferable.

The outlet side diameter of the discharge hole 19 is preferably in the range of 1 [μm] to 40 [μm].
If it is smaller than 1 [μm], the formed droplets will be very small, and toner may not be obtained. In particular, when solid fine particles such as a pigment are contained as a constituent component of the toner, the solid fine particles may block the discharge holes 19 and may reduce the productivity of the toner. On the other hand, if it is larger than 40 [μm], the diameter of the droplet is large, so that it is dried and solidified to obtain a toner particle diameter of 3 [μm] or more and 6 [μm] or less. Needs to be diluted to a very dilute solution. In this case, a large amount of drying energy is required to obtain a certain amount of toner, which is inconvenient.

  In the present embodiment, the row of discharge holes (see FIG. 1) in which a plurality of discharge holes 19 are arranged is arranged in the width direction in the liquid column resonance liquid chamber 18 (left-right direction in FIG. 2), as shown in FIG. ) Are arranged in parallel. With such a configuration, more liquid droplets can be ejected by a single ejection operation, which increases production efficiency. Since the liquid column resonance frequency varies depending on the arrangement of the discharge holes 19, it is desirable that the liquid column resonance frequency is appropriately determined while confirming the discharge of the droplet.

Next, the mechanism of droplet formation by the liquid column resonance droplet forming unit 10 will be described.
First, the principle of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber 18 in the droplet discharge section 11 shown in FIG. 1 will be described.
When the sound velocity of the toner component liquid in the liquid column resonance liquid chamber is “c” and the drive frequency applied to the toner component liquid as a medium from the vibration generating unit 20 is “f”, the wavelength λ at which the liquid resonance occurs is It can be calculated from the following equation (1).
λ = c / f (1)

In the present embodiment, the side wall portion (opening side wall portion) of the liquid column resonance liquid chamber 18 in which the communication passage for communicating with the liquid common supply passage 17 is formed is the opposite side wall portion (where the communication passage is not formed) ( It can be considered that it is equivalent to the closed side wall. In this case, when the longitudinal length L of the liquid column resonance liquid chamber 18 coincides with an even multiple of a quarter of the wavelength λ, the vibration in the liquid column resonance liquid chamber 18 is changed by the vibration of the vibration generating means 20. Resonant vibration occurs most efficiently. The optimum liquid column resonance condition in which such liquid column resonance occurs most efficiently can be expressed by the following equation (2). Note that the optimum condition of the liquid column resonance shown in the above formula (2) holds true even when the both side walls in the longitudinal direction of the liquid column resonance liquid chamber 18 are completely opened.
L = (N / 4) × λ (2)

  On the other hand, when one of the longitudinal side walls of the liquid column resonance liquid chamber 18 is open and the other is closed, the length L of the liquid column resonance liquid chamber 18 is the wavelength. Liquid column resonance is most efficiently formed when it coincides with an odd multiple of λ. In other words, the optimum condition for liquid column resonance in this case is expressed by an odd number of “N” in the above formula (2).

The driving frequency f with the highest liquid column resonance efficiency is represented by the following equation (3) from the above equations (1) and (2). However, in reality, since the liquid has a viscosity that attenuates resonance, the vibration is not amplified infinitely. It has a Q value and, as shown in equations (4) and (5) described later, the above equation Resonance also occurs at a frequency in the vicinity of the most efficient drive frequency f shown in (3).
f = N × c / (4L) (3)

FIGS. 3A to 3D are explanatory views for explaining the standing wave of the velocity distribution and the pressure distribution generated in the liquid in the liquid column resonance liquid chamber 18 when N = 1, 2, and 3. FIG. FIG.
However, FIG. 3A is an example in the case of N = 1, in which one of the longitudinal ends of the liquid column resonance liquid chamber 18 is open and the other is closed. FIG. 3B shows an example in which N = 2 and both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 are closed. FIG. 3C shows an example in which N = 2 and both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 are open, and FIG. , N = 3, where one of the longitudinal ends of the liquid column resonance liquid chamber 18 is open and the other is closed.

FIGS. 4A to 4C are diagrams for explaining the standing wave of the velocity distribution and pressure distribution generated in the liquid in the liquid column resonance liquid chamber 18 when N = 4 and 5. FIG.
However, FIG. 4A is an example in the case where N = 4 and both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 are closed, and FIG. FIG. 4C shows an example in which N = 4 and both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 are open. FIG. 4C shows the case where N = 5. This is an example in which one end of both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 is open and the other is closed.

  3 and 4, the solid line represents the velocity standing wave, and the dotted line represents the pressure standing wave. In addition, the wave generated in the liquid in the liquid column resonance liquid chamber 18 is actually a sparse wave (longitudinal wave), but in FIG. 3 and FIG. 4, this is expressed in the form of a sine wave (cosine wave). . For example, looking at the velocity distribution in FIG. 3 (a), it can be intuitively understood that the amplitude of the velocity distribution becomes zero at the closed closed side wall, and the amplitude becomes maximum at the opened side wall portion, Since it is easy to understand, sine wave notation is used here. Since the standing wave pattern varies depending on the open / closed state of the both side walls in the longitudinal direction (combination pattern of the open end and the fixed end), in FIGS. 3 and 4, the liquid column resonance liquid chamber of the present embodiment is used for explanation. The combination pattern of the open end and the fixed end that do not match 18 is also shown.

  As will be described in detail later, the end condition is determined by the state of the opening of the discharge hole 19 and the opening of the communication path that connects the liquid column resonance liquid chamber 18 and the liquid common supply path 17. In acoustics, at the open end (open end), the moving speed of the medium (liquid) in the longitudinal direction is maximum, and the pressure is zero. On the other hand, at the fixed end (closed end), on the contrary, the moving speed of the medium becomes zero and the pressure becomes maximum. The fixed end (closed end) is considered as an acoustically hard wall, and on the assumption that the wave is completely reflected, if the end is ideally completely closed or open, the wave superposition is shown in FIG. It is assumed that a standing wave as shown in FIG. 4 is generated. If there are openings such as the discharge holes 19 and the communication passages as in the liquid column resonance liquid chamber 18 of the present embodiment, the number of the discharge holes 19, the positions of the discharge holes 19, the size and position of the communication passages, and the like. However, the standing wave pattern fluctuates. Therefore, the actual resonance frequency appears at a position shifted from the ideal resonance frequency obtained from the above equation (3). However, even if there is such a shift, there is no problem because the drive frequency may be adjusted as appropriate while confirming the actual discharge state.

  1200 [m / s] is used as the sound velocity c of the liquid, the longitudinal length L of the liquid column resonance liquid chamber 18 is 1.85 [mm], walls are present at both ends in the longitudinal direction, and both ends are fixed. In the case of N = 2 resonance mode equivalent to the end model, the ideal resonance frequency for causing liquid column resonance most efficiently in the liquid in the liquid column resonance liquid chamber 18 is 324 [kHz] from the above equation (2). ]. On the other hand, 1200 [m / s] is used as the sound velocity c of the liquid, the longitudinal length L of the liquid column resonance liquid chamber 18 is 1.85 [mm], walls are present at both ends, and both ends are fixed. In the case of N = 4 resonance mode equivalent to the end model, from the above equation (2), the ideal resonance frequency that causes the liquid column resonance in the liquid in the liquid column resonance liquid chamber 18 most efficiently is 648 [kHz. ]. Thus, higher-order resonance can be used also in the liquid column resonance liquid chamber 18 having the same configuration.

  The liquid column resonance liquid chamber 18 of the present embodiment has a configuration in which both ends in the longitudinal direction are equivalent to the closed end, or can be described as an acoustically soft wall due to the opening of the discharge hole 19. Although it is preferable for increasing the resonance frequency, the present invention is not limited to this, and for example, a configuration in which both ends in the longitudinal direction are equivalent to the open ends may be employed. The influence of the opening of the discharge hole 19 here means that the acoustic impedance is reduced, and in particular, the compliance component is increased. As shown in FIG. 1, the discharge hole 19 provided in the liquid column resonance liquid chamber 18 of the present embodiment is arranged so as to be close to one end side in the longitudinal direction (the side opposite to the liquid common supply path 17). . For this reason, the one end side can be regarded as an open end (open end) due to the influence of the opening of the discharge hole 19. As a result, when the longitudinal both end walls of the liquid column resonance liquid chamber 18 as shown in FIGS. 3B and 4A are configured to be equivalent to closed ends, only the resonance mode in which both ends are fixed ends is used. It is also possible to use a resonance mode in which one end is an open end and the other end is a fixed end.

  In addition, the number of ejection holes 19, the arrangement of the ejection holes 19, and the cross-sectional shape of the ejection holes 19 are factors that determine the driving frequency, and the driving frequency can be appropriately determined according to this. For example, the closer the arrangement of the discharge holes 19 is to the one end side in the longitudinal direction, the more restrained the wall portion of the liquid column resonance liquid chamber 18 becomes at the end portion in the longitudinal direction. Therefore, as the arrangement of the discharge holes 19 is moved closer to one end in the longitudinal direction, the end in the longitudinal direction is almost close to the opening end, and the drive frequency is changed. Further, for example, when the number of the discharge holes 19 is increased, the restriction by the wall portion of the liquid column resonance liquid chamber 18 becomes loose at one end in the longitudinal direction where the arrangement of the discharge holes 19 is approached, and the end in the longitudinal direction is almost the open end. It is changed so that the drive frequency becomes high in a state close to. In addition, for example, when the cross-sectional shape of the discharge hole 19 is changed or the dimension of the discharge hole 19 is changed, the drive frequency needs to be changed.

When an AC voltage is applied to the vibration generating means 20 at the drive frequency determined in this way, the piezoelectric body 20a of the vibration generating means 20 is deformed according to the voltage fluctuation, and thereby the elastic plate 20b is displaced. As a result, vibration corresponding to the driving frequency is applied to the liquid in the liquid column resonance liquid chamber 18, and a liquid column resonance standing wave is generated in the liquid in the liquid column resonance liquid chamber 18. However, if the liquid column resonance standing wave has a frequency close to the drive frequency at which it is most efficiently generated, the liquid column resonance standing wave is generated. Specifically, when the distance between the longitudinal wall on the liquid common supply path 17 side and the discharge hole arranged closest to the liquid common supply path 17 is Le, the length of the liquid column resonance liquid chamber is defined as Le. The range of the driving frequency f for generating the liquid column resonance standing wave using the length L between the directional walls can be defined by, for example, the following equations (4) and (5). By vibrating the vibration generating means 20 using a drive waveform whose main component is the drive frequency f within the range determined by these formulas (4) and (5), a liquid column resonance is induced to cause a droplet to It is possible to discharge appropriately from the discharge hole 19. However, the ratio of L to Le is preferably Le / L> 0.6.
N × c / (4L) ≦ f ≦ N × c / (4Le) (4)
N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le) (5)

  Using the principle of the liquid column resonance phenomenon described above, in this embodiment, a liquid column resonance pressure standing wave is formed in the liquid column resonance liquid chamber 18 shown in FIG. The continuous droplet discharge is caused from the discharge hole 19. Therefore, it is preferable to dispose the discharge hole 19 at a position where the standing wave of the pressure fluctuates the most, because the discharge efficiency is increased and the driving voltage can be further suppressed.

  Further, although one discharge hole 19 may be provided for one liquid column resonance liquid chamber 18, it is preferable to arrange a plurality of discharge holes 19 for one liquid column resonance liquid chamber 18 from the viewpoint of productivity. Specifically, it is preferably between 2 and 100. When the number exceeds 100, if the droplets are appropriately discharged from the respective discharge holes 19, it is necessary to set a high drive voltage to the vibration generating means 20, and the behavior of the piezoelectric body 20a of the vibration generating means 20 is changed. Prone to instability.

  When a plurality of discharge holes 19 are formed for one liquid column resonance liquid chamber 18, the pitch between the discharge holes is preferably 20 [μm] or more. When the pitch between the discharge holes is smaller than 20 [μm], there is a high probability that the liquid droplets discharged from the adjacent discharge holes come into contact with each other to form large liquid droplets, and the toner particle size distribution deteriorates. This is because the possibility increases.

Next, the state of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber 18 in the droplet discharge section 11 in the liquid column resonance droplet forming unit 10 will be described.
FIGS. 5A to 5D are explanatory views schematically showing the state of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber 18.
5 indicates the velocity distribution obtained by plotting the velocity at an arbitrary measurement position in the longitudinal direction of the liquid column resonance liquid chamber 18. The direction from the closed side wall portion side to the opening side wall portion on the right side in the figure is positive, and the opposite direction is negative. Further, the dotted line shown in the liquid column resonance liquid chamber 18 in FIG. 5 indicates the pressure distribution obtained by plotting the pressure value at an arbitrary measurement position in the longitudinal direction of the liquid column resonance liquid chamber 18. Positive pressure is positive with respect to atmospheric pressure, negative pressure is negative.

  In the present embodiment, as shown in FIG. 1, the height h <b> 1 (= about) from the bottom surface of the liquid column resonance liquid chamber 18 in the droplet discharge unit 11 to the lower end of the communication path communicating with the liquid common supply path 17. 80 [μm]) is set to about twice the height h2 (= about 40 [μm]) of the communication port. Therefore, the liquid column resonance liquid chamber 18 of the present embodiment can be approximately considered that both ends in the longitudinal direction are substantially fixed ends. 5A to 5D show temporal changes in the velocity distribution and the pressure distribution under such a concept.

  FIG. 5A shows a pressure waveform and a velocity waveform in the liquid column resonance liquid chamber 18 at the time of droplet discharge. At this time, the liquid portion on the closed side wall portion side in the liquid column resonance liquid chamber 18, that is, the liquid portion in the liquid chamber region where the discharge hole 19 is provided (liquid in the vicinity of the discharge hole) has a maximum pressure. . As a result, the meniscus pressure increases, and the liquid comes out from each discharge hole 19. Thereafter, as shown in FIG. 5B, the pressure of the liquid near the discharge hole 19 decreases, and the liquid droplet 21 is discharged from the discharge hole 19 by shifting in the negative pressure direction.

  Thereafter, as shown in FIG. 5C, the pressure of the liquid in the vicinity of the discharge hole 19 becomes minimum. From this time, replenishment of the toner component liquid 14 from the liquid common supply path 17 to the liquid column resonance liquid chamber 18 starts. Then, as shown in FIG. 5D, the pressure of the liquid in the vicinity of the discharge hole 19 gradually increases and shifts in the positive pressure direction. At this time, the replenishment of the toner component liquid 14 is completed, and the pressure of the liquid near the discharge hole 19 of the liquid column resonance liquid chamber 18 becomes the maximum again as shown in FIG.

  Thus, a standing wave due to liquid column resonance is generated in the liquid near the discharge hole 19 in the liquid column resonance liquid chamber 18 by the high frequency driving of the vibration generating means 20. And since the discharge hole 19 is arrange | positioned in the location equivalent to the antinode of the standing wave by liquid column resonance used as the position where a pressure fluctuates the most, the droplet 21 is discharged to the discharge hole 19 according to the period of the antinode. Are continuously discharged.

  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 discharge holes are provided. FIG. 6 shows a state in which a discharge hole is arranged at the antinode of the N = 2 mode pressure standing wave and a discharge performed with a sine wave having 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. 7 is a characteristic diagram showing droplet velocity frequency characteristics when driven by the same amplitude sine wave with a drive frequency of 290 [kHz] to 395 [kHz]. As can be seen from the figure, 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.

Next, an indirect vibration type discharge means and a direct vibration type discharge means will be outlined as film vibration type droplet discharge means.
FIG. 8 is a schematic cross-sectional view showing the configuration of the indirect vibration type discharge means. In the figure, the same reference numerals as those in FIG. 1 denote the same components. The indirect vibration type discharge means 100 shown in the figure includes a thin film 101 in which a plurality of discharge holes 19 are formed, a mechanical vibration means 102 that vibrates the thin film 101, and between the thin film 101 and the mechanical vibration means 102. And a frame 103 that forms a liquid flow path 7 for supplying the toner composition liquid 14. The toner composition liquid 14 is supplied from a raw material container (not shown) through a liquid supply pipe by a liquid circulation pump from the toner composition liquid supply port 6, passes through the liquid flow path 7, and is discharged from the toner composition liquid discharge port 8. It returns to the raw material container again through the liquid return pipe.

  The thin film 101 having a plurality of discharge holes 19 is installed in parallel to the vibration surface 104 of the mechanical vibration means 102, and a part of the thin film 101 is bonded and fixed to the frame 103. Thereby, the positional relationship is substantially perpendicular to the vibration direction of the mechanical vibration means 102. A drive circuit 105 is provided so that a voltage signal is applied to the upper and lower surfaces of the vibration generating means 20 of the mechanical vibration means 102. Then, a signal from the drive signal generation source 106 is applied to the vibration generating means 20 and converted into mechanical vibration. As a circuit for supplying an electric signal, a lead wire having an insulating coating on the surface is suitable. In addition, it is suitable for efficient and stable toner production that the mechanical vibration means 102 uses elements having a large vibration amplitude such as various horn type vibrators and bolted Langevin type vibrators described later.

  The mechanical vibration unit 102 includes a vibration generation unit 20 that generates vibration and a vibration amplification unit 107 that amplifies the vibration generated by the vibration generation unit 20. When a drive voltage (drive signal) having a required frequency is applied between the electrodes 109 of the vibration generating means 20 from the drive signal generating source 106, vibration is excited in the vibration generating means 20. This vibration is amplified by the vibration amplification means 107, and the vibration surface 104 arranged in parallel with the thin film 101 vibrates periodically. As a result, the thin film 101 vibrates at a required frequency due to the periodic pressure caused by the vibration of the vibration surface 104. 8 has a structure in which one vibration generating member 108 is sandwiched between electrodes 109, but a plurality of the members may be stacked.

  The vibration generating means 20 is not particularly limited as long as it can apply a certain longitudinal vibration to the thin film 101 at a constant frequency, and can be appropriately selected and used. However, since the thin film 101 is vibrated, the vibration generating member 108 of the vibration generating means 20 is preferably a piezoelectric body in which bimorph type flexural vibration is excited. The piezoelectric body has a function of converting electrical energy into mechanical energy. Specifically, by applying a voltage, flexural vibration is excited and the thin film 101 can be vibrated.

  As shown in FIG. 10, the bending vibration has a cross-sectional shape in which the displacement ΔL is maximum (ΔLmax) at the center of the thin film 101, and periodically vibrates in the vibration direction. As the thin film 101 periodically vibrates up and down, the toner droplets 21 are periodically ejected from the ejection holes 19. The speed range of the thin film 101 from which the toner droplets 21 can be ejected has a relationship as shown in FIG. 10, and the area range that can be ejected is limited, so it is desirable to form the ejection holes 19 in this area range. As shown in FIG. 9, the discharge hole 19 is disposed at the center of the thin film 101.

Examples of the piezoelectric body of the vibration generating member 108 that constitutes the vibration generating means 20 include piezoelectric ceramics such as lead zirconate titanate (PZT). There are many. 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.

  The mechanical vibration means 102 may be arranged in any way as long as it gives vibration in the vertical direction to the thin film 101 having the discharge holes 19, but the vibration surface 104 and the thin film 101 are arranged in parallel.

  In the illustrated example, a horn type vibrator is used as the mechanical vibration means 102 including the vibration generation means 20 and the vibration amplification means 107. Since this horn type vibrator can amplify the amplitude of the vibration generating means 20 such as a piezoelectric element by the vibration amplifying means 107, the vibration generating means 20 itself for generating mechanical vibration may be a small vibration and a mechanical load. Therefore, it will lead to longer life as a production device. As the horn type vibrator, a known typical horn shape may be used. The shape can be appropriately selected according to the purpose. Further, as the vibration generating means 20, a particularly high-strength bolted Langevin type vibrator can be used. This bolted Langevin type vibrator is mechanically coupled with piezoelectric ceramics and will not be damaged during high amplitude excitation.

  The size of the mechanical vibration means 102 is generally increased as the oscillation frequency is decreased. Depending on the required frequency, the vibration means can be directly drilled to provide a reservoir. It is also possible to vibrate the entire storage part efficiently.

  FIG. 11 is a schematic cross-sectional view showing the configuration of the direct vibration type discharge means. In the figure, the same reference numerals as those in FIG. 8 denote the same components. The direct vibration type discharge means 200 shown in the figure includes a thin film 101 provided with at least a discharge hole 19 for discharging a toner droplet 21, an annular vibration generating means 201 for vibrating the thin film 101, and a toner composition liquid 14. And a frame 103 provided with a flow path 7 to be supplied. The toner composition liquid 14 is supplied from a raw material container (not shown) through a liquid supply pipe by a liquid circulation pump from the toner composition liquid supply port 6. The toner composition liquid 14 passes through the flow path 7, is discharged from the toner composition liquid discharge port 8, and returns to the raw material container again through a liquid return pipe (not shown).

  The thin film 101 is bonded and fixed to the frame 103 at the outer periphery. The annular vibration generating means 201 is arranged around the area where the discharge holes 19 of the thin film 101 are provided. The annular vibration generating means 201 includes an annular piezoelectric body 202 and an electrode 109. A drive voltage (drive signal) having a required frequency is applied to the electrode 109 from the drive signal generation source 106 through the drive circuit 105. Thereby, for example, bending vibration is generated. As the kind of the annular piezoelectric body 202 and the electrode 109, the same one as that used in the indirect vibration type ejection unit 100 can be used.

  Similar to the indirect vibration type ejection means 100, the bending vibration has a cross-sectional shape in which the displacement ΔL is maximum (ΔLmax) at the center of the thin film as shown in FIG. 10, and periodically vibrates in the vibration direction. The toner droplets 21 are periodically ejected from the ejection holes 19 by periodically vibrating the film. The speed range of the thin film 101 from which the toner droplets 21 can be ejected has a relationship as shown in FIG. 10, and the area range that can be ejected is limited, so it is desirable to form the ejection holes 19 in this area range. As shown in FIG. 12, the discharge hole 19 is disposed at the center of the thin film 101 and the annular vibration means 201.

Next, the mechanism of droplet formation by the indirect vibration type droplet discharge means 100 and the direct vibration type droplet discharge means 200 will be outlined.
According to any of the droplet discharge means as described above, the thin film 101 having a plurality of discharge holes 19 facing the flow path 7 is propagated to the thin film 101 to vibrate the thin film 101 periodically. . A plurality of discharge holes 19 are arranged in a relatively large area, and droplets can be periodically formed and discharged stably from the plurality of discharge holes 19.

Due to the vibration of the circular thin film, a sound pressure Pac proportional to the vibration speed Vm of the film is generated in the liquid in the vicinity of the nozzles provided in the circular film. It is known that the sound pressure is generated as a reaction of the radiation impedance Zr of the medium (toner composition liquid), and the sound pressure is a product of the radiation impedance and the membrane vibration velocity Vm using the equation (6) below. Is done.
Pac (r, t) = Zr · Vm (r, t) (Formula 6)
Since the vibration velocity Vm of the film varies periodically with time, it is a function of time (t), and various periodic variations such as a sine waveform and a rectangular waveform can be formed. Further, as described above, the vibration displacement in the vibration direction is different in each part of the film, and Vm is also a function of the position coordinates on the film. As described above, the vibration mode of the film used here is an axial object. Therefore, it is substantially a function of the radius (r) coordinate.

  As described above, a sound pressure proportional to the vibration displacement speed of the distributed film is generated, and the toner composition liquid is discharged into the gas phase in response to the periodic change of the sound pressure. Since the toner composition liquid periodically discharged to the gas phase forms a sphere due to a difference in surface tension between the liquid phase and the gas phase, droplet formation occurs periodically.

  As the vibration frequency of the film that enables droplet formation, a region of 20 kHz to 2.0 MHz is used, and a range of 50 kHz to 500 kHz is more preferably used. If the vibration period is 20 kHz or more, the dispersion of fine particles such as pigment and wax in the toner composition liquid is promoted by the excitation of the liquid. Furthermore, when the displacement amount of the sound pressure is 10 kPa or more, the above-described fine particle dispersion promoting action is more preferably generated.

(Thin film with multiple nozzles)
As described above, the thin film 101 having the discharge holes 19 is a member that discharges the dissolved or dispersed liquid of the toner composition to form droplets. There is no restriction | limiting in particular as the material of this thin film 101, and the shape of the discharge hole 19, It can be set as the shape selected suitably. For example, when the thin film 101 is formed of a metal plate having a thickness of 5 to 500 μm and the opening diameter of the discharge hole 19 is 3 to 30 μm, the toner droplet 21 of the toner composition liquid 14 is ejected from the discharge hole 19. From the viewpoint of generating fine droplets having a very uniform particle size. The opening diameter of the discharge hole 19 means a diameter if it is a perfect circle, and means a short diameter if it is an ellipse. The number of the plurality of discharge holes 19 is preferably 2 to 3000. The cross-sectional shape of the discharge hole 19 is a shape in which the size does not change between the opening of the discharge hole 19 and the liquid contact surface in FIG. 8 showing the indirect vibration type droplet discharge unit and FIG. 11 showing the direct vibration type droplet discharge unit. However, the cross-sectional shape can be changed as appropriate.

FIGS. 13A to 13D are cross-sectional views illustrating various cross-sectional shapes that can be adopted as the cross-sectional shape of the discharge hole 19.
In the present embodiment, the case where the cross-sectional shape of the discharge hole 19 is a tapered shape whose diameter decreases toward the outlet side as shown in FIG. 1 is illustrated, but this cross-sectional shape is appropriately selected. can do. The cross-sectional shape of the discharge hole 19 shown in FIG. 13A is a cross-sectional shape in which the diameter becomes narrower while having a round shape (curved shape) from the inlet side to the outlet side of the discharge hole 19. This cross-sectional shape maximizes the pressure applied to the liquid near the outlet of the discharge hole 19 when the discharge hole thin film 41 constituting the bottom wall portion of the liquid column resonance liquid chamber 18 in which the discharge hole 19 is formed vibrates. For this reason, it is a preferable shape for the stabilization of discharge.

  The cross-sectional shape of the discharge hole 19 shown in FIG. 13 (b) is a cross-sectional shape having a taper shape with a certain angle from the inlet side to the outlet side of the discharge hole 19 and the diameter thereof being narrowed. The embodiment is employed. Since this cross-sectional shape is a taper shape, similar to the cross-sectional shape shown in FIG. 13A, the vicinity of the outlet of the discharge hole 19 when the thin plate-shaped discharge hole thin film 41 vibrates. The pressure applied to the liquid can be increased. The taper angle 24 can be appropriately changed, but is preferably in the range of more than 60 ° and not more than 90 °. This is because when the nozzle angle 24 is 60 ° or less, it is difficult for pressure to be applied to the liquid, and the processing of the thin film 41 becomes difficult. On the other hand, when the nozzle angle 24 is 90 °, the cross-sectional shape as shown in FIG. 13C is obtained, but pressure is hardly applied to the vicinity of the outlet of the discharge hole 19, and therefore a suitable angle range of the taper angle 24. As a result, 90 ° is the maximum value. If the taper angle 24 is larger than 90 °, no pressure is applied to the vicinity of the outlet of the discharge hole 19, so that the droplet discharge becomes very unstable.

  The sectional shape of the discharge hole 19 shown in FIG. 13D is a combination of the sectional shape shown in FIG. 13A and the sectional shape shown in FIG. In this way, the cross-sectional shape may be changed step by step.

  The toner of the present invention can be obtained by drying and collecting the droplets of the toner composition liquid discharged into the gas from the droplet discharge means described above. This section outlines the means for drying and collecting.

  FIG. 14 is a schematic view showing the configuration of an example of an apparatus for carrying out the toner manufacturing method. The toner manufacturing apparatus 1 mainly includes a droplet discharge means 2 and a dry collection unit 400. As described above, the droplet discharge means 2 can appropriately use several types of droplet discharge means. Connected to the droplet discharge means 2 are a liquid supply pipe 16 through which the toner composition liquid 14 accommodated in the raw material container 13 that stores the toner composition liquid 14 and a liquid return pipe 22 that returns to the raw material container 13. ing. Further, a liquid circulation pump 15 for pumping the toner composition liquid 14 in the liquid supply pipe 16 to return to the raw material container 13 through the liquid supply pipe 16 is connected, so that the toner composition liquid 14 is discharged as needed from the droplet discharge means 2. Can supply. The liquid supply pipe 16 is provided with a pressure measuring device P1, and the dry collection unit is provided with a pressure measuring device P2. The liquid supply pressure to the droplet discharge means 2 and the pressure in the dry collection unit are managed by pressure measuring devices P1 and P2. At this time, if the relationship of (pressure value P1 of the pressure measuring device P1)> (pressure value P2 of the pressure measuring device P2) is satisfied, the toner composition liquid 14 may ooze out from the ejection hole (not shown). On the contrary, when the pressure value P1 <the pressure value P2, there is a possibility that gas enters the droplet discharge means 2 from the discharge hole and the discharge stops. For this reason, it is desirable that the pressure value P1≈the pressure value P2. That is, it is desirable that the pressure state in the droplet discharge means 2 and the gas phase is kept uniform.

  A dry collection unit 400 shown in FIG. 14 includes a chamber 401, a toner collection unit 402, and a toner storage unit 403. The mechanism of the drying process is shown below. The toner droplet 21 composed of the toner composition liquid 14 is in a liquid state immediately after being ejected from the droplet ejection means 2, but the volatile solvent contained in the toner composition liquid is volatilized while being transported in the chamber. As a result, drying proceeds and the liquid changes to a solid. In such a state, even if the particles are brought into contact with each other, coalescence does not occur any more, so that the toner collecting unit 402 can collect the toner powder and store it in the toner storage unit 403. The toner stored in the toner storage unit 403 is further dried in another process as necessary.

  In the chamber 401, a descending carrier airflow created from the carrier airflow inlet 404 is formed. Since the toner droplet 21 ejected from the droplet ejection means 2 is transported downward not only by gravity but also by a transport airflow, the ejected toner droplet 21 is decelerated by air resistance. Can be suppressed. Accordingly, when the toner droplets 21 are continuously ejected, the toner droplets 21 ejected before are decelerated by air resistance before drying, and the toner droplets 21 ejected later are ejected before. It catches up with the toner droplet 21. Then, it is possible to prevent the toner droplets 21 from being united and united and the toner droplets 21 to have a large particle size. In FIG. 14, the droplet discharge means 2 discharges the toner droplet 21 in the direction of gravity, but this is not always necessary, and the discharge angle can be selected as appropriate. As the air flow generation means, either a method of providing a blower at the transport air flow inlet 404 at the top of the chamber 401 and pressurizing, or a method of suctioning from the transport air flow outlet 405 can be employed. As the toner collecting means 402, a known collecting device can be used, and a cyclone collecting machine, a back filter, or the like can be used.

  The conveying airflow is not particularly limited as a state of the airflow as long as the coalescence of the toner droplets 21 can be suppressed, and may be a laminar flow, a swirl flow, or a turbulent flow. There are no particular limitations on the type of gas constituting the carrier airflow, and air or a nonflammable gas such as nitrogen may be used. As described above, since the toner droplets 21 do not coalesce when dried, it is preferable to have conditions that can promote drying of the toner droplets 21. For this reason, it is desirable that the solvent vapor contained in the toner composition liquid 14 is not included. Further, the temperature of the conveying airflow can be adjusted as appropriate, and it is desirable that there is no fluctuation during production. Further, a means for changing the airflow state of the carrier airflow in the chamber 401 may be taken. The carrier airflow may be used not only to prevent the toner droplets 21 from coalescing but also to prevent the droplets from adhering to the chamber 401.

  As described above, in the droplet drying and collecting means, coalescence is suppressed by the conveying airflow, but if this is not sufficient, further coalescence prevention means can be incorporated. Examples of the coalescence prevention means include introduction of an auxiliary transport airflow in the vicinity of the droplet discharge means, charging of the same polarity to the droplets, electric field control, and the like, which can be used as appropriate.

  FIG. 15 is a schematic cross-sectional view showing the configuration of the coalescence prevention means using one auxiliary transport airflow. A shroud 501 is disposed around the droplet discharge means 2, and an auxiliary transport airflow inlet 502 is disposed in a part of the shroud 501. The gas introduced from the auxiliary conveyance airflow inlet 502 passes through the airflow passage 12 formed by the shroud 501, and an auxiliary conveyance airflow 503 is created around the discharge hole 19 of the droplet discharge means 2. However, the auxiliary transport airflow 503 is not only introduced from the auxiliary transport airflow introduction port 502, but may also be generated by gas drawn by the suction pressure from the transport airflow discharge port. The toner droplets 21 discharged from the droplet discharge means 2 are moved in the vicinity of the droplet discharge means 2 by the auxiliary transport airflow 503 in order without decreasing the speed, so that the frequency of coalescence of the droplets is extremely low. Can be suppressed. The speed of the auxiliary transport airflow 503 is desirably the same as or faster than the droplet velocity immediately after being ejected from the droplet ejecting means 2, and if it is slower than that, there may be an adverse effect.

  As shown in FIG. 15, the auxiliary transport airflow 503 is preferably the same as the traveling direction of the toner droplets 21, but the droplet discharge direction and the auxiliary transport airflow direction must be the same if coalescence can be prevented. There is no. Although the shape of the shroud 501 may be controlled by narrowing the opening in the vicinity of the discharge hole 19 of the droplet discharge means 2, the flow rate may be controlled, or may be appropriately selected without having a restriction. There is no particular limitation on the type of gas constituting the auxiliary conveying airflow 503, and air or a nonflammable gas such as nitrogen may be used. As can be seen from FIG. 16 showing the particle size distribution of the toner collected in this way, it can be seen that there are almost only toner particles having a single particle size. This indicates that toner particles having a single particle diameter are obtained by drying without causing the toner droplets 21 discharged as described above to coalesce. In the present embodiment, the uniting prevention means by one auxiliary transport airflow is provided, but a configuration in which two or more auxiliary transport airflows are supplied into the gas phase may be employed.

  On the other hand, as can be seen from FIG. 17 showing the particle size distribution of the collected toner when the droplet states are united, other configurations and conditions are not merely using a very small amount of carrier airflow or auxiliary carrier airflow. The same as in FIG. The toner droplet 21 discharged from the droplet discharge means 2 receives air resistance, the discharge speed rapidly decreases, and starts to fall naturally. When the discharge speed is lowered, the distance between the droplets is shortened, and eventually the coalescence between the droplets occurs. In addition, the coalesced particles have increased air resistance and are delayed in drying, so that they coalesce with other droplets. And several droplets may coalesce, and when they are dried, they coalesce and produce dried particles, resulting in a broader particle size distribution of the toner. The particle size distribution shown in FIG. 17 is an example of the collected toner, but the dry particles constituting the basic particle size and the peak shown in FIG. is there. The dry particles forming the peak described as twice are those obtained by drying and solidifying after the toner droplets 21 are merged after ejection. Similarly, it can be inferred from the particle size distribution measurement results that unification of 3 times, 4 times, or more is proceeding. Here, the particle size distribution measurement can be performed using a flow type particle image analyzer (Sysmex Corp. FPIA-2000). The particle size distribution can be compared by the ratio of the volume average particle diameter (Dv) and the number average particle diameter (Dn), and can be expressed by Dv / Dn. The smallest Dv / Dn value is 1.0, which indicates that all the particle sizes are the same. A larger Dv / Dn indicates a wider particle size distribution. A general pulverized toner has Dv / Dn = 1.15 to 1.25. The polymerized toner has a Dv / Dn of about 1.10 to 1.15. The toner of the present invention is confirmed to have an effect on print quality by setting Dv / Dn = 1.15 or less, more preferably Dv / Dn = 1.10 or less. In an electrophotographic system, a narrow particle size distribution is required for the development process, the transfer process, and the fixing process. Also, Dv / Dn = 1.15 or less is desirable for stably obtaining a high-definition image, and Dv / Dn = 1.10 or less is desirable for obtaining a higher-definition image.

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

  FIG. 18 is an overall schematic diagram showing an example of the fine particle production apparatus of the present embodiment. In the drawing, a fine particle production apparatus 600 includes a droplet discharge head 601, an air flow path 602, a cyclone collection device 603, a toner storage box 604, a filter 605, a blower 606, a solvent recovery box 607, a heater for heating 608, and a solvent recovery capacitor. 609, including a heat pump structure 610. The air flow path 602 communicates with the communication port of the cyclone collection device 603, and the toner particles conveyed through the air flow channel 602 are dried and solidified in the air flow channel 602 and in the cyclone portion of the cyclone collection device 603. Is done. The cyclone portion of the cyclone collection device 603 communicates with the solvent recovery condenser 609 via the filter 605 and the blower 606, and the gas generated in the cyclone collection device 603 is liquefied by the heat pump system 610. In detail, the heat pump system 610 is configured to circulate between the solvent recovery condenser 609 and the heater 608 by two blowers 611 and 612. The gas conveyed from the cyclone collector 603 is liquefied by alternately repeating heating by the heater 608 and cooling by the solvent recovery capacitor 609. The liquid solvent recovered by the solvent recovery capacitor 609 is recovered in the solvent recovery box 607. The gas from which the solvent is removed is conveyed again into the air flow path 602. When a predetermined amount of toner has accumulated at the bottom of the cyclone of the cyclone collector 603, the bottom cover is opened and discharged to the toner storage box 604. When the lid of the cyclone bottom is closed, the communication pipe including the air flow path 602 is a closed space. In the closed space, an air flow of about 10 [m / s] is generated by the blower 606, and the air flow circulates in the closed space as described above. As the gas in the closed space at this time, it is desirable to use an inert gas such as nitrogen in order to promote the drying of the toner. Energy recovery can be improved by performing recovery and reuse of the solvent by heat management using the heat pump system 610 or the like.

  FIG. 19 is an enlarged view of a portion surrounded by a broken line in FIG. As shown in the figure, the air flow path in the fine particle production apparatus is divided into two air flow paths 701 and 702 by a partition wall 703. Further, on the upstream side of the air flow paths 701 and 702, flow speed adjusting means 706 for adjusting the flow speed of each air flow path is installed. By this flow rate adjusting means 706, the speed A of the airflow flowing through the air flow path 702 is adjusted to be slower than the speed B of the airflow flowing through the air flow path 701. The flow rate adjusting means 706 includes a plate-like member that pivots in the flow path of each air flow path, and adjusts the amount of gas that passes by rotating the plate-shaped member to rotate the flow speed of each air flow path. Each is adjusted. The flow path adjusting unit 706 is configured by a valve, a honeycomb, or a unit that adjusts the flow rate of the gas by changing the angle of the surface of the plate-like member that rotates about the airflow direction. An opening 704 that penetrates in the thickness direction of the partition wall 703 is provided in part of the partition wall 703. A droplet ejection head 705 is provided in a part of the wall portion 708 constituting the air flow path 702 that faces the opening space in the opening 704 so that the discharge surface is flush with the wall surface. The opening space surface of the opening 704 faces the ejection surface. A plurality of vent holes 707 are provided in a part of the partition wall 703 on the downstream side of the installation position of the opening 704. Gas is ejected from the air flow path 702 to the air flow path 701 through these ventilation holes 707, and an air flow is generated from the inner wall of the air flow path 701 toward the center of the air flow path. This suppresses toner particles from adhering to the inner wall of the air flow path 701.

  FIG. 20 is an enlarged view of a portion surrounded by a broken line in FIG. As described above, the gas at the predetermined speed B flows through the air flow path 701. A gas having a predetermined velocity A flows through the air flow path 702. For this reason, a pressure difference occurs between the air flow path 701 and the air flow path 702 and in the vicinity of the opening 704 in accordance with the speed difference. Therefore, a gas flow is generated from the air flow path 702 to the air flow path 701 through the opening 704 communicating with each air flow path. Here, the interval between the ejection surface of the droplet ejection head 705 and the partition wall 703 is very narrow, and the ejection surface is close to the partition wall 703. For this reason, the partition 703 functions as a current plate of the prior application. That is, the partition 703 restricts the generation of a reverse airflow that reversely moves the liquid droplets ejected from the ejection holes of the liquid droplet ejection head 705 toward the ejection surface. As a result, the momentum of the reverse airflow generated around the outlet of the discharge hole is reduced, and droplets and the like that adhere to the discharge surface due to the reverse airflow can be reduced.

  According to the fine particle manufacturing apparatus having such a configuration, the toner component liquid droplets ejected from the respective ejection holes of the liquid droplet ejection head 705 move according to a predetermined flow from the air channel 701 toward the opening 704. At this time, since the air flow path 702 is separated from the air flow path 701 by the partition wall 703, there is no influence of the air flow in the air flow path 701. The air flow path 701 is a continuous surface and is constituted by a partition wall 703 having a wall surface without a step, so that there is no negative pressure even inside the air flow path 701. Therefore, the airflow flowing from the air flow path 702 through the opening 704 to the air flow path 701 is a stable air flow. Accordingly, the flow in the ejection direction of the toner component droplets after ejection is stabilized until reaching the air flow path 701, and the coalescence and division of the droplets can be reduced, and the production of fine particles having a narrow particle size distribution is enabled.

  FIG. 21 is a partial cross-sectional view showing Modification 1 of the fine particle production apparatus of the present embodiment. As shown by the dotted line in the figure, the partition wall 703 in the fine particle manufacturing apparatus of Modification 1 shown in the same figure has a narrow space between the upstream edge of the air flow and the wall 708 of the air flow path 701, and the partition wall 703. The cross section in the airflow direction at the upstream end is tapered. As a result, the flow rate of the gas entering the air channel 702 from the air channel 701 is limited. Therefore, with a simple structure, the flow rate of the air channel 702 is made slower than the flow rate of the air channel 701.

[Unification unit and satellite unit]
Next, coalescence prevention means and satellite prevention means for obtaining ultimate uniformity in fine particles such as toner particles will be described. These means minimize satellites (which are thin rod-like liquid particles stretched from the ejected droplets) and coalesced particles that cause particle size distribution. FIG. 22A shows a state in which toner component droplets are ejected from one head. Actually, the yield is ensured by arranging a plurality of heads. FIG. 22B shows normal ejection. In many cases, the formed toner component droplets are likely to be separated into main droplets and satellites in the vicinity of the ejection holes. After that, the air flow rapidly decreases and the liquid flow velocity decreases, and the satellite is absorbed by the main droplet, and then the coalescence of the droplets begins as the droplet velocity decreases, resulting in a larger toner component droplet, Dry and solidify. On the other hand, FIG. 22 (c) shows an example in which an air flow is added immediately after discharge, and the coalescence of main droplets disappears but satellite particles remain unabsorbed.

  On the other hand, as shown in FIG. 22 (d), the discharged toner component droplets are broken down into three stages: a droplet formation area, a satellite absorption area, and a main droplet coalescence prevention area. Then, the toner component droplets sent out from the ejection holes at the speed of VJ1 are lowered to VJ2 in the satellite absorption area by the resistance of the ambient atmosphere gas. After that, while passing through the throttle part, it is naturally accelerated to VJ3, and the distance between the main drops is released. Thereafter, the air flow is assisted from the periphery in accordance with the re-accelerated droplet speed, and the solid droplets are dried and solidified without causing the main droplets to coalesce.

