JP5500353B2 - Toner manufacturing method, toner manufacturing apparatus and toner - Google Patents

Description

The present invention relates to a method for producing a toner used as a developer for developing an electrostatic charge image in electrophotography, a toner production apparatus, and a produced toner.

  Conventionally, the only production method of toner for electrophotography used in copying machines, printers, fax machines, and composite machines based on the electrophotographic recording method has been a pulverization method, but in recent years, in an aqueous medium called a polymerization method. The forming method is widely performed and has a momentum that surpasses the pulverization method (see, for example, JP-A-7-152202 of Patent Document 1). Note that the polymerization method includes a production method that does not necessarily involve a polymerization process for convenience, as the polymerization method toner is called “polymerization toner” or “chemical toner” in some countries. 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, a sharp particle size distribution, and a shape close to a sphere, but usually the solvent is removed from the toner particles in an aqueous medium. Therefore, 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 toner (patent) Reference 2003-262276 of literature 2). Furthermore, a method has also been proposed in which fine droplets are formed using the thermal expansion in the nozzle and then solidified by drying to form a toner (see Japanese Patent Application Publication No. 2003-280236). Furthermore, a method for performing the same processing using an acoustic lens has been proposed (see Japanese Patent Laid-Open No. 2003-262977). However, in these methods, the number of droplets that can be ejected from one nozzle per unit time is small, and there is a problem that productivity is low, and at the same time, the spread of particle size distribution due to coalescence of droplets is unavoidable, Also in terms of monodispersity, it was not satisfactory.
It has been proposed to improve productivity by forming micro droplets using high frequency vibration and multiple nozzles. However, when high-frequency vibration and a plurality of nozzles are used, liquid ooze from the nozzles and coalescence of the droplets become a major problem that deteriorates the particle size distribution of the toner. As countermeasures, a nozzle plate having a convex portion at the outlet or a soaking treatment of the nozzle plate has been proposed. These measures reduce the size of the problem, but do not completely eliminate it.
Therefore, it is necessary to periodically clean the nozzles, and some wiping is conventionally performed. However, since the wiping cannot be applied by changing the nozzle shape, it becomes difficult to clean the nozzle. Further, even in the case of a flat nozzle shape having no convex portion, the surface deterioration due to wiping occurs, the effect of the smoky treatment is gradually reduced, and the particle size distribution of the toner is deteriorated.

  SUMMARY OF THE INVENTION An object of the present invention is to solve the following problems and solidify droplets formed by droplet forming means for discharging a toner composition liquid containing a resin and a colorant from a nozzle to form toner particles. In a toner manufacturing technique using a toner manufacturing apparatus equipped with a particle forming means for forming a nozzle, deterioration of the nozzle surface due to wiping is avoided by providing a cleaning liquid discharging means for discharging a liquid for cleaning the nozzle in a specific arrangement. Smooth and reliable nozzle cleaning, solves the problem of liquid oozing from nozzles and coalescence of liquid droplets, degrading the toner particle size distribution, and stable production of high-quality toner To provide a toner manufacturing technology. Furthermore, the objective of this invention includes provision of the aspect technique of the more excellent nozzle cleaning by discharging a specific nozzle cleaning liquid in a specific aspect from such a nozzle cleaning liquid discharge means.

The above-mentioned subject is solved by the present invention including the following inventions (1) to ( 4 ).
(1) “Dropping means for discharging a toner composition liquid containing a resin and a colorant from a plurality of nozzles to form droplets; and solidifying the droplets formed by the droplet forming means to form toner particles A toner production apparatus comprising: a particle forming unit that forms a droplet; and a cleaning liquid discharge unit that discharges a liquid for cleaning the nozzle, facing the nozzle of the droplet forming unit, and the cleaning liquid In the discharge means, a solvent that is more volatile than the solvent used in the toner composition liquid or the same solvent as the solvent used in the toner composition liquid is used as the cleaning solvent, and the discharge direction of the cleaning solvent is However, the angle θ with respect to the toner composition droplet discharge direction satisfies θ> 0 °, and the pressure of the toner composition liquid is the same as the surrounding gas at the nozzle outlet when the nozzle is cleaned. Pressure value or better Toner production apparatus which is characterized in that is maintained at a higher pressure value ";
( 2 ) “The cleaning liquid droplet discharge means uses a warmed solvent as a cleaning solvent so that the temperature becomes higher than the ambient temperature at the time of discharge of the toner composition liquid discharge head. 1 ) toner production apparatus according to item
( 3 ) “A step of forming droplets by a droplet forming means for discharging a toner composition liquid containing a resin and a colorant from a plurality of nozzles to form droplets; and solidifying the formed droplets to form toner particles And a particle forming step for forming a liquid droplet, wherein a liquid for cleaning the nozzle is discharged opposite to the nozzle of the droplet forming means between the execution of the droplet forming step. look-containing cleaning solution discharge step, in the cleaning solution discharge step, the toner solvent or easily volatilized than the solvent used in the composition solution, or the solvent for cleaning the same solvent as used in the toner composition liquid The cleaning solvent discharge direction has an angle θ with respect to the toner composition droplet discharge direction, and the angle θ satisfies θ> 0 °. The pressure around the nozzle outlet A method for producing a toner, characterized by being maintained at a pressure value equal to or higher than that of the surrