JP2012185411A - Production method of toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a toner, for preventing a toner composition liquid from solidifying when a production of a toner is stopped for maintenance or the like in the process of producing the toner using a plurality of discharge holes, and for improving production efficiency of particles.SOLUTION: The production method of a toner includes: a periodical droplet formation step of periodically forming and discharging droplets of a toner composition liquid 10 containing at least a resin and a colorant through a plurality of discharge holes 11 while vibrating the liquid; and a granulation step of solidifying the discharged droplets 31 of the toner composition liquid 11 to form toner particles. When formation and discharge of the liquid droplets are stopped in the periodical droplet formation step, a liquid surface 101 in the discharge hole 11 is vibrated.

Description

  The present invention relates to a method for producing a toner used as a developer for developing an electrostatic image in electrophotography.

  Conventionally, the pulverization method has been the only production method for electrophotographic toners used in image forming apparatuses such as copying machines, printers, fax machines, and composite machines based on the electrophotographic recording method. However, in recent years, a method of forming in an aqueous medium called a polymerization method has been widely performed, and has a tendency to surpass the pulverization method (for example, see Patent Document 1). The toner by the polymerization method is called “polymerized toner” or “chemical toner” in some countries, but the polymerization method includes a manufacturing method that does not necessarily involve a polymerization process for convenience. Currently used polymerization methods are suspension polymerization, emulsion aggregation, polymer suspension (polymer aggregation), and ester elongation.

  Compared with the pulverization method, the polymerization method generally has advantages such that it is easy to obtain a toner having a small particle size, the particle size distribution is sharp, and the shape is almost spherical. However, since the toner particles are usually removed from the toner particles in an aqueous medium, the solvent removal efficiency is poor and a long time is required for the polymerization process. Further, after the solidification is completed, it is necessary to separate the toner particles and water, and then repeat washing and drying, which requires a lot of time, a lot of water, and a lot of energy.

As an alternative toner manufacturing method, a so-called spray-drying method in which a toner composition liquid is formed into droplets in a gas phase without using water and then solidified has been proposed, but has a drawback of wide particle size distribution.
As an attempt to make the toner composition liquid droplets in the gas phase and narrow the particle size distribution, a method has been proposed in which fine droplets are formed using piezoelectric pulses, which are then dried and solidified to become toners ( Patent Document 2).
Alternatively, a method has been proposed in which fine droplets are formed by using thermal expansion in the discharge holes, and then dried and solidified to form a toner (see Patent Document 3). Or the method of performing the same process using an acoustic lens is proposed (refer patent document 4).
However, these toner manufacturing methods have the problem that the number of droplets that can be ejected from a single ejection hole per unit time is small and the productivity is poor, and at the same time, the particle size distribution is broadened due to the coalescence of the droplets. Inevitable, it was not satisfactory in terms of monodispersibility.
Therefore, it has been proposed to improve productivity by forming micro droplets using high frequency vibration and a plurality of discharge holes.
However, it is difficult to continuously discharge stable fine droplets from a plurality of discharge holes at a high frequency. It has been confirmed that the discharge holes influence each other due to the spread of the exuded droplets, the number of discharge holes normally discharged decreases with time, and the production efficiency decreases.
In addition, when the production of toner is stopped for maintenance, etc., the toner composition liquid is solidified, and a discharge hole that is blocked is produced. is there.

  Therefore, the present invention has been made in view of the above problems, and the problem is that the toner composition liquid produced when the toner production is stopped for maintenance or the like in the production of toner associated with the use of a plurality of ejection holes. It is an object of the present invention to provide a toner manufacturing method that prevents solidification and improves the production efficiency of particle formation.

The features of the present invention, which is a means for solving the above problems, are listed below.
The toner manufacturing method of the present invention includes a periodic droplet forming step in which a toner composition liquid containing at least a resin and a colorant is periodically formed into droplets while being oscillated from a plurality of ejection holes, and is discharged. In a method for producing a toner having a particle forming step of solidifying droplets of a toner composition liquid to form toner particles, an ejection hole is formed when stopping the droplet formation and discharge in the periodic droplet forming step. The liquid surface is vibrated.
Further, the toner manufacturing method of the present invention is further characterized in that the means for vibrating the liquid surface provides continuous low vibrations that do not cause the discharge head to discharge droplets.
In addition, the toner manufacturing method of the present invention is further characterized in that the vibration is a vibration having the same frequency as that when a droplet is discharged with a reduced vibration amplitude.
The toner manufacturing method of the present invention is further characterized in that the low vibration is a vibration whose frequency is changed from a vibration (resonance) during ejection.
The toner manufacturing method of the present invention is further characterized in that the periodic droplet forming step employs a liquid column resonance ejection method.

The present invention, which is a means for solving the above problems, has the following specific effects.
In the toner production method of the present invention, the toner composition liquid is ejected from a plurality of ejection holes and dried to obtain a toner, so that the ejection holes are dried and blocked when the production of the toner is stopped for maintenance or the like. By preventing this, it was possible to improve the production efficiency of toner production by particle formation.

1 is a diagram illustrating a configuration of a toner manufacturing apparatus to which a toner manufacturing method of the present invention is applied. FIG. FIG. 3 is a diagram illustrating a configuration of a droplet ejecting unit in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied. It is a figure which shows the structure of the lower side of the droplet ejection unit in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied. FIG. 3 is a diagram illustrating a configuration of a step-type horn-type vibrator in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied. FIG. 6 is a diagram illustrating an example of an exponential horn-type vibrator in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied. FIG. 5 is a diagram illustrating an example of a conical horn-type vibrator in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied. It is a figure which shows the other structure of the droplet ejection unit in the toner manufacturing apparatus to which the manufacturing method of the toner of this invention is applied. It is a figure which shows the other structure of the droplet ejection unit in the toner manufacturing apparatus to which the manufacturing method of the toner of this invention is applied. It is a figure which shows the other structure of the droplet ejection unit in the toner manufacturing apparatus to which the manufacturing method of the toner of this invention is applied. FIG. 3 is a diagram illustrating a configuration in which a plurality of droplet ejection units are arranged in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied. FIG. 4 is a diagram illustrating a cross-sectional configuration of a droplet ejecting unit in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied. It is a figure which shows the structure of the lower side of the droplet ejection unit in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied. It is a figure explaining the droplet formation means in the droplet jetting unit in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied. It is a figure explaining the conventional droplet formation means. It is a figure explaining the vibration of the thin film of the droplet jetting unit in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied. It is a figure which shows the relationship between the vibration possible area | region in the fundamental vibration mode of the thin film of the droplet ejection unit in the toner manufacturing apparatus to which the toner manufacturing method of this invention is applied, and the vibration displacement of the thin film. It is a figure which shows the relationship between the vibration possible area | region in the secondary vibration mode of the thin film of the droplet ejection unit in the toner manufacturing apparatus to which the toner manufacturing method of this invention is applied, and the vibration displacement of the thin film. It is a figure which shows the relationship between the vibration possible area | region in the 3rd vibration mode of the thin film of the droplet ejection unit in the toner manufacturing apparatus to which the toner manufacturing method of this invention is applied, and the vibration displacement of the thin film. It is a figure which shows the thin film from which a shape differs in the droplet ejection unit in the toner manufacturing apparatus to which the manufacturing method of the toner of this invention is applied. 1 is a cross-sectional view illustrating an overall configuration of a toner manufacturing apparatus according to an embodiment of the present invention. It is sectional drawing which shows the structure of the droplet discharge head in the droplet formation unit of FIG. It is AA 'line sectional drawing which shows the structure of the droplet formation unit of FIG. It is the schematic which shows the standing wave of the speed and pressure fluctuation in the case of N = 1,2,3. FIG. 5 is a schematic diagram illustrating a liquid column resonance phenomenon that occurs in a liquid column resonance liquid chamber in a droplet discharge head in a droplet forming unit. 2A and 2B are diagrams illustrating a state of a toner composition liquid in an ejection hole, where FIG. 3A illustrates the state of the toner composition liquid when ejected from the ejection hole, and FIG. Is shown. It is a figure which shows the structure of the other toner manufacturing apparatus to which the manufacturing method of the toner of this invention is applied. 2A and 2B are diagrams illustrating a droplet ejecting unit in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied, in which FIG. 3A is a schematic cross-sectional explanatory view of the droplet ejecting unit 2 and FIG. (C) is an explanatory view of droplet formation by the droplet ejection unit. It is a figure which shows the shape of the discharge hole in the toner manufacturing apparatus to which the manufacturing method of the toner of this invention is applied. FIG. 6 is a diagram for explaining a method of making the cross-sectional shape of the ejection hole a two-stage type in a liquid column resonance ejection type toner production apparatus to which the toner production method of the present invention is applied.

  The best mode for carrying out the present invention will be described below with reference to the drawings. Note that it is easy for a person skilled in the art to make other embodiments by changing or correcting the present invention within the scope of the claims, and these changes and modifications are included in the scope of the claims. The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.

(Toner production method)
A pulverization method that is a conventional toner manufacturing method and a spraying method and a vibration jetting method that are toner manufacturing methods of the present invention will be described.
<Crushing method>
This is a conventional method for producing toner, and the toner composition is melt-kneaded with a two-roll or twin-screw extruder, etc., and after cooling, coarsely pulverized, finely pulverized and classified, and if necessary In this method, external additives such as a fluidizing agent are mixed using a Henschel mixer. A known production apparatus such as a rotoplex or pulverizer can be used for coarse pulverization, a jet mill or a turbo mill can be used for fine pulverization, and an elbow jet or various air classifiers can be used for classification.

<Spraying method>
One fluid nozzle (pressurizing nozzle) sprayer that pressurizes liquid and sprays it from the discharge hole, multi-fluid spray nozzle sprayer that mixes and sprays liquid and compressed gas, liquid using centrifugal force to rotate liquid In this method, the toner composition liquid is formed into droplets in a gas phase using a rotating disk type sprayer or the like. Commercially available equipment can be used as a spray-drying system that performs spraying and drying at the same time, but if sufficient drying is not possible, secondary drying such as fluidized bed drying is performed, and if necessary, fluidizing agent etc. with a Henschel mixer etc. The external additive is mixed.

<Vibration injection method>
By mechanically vibrating a thin film having a plurality of discharge holes having the same opening diameter, a toner composition liquid is periodically discharged from the discharge holes to generate droplets having a uniform particle diameter, and then dried to form toner particles. Is the way to get. The mechanical vibration means may be arranged in any manner as long as it vibrates in the direction perpendicular to the film having the discharge holes. In the present invention, the following two systems are preferably used.
One is a method using mechanical means (mechanical longitudinal vibration means) having a vibration surface parallel to the thin film having a plurality of discharge holes and longitudinally vibrating in the vertical direction. This is a system in which mechanical vibration means (annular mechanical vibration means) formed in an annular shape is provided around a region where a thin film discharge hole having a plurality of discharge holes is provided.
Hereinafter, each method will be described.

(Mechanical longitudinal vibration means)
First, an example of a toner manufacturing apparatus provided with mechanical longitudinal vibration means will be described with reference to a schematic configuration diagram shown in FIG.
FIG. 1 is a diagram showing the configuration of a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
The toner manufacturing apparatus 1 periodically discharges the toner composition liquid 10 from a plurality of discharge holes 11 having the same opening diameter, and droplets as droplet forming means in a periodic droplet forming process in which droplets are formed in a gas phase. Particle formation in which the ejection unit 2 and the droplet ejection unit 2 are arranged at the upper side and solidify the droplets of the toner composition liquid 10 formed into droplets discharged from the droplet ejection unit 2 to form toner particles T The particle forming unit (solvent removing unit) 3 as the particle forming means in the process, the toner collecting unit 4 for collecting the toner particles T formed by the particle forming unit 3, and the toner collecting unit 4 The toner particles T are transferred through the tube 5, the toner storage unit 6 as a toner storage unit that stores the transferred toner particles T, the raw material storage unit 7 that stores the toner composition liquid 10, and the raw material storage unit 7. From inside to the droplet ejection unit 2 A pipe (liquid feed pipe) 8 for feeding the toner composition liquid 10, and a pump 9 for pumping supplying toner composition liquid 10, such as during operation.
Further, the toner composition liquid 10 delivered from the raw material container 7 is supplied to the droplet ejection unit 2 in a self-sufficient manner due to the droplet formation phenomenon by the droplet ejection unit 2, but as described above when the apparatus is in operation, etc. In addition, the liquid is supplied by using the pump 9 as an auxiliary. In FIG. 1, reference numeral 31 denotes a droplet, 35 denotes a dry gas, 41 denotes a tapered surface of the toner collecting unit 4, 42 denotes an air flow (vortex), and 43 denotes a charge removing unit that neutralizes the charge of the toner particles.

Next, the droplet ejecting unit 2 will be described with reference to FIGS.
FIG. 2 is a diagram showing a configuration of a droplet ejecting unit in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
FIG. 3 is a diagram showing a lower configuration of the droplet ejecting unit in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
The droplet ejecting unit 2 includes a thin film 12 in which a plurality of discharge holes (hereinafter may be referred to as “discharge ports” or “nozzles”) 11 and mechanical vibration means for vibrating the thin film 12. (Hereinafter referred to as “vibration means”) 13 and a flow path member 15 that forms a reservoir (liquid flow path) 14 for supplying the toner composition liquid 10 between the thin film 12 and the vibration means 13.
The thin film 12 having the plurality of ejection holes 11 is installed in parallel to the vibration surface 131 of the vibration means 13, and a flow path is formed by a resin binding material in which a part of the thin film 12 does not dissolve in the solder or toner composition liquid. It is bonded and fixed to the member 15 and has a substantially vertical positional relationship with the vibration direction of the vibration means 13.
The shape of the discharge hole will be described later.
The communication means 24 is provided so that a voltage signal is applied to the upper and lower surfaces of the vibration generating means 21 of the vibration means 13, and the signal from the drive signal generating source 23 can be converted into mechanical vibration. As a communication means for providing an electrical signal, a lead wire whose surface is insulated is suitable. In addition, it is suitable for efficient and stable toner production that the vibration means 13 uses elements having a large vibration amplitude such as various horn type vibrators and bolted Langevin type vibrators described later.

The vibration unit 13 includes a vibration generation unit 21 that generates vibrations and a vibration amplification unit 22 that amplifies the vibrations generated by the vibration generation unit 21. The drive unit (drive signal generation source) 23 drives a required frequency. When a voltage (drive signal) is applied between the electrodes 21 a and 21 b of the vibration generating means 21, vibration is excited in the vibration generating means 21, and this vibration is amplified by the vibration amplifying means 22 and arranged in parallel with the thin film 12. The vibrating surface 131 is periodically vibrated, and the thin film 12 is vibrated at a required frequency by the periodic pressure caused by the vibration of the vibrating surface 131.
The vibrating means 13 is not particularly limited as long as it can give a certain longitudinal vibration to the thin film 12 at a constant frequency, and can be appropriately selected and used, but the thin film 12 is vibrated. Therefore, the vibration generating means 21 is preferably a piezoelectric body that is excited by a bimorph-type flexural vibration. The piezoelectric body that is the vibration generating means 21 has a function of converting electrical energy into mechanical energy. When a piezoelectric body is used as the vibration generating means 21, a flexural vibration is excited by applying a voltage to the piezoelectric body, and the thin film 12 can be vibrated.

Examples of the piezoelectric body constituting the vibration generating means 21 include piezoelectric ceramics such as lead zirconate titanate (PZT), and these are generally used in a stacked manner because of their small displacement. Other examples of the piezoelectric body include piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , and KNbO ₃ .
The vibration means 13 may be arranged in any manner as long as it can vibrate in the vertical direction with respect to the thin film 12 having the ejection holes 11, but the vibration surface 131 and the thin film 12 are arranged in parallel.
In the example shown in FIG. 2, a horn type vibrator is used as the vibration means 13 including the vibration generation means 21 and the vibration amplification means 22, and a horn is used as the vibration amplification means 22. The horn-type vibrator can amplify the amplitude of the vibration generating means 21 such as a piezoelectric element by the vibration amplifying means 22 such as a horn. Since the mechanical load is reduced, the life of the production apparatus is extended.

FIG. 4 is a diagram showing a configuration of a step-type horn-type vibrator in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
FIG. 5 is a diagram showing a configuration of an exponential horn-type vibrator in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
FIG. 6 is a diagram showing the configuration of a conical horn-type vibrator in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
As the horn type vibrator as the vibration means 13, a known typical horn shape may be used. For example, a step type horn type vibrator as shown in FIG. 4 or an exponential horn type as shown in FIG. Examples thereof include a vibrator and a conical horn vibrator as shown in FIG.
In these horn type vibrators, as shown in FIG. 2, a piezoelectric body (vibration generating means 21) is arranged on the surface of the horn (vibration amplifying means 22) having a large area, and the piezoelectric body (vibration generating means 21) is longitudinal. The vibration is used to induce efficient vibration of the horn (vibration amplifying means 22), and the surface of the horn (vibration amplifying means 22) is defined as a vibration surface 131 so that the vibration surface 131 becomes the maximum vibration surface. Designed to. A communication means (lead wire) 24 is disposed above and below the piezoelectric body (vibration generating means 21), and an AC voltage signal is given from the drive circuit 23. The maximum vibration surface of these horn vibrators is designed so as to be the vibration surface 131.
Further, as the vibration means 13, 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.

Next, the structure of the storage part 14, the vibration means 13, and the thin film 12 shown in FIG. 1 is demonstrated in detail using the schematic of FIG.
The reservoir 14 is provided with at least one liquid supply tube 18, and the toner composition liquid 10 is introduced into the reservoir 14 through a flow path as shown in a partial cross-sectional view. Moreover, it is also possible to provide the bubble discharge tube 19 as needed. The droplet ejection unit 2 is installed and held on the top surface portion of the particle forming unit 3 by a support member (not shown) attached to the flow path member 15. In the toner manufacturing apparatus shown in FIG. 1, the example in which the droplet ejecting unit 2 is arranged on the top surface of the particle forming unit 3 has been described. It can also be set as the structure which installs the droplet ejection unit 2. FIG.

In general, the size of the vibration means 13 that generates mechanical vibration increases as the oscillation frequency decreases. Can be provided. It is also possible to vibrate the entire storage unit 14 efficiently.
In this case, the vibration surface is defined as a surface on which the thin film having the plurality of ejection holes is bonded.
Different examples of the droplet ejecting unit having such a configuration will be described with reference to FIGS.
FIG. 7 is a diagram showing another configuration of the droplet ejecting unit in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
The droplet ejecting unit 2 shown in FIG. 7 uses a horn-type vibrator 13 including a piezoelectric body 81 as a vibration generating unit and a horn 82 as a vibration amplifying unit as a vibrating unit, and a part of the horn 82 is used. A reservoir (flow path) 14 is formed. The droplet jetting unit 2 is fixed to the wall surface of the particle forming unit 3 (drying means) shown in FIG. 1 by a fixing unit (flange unit) 83 formed integrally with the horn 82 of the horn type vibrator 13. From the viewpoint of preventing vibration loss, it may be fixed using an elastic body (not shown). In FIG. 7, 131 is a vibration surface, 11 is a discharge hole, 12 is a thin film, 18 is a liquid supply tube, and 19 is a bubble discharge tube.

FIG. 8 is a diagram showing another configuration of the droplet ejecting unit in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
The droplet jetting unit 2 shown in FIG. 8 vibrates a bolt-clamped Langevin type vibrator 13 configured by mechanically firmly fixing piezoelectric bodies 211 and 212 and horns 221 and 222 as vibration generating units with bolts. In this case, the storage part (flow path) 14 is formed in the horn 221. Depending on the frequency conditions, the horn 221 may become large, and a metal thin film having a plurality of thin films by processing the liquid supply tube 18 (fluid introduction / discharge path) and the reservoir 14 in a part of the horn 221 as shown in the figure. Can be pasted. In FIG. 8, 131 is a vibration surface, 11 is a discharge hole, 12 is a thin film, and 19 is a bubble discharge tube.
FIG. 1 shows an example in which only one droplet jetting unit 2 is attached to the particle forming unit 3, but a plurality of droplet jetting units 2 are arranged above the particle forming unit 3 (drying tower). Paralleling is preferable from the viewpoint of improving productivity. The number of droplet ejection units is preferably in the range of 100 to 1000 from the viewpoint of controllability. In this case, the toner composition liquid 10 is supplied to each storage section 14 of the droplet ejection unit 2 through the pipe 8 to the raw material storage section (common liquid reservoir) 7. The toner composition liquid 10 can be configured to be supplied in a self-contained manner along with droplet formation, or can be configured to supply the liquid supplementarily using the pump 9 during operation of the apparatus. You can also.

Another example of the droplet ejecting unit will be described with reference to FIG.
FIG. 9 is a diagram showing another configuration of the droplet ejecting unit in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
The droplet ejecting unit 2 shown in FIG. 9 uses a horn type vibrator 13 as a vibrating means. A flow path member 15 for supplying the toner composition liquid 10 is disposed so as to surround the horn type vibrator 13, and a storage portion 14 is formed on a horn 221 of the horn type vibrator 13 at a portion facing the thin film 12. Yes. Further, an air flow path forming member 36 that forms an air flow path 37 through which the air flow 35 flows is disposed around the flow path member 15 at a required interval. In addition, in order to simplify illustration, although the single discharge hole 11 of the thin film 12 is shown, as described above, a plurality of discharge holes 11 are provided. In FIG. 9, 18 is a liquid supply tube, and 211 is a piezoelectric body.
FIG. 10 is a diagram showing a configuration in which a plurality of droplet ejection units are arranged in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
As shown in FIG. 10, from the viewpoint of controllability, a plurality of, for example, 100 to 1000 droplet ejection units 2 are arranged side by side on the top of the drying tower constituting the particle forming unit 3 shown in FIG. Thereby, productivity can be further improved.

(Annular mechanical vibration means)
The ring type droplet ejecting unit 2 will be described with reference to FIGS.
FIG. 11 is a diagram showing a cross-sectional configuration of a droplet ejecting unit in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
FIG. 12 is a diagram showing a lower configuration of the droplet ejecting unit in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
FIG. 13 is a diagram illustrating droplet forming means in a droplet ejecting unit in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
As shown in FIG. 11, the droplet ejecting unit 2 includes at least a droplet forming unit 16 that discharges the toner composition liquid 10 into droplets, and a storage unit that supplies the toner composition liquid 10 to the droplet forming unit 16. (Liquid flow path) 14 having a flow path member 15 formed thereon.
The droplet forming unit 16 includes a thin film 12 having a plurality of discharge holes (discharge ports) 11 and an annular vibration generating unit (electromechanical conversion unit) 17 that vibrates the thin film 12. Here, the thin film 12 is bonded and fixed to the flow path member 15 with a resin binding material that does not dissolve in the solder or the toner composition liquid at the outermost peripheral portion (the region indicated by hatching in FIG. 12).
The vibration generating means 17 is arranged around a region provided with the discharge holes 11 in the deformable region 161 (region not fixed to the flow path member 15) of the thin film 12 shown in FIG. As shown in FIG. 11, a drive voltage (drive signal) having a required frequency is applied to the vibration generating means 17 from a drive circuit (drive signal generating source) 23 through a communication means (lead wire) 24. Generates flexural vibration. In FIG. 11, 20 is a support member, 18 is a liquid supply tube, and 19 is a bubble discharge tube.

  In the droplet forming means 16, an annular vibration generating means 17 is arranged around a region where the discharge holes 11 are provided in the deformable region 161 of the thin film 12 having a plurality of discharge holes 11 facing the storage portion 14. Accordingly, for example, as compared with the configuration in which the vibration generating means 17 holds the periphery of the thin film 12 as in the comparative example configuration shown in FIG. A plurality of discharge holes 11 can be arranged in a region having a relatively large area (φ1 mm or more) to be obtained, and more liquid droplets can be stably formed and discharged at once from the plurality of discharge holes 11. It becomes like this.

FIG. 14 is a diagram for explaining a conventional droplet forming means.
(Droplet formation mechanism)
Next, the mechanism of droplet formation by the droplet ejecting unit 2 as the droplet forming means will be described.
As described above, the droplet ejecting unit 2 causes the thin film 12 having a plurality of ejection holes 11 facing the storage portion 14 to propagate the vibration generated by the vibration means 13 that is a mechanical vibration means, thereby causing the thin film 12 to periodically move. So that a plurality of discharge holes 11 are arranged in a relatively large area (φ1 mm or more), and droplets can be periodically and stably formed and discharged from the plurality of discharge holes 11. Become.
FIG. 15 is a diagram for explaining the vibration of the thin film of the droplet ejecting unit in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
FIG. 16 is a diagram showing the relationship between the vibratable region and the vibration displacement of the thin film in the basic vibration mode of the thin film of the droplet jetting unit in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
As shown in FIGS. 15 (a) and 15 (b), when the peripheral portion 121 of the simple circular thin film 12 is fixed, the periphery of the basic vibration is a node, and as shown in FIG. The cross-sectional shape is such that the displacement ΔL is maximum (ΔLmax), and the vertical vibration is periodically performed in the vibration direction.
FIG. 17 is a diagram showing the relationship between the vibrable region and the thin film vibration displacement in the secondary vibration mode of the thin film of the droplet ejecting unit in the toner production apparatus to which the toner production method of the present invention is applied.
FIG. 18 is a diagram showing the relationship between the vibrable region and the vibration displacement of the thin film in the third vibration mode of the thin film of the droplet ejecting unit in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
Further, it is known that higher order modes as shown in FIGS. 17 and 18 exist. These vibration modes have one or a plurality of nodes concentrically in the circular thin film 12, and are substantially axisymmetric deformation shapes.
FIG. 19 is a diagram showing thin films having different shapes in a droplet jetting unit in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
In addition, as shown in FIG. 19, by making the central portion of the thin film 12 have a convex shape 122, the traveling direction of the droplet 31 can be controlled and the vibration amplitude can be adjusted.

Due to the vibration of the circular thin film 12, a sound pressure P _ac proportional to the vibration velocity V _m of the thin film 12 is generated in the liquid in the vicinity of the discharge holes 11 provided at various locations on the circular thin film. Sound pressure, medium to occur as a reaction of the radiation impedance Z _r are known for (toner constituent liquid 10), sound pressure, using Equation (1) below the product of the radiation impedance and film vibration velocity Vm expressed.
P _ac (r, t) = Z _r · V _m (r, t) (1)
Is a function of time (t) since the vibration velocity V _m of the thin film 12 fluctuates periodically with time, for example a sine wave, such as a rectangular waveform, it is possible to form various periodic variations. Further, as described above, the vibration displacement in the vibration direction is different in each part of the thin film 12, and V _m is also a function of position coordinates on the thin film 12. As described above, the vibration mode of the thin film 12 used in the present invention is symmetric with respect to the central axis. 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 thin film 12 having a distribution is generated, and the toner composition liquid 10 is discharged to the outside in accordance with the periodic change of the sound pressure.
The toner composition liquid 10 periodically discharged to the outside forms spheres due to a difference in surface tension between the liquid phase of the toner composition liquid 10 and the gas phase, which is external air, and thus droplet formation occurs periodically. .

As the vibration frequency of the thin film 12 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 10 is promoted by the excitation of the liquid.
Furthermore, when the displacement of the sound pressure is 10 kPa or more, the fine particle dispersion promoting action is more preferably generated.
Here, the diameter of the formed droplet 31 tends to increase as the vibration displacement in the vicinity of the discharge hole 11 of the thin film 12 increases. When the vibration displacement is small, a droplet is formed or the droplet is formed. do not do. In order to reduce the variation in the droplet size at each discharge hole 11 as described above, it is necessary to define the arrangement of the discharge holes 11 at the optimum position of the membrane vibration displacement.

In the toner manufacturing method of the present invention, as will be described with reference to FIGS. 16 to 18, the maximum value ΔLmax and the minimum value ΔLmin of the vibration direction displacement ΔL of the thin film 12 in the vicinity of the discharge hole 11 generated by the mechanical vibration means 13 are used. When the ejection holes 11 are arranged in a portion where the ratio R (= ΔLmax / ΔLmin) is 2.0 or less, variation in droplet size is necessary as toner fine particles capable of providing a high-quality image. A particle size distribution can be obtained.
The conditions of the toner composition liquid 10 were changed, and since the satellite generation start region was the same in the region where the viscosity was 20 mPa · s or less and the surface tension was 20 to 75 mN / m, the displacement of the sound pressure was 500 kPa or less. It will be necessary. More preferably, it is 100 kPa or less.

(Thin film with multiple discharge holes)
As described above, the thin film 12 having the discharge holes 11 is a member that discharges the dissolved or dispersed liquid of the toner composition 10 to form droplets. The material of the thin film 12 and the shape of the discharge hole 11 will be described later.

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

  Further, the dry collection unit 30 shown in FIG. 20 includes a chamber 31 and a toner collection unit 32. In the chamber 31, a large descending airflow is formed by combining the airflow generated by the airflow generating means (not shown) and the descending airflow 33. Since the toner droplet 21 ejected from the droplet ejection head 11 of the droplet ejecting unit 10 is conveyed downward not only by gravity but also by a descending airflow 33, the ejected toner droplet 21 is air. It can suppress decelerating by resistance. Thereby, when the toner droplet 21 is continuously ejected, the toner droplet 21 ejected before is decelerated by the air resistance, and the toner droplet 21 ejected later is the toner droplet 21 ejected before. By catching up with the toner droplets 21, it is possible to prevent the toner droplets 21 from being joined and integrated to increase the particle size of the toner droplets 21. As the air flow generation means, either a method of providing a blower in the upstream portion and pressurizing, or a method of suctioning from the toner collecting unit 32 and reducing the pressure can be employed. In addition, a rotating airflow generator (not shown) that generates a rotating airflow that rotates around an axis parallel to the vertical direction is disposed in the toner collecting unit 32. Further, the toner collecting unit 32 has a toner storing unit 35 that stores dried and solidified toner particles that have passed through a toner collecting tube 34 that communicates with the chamber 31.

Next, an outline of the toner manufacturing process in the toner manufacturing apparatus of the present embodiment will be described.
The toner composition liquid 14 accommodated in the raw material container 13 shown in FIG. 20 is passed through the liquid supply pipe 16 by the liquid circulation pump 15 for circulating the toner composition liquid 14, and then the droplet forming unit shown in FIG. The liquid common resonance supply chamber 17 of the liquid droplet ejection head 11 shown in FIG. A pressure distribution is formed in the liquid column resonance liquid chamber 18 filled with the toner composition liquid 14 by the liquid column resonance standing wave generated by the vibration generating means 20. Then, the toner droplet 21 is ejected from the ejection hole 19 arranged in a region where the amplitude of the liquid column resonance standing wave has a large amplitude and the pressure fluctuation is large and becomes the antinode of the standing wave. The region that becomes the antinode of the standing wave due to the liquid column resonance means a region other than the node of the standing wave. Preferably, it is a region where the pressure fluctuation of the standing wave has an amplitude large enough to discharge the liquid, and more preferably a position where the amplitude of the pressure standing wave becomes a maximum (a section as a velocity standing wave). ) To a minimum position in a range of ± 1/4 wavelength. If the region is an antinode of a standing wave, even if there are a plurality of discharge holes, substantially uniform droplets can be formed from each, and moreover, the droplets can be discharged efficiently. And clogging of the discharge holes is less likely to occur. The toner composition liquid 14 that has passed through the common liquid supply path 17 flows through the liquid return pipe 22 and is returned to the raw material container 13. When the amount of the toner composition liquid 14 in the liquid column resonance liquid chamber 18 decreases due to the ejection of the toner droplets 21, a suction force due to the action of the liquid column resonance standing wave in the liquid column resonance liquid chamber 18 acts, and the liquid common The flow rate of the toner composition liquid 14 supplied from the supply path 17 increases, and the toner composition liquid 14 is replenished into the liquid column resonance liquid chamber 18. Then, when the toner composition liquid 14 is replenished in the liquid column resonance liquid chamber 18, the flow rate of the toner composition liquid 14 passing through the liquid common supply path 17 is restored to the original, and the liquid supply pipe 16 and the liquid return pipe 22 are supplied. The flow of the toner composition liquid 14 circulating in the apparatus is again formed. On the other hand, the toner droplets 21 ejected from the droplet ejection head 11 of the droplet ejecting unit 10 are not only caused by gravity but also air current generated by air current generating means (not shown) as shown in FIG. 12 is conveyed downward by a descending airflow 33 formed through 12. Next, a spiral airflow is formed along the conical inner wall surface of the toner collecting portion 32 by the rotating airflow and the descending airflow 33 generated by a rotating airflow generator (not shown) in the toner collecting portion 32, The toner particles are dried and solidified in a laminar flow state on the spiral airflow. The dried and solidified toner particles are stored in the toner storage unit 35 through the toner collecting tube 34.
The liquid column resonance liquid chamber 18 in the droplet discharge head 11 is joined to a frame formed of a material having such a high rigidity that does not affect the resonance frequency of the liquid at a driving frequency such as metal, ceramics, or silicon. Has been formed. As shown in FIG. 21, the length L between the wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 is determined based on the liquid column resonance principle. Further, the width W of the liquid column resonance liquid chamber 18 shown in FIG. 22 is desirably smaller than one half of the length L of the liquid column resonance liquid chamber 18 so as not to give an extra frequency to the liquid column resonance. . Furthermore, it is preferable that a plurality of liquid column resonance liquid chambers 18 are arranged for one droplet forming unit 10 in order to dramatically improve productivity. The range is not limited, but one droplet forming unit provided with 100 to 2000 liquid column resonance liquid chambers 18 is most preferable because both operability and productivity can be achieved. In addition, for each liquid column resonance liquid chamber, a flow path for supplying liquid is connected from the common liquid supply path 17, and the common liquid supply path 17 communicates with a plurality of liquid column resonance liquid chambers 18. .

The vibration generating means 20 in the droplet discharge head 11 is not particularly limited as long as it can be driven at a predetermined frequency, but a form in which a piezoelectric body is bonded to an elastic plate is desirable. The elastic plate constitutes a part of the wall of the liquid column resonance liquid chamber so that the piezoelectric body does not come into contact with the liquid. 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. Further, it is desirable that the block-shaped vibrating member can be individually controlled through the elastic plate in accordance with the arrangement of the liquid column resonance liquid chambers. Adopting a configuration in which the discharge holes 19 are provided in the width direction in the liquid column resonance liquid chamber 18 is preferable because a large number of openings of the discharge holes 19 can be provided, thereby increasing the production efficiency. Further, since the liquid column resonance frequency varies depending on the arrangement of the discharge holes 19, it is desirable to appropriately determine the liquid column resonance frequency after confirming the discharge of the droplet.
Next, the mechanism of droplet formation by the droplet formation unit in the toner manufacturing apparatus of the present invention will be described.
First, the principle of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber 18 in the liquid droplet ejection head 11 of FIG. 21 will be described. The sound velocity of the toner composition liquid in the liquid column resonance liquid chamber is c, and the vibration generating means 20 When the driving frequency applied to the toner composition liquid as a medium is f, the wavelength λ at which the liquid resonance occurs is
λ = c / f (Formula 1)
Are in a relationship.
Further, in the liquid column resonance liquid chamber 18 of FIG. 21, the length from the end of the frame on the fixed end side to the end on the liquid common supply path 17 side is L, and further, the end of the frame on the liquid common supply path 17 side. The height h1 is about twice the height h2 of the communication port, and in the case of a both-side fixed end that is equivalent to the fixed end with the end closed, the length L is a quarter of the wavelength λ. Resonances are most efficiently formed when they match even multiples of. That is, it is expressed by the following formula 2.
L = (N / 4) λ (Expression 2)
(However, N is an even number.)
Furthermore, the above formula 2 is also established in the case of a double-sided open end where both ends are completely open.
Similarly, when one side is equivalent to an open end with a pressure relief portion and the other side is closed (fixed end), that is, one side fixed end or one side open end, the length L is the wavelength λ. Resonance is most efficiently formed when it matches an odd multiple of a quarter. That is, N in Expression 2 is expressed as an odd number.
The most efficient drive frequency f is obtained from the above formula 1 and the above formula 2.
f = N × c / (4L) (Formula 3)
It is guided. However, in reality, since the liquid has a viscosity that attenuates the resonance, the vibration is not amplified infinitely, and has a Q value. As shown in equations 4 and 5, which will be described later, Resonance also occurs at frequencies near the highly efficient drive frequency f.

FIG. 23 is a diagram showing the shape (resonance mode) of standing waves of velocity and pressure fluctuations when N = 1, 2, and 3. Originally a sparse / dense wave (longitudinal wave), it is generally expressed as shown in FIG. The solid line is the velocity standing wave, and the dotted line is the pressure standing wave. For example, as can be seen from FIG. 23A showing the case of a fixed end with N = 1, in the case of velocity distribution, the amplitude of the velocity distribution is zero at the closed end, and the amplitude is maximum at the open end. Easy to understand. When the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is L, the wavelength at which the liquid resonates is λ, and the standing wave is most efficiently generated when the integer N is 1 to 5. . In addition, since the standing wave pattern varies depending on the open / closed state of both ends, they are also shown. As will be described later, the condition of the end is determined by the state of the opening of the discharge hole and the opening of the supply side. In acoustics, the open end is an end at which the moving speed of the medium (liquid) in the longitudinal direction becomes zero, and conversely, the pressure becomes maximum. Conversely, the closed end is defined as an end where the moving speed of the medium becomes zero. The closed end is considered as an acoustically hard wall and wave reflection occurs. When ideally completely closed or open, a resonant standing wave having a form as shown in FIG. 23 is generated by superposition of waves, but the standing wave pattern also depends on the number of discharge holes and the opening position of the discharge holes. Fluctuates and the resonance frequency appears at a position shifted from the position obtained from the above equation 3. However, a stable ejection condition can be created by appropriately adjusting the driving frequency.
The liquid column resonance liquid chamber in the droplet discharge head of the droplet forming unit of the present embodiment shown in FIGS. 20 and 21 is equivalent to the closed end state at both ends or due to the influence of the opening of the discharge hole. An end portion that can be described as an acoustically soft wall is preferable for increasing the frequency, but is not limited thereto, and may be an open end. The influence of the opening of the discharge hole here means that the acoustic impedance is reduced, and in particular, the compliance component is increased. Therefore, the configuration in which the wall surfaces are formed at both ends in the longitudinal direction of the liquid column resonance liquid chamber as shown in FIG. This is the preferred configuration because of the mode available.

In addition, the numerical aperture of the discharge holes, the opening arrangement position, and the cross-sectional shape of the discharge holes are factors that determine the drive frequency, and the drive frequency can be appropriately determined accordingly. For example, when the number of ejection holes is increased, the restriction at the tip of the liquid column resonance liquid chamber, which has been the fixed end, gradually loosens, a resonance standing wave that is almost close to the open end is generated, and the drive frequency increases. Furthermore, the loosely constrained condition starts from the opening arrangement position of the discharge hole existing on the most liquid supply path side, and the actual standing wave has a short wavelength and is higher than the driving frequency. When a voltage is applied to the vibration generating means at the drive frequency determined in this way, the vibration generating means is deformed, and a resonant standing wave is generated most efficiently at the drive frequency. Further, the liquid column resonance standing wave is generated even at a frequency in the vicinity of the drive frequency at which the resonance standing wave is generated most efficiently. That is, when the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is L and the distance to the discharge hole closest to the end on the liquid supply side is Le, both the lengths of L and Le are used. It is possible to oscillate the vibration generating means by using a drive waveform whose main component is the drive frequency f in the range determined by the following formulas 4 and 5, and induce liquid column resonance to eject liquid droplets from the ejection holes. It is.
N × c / (4L) ≦ f ≦ N × c / (4Le) (Formula 4)
N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le) (Formula 5)
The ratio of the length L between both ends in the longitudinal direction of the liquid column resonance liquid chamber to the distance Le to the discharge hole closest to the end on the liquid supply side is preferably Le / L> 0.6.
By using the principle of the liquid column resonance phenomenon described above, a liquid column resonance pressure standing wave is formed in the liquid column resonance liquid chamber 18 of FIG. 21, and the discharge hole 19 disposed in a part of the liquid column resonance liquid chamber 18. In this case, droplet discharge occurs continuously. Note that it is preferable to dispose the discharge hole 19 at a position where the pressure of the standing wave fluctuates the most, since the discharge efficiency is increased and the driving can be performed with a low voltage. Further, one discharge hole 19 may be provided for one liquid column resonance liquid chamber 18, but it is preferable to arrange a plurality of discharge holes 19 from the viewpoint of productivity. When the plurality of discharge holes 19 are opened, the pitch between the discharge holes is preferably 20 [μm] or more and not more than the length of the liquid column resonance liquid chamber. When the pitch between the discharge holes is larger than 20 [μm], there is a high probability that the droplets discharged from the adjacent discharge holes collide with each other to form large droplets, leading to deterioration in the toner particle size distribution.

Next, the state of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber in the droplet discharge head in the droplet forming unit will be described with reference to FIG.
FIG. 24 is a schematic diagram showing the state of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber in the droplet discharge head in the droplet forming unit. In FIG. 24, the solid line written in the liquid column resonance liquid chamber indicates a velocity distribution in which the velocity at each arbitrary measurement position between the fixed end side and the liquid common supply path side end in the liquid column resonance liquid chamber is plotted, The direction from the liquid common supply path side to the liquid column resonance liquid chamber is defined as +, and the opposite direction is defined as-. In addition, the dotted line marked in the liquid column resonance liquid chamber indicates a pressure distribution in which the pressure value at each arbitrary measurement position between the fixed end side and the liquid common supply path side end in the liquid column resonance liquid chamber is plotted. The positive pressure is + with respect to the atmospheric pressure, and the negative pressure is-. Moreover, if it is a positive pressure, a pressure will be applied to the downward direction in the figure, and if it is a negative pressure, a pressure will be applied to the upward direction in the figure. Further, in FIG. 24, the liquid common supply path side is opened as described above, but the height of the opening where the liquid common supply path 17 and the liquid column resonance liquid chamber 18 communicate with each other (height h2 shown in FIG. 21). On the other hand, since the height of the frame serving as the fixed end (height h1 shown in FIG. 21) is about twice or more, the approximate condition is that the liquid column resonance liquid chamber 18 is substantially fixed on both sides. The change in the velocity distribution and the pressure distribution over time is shown.
FIG. 24A shows a pressure waveform and a velocity waveform in the liquid column resonance liquid chamber 18 when droplets are discharged.
In FIG. 24B, the meniscus pressure increases again after the liquid is drawn immediately after the droplet is discharged. As shown in FIGS. 24A and 24B, the pressure in the flow path provided with the discharge hole 19 in the liquid column resonance liquid chamber 18 is maximum. Thereafter, as shown in FIG. 24C, the positive pressure in the vicinity of the ejection hole 19 decreases, and the liquid droplet 21 is ejected in a negative pressure direction.
And as shown in FIG.24 (d), the pressure of the discharge hole 19 vicinity becomes minimum. From this time, the filling of the toner composition liquid 14 into the liquid column resonance liquid chamber 18 starts. Thereafter, as shown in FIG. 24 (e), the negative pressure in the vicinity of the discharge hole 19 becomes smaller and shifts to the positive pressure direction. At this time, the filling of the toner composition liquid 14 is completed. Then, again, as shown in FIG. 24A, the positive pressure in the droplet discharge region of the liquid column resonance liquid chamber 18 becomes maximum, and the droplet 21 is discharged from the discharge hole 19. In this way, a standing wave due to liquid column resonance is generated in the liquid column resonance liquid chamber by high-frequency driving of the vibration generating means, and corresponds to an antinode of standing wave due to liquid column resonance where the pressure changes most. Since the discharge holes 19 are arranged in the droplet discharge area to be discharged, the toner droplets 21 are continuously discharged from the discharge holes 19 according to the antinode period.

(Initial stability)
Regardless of which method is employed, if the droplets 31 are continuously ejected from the ejection holes 11, the number of ejection holes 11 that are normally ejected decreases with time. It may ooze out for some reason, causing droplets to fly obliquely, unstable ejection, and ejection stoppage.
The discharge holes 11 that have stopped discharging normally may adversely affect the discharge state of the surrounding discharge holes 11. For example, when it oozes out, the oozed droplet grows and tends to engulf the peripheral discharge holes and stop the discharge. In the case of unstable ejection, the uniformity of the size of the droplets 31 is lost, and the distribution may be widened with the toner particle size distribution. Further, when the ejection directionality is obliquely lost, the probability of coalescence with adjacent droplets increases, which also appears to be a wide distribution due to the toner particle size distribution. In addition, oblique discharge and abnormal discharge such as unstable discharge tend to cause bleeding and stop of discharge, and the spread of the bleeding to the peripheral discharge holes 11 causes further discharge reduction of the discharge holes 11. The operation efficiency of the toner manufacturing apparatus is lowered, and the toner productivity is lowered.
It is difficult to completely eliminate the above phenomenon, but it is possible to reduce it. The filtering of the toner composition liquid 10 is effective for clogging the ejection holes 11, and the surface treatment of the plate on which the ejection holes 11 are arranged has an effect on the spread of the seepage, and has been used for some time. It has been found that exudation and abnormal discharge depend on the state / state of the discharge hole 11 at the start of discharge. Therefore, stability can be further improved by improving the state of the discharge hole 11 at the start of discharge.
The discharge hole 11 is blocked by drying while the discharge hole 11 is filled with liquid and the discharge is stopped before the vibration for discharging is applied. This is particularly the case when a highly volatile solvent is used for the toner composition liquid 10. When the discharge hole 11 is completely closed, no discharge is performed even when vibration is applied. In the case of partial occlusion, when vibration is applied, the liquid oozes out and spreads to the discharge holes 11 around it, or it flies diagonally or flies unstable, and abnormal discharge occurs. Abnormal discharge tends to cause bleeding, and when it spreads, the peripheral discharge holes 11 are involved and the productivity of the droplet ejection unit 2 as a whole is lowered.
The liquid level (meniscus) in the discharge hole 11 is used as a means for suppressing the blockage of the discharge hole 11 due to drying when the discharge is stopped when the liquid droplet is released by maintenance or the like in the periodic droplet forming process. It is effective to move. It has the same effect as mixing the toner composition liquid 10, and can be leathered on the surface to prevent or delay drying and solidification.

25A and 25B are diagrams showing the state of the toner composition liquid in the discharge hole, where FIG. 25A shows the state of the toner composition liquid when discharged from the discharge hole, and FIG. 25B shows the toner in the discharge hole when discharge is stopped. The state of the composition liquid is shown.
There are several ways to move the meniscus.
Although not limited to the following two methods, for example, the vibration means 13 is continuously moved by reducing the amplitude of vibration used at the time of discharge, or the vibration means 13 is continuously moved by changing the frequency of vibration used at the time of discharge. The meniscus can be exercised.
When operating with a reduced amplitude, it is sufficient if the droplets 31 are not ejected, so the voltage of a vibration source such as a transmitter may be lowered. Since the minimum amplitude at which the droplet 31 is ejected depends on the liquid characteristics such as viscosity, the amplitude set for operation when ejection is stopped differs depending on the toner composition liquid 10 to be ejected. Even when the vibration means 13 is operated by changing the frequency, the frequency may be changed by the vibration source. Therefore, as shown in (a), when droplets are ejected at the normal resonance frequency, the amplitude is reduced by changing the frequency as shown in (b). Although the droplet 31 is not ejected, the meniscus can be moved between both ends of the arrow as shown by the arrow in (b).
Since the frequency characteristics vary depending on the toner composition liquid 10 and the structure of the vibration means 13, the appropriate set frequency also changes accordingly.
Thereby, the blockage of the discharge holes 11 can be suppressed, the state of the initial discharge can be improved, the discharge stability can be improved, and the productivity can be improved.

(Collection)
Although the toner production method by characteristic ejection has been described above, a mechanism relating to collection is omitted for the sake of simplicity. Since collection is the same for any injection method, an explanation will be given with an annular mechanical vibration means as a representative.
FIG. 26 is a diagram showing the configuration of another toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
Also, at this time, FIG. 27 is a diagram showing a droplet ejecting unit in a toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied, and (a) is a schematic sectional explanatory view of the droplet ejecting unit 2. (B) is an assembly diagram for explaining in more detail, and (c) is an explanatory diagram of droplet formation by the droplet ejection unit.
This droplet jetting unit 2 includes a thin film 12 having a plurality of discharge holes (discharge ports) 11 formed therein, a vibrating means 13, and at least a resin, a colorant, and a specific material between the thin film 12 and the vibrating means 13. And a reservoir constituting member 15 that forms a reservoir (liquid channel) 14 for supplying the toner composition liquid 10 containing a phenolic resin. A configuration in which the position is fixed between the vibration means 13 and the wall of the storage portion 14 by a vibration separating member 26 so as not to transmit vibration is desirable. It may be configured to be fixed directly to the wall via 27. The toner composition liquid 10 is supplied to the liquid storage section 14 through a pipe 8 used for liquid supply and liquid circulation.
As the vibration means 13, the vibration generation means 21, and the vibration amplification means 22, those exemplified in the description of the membrane vibration method using the mechanical longitudinal vibration means described above can be used similarly.

The partition wall of the storage unit 14 is made of a general material such as metal, ceramics, or plastic that does not dissolve in the toner composition liquid 10 and does not cause modification of the toner composition liquid 10. In addition, the liquid storage unit 14 is divided into a plurality of liquid storage regions 29 by a plurality of partition walls. By dividing the partition wall in this manner, the vibration pressure distribution in the liquid storage region 29 becomes uniform in driving several tens of kHz, so that uniform discharge is possible and the effect of increasing the resonance frequency can be expected. In (b), A is the length of the liquid chamber, B is the width of the liquid chamber, and H is the height of the liquid chamber.
Next, the mechanism of droplet formation by the droplet ejecting unit 2 as droplet forming means will be described with reference to (c).
The vibration generated on the vibration surface 131 by the vibration means 13 is transmitted to the liquid in the storage unit 14, and the liquid in the storage unit 14 causes a liquid resonance phenomenon. In the plurality of discharge holes 11 provided in the thin film 12, the toner composition liquid 10 is discharged to the outside in a state where the toner composition liquid 10 is uniformly pressurized. The toner composition liquid 10 is evenly ejected from all the ejection holes 11 by the action of resonance of the entire toner composition liquid 10 in the reservoir 14. Further, since the dispersed fine particles contained in a large amount in the toner composition liquid 10 float in the reservoir 14 without depositing on the surface of the reservoir 14 of the thin film 12, the liquid can be stably ejected stably. ing.
Any vibration means 13 can be used as long as it can apply mechanical ultrasonic vibration to the liquid at a high amplitude, such as a laminated PZT or a combination of an ultrasonic vibrator and an ultrasonic horn described later. It doesn't matter.
When the thin film 12 provided with a plurality of discharge holes 11 is mechanically vibrated, there is an advantage that clogging of the discharge holes 11 is difficult to occur. However, when the thin film 12 has a large area, uniform vibrations cannot be obtained and the droplets 31 can be obtained. May have a wide particle size distribution. On the other hand, in the liquid resonance method, substantially equal oscillating pressure is applied to each ejection hole 11, so that a droplet 31 having a narrow particle size distribution is easily obtained even with a wide thin film 12.

In the present embodiment, the droplet ejecting unit 2 has a shroud portion 30, and has a transport air flow 95 around the flow 311 of the droplet 31, and the flow of the ejected droplet 31 by the transport air flow 95. The group speed 311 is increased, and when the discharge initial speed is high, the group speed is decreased. As a result, it is possible to efficiently prevent coalescence caused by colliding with each other during the drying process until the ejected droplets 31 are solidified, and the resulting toner has very little coalescence, resulting in productivity including yield. Can be improved.
Also in this embodiment, the liquid droplet ejecting unit 2 is provided in the upper part of the apparatus, and a chamber part 180 for ejecting liquid droplets and drying, and a guide tube for sending the toner obtained in the chamber part 180 to the toner storage part 6 are provided. It is configured.
The droplet ejecting unit 2 includes droplet forming means 16 for discharging the toner composition liquid 10 in which a toner composition containing at least a resin and a colorant is dispersed or dissolved in an organic solvent into droplets, and the droplet forming unit 16. And a container 130 having a reservoir 14 for supplying the toner composition liquid 10 to the means 16.
The droplet forming means 16 is the same as in the membrane vibration system. A liquid supply hole 200 and a discharge hole 210 for supplying the toner composition liquid 10 to the storage unit 14 are connected to the toner container 130, respectively. A droplet 31 is discharged from the discharge hole 11 by the droplet forming means 16.
An outside of the container 13 has an opening 301 that opens at a portion facing the discharge hole 11. A shroud portion 30 that forms an air flow path is attached. The shroud portion 30 is composed of double pot-shaped walls 302 and 303 having discharge holes, and the lid portions 310 are connected to each other. A gas blowing pipe 91 is fitted into the side surface of the shroud portion 30. Of the double walls, the inner wall 303 ends near the lower end of the container 130. Out of the double walls, the outer wall 302 wraps around to the lower part of the discharge hole 11 and ends with a lower circular opening 301 facing the discharge hole 11. The diameter of the opening 301 is “D”, and the clearance G is maintained between the inner wall of the bottom 304 of the outer wall 302 and the lower end of the discharge hole 11. Since G is smaller than D, G is the main factor that determines the flow velocity of the carrier airflow.