  FIG. 23 shows an example of a droplet conveyance path of the coalescence prevention means. The end of the opening is arranged so that there is no returning airflow in the vicinity of the discharge surface, and after the discharged droplet is decelerated and absorbs the satellite. Designed to be quickly accelerated again.

  FIG. 24 is an example of a diagram illustrating the aperture portion. FIG. 24A is a schematic diagram of the throttle portion, and has a shape in which the flow path becomes narrower in the discharge direction. The mist generated at this time may adhere to the wall surface. For this reason, the wall surface is subjected to a liquid repellent treatment to reduce the adhesion of droplets. Furthermore, as shown in FIG. 24 (b), the adhering liquid flows along the wall, and as shown in FIG. 24 (c), which is an enlarged view of FIG. It is structured to be collected.

  FIG. 25 is a partial perspective view showing a second modification of the fine particle production apparatus of the present embodiment. In the drawing, in the fine particle manufacturing apparatus as this modified example, the opening 704 itself shown in FIG. That is, the opening cross-sectional shape of the opening 704 is formed to be the cross-sectional shape of the opening of the coalescence prevention means 709 having the above-described stop portion and the like. According to this modification of the fine particle manufacturing apparatus, the toner component droplets discharged from the discharge holes 705-2 of the droplet discharge head 705 pass through the air flow path 702 and flow to the opening of the coalescence prevention means 709. Go on board. Then, in the area where the opening cross-sectional area does not change or gradually increases (corresponding to the satellite absorption area in FIG. 22), it is intended to separate from the discharged main droplet and the main droplet by the resistance of the gas. The speed of each satellite you play will decrease. Since the main droplet is larger than the size of the satellite, the resistance of the gas received by the main droplet is larger than the resistance of the gas received by the satellite. For this reason, the velocity of the main droplet becomes slower than the velocity of the satellite, the satellite and the main droplet come into contact so that the satellite is attracted to the main droplet, and the satellite is absorbed by the main droplet. And it accelerates while passing through the aperture | diaphragm | squeeze part of the area (equivalent to the main droplet coalescence prevention area of FIG. 22) where an opening cross-sectional area reduces gradually, and the distance between main droplets spreads. As a result, the main droplets can be moved to the air channel 701 without coalescence. Therefore, a large amount of toner component droplets can be stably discharged for a long time. Thereby, productivity can be raised.

The inner wall surface of the opening of the coalescence prevention means 709 and the wall surface of the partition wall 703 on the air flow path 701 side are subjected to water repellent treatment. For example, TiO ₂ , SiO ₂ , and OPTOOL are vapor-deposited on the metal partition surface. Further, a profile is used in which the shape of the opening of the coalescence prevention means 709 is a convex portion toward the air flow path side. By these, liquid adhesion in the vicinity of the opening can be reduced as much as possible. Further, by scanning the inner wall of the partition wall 703 including the periphery of the opening of the coalescence prevention means 709 on the side of the air flow path 701 with a rubber blade (not shown), the toner component droplets adhering to the inner wall can be easily removed. it can. The rubber plate is retracted from the air flow path 701 to the outside when discharging the toner component droplets.

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

Next, 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 if necessary, 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, vinyl such as styrene monomer, acrylic monomer, methacrylic monomer, etc. 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 can be mentioned.

  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, etc. (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 a usage-amount of a 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 [μm] to 2 [μm], and more preferably 0.1 [μm] 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.

Further, as magnetic characteristics of the magnetic material, the magnetic characteristics at 10 k oersted application are coercive force 20 to 150 oersted, saturation magnetization 50 to 200 [A · m ² / kg], remanent magnetization 2 to 20 [A · m, respectively. ² / kg] is preferable. The magnetic material can also be used as a colorant.

[Colorant]
The colorant is not particularly limited, and a commonly used resin can be appropriately selected and used. 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, Phi -Red, Parachlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine 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, Kina Redon 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, 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 Lake , 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 the master batch resin and the colorant under high shear. 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 a usage-amount of a 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] or less. More preferably, the amine value is 10 to 50 and the colorant is dispersed. 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 molecular weight of the maximum value of the main peak in terms of styrene 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 waxes are further 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, valinalic acid, etc. Unsaturated fatty acids, stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnupyl alcohol, seryl alcohol, mesyl alcohol, saturated alcohols such as long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acid amides , Fatty acid amides such as lauric acid amide, methylene biscapric acid amide, ethylene bis lauric acid amide, saturated fatty acid bisamides such as hexamethylene bis stearic acid amide, ethylene bisoleic acid amide, hexamethylene bisoleic acid Unsaturated fatty acid amides such as acid amide, N, N′-dioleyl adipate amide, N, N′-dioleyl sepasin 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 [° C.] to 120 [° C.] in order to balance the fixing property and the offset resistance. If it is less than 70 [° C.], the blocking resistance may be lowered, and if it exceeds 140 [° C.], the offset resistance effect may be difficult to be exhibited.

  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 [° C.] to 100 [° C.], functional separation is effectively exhibited. 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 easily exhibited, the melting point of at least one wax is preferably 70 to 120 [° C.], and more preferably 70 [° C.] to 100 [° C.]. preferable.

  As for 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 exert a plastic action, and those having a more linear structure or functional group Non-polar and non-denatured straight ones that do not have 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.

  As a DSC measuring instrument for wax or toner, it is preferable to measure with a differential scanning calorimeter of high accuracy internal heat type input compensation type. 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.

[Flowability 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 titanium oxide, fine powder. Examples include non-alumina, treated silica obtained by subjecting them to a surface treatment with a silane coupling agent, a titanium coupling agent, or silicone oil, treated titanium oxide, and treated alumina. Among these, fine powder silica, fine powder 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 [μm] to 2 [μm], and preferably 0.002 [μm] to 0.2 [μm] as an average primary particle size. More preferred.

  Fine powder silica is fine powder produced by vapor phase oxidation of silicon halide inclusions, 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 preferred 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 inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. The primary particle size of the inorganic fine particles is preferably 5 [nm] to 2 [μm], more preferably 5 [nm] to 500 [nm].

The specific surface area according to the BET method is preferably 20 [m ² / g] to 500 [m ² / g]. The use ratio of the inorganic fine particles is preferably 0.01 [mass%] to 5 [mass%] of the toner, and more preferably 0.01 [mass%] 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, and modified silicone oil. 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]. The specific surface area by the BET method is preferably 20 [m ² / g] to 500 [m ² / g]. The proportion of the inorganic fine particles used is preferably 0.01 [wt%] to 5 [wt%] of the toner, more preferably 0.01 [wt%] to 2.0 [wt%]. preferable.

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

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

(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 liquid temperature 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 bead mill (LMZ type manufactured by Ashizawa Finetech Co., Ltd., zirconia bead diameter 0.3 mm), and the maximum diameter was adjusted to 1 [μm] or less.

(Dissolution or preparation of dispersion)
Next, a toner composition 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 weight of a polyester resin as a binder resin, 30 parts by weight of the colorant dispersion, 30 parts by weight of the wax dispersion, 840 parts by weight 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.

(Toner production equipment)
The toner manufacturing apparatus 1 having the configuration shown in FIG. 14 was used, and toner was manufactured using several droplet discharge means as the droplet discharge means.
The size and conditions of each component are shown below.

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

(Direct membrane vibration droplet discharge means)
The outer diameter of the frame is 26 [mm], the thin film 101 is a nickel plate having a diameter of 20 [mm] and a thickness of 40 [μm]. The outlet diameter of the plurality of discharge holes is 10 [μm], and 100 holes are provided in the area of the central portion φ1 [mm] of the thin film 101. The vibration generating member 202 of the vibration generating means 201 has an outer diameter of φ15.0 [mm], an inner diameter of φ4.0 [mm] and a thickness of 0.5 [mm], and the electrode 109 is made of silver paste. Yes. The drive signal generation source 106 uses an NF company function generator WF 1973, and the drive circuit 105 is connected to vibration generation means by a polyethylene-coated lead wire. The driving frequency at this time is 108 [kHz] in accordance with the liquid resonance frequency.

(Toner collecting part)
The shroud 501 in FIG. 15 has a cylindrical shape, the diameter is 50 [mm], and the diameter of the opening is φ10 [mm]. The chamber 401 in FIG. 14 has a cylindrical shape with an inner diameter of φ400 [mm] and a height of 2000 [mm], and is fixed vertically. And the upper end part and the lower end part are restrict | squeezed, the diameter of a conveyance airflow introduction port is (phi) 50 [mm], and the diameter of a conveyance airflow exit is (phi) 50 [mm]. The droplet discharge means 2 is disposed in the center of the chamber 401 at a height of 300 mm from the upper end in the chamber 401. The carrier airflow was 10.0 [m / s] and 40 [° C.] nitrogen.