  The stream 311 containing the droplets 31 is then directed into the large volume shroud 30 with the shroud 30 and container 130 attached to the top. A downward airflow 96 is formed in the chamber portion 180 by a chamber portion outlet 93 described later. The air flow 96 is a uniform laminar flow, and the flow 311 including the droplets 31 is sent to a guide tube 92 connected to the toner collecting unit 4 at the bottom while being dried and solidified in a laminar flow state by the air flow 96. . The guide tube 92 is connected to a cyclone (not shown), collected while being dried, and fed to the toner storage unit 6. On the upper side surface of the shroud portion 30, a gas blowing pipe 91 is fitted in an airtight manner. A pressure gauge PG <b> 1 is inserted on the opposite side surface of the chamber portion 180. A pressure gauge PG <b> 2 is also inserted into the side surface of the blowing pipe of the shroud portion 30.

Next, the operation of the toner manufacturing apparatus according to this embodiment will be described. Here, the case where the toner composition liquid 10 is circulated will be described.
When the annular vibration means 17, which is a vibration means, is vibrated at, for example, 100 kHz by a driving device (not shown) while the toner composition liquid 10 is accommodated in the container 130 at an appropriate pressure, the thin film 12 is vibrated. Propagating, and the toner composition liquid 10 is ejected from the plurality of ejection holes 11 at a discharge frequency that matches the frequency of vibration drive. The released initial velocity V ₀ tends to decelerate due to resistance due to the viscosity of the gas in the shroud portion 30.
On the other hand, gas is blown out by the blow pipe 91 into the shroud portion 30, forms a carrier air flow 95 through the shroud portion 30, and is discharged from the opening 301 to the chamber portion 180. The formed conveying airflow 95 is uniform and downward in the circumferential direction, and since the lower end portion of the wall 302 of the shroud portion 30 is rounded, the airflow smoothly changes in the horizontal direction and merges under the discharge hole 15. Further, it is discharged from the opening 301. If the airflow at this time is a turbulent flow, the droplets 31 are likely to coalesce with each other.
The discharged droplet 31 rides on the carrier airflow 95 and is released from the opening 301 into the chamber portion 180, where it rides on the airflow 96 which is a laminar flow and is sent to the toner collecting portion 4 without being attached.
In this example, the flow velocity V ₁ of the carrier airflow 95 is larger than the initial velocity V _{0 of} the droplet 31, and the droplet 31 is accelerated and then sent along the carrier airflow 95. V ₁ may be higher than the free fall speed, and may be lower than the initial speed V ₀ . An air flow 96 having a flow velocity V ₂ faster than V ₁ is formed in the chamber. As the flow velocity V ₂ of the air flow 96 is large, preferable in terms of preventing coalescence. As the air flow 96 in the chamber portion 180 is blown out from the blowing pipe 93, a uniform and uniform air flow is formed in the circumferential direction as in the shroud portion 30. A laminar flow is preferable in the chamber portion 180. Since the flow 311 of the liquid droplet (the flow velocity is V ₁ ) including the liquid droplet 31 immediately after being discharged into the chamber portion 180 does not cause turbulent flow and flows down smoothly, the flow velocity of the air flow 96 in the chamber portion 180 to V _2, it is preferable that _{V 2} ≧ _{V 1.}

The flow rates of the carrier airflow 95 in the shroud section 30 and the airflow 96 in the chamber section 180 are managed by pressure gauges PG1 and PG2. It is preferable that the pressure P1 in the shroud part 30 and the pressure P2 in the chamber part 18 have a relationship of P1 ≧ P2. If this relationship is not satisfied, there is a possibility that a negative pressure acts on the droplet 31 and the liquid flows backward.
As described above, the rate-determining rate for determining the flow velocity of the conveying airflow 95 in the shroud portion 30 is G, that is, the clearance between the wall 302 and the head 25 because D> G.
The carrier airflow 95 in the shroud portion 30 and the airflow 96 in the chamber portion 180 are both formed by blowing gas from the blowing pipe 91 and the chamber portion outlet 93 at the top of the chamber portion 18. An air flow may be formed by suction from a pipe 92 provided at the lower part of the pipe.
The cross section of the opening 301 of the wall 302 of the shroud 30 preferably has a taper 305 in the direction in which the diameter increases along the gas discharge direction, that is, the outer diameter increases. Thus, by forming the taper 305 in the opening 301, it is possible to avoid the droplet 31 from coming into contact with the wall surface of the opening 301 when the droplet 31 passes through the opening 301.
In the present embodiment, nitrogen gas is used for the shroud portion 30 and the chamber portion 180 as the gas to be blown out. However, the gas may be any gas, and may be air or other gases. Further, although the shroud portion 30 is configured by the double pot-shaped walls 302 and 303, the wall of the inner side 303 may also be used as the outer peripheral wall configuring the container 130. Further, by using a configuration in which a plurality of droplet ejecting units 2 and a shroud portion 30 are arranged in one chamber portion 180, the toner production efficiency can be further increased.
The discharged droplets 31 are removed by the solvent while passing through the particle forming unit 3 and collected in the toner storage unit 6 in a solid form. In FIG. 26, 25 is a head, 32 is a valve, 70 is a liquid feed pipe, 71 is a drain pipe, 10 is a pump, and 7 is a raw material container.

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

<Discharge hole shape>
As described above, there are various types of droplet discharge means applied in the present invention. In the droplet discharge means as described above, if no countermeasure is taken against the seepage of the toner composition liquid 10 in the discharge holes 11 and the thin film 12, the toner composition liquid 10 exudes in an unexpected state during ejection, and as a result, the discharge holes 11 It has become clear that the toner composition liquid 10 is entirely covered and falls into a situation where the ejection is hindered. Further, even when the toner composition liquid itself does not hinder the ejection, the toner composition liquid 10 is eventually dried, and due to the clogging of the discharge holes 11 and the change in shape due to the dried material, the ejection is lowered or the ejection is stopped. . For this reason, the liquid surface 101 of the toner composition liquid 10 for preventing the bleeding from flowing into the discharge hole 11 is vibrated, and the discharge surface is a flat plate that has been conventionally implemented, so that the discharge surface is convex. In the processed shape, the discharge hole 11 having an octopus shape on the droplet discharge side is used. Here, the octopus shape means a shape having a convex shape on the droplet discharge side, and the convex shape being a cylindrical object formed around the inner wall of the discharge hole. Examples of the cross section of the cylindrical object include circles, ellipses, triangles, quadrangles, hexagons, octagons, and other polygons.
FIG. 28 is a diagram showing the shape of the ejection holes in the toner manufacturing apparatus to which the toner manufacturing method of the present invention is applied.
As shown in FIG. 28, the shape of the discharge hole of the present invention is convex on the jet outlet side. The discharge hole shown in FIG. 28 satisfies the relationship of the following formulas (1) and (2), where a is the diameter of the discharge hole A, b is the diameter of the protrusion B, and h is the height of the protrusion.
a <b ≦ 3a (1)
1 / 2a ≦ h ≦ 2a (2)

In the shape of the discharge hole shown in FIG. 28, as shown in the equation (1), when the diameter of the discharge hole A is equal to or larger than the diameter of the convex portion B (a ≧ b), the convex B can substantially exist. Absent. The diameter b of the convex B is 3 times or less (b ≦ 3a) of the diameter a of the discharge hole A, and preferably 2 times or less (b ≦ 2a). If the diameter b of the convex B exceeds three times the diameter a of the discharge hole A, the diameter of the meniscus of the discharge hole becomes too large, and there is no change in the state where the convex B does not exist, and the droplet diameter is not stabilized. The particle size distribution becomes wide, which is not a preferable state.
In the shape of the discharge hole 11 shown in FIG. 28, the height h of the convex B needs to be 1/2 or more of the diameter of the discharge hole A as shown in the equation (2). If it is less than ½, the meniscus is substantially unchanged due to vibration of the meniscus and turbulence of the airflow, and the meniscus spreads and the droplet discharge directionality does not become stable and the droplet size distribution is wide. Become. The height h of the protrusion B needs to be not more than twice the diameter of the discharge hole A, and is preferably 1.5 times. If it exceeds twice, since the thickness of the discharge hole plate is large, the ratio (L / a) between the height L of the discharge hole A and the diameter a is substantially increased, and the discharge hole is processed. Not only is it difficult, the pressure loss during discharge increases, and the discharge voltage increases. This makes it impossible to save energy in the production of toner.

  In the present invention, the material of the discharge hole 11 is not particularly limited, and an appropriately selected material can be used. However, since an organic solvent is often used for the toner composition liquid, a metal plate is desirable. A photo-etching method or an electroforming method is preferably used for processing holes as in the present invention. Examples of materials suitable for photoetching include silicon, stainless steel, copper, copper alloys, brass, aluminum, phosphor bronze, beryllium copper, nickel, permalloy, etc., and materials suitable for electroforming include nickel and copper. desirable. Among these, silicon, stainless steel and nickel are particularly desirable in order to ensure processing accuracy and filter strength.

  In the present invention, the actual size of the discharge hole 11 is determined by the size of the target droplet 31. The thin film 12 described in FIGS. 1, 2, 3, 7, 8, 9, 10, 11, 12, 13, 14, 15, 17 in the present application is formed of a metal plate having a thickness of 5 to 500 μm, and the discharge hole 11 Is preferably 3 to 30 μm from the viewpoint of generating fine liquid droplets having a very uniform particle diameter when the liquid droplets of the toner composition liquid 10 are ejected from the ejection holes 11. In addition, the opening diameter of the discharge hole 11 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 11 is preferably 2 to 3000.

When the film thickness is very large with respect to the opening diameter of the discharge hole 11, the discharge performance is improved by making the cross-sectional shape of the discharge hole a two-stage type.
Next, a method of making the cross-sectional shape of the discharge hole a two-stage type will be described with reference to FIG.
FIG. 29 is a diagram for explaining a method of setting the cross-sectional shape of the ejection holes to a two-stage type in a liquid column resonance ejection type toner production apparatus to which the toner production method of the present invention is applied.
First, as shown in (a), a resist 1110 is coated on both sides of a silicon substrate.
Next, as shown in FIG. 5B, the resist is covered with a photomask on which a discharge hole pattern is formed, exposed to ultraviolet rays, and a resist 1110 is formed as a discharge hole pattern.
Next, as shown in (c), anisotropic dry etching using ICP discharge (inductively coupled plasma discharge) is performed from the surface side of the support layer 1120 to form the first discharge hole 1150, and the surface of the active layer 1140 A second discharge hole 1160 is formed by performing similar anisotropic dry etching on the side.
Finally, as shown in (d), the dielectric layer 1130 is removed with a hydrofluoric acid-based etching solution to obtain two-stage through holes.
This method is the most preferable method for uniformly forming the deep discharge hole shape. Although not shown, even when a single-layer silicon substrate is used as the silicon substrate, the discharge holes can be formed by the same method as that for the SOI substrate. In that case, the depth of the first discharge hole and the depth of the second discharge hole can be adjusted by adjusting the etching time.

(toner)
Next, the toner according to the present invention will be described. The toner according to the present invention is a toner manufactured by a toner manufacturing method using the above-described toner manufacturing apparatus, and a monodispersed particle size distribution is obtained by this manufacturing method.
Specifically, the particle size distribution (volume average particle diameter (Dv) / number average particle diameter (Dn)) of the toner is preferably in the range of 1.00 to 1.15. More preferably, it is 1.00 to 1.05. Moreover, as a volume average particle diameter, it is preferable to exist in the range of 1-20 micrometers, More preferably, it is 3-10 micrometers.
Next, the toner material (toner composition liquid) 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. It is also possible to obtain a target toner by drying and solidifying a liquid obtained by dissolving or dispersing a kneaded material obtained by hot-melting and kneading the above materials in various solvents into fine droplets by the toner production method. is there.

[Toner material]
The toner material contains at least a resin and a colorant and, if necessary, other components such as a carrier and wax.

〔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, etc.
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, and 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, p -Styrene such as chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or derivatives thereof.

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

Examples of other monomers that form the vinyl polymer or vinyl copolymer include the following (1) to (18).
(1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, 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, methacrylate. Ronitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic anhydride and alkenyl succinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; ) 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- Monomers having a hydroxy group such as hydroxy-1-methylhexyl) styrene.

  The vinyl polymer or vinyl copolymer 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 divinylbenzene and divinylnaphthalene as aromatic divinyl compounds. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6. Examples include xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing the acrylate of these compounds with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.

Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).
Polyfunctional crosslinking agents include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate, triallyl cyanide. Examples thereof include nurate and triallyl trimellitate. Changing These crosslinking agents are preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, based on 100 parts by weight of the other monomer components. Among these crosslinkable monomers, they are connected by a bond chain containing one aromatic bond and one ether bond, an aromatic divinyl compound (especially divinylbenzene) from the viewpoint of imparting fixing property and offset resistance to the toner resin. Preferred are diacrylate compounds. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

  As a polymerization initiator used for manufacture of the vinyl polymer or vinyl copolymer used in the present invention, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo- 2 ', 4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide , Ketone peroxides such as cyclohexanone peroxide; 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethyl Butyl 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-isopropyl peroxydicarbonate, di-2-ethylhexyl -Oxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetyl Cyclohexylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaurate, tert-butyl-oxybenzoate, tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisophthalate, tert-butylperoxyallyl carbonate, isoamylperoxy-2-ethylhexanoate , Di-tert-butylperoxyhexahydroterephthalate, tert-butylperoxyazelate and the like.

When the binder resin is a styrene-acrylic resin, the molecular weight distribution measured by gel permeation chromatography (GPC) of the soluble component in tetrahydrofuran (THF) as a resin component has a molecular weight of 3000 to 50000 (in terms of number average molecular weight). A resin having at least one peak in a region and 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 5000 to 30000 is more preferable. A binder resin having a main peak in the 20000 region is most preferred.
The acid value when the binder resin is a vinyl polymer such as styrene-acrylic resin is preferably 0.1 to 100 mgKOH / g, more preferably 0.1 to 70 mgKOH / g, and 0 More preferably, it is 1-50 mgKOH / g.

The following are mentioned as a monomer which comprises the said 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, diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, and the like Can be 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-butane. Triol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, etc. Is mentioned.

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

When the binder resin is a polyester-based resin, the toner fixing property is that at least one peak is present in the region of molecular weight 3000 to 50000 (in terms of number average molecular weight) in the molecular weight distribution of the THF soluble component of the resin component. From the viewpoint of offset resistance, the THF-soluble component is preferably a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100%, and has at least one peak in the molecular weight region of 5000 to 20000. The binder resin present is more preferred.
When the binder resin is a polyester resin, the acid value is preferably 0.1 to 100 mgKOH / g, more preferably 0.1 to 70 mgKOH / g, and 0.1 to 50 mgKOH / g. More preferably it is.
In the present invention, the molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.

As the binder resin that can be used in the toner according to the present invention, 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 another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin is 0.1-50 mgKOH / g is preferable.
In the present invention, the acid value of the binder resin component of the toner composition can be determined by the following method, 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. . A sample ground product of 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 an ethanol solution of 0.1 mol / L KOH using a potentiometric titrator.
(4) The amount of KOH solution used at this time is S (mL), a blank is measured at the same time, and the amount of KOH solution used at this time is B (mL). 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., more preferably 40 to 75 ° C., from the viewpoint of toner storage stability. If the Tg is lower than 35 ° C., the toner is likely to deteriorate in a high temperature atmosphere, and offset may easily occur during fixing. On the other hand, when Tg exceeds 80 ° C., fixability may be deteriorated.
Examples of the magnetic material that can be used in the present invention include (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 these And the like.
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 Fe ₃ O ₄ (triiron tetroxide) and γ-Fe ₂ O ₃ (γ-iron trioxide) are particularly suitable.
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, Examples include gallium. As a preferable different element, it is an element selected from magnesium, aluminum, silicon, phosphorus and zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may exist as an oxide or hydroxide on the surface. Is preferably contained as an oxide.

The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grains production | generation, or adding salt of each element and adjusting pH.
As the usage-amount of the said magnetic body, 10-200 mass parts of magnetic bodies are preferable with respect to 100 mass parts of binder resin, and 20-150 mass parts is more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 μm, and more preferably 0.1 to 0.5 μm. The number average diameter can be obtained by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.
Further, as the magnetic properties of the magnetic material, those having a coercive force of 20 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g are preferable.
The magnetic material can also be used as a colorant.

[Colorant]
The colorant is not particularly limited and may be appropriately selected from commonly used resins. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fu Issey Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Nacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide , Pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green , Malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.
The content of the colorant is preferably 1 to 15% by mass and more preferably 3 to 10% by mass based on the total amount of 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 with the production of the master batch or the master batch, in addition to the modified polyester and unmodified polyester resin mentioned above, for example, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and the substituted products thereof Polymers of: styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-acrylic acid Ethyl copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, Styrene-α-Chlormethacryl Acid methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer Polymers, styrene copolymers such as styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, Examples include polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, there is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.
As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.
The resin for the masterbatch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and a colorant dispersed therein. The acid value is 20 mgKOH / g or less and the amine value is 10 It is more preferable that the colorant is dispersed and used at ˜50. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered, and the pigment dispersibility may be insufficient. 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 weight average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene weight in gel permeation chromatography, preferably 500 to 100,000, and more preferably 3000 to 100,000 from the viewpoint of pigment dispersibility. In particular, 5000 to 50000 is preferable, and 5000 to 30000 is most preferable. When the molecular weight is less than 500, the polarity becomes high and the dispersibility of the colorant may be lowered. When the molecular weight exceeds 100,000, the affinity with the solvent is increased and the dispersibility of the colorant is lowered. There is.
The addition amount of the dispersant is preferably 1 to 200 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the colorant. When the addition amount is less than 1 part by mass, the dispersibility of the colorant may be lowered, and when it exceeds 200 parts by mass, the chargeability may be lowered.

<Wax>
In the present invention, the toner may contain a wax together with the binder resin and the colorant.
The wax is not particularly limited and can be appropriately selected from commonly used ones such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, and sazol wax. Oxides of aliphatic hydrocarbon waxes such as aliphatic hydrocarbon waxes, polyethylene oxide waxes or block copolymers thereof, plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax, beeswax, lanolin Waxes mainly composed of fatty acid esters such as animal waxes such as whale wax, mineral waxes such as ozokerite, ceresin, and petrolatum, and montanic acid ester waxes and castor waxes. Deoxidized carnauba wax and other fatty acid esters are partially or wholly deoxidized.
Examples of the wax include non-saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, and linear alkyl carboxylic acids having a linear alkyl group, prandidic acid, eleostearic acid, and valinal acid. Saturated fatty acids, stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesyl alcohol, saturated alcohols such as long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acid amides, laurin Fatty acid amides such as acid amides, methylene biscapric acid amides, ethylene bislauric acid amides, saturated fatty acid bisamides such as hexamethylene bis stearic acid amides, ethylene bis oleic acid amides, hexamethylene bis olein Unsaturated fatty acid amides such as amide, N, N′-dioleyl adipate amide, N, N′-dioleyl sepasin amide, m-xylene bisstearic amide, N, N-distearyl isophthalic amide, etc. Aromatic bisamides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate, waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid, Examples thereof include a partial ester compound of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol, and a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oil.

More preferable waxes 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 polymerizations using catalysts such as Ziegler catalysts and metallocene catalysts under low pressures. 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. Synthetic 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 hydroxyl group or carboxyl group, hydrocarbon wax and functional group Mixture of hydrogen wax, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.
In addition, these waxes have a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.

The melting point of the wax is preferably 70 to 140 ° C., and more preferably 70 to 120 ° C., in order to balance the fixability and the offset resistance. If it is less than 70 degreeC, blocking resistance may fall, and if it exceeds 140 degreeC, an offset-proof effect may become difficult to express.
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 types of wax having a plasticizing action include waxes having a low melting point, those having a branch on the molecular structure, and those having a polar group.
Examples of the wax having a releasing action include a wax having a high melting point, and the molecular structure includes a linear structure and a non-polar one having no functional group. Examples of use include a combination of two or more different waxes having a difference in melting point of 10 to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.
When selecting two types of wax, in the case of a wax having the same structure, a wax having a relatively low melting point exhibits a plasticizing action, and a wax having a high melting point exhibits a releasing action. At this time, when the difference in melting point is 10 to 100 ° C., functional separation is effectively expressed. If it is less than 10 ° C., the function separation effect may be difficult to appear, and if it exceeds 100 ° C., the function may not be emphasized by interaction. At this time, the melting point of at least one of the waxes is preferably 70 to 120 ° C, and more preferably 70 to 100 ° C, because the function separation effect tends to be easily exhibited.

  As for the wax, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exert a plastic action, and those having a linear structure or a 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-based wax Like a combination of.

In any case, since it becomes easy to balance the toner storage stability and the fixing property, the peak top 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. Preferably, it has a maximum peak in the region of 70 to 110 ° C.
The total content of the wax is preferably 0.2 to 20 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin.
In the present invention, the peak top temperature of the endothermic peak of the wax measured by DSC is defined as the melting point of the wax.
The wax or toner DSC measuring device is preferably measured with a high-precision internal heat input compensation type differential scanning calorimeter. As a measuring method, it carries out according to ASTM D3418-82. The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 ° C./min after the previous history is obtained by raising and lowering the temperature once.