Example 1
The head unit configuration shown in FIG. 15 was used to observe and evaluate the droplet discharge status. At this time, the discharge hole array is formed in a width of 2 [mm] and a length of 40 [mm], and about 1600 discharge holes are arranged. The gap between the discharge hole and the opening of the drying channel was discharged at 2 [mm], and the discharge of the droplet was observed with a video. The openings are formed in accordance with the arrangement of the discharge holes, and the convex shape of the openings has a height of 1 [mm] and the tip protrudes at an acute angle. Thereafter, the toner collected through the dry air flow path was taken out of the toner storage container to obtain a toner. The particle size distribution of the toner was measured with a flow particle image analyzer (FPIA-2000; Sysmex Corporation) under the measurement conditions shown below. When this was repeated three times, the average of the volume average particle diameter (Dv) was 5.4 [μm], the average of the number average particle diameter (Dn) was 5.2 [μm], and the average of Dv / Dn was 1.04.

A measurement method using a flow particle image analyzer (Flow Particle Image Analyzer) will be described below. Measurement of toner, toner particles and external additives by a flow type particle image analyzer can be performed using, for example, a flow type particle image analyzer FPIA-2000 manufactured by Toa Medical Electronics. In the measurement, fine dust is removed 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. A few drops of nonionic surfactant (preferably Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.) is added to 10 [ml] of 20 or less water, and further 5 [mg] of a measurement sample is added, and an ultrasonic disperser ( UH-50 (manufactured by STM) at 20 [kHz] and 50 [W / 10 cm ³ ] for 1 minute, and further dispersed for a total of 5 minutes. Using a sample dispersion liquid of 8000 [pieces / 10 ⁻³ cm ³ ] (for particles in the measurement equivalent circle diameter range), it has an equivalent circle diameter of 0.60 [μm] or more and less than 159.21 [μm]. The particle size distribution of the particles was measured.

  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 has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area was calculated as the equivalent circle diameter.

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

(Example 2)
Similarly, the toner composition liquid is discharged from all the discharge holes at a 340 [kHz] droplet initial velocity of 15 [m / s], and the distance between the head discharge hole and the outer wall of the air flow path is 0.5 [mm], 1 [mm], 2 [mm], and 3 [mm] were separated, and the number of non-ejection holes after 10 minutes was measured. At the time of initial discharge, discharge of all 1600 discharge holes is confirmed. Approximately 170 discharge holes at 0.5 [mm], 1 [mm] total discharge, 2 [mm] total discharge, 3 [mm] 300 discharge holes or more, and a distance of 1 [mm] to 2 [mm] was placed When was the most stable.

(Comparative Example 1)
In the same manner as in Experimental Example 2 described above, the interval was set to 1.5 [mm], and ejection from 1600 ejection holes was performed, and the number of ejection failure holes was recorded for 1 hour. Non-discharge of 8 discharge holes after 30 minutes and 12 discharge holes after 1 hour was observed. On the other hand, when the head was installed in the air flow path so that the discharge holes were flush with the inner wall and discharged, and the number of non-discharge holes was measured, about 200 discharge holes after 10 minutes and 300 after 20 minutes. After about 30 minutes, about 800 discharge holes were not discharged. Since liquid dripping occurred on the discharge hole surface, measurement was stopped in 30 minutes. After the discharge hole plate was cleaned, it was discharged again, but after 30 minutes, liquid dripping occurred.

  As described above, it is shown that an unprecedented particle size distribution can be obtained by providing a restriction at an appropriate position and appropriately giving the flow velocity of the atmospheric gas.

  In an electrophotographic system, a narrow particle size distribution is required for the development process, the transfer process, and the fixing process. Therefore, such spread of the particle size distribution is not desirable, and in order to stably obtain high-definition image quality. Dv / Dn = 1.15 or less is preferable, and in order to obtain a higher definition image, Dv / Dn = 1.10 or less is more preferable. More preferably, it is 1.00 to 1.05. Moreover, it is preferable that a weight average particle diameter exists in the range of 1-20 micrometers, More preferably, it is 3-10 micrometers.

What has been described above is merely an example, and the present invention has a specific effect for each of the following modes.
(Aspect 1)
Droplet discharge means for discharging droplets of a liquid containing a fine particle component that becomes fine particles when the droplets solidify from a plurality of discharge holes opened on the discharge surface, and an air flow path into which the droplets discharged from the plurality of discharge holes are introduced When, in the fine particle manufacturing apparatus and a stream generating means for generating an air flow in the air flow path, the air flow path is divided into two air flow path in the droplet ejection direction from the airflow upstream side of the or one droplet discharge means , comprising a partition wall for connection communicates to the air flow direction downstream of the droplet discharge means, the partition, the position of the ejection surface and the facing of the droplet discharge means, through holes for communicating the two air flow paths are provided, the liquid droplets ejected by the droplet discharging means is introduced into the other air flow path of the two air flow path through the through hole from the two one gas flow path in the inner droplet discharging means side of the air passage It is characterized by that . According to this, as described in the above embodiment, the air flow path for discharging liquid droplets from the plurality of discharge holes opened on the discharge surface of the liquid droplet discharge head 705 is divided into two air flow paths 701 and 702 by the partition wall 703. To do. Then, the partition wall 703, the air flow direction upstream of the droplet discharge head 705 are provided to continue communication until air flow direction downstream of the droplet discharge head 705. Due to the flow of the air flow path 701, there is no space that extends downstream in the air flow direction of the partition wall 703, and no return air flow is generated. Liquid droplets ejected from the ejection holes of the droplet discharge head 705, the discharge speed, the air flow path serving the airflow path other through a through-hole serving as an opening 704 provided in one air flow path serving the airflow duct 702 and the partition 703 It is conveyed to 701. When the liquid droplets are conveyed while pushing the gas in the air flow path 702 and the opening 704, a gas flow is generated from the air flow path 701 to the air flow path 701 through the opening 704. Since the air flow paths 701 and 702 are partitioned by the partition wall 703, the air flow in the air flow path 701 does not interfere with the air flow passing through the opening 704 from the air flow path 701. For this reason, there is no airflow that returns to the discharge surface in the vicinity of the discharge hole of the droplet discharge head 705 provided on the air flow path 702 side, and there is only an air flow that goes from the air flow path 702 through the opening 704. It is. The airflow around the discharge hole and the airflow to the opening are stabilized. Thereby, coalescence and division of the discharged droplets can be reduced. Therefore, it is possible to produce fine particles having a narrow particle size distribution.
(Aspect 2)
(Aspect 1), one of the gas flow path of the flow velocity and the other of the air flow path and the flow rate with the flow rate adjustment means for adjusting each of the other air flow path to a flow rate of one of the gas flow path by flow rate adjustment means It is adjusted so as to be slower than the flow velocity of. According to this, as above described, a between the gas flow path 701 and the air flow path 702 occurs speed difference about the periphery of the opening 704, the pressure differential in response to the speed difference Arise. For this reason, a gas flow is generated from the air flow path 702 to the air flow path 701 through the opening 704 communicating with each air flow path. The flow rate of the gas flow is larger than the flow rate of the flow generated only by the discharge of the droplets. As a result, there is no air flow that returns to the discharge surface around the discharge hole of the droplet discharge head 705, and there is only an air flow that passes from the air flow path 702 through the opening 704. The airflow around the discharge hole and the airflow to the opening are stabilized. Thereby, coalescence and division of the discharged droplets can be reduced. Therefore, it is possible to produce fine particles having a narrow particle size distribution.
(Aspect 3)
(Aspect 2), the flow rate adjusting means, the direction of the cross-sectional area orthogonal to the airflow direction of the hand air flow path is smaller than the cross-sectional area in a direction orthogonal to the airflow direction of the other side the gas flow path It is comprised so that it may become . According to this, as described in the second modification of the above embodiment, the flow velocity of each air flow path can be adjusted with a simpler configuration. For this reason, the airflow around the discharge hole and the airflow to the opening can be set to a desired flow rate. Thereby, coalescence and division of the discharged droplets can be reduced, and fine particles with a narrow particle size distribution can be produced.
(Aspect 4)
(Aspect 2), the flow rate adjusting means is a one of the airflow upstream side and the other respectively provided are valve or honeycomb in the airflow upstream side of the airflow path of the air flow path. According to this, as explained about the above-mentioned embodiment, it is possible to adjust the flow velocity of each air flow path with a simpler configuration. For this reason, the airflow around the discharge hole and the airflow to the opening can be set to a desired flow rate. Thereby, coalescence and division of the discharged droplets can be reduced, and fine particles with a narrow particle size distribution can be produced.
(Aspect 5)
In (Aspect 2), the flow rate adjusting means is provided on the upstream side in the air flow direction of one air flow path and on the upstream side in the air flow direction of the other air flow path, so that the angle of the plate surface relative to the air flow direction changes. It is comprised by the plate-shaped member which can be pivoted. According to this, as explained about the above-mentioned embodiment, it is possible to adjust the flow velocity of each air flow path with a simpler configuration. For this reason, the airflow around the discharge hole and the airflow to the opening can be set to a desired flow rate. Thereby, coalescence and division of the discharged droplets can be reduced, and fine particles with a narrow particle size distribution can be produced.
(Aspect 6)
(Aspect 1) to (embodiment 5), without changing the opening cross-sectional area of the through-hole from the inlet of the through-hole to a predetermined position, or is gradually increased, the through-hole from a predetermined position to the exit of the through hole The through hole is configured to gradually reduce the opening cross-sectional area. According to this, as described in the second modification of the above embodiment, in the vicinity of the ejection hole, in many cases, the main droplet and the satellite are separated. By changing or gradually increasing the opening cross-sectional area of the opening from the opening of the droplet to a predetermined location, the air flow is rapidly reduced by the air resistance, and the satellite is absorbed by the main droplet. By gradually reducing the opening cross-sectional area of the opening from a predetermined location to the opening outlet and increasing the speed of the main droplet to increase the distance between the main droplets, coalescence of the main droplets is suppressed. . Therefore, it is possible to produce fine particles having a narrow particle size distribution.
(Aspect 7)
(Aspect 1) to (embodiment 6), the droplet discharge means is provided to discharge surface is the wall surface flush constituting the air flow path while One only opposed to the wall surface of the partition wall of one of the air flow path side ing. According to this, as described in the above embodiment, when the discharge surface of the droplet discharge head 705 protrudes from the wall surface constituting the air channel 702, the droplet discharge in which the gas flowing through the air channel 702 protrudes. airflow generated by striking the end face of the air flow upstream side of the head or the droplet stream airflow downstream side space extending air flow direction downstream side from an end portion of the discharge head is produced by a negative pressure discharge hole peripheral, This affects the air flow and the discharge direction deviates from the target direction. By providing the discharge surface of the droplet discharge head 705 so as to be flush with the wall surface constituting the air flow path 702, an airflow that affects the airflow around the discharge holes is not generated. Therefore, coalescence and division of the discharged droplets can be reduced. Therefore, it is possible to produce fine particles having a narrow particle size distribution.
(Aspect 8)
(Aspect 1) to (embodiment 7), a part of the partition wall, providing a vent hole communicating with one of the gas flow path and the other air flow path. According to this, as described in the above embodiment, the toner particles transported through the air channel 701 are suppressed from adhering to the inner wall of the air channel 701.
(Aspect 9)
(Aspect 1) to (embodiment 8), at least one inner wall surface of the partition walls forming the wall or through-hole of the other of the gas flow path side of the partition wall is subjected to water repellent treatment. According to this, as described in the above embodiment, the adhesion of the toner component droplets to the wall surface of the partition on the other air flow path side around the opening 704 is reduced as much as possible, and the air flow generated by the toner deposited around the opening is prevented. To do. For this reason, it is assumed that there is only an airflow passing through the opening 704 from the air flow path 702, and the airflow around the discharge hole and the airflow to the opening are stabilized. Thereby, coalescence and division of the discharged droplets can be reduced. Furthermore, the adhesion of the toner component droplets to the inner wall surface of the partition wall forming the through hole is reduced as much as possible, and the turbulence of the air flow in the through hole is suppressed. Therefore, it is possible to produce fine particles having a narrow particle size distribution.
(Aspect 10)
(Aspect 1) using any of the particulate manufacturing equipment to (embodiment 9), is characterized in that the production of fine particles. According to this, as described in the above embodiment, the toner component droplets ejected from the droplet ejection head 706 move according to a stable flow from the air flow path 702 to the opening 704 and pass through the opening to generate an air flow. Released to the path 701. For this reason, coalescence and division of the ejected droplets can be reduced. Therefore, it is possible to produce fine particles with a narrow particle size distribution and uniformity .