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

The fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.
Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include AEROSIL (trade name of Nippon Aerosil Co., Ltd., hereinafter the same) -130, -300, -380, -TT600, -MOX170, -MOX80, -COK84: Ca-O-SiL (trade name of CABOT)-M-5, -MS-7, -MS-75, -HS-5, -EH-5, Wacker HDK (trade name of WACKER-CHEMIE)- N20 V15, -N20E, -T30, -T40: D-CFineSi1ica (trade name of Dow Corning): Franco1 (trade name of Franci1), and the like.
Furthermore, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is more preferable. In the treated silica fine powder, it is particularly preferred to treat the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is preferably 30 to 80%. Hydrophobization is imparted by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, a method of treating 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, and dimethylvinylchlorosilane. , Divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchloro Silane, 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 measuring nitrogen adsorption by the BET method of fluidity improving agent, preferably at least ^{30m 2 / g, 60~400m 2 /} g is more preferable. Specific surface area of the surface-treated fine powder is preferably at least ^{20m 2 / g, 40~300m 2 /} g is more preferable.
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.

When preparing the toner, an external additive such as the above-mentioned hydrophobic silica fine powder may be added and mixed in order to improve the fluidity, storage stability, developability and transferability of the toner. 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. The material is mechanically adjusted using a hybridizer, mechano-fusion, etc., 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 removed using a spray drying device. Examples thereof include a method of obtaining a spherical toner by forming a solvent, and a method of forming a spherical toner by heating in an aqueous medium.

As the external additive, inorganic fine particles can be preferably used. Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, 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 diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 to 500 nm.
The specific surface area of the inorganic fine particles by the BET method is preferably 20 to 500 m ² / g.
The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass and more preferably 0.01 to 2.0% by mass in the total amount of the toner.

In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylate esters, acrylate copolymers, polycondensation systems such as silicone, benzoguanamine, and nylon, thermosetting Examples thereof include polymer particles made of a resin.
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. Preferably mentioned.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, more preferably 5 to 500 nm. Moreover, as a specific surface area by BET method, it is preferable that it is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and more preferably 0.01 to 2.0% by mass.

Examples of the cleaning property improver for removing the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymethyl methacrylate. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.
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, specific examples in this embodiment will be described. In addition, this invention is not limited to the following Example at all.
Example 1
-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
17 parts by mass of carbon black (Regal 400; manufactured by Cabot) and 3 parts by mass of a pigment dispersant were primarily dispersed in 80 parts by mass of ethyl acetate using a mixer having stirring blades. As the pigment dispersant, Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion in which aggregates of 5 μm or more were completely removed.

-Preparation of wax dispersion-
Next, a wax dispersion was prepared.
18 parts by mass of carnauba wax and 2 parts by mass of a wax dispersant were primarily dispersed in 80 parts by mass of ethyl acetate using a mixer having stirring blades. The primary dispersion was heated to 80 ° C. with stirring to dissolve the carnauba wax, and then the 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 dyno mill and adjusted so that the maximum diameter was 1 μm or less.

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

-Preparation of toner-
The obtained toner composition liquid (500 mL) was supplied to the discharge hole 11 of the droplet forming means 16 in FIG. The used thin film 16 (discharge hole plate) was prepared by forming a discharge hole 11 having a perfect circle shape of 10 μm in diameter on a nickel plate having an outer diameter of 15.0 mm and a thickness of 50 μm by electroforming. The discharge holes were provided only in a range of about 5 mmφ at the center of the thin film 12 in a staggered pattern so that the distance between the discharge holes was 100 μm pitch. In this case, the number of effective discharge holes in calculation is 1000.
After the dispersion was prepared, the droplets were discharged under the following toner production conditions, and then the droplets were dried and solidified to produce toner base particles.

[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.888 g / cm ³
Dry air flow rate: Dry nitrogen in the device 30.0 L / min Temperature in the device: 27-28 ° C
Vibration frequency: 98 kHz
Applied voltage sine wave peak value: 10.5V
(Discharge head specifications)
Thin film (discharge hole plate) thickness: 50μm
Discharge hole diameter: 10 μm
“Vibration frequency” means “frequency of thin film 16”. Under this condition, the toner composition liquid was stably ejected without causing clogging (clogging) of ejection holes. The toner particles after the drying and solidification step were collected by suction with a filter having 1 μm pores. Particle size of collected particles The particle size distribution of the collected particles was measured with a flow particle image analyzer (FPIA-2000) under the following measurement conditions. Toner base particles having a particle diameter (Dn) of 4.8 μm and D4 / Dn of 1.10 were obtained.

A measurement method using a flow particle image analyzer (Flow Particle Image Analyzer) will be described below. The measurement of toner, toner particles and external additives using a flow particle image analyzer can be performed using, for example, a flow particle image analyzer FPIA-2000 manufactured by Toa Medical Electronics Co., Ltd.
The measurement is performed by removing fine dust through a filter, and as a result, in ^10-3 water of 10 ⁻³ cm ³ of water having a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) of 20 or less particles. Add a few drops of a nonionic surfactant (preferably Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.), add 5 mg of a measurement sample, and UH-50 manufactured by an ultrasonic disperser STM under the conditions of 20 kHz and 50 W / 10 cm ³ . for 1 minute dispersion treatment, further, the sample dispersion liquid of the total particle concentration of sample was dispersed for 5 minutes from 4000 to 8000 pieces ^{/ 10} -3 cm ³ (as the target particles measuring circle equivalent diameter range) The particle size distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is measured.

The sample dispersion liquid is passed through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, the strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter.
In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the range of 0.06-400 μm into 226 channels (divided into 30 channels for one octave). In actual measurement, particles are measured in the range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.
From the above results, it was determined that Example 1 can implement a toner production method with high stability and high production efficiency.

(Examples 2-9)
Table 2 shows the results of Examples 2 to 16 evaluated in the same manner as Example 1 using the conditions shown in Table 1. Note that the same toner liquid and peripheral devices are used.

-Explanation of evaluation items-
Stop drive voltage: This is the amplitude of the electrical signal of the discharge sine wave given to the head while the discharge head is filled with liquid and the discharge before the start of discharge is not stopped. In order to ensure the accuracy of the experiment, ultrasonically clean the discharge head with pure solvent before each experiment, fill the head until the discharge liquid oozes out from the discharge hole, and stop in the state where it oozes out The liquid that exuded was wiped off after a slight drive vibration was applied.
With the fine drive signal turned on, the exuded liquid was wiped off and allowed to stand for 30 seconds before switching to a normal ejection signal (98 kHz, 10.5 V sine wave).
The vibration source of the head was a transmitter (WF 1973 manufactured by nf) through an amplifier (HSA-4014 manufactured by nf 10 times setting).
Stop drive frequency: This is the frequency of the electrical signal of the discharge sine wave that is given to the head while the discharge head is filled with liquid and the discharge before the start of discharge is not stopped.
Discharge time: The time during which a normal discharge signal (98 kHz, 10.5 V sine wave) is continuously applied to the head. Time during which droplets are continuously ejected.
Discharge level: The ratio of discharge holes that discharge normally with respect to all the discharge holes in a state where a discharge signal is input. The discharge level at the start was calculated by directly counting from the enlarged image taken with the camera immediately after the start of discharge. The discharge level at the end was calculated by directly counting from the enlarged image taken with the camera immediately before the end of the discharge time.
Particle size distribution: Average particle size distribution of the collected toner.

以上の結果より、本発明の乾燥、固化方法を用いることによって、高品質のトナーを効率良く生産できることが示された。

From the above results, it was shown that high quality toner can be efficiently produced by using the drying and solidifying method of the present invention.

1-19, 25-29
DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet injection unit 3 Particle formation part 301 Top surface part 4 Toner collection part 5 Tube 6 Toner collection part 7 Raw material storage part 8 Pipe 9 Pump 10 Toner composition liquid 101 Liquid surface 11 Discharge hole
DESCRIPTION OF SYMBOLS 12 Thin film 121 Peripheral part 122 Convex shape 13 Vibration means 131 Vibration surface 14 Storage part 15 Flow path member 16 Droplet formation means 161 Deformable area 17 Vibration generation means (electromechanical conversion means)
18 Liquid supply tube 19 Bubble discharge tube 20 Support member 21 Vibration generating means 211, 212 Piezoelectric bodies 21a, 21b Electrode 22 Vibration amplifying means 221, 222 Horn 23 Drive circuit (drive signal generation source)
24 Communication means 25 Head 26 Vibration separation member 27 Node portion 29 having small vibration amplitude Liquid storage region 30 Shroud portion 301 Opening portion 302, 303 Wall 304 Bottom portion 305 Taper 31 Droplet 311 Droplet flow 32 Valve 35 Dry gas 36 Airflow Path forming member 37 Air flow path 41 Tapered surface 42 Air flow (vortex flow)
43 Static elimination means 70 Liquid supply pipe 71 Drainage pipe 81 Piezoelectric body 82 Horn 83 Fixing part 91 Ejection pipe 92 Guide pipe 93 Outlet 95 Carrying airflow 96 Airflow 100 Pump 130 Container 170 Annular vibration means 180 Chamber part 200 Liquid supply Hole 210 Ejection hole 310 Lid 1110 Resist 1120 Support layer 1130 Dielectric layer 1140 Active layer 1150 First discharge hole 1160 Second discharge hole PG1 Pressure gauge PG2 Pressure gauge T Toner particles FIGS. 20 to 24
DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 10 Droplet formation unit 11 Droplet discharge head 12 Air flow path 13 Raw material container 14 Toner composition liquid 15 Liquid circulation pump 16 Liquid supply pipe 17 Liquid common supply path 18 Liquid column resonance liquid chamber 19 Discharge hole 20 Vibration generation Means 21 Toner droplet 22 Liquid return tube 30 Dry collection unit 31 Chamber 32 Toner collection unit 33 Downstream air flow 34 Toner collection tube 35 Toner storage unit

JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977

Claims (5)

A periodic droplet forming step of periodically discharging and discharging a toner composition liquid containing at least a resin and a colorant from a plurality of ejection holes;
In a method for producing a toner, the droplets of the discharged toner composition liquid are solidified to form toner particles.
A method for producing a toner, characterized in that the liquid surface in the ejection hole is vibrated when the liquid droplet formation in the periodic liquid droplet forming step is stopped. The toner production method according to claim 1, wherein:
A toner manufacturing method, wherein the means for vibrating the liquid surface provides continuous low vibration that does not cause droplets to be discharged to an ejection head. In the toner production method according to claim 1 or 2,
The method for producing a toner, wherein the vibration is a vibration having the same frequency as that of a droplet discharged with a reduced vibration amplitude. The method for producing a toner according to any one of claims 1 to 3,
The method for producing toner, wherein the low vibration is a vibration whose frequency is changed from vibration (resonance) during ejection. The method for producing a toner according to claim 1, wherein:
The method for producing toner, wherein the periodic droplet forming step employs a liquid column resonance ejection method.

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