DESCRIPTION OF SYMBOLS 10 Liquid column resonance droplet formation unit 11 Droplet discharge part 14 Toner component liquid 18 Liquid column resonance liquid chamber 19 Discharge hole 20 Vibration generating means 21 Droplet 400 Dry collection unit 401 Chamber 402 Toner collection means 403 Toner storage part 404 Transport airflow inlet 405 Transport airflow outlet 501 Shroud 502 Auxiliary transport airflow inlet 503 Auxiliary transport airflow 600 Fine particle production device 601 Droplet discharge head 602 Air flow path 603 Cyclone collection device 604 Toner storage box 605 Recovery filter 606 Blower 607 Solvent recovery Box 608 Heating heater 609 Solvent recovery condenser 610 Heat pump system 611 Blower 612 Blower 701 Air flow path 702 Air flow path 703 Partition 704 Opening 705 Droplet discharge head 706 Flow rate adjusting means 707 Vent hole 708 Wall 709 Stage 801 blower 802 air passage 803 droplet discharge head 804 rectifying plate 805 openings 806 mounting screws 807 discharge hole

Japanese Patent No. 3786034 Japanese Patent No. 3786035 JP-A-57-201248 JP 2006-293320 A

Claims (10)

Droplet discharge means for discharging droplets of a liquid containing a fine particle component that becomes fine particles when the droplets solidify are discharged from a plurality of discharge holes opened on the discharge surface, and a gas discharged from the plurality of discharge holes is introduced. and the flow path, the particle production apparatus and a stream generating means for generating an air flow in the gas flow path,
The air flow path is divided into two air flow path in the droplet ejection direction from the airflow upstream side of the or One prior Symbol droplet discharging means, a partition wall for connection communicates to the air flow direction downstream of the droplet discharge means Prepared,
The partition wall is provided with a through-hole communicating with the two air flow paths at a position facing the ejection surface of the droplet ejection means ,
Droplets ejected by the droplet discharge means, the other of the two air flow paths through said through hole from said two one gas flow path in the droplet discharge means side of the air passage particle manufacturing apparatus characterized by being introduced into the gas flow path. The fine particle production apparatus according to claim 1,
The flow rate of the flow rate comprises adjusting means, the other air flow path the flow rate of the one air flow path by the flow velocity adjustment means for adjusting the one of the flow velocity of the gas flow path the other air flow path and flow velocity, respectively particle manufacturing apparatus characterized by being adjusted so that slower. In the fine particle manufacturing apparatus according to claim 2,
The flow rate adjustment means, adapted to the cross-sectional area in a direction orthogonal to the air flow direction of the gas flow path of the hand is smaller than the cross-sectional area in a direction orthogonal to the air flow direction of the gas flow path of said other side An apparatus for producing fine particles, wherein In the fine particle manufacturing apparatus according to claim 2,
The fine particle manufacturing apparatus according to claim 1, wherein the flow rate adjusting means is a valve or a honeycomb provided on the upstream side in the air flow direction of the one air flow path and on the upstream side in the air flow direction of the other air flow path . In the fine particle manufacturing apparatus according to claim 2,
The flow rate adjusting means is provided on the upstream side in the air flow direction of the one air flow path and on the upstream side in the air flow direction of the other air flow path , and pivots so that the angle of the plate surface with respect to the air flow direction changes. An apparatus for producing fine particles, characterized in that it is made of a plate-like member capable of being used. In the fine particle manufacturing apparatus according to any one of claims 1 to 5 ,
Wherein the inlet of the through-hole to a predetermined position without changing the cross-sectional area of the opening of the through hole, or is gradually increased, gradually opening cross-sectional area of the through hole from the predetermined position to the exit of the through hole An apparatus for producing fine particles, wherein the through hole is configured to be small. In the fine particle manufacturing apparatus according to any one of claims 1 to 6 ,
The droplet discharge means, characterized in that the pre-Symbol discharge surface is provided so that the wall surface flush constituting the opposing vital said one air passage of the wall surface of the partition wall of one of the air flow path side the A fine particle manufacturing apparatus. In the fine particle manufacturing apparatus according to any one of claims 1 to 7 ,
Some of the partition walls, particulates manufacturing apparatus characterized by providing a vent hole communicating said the one air flow path and the other air flow path. In the fine particle manufacturing apparatus according to any one of claims 1 to 8 ,
The other wall surface of the partition wall of the gas flow path or the at least one inner wall surface of the partition wall forming the through hole, particulates manufacturing apparatus characterized by performing water-repellent treatment. A method for producing fine particles, comprising producing fine particles using the fine particle production apparatus according to claim 1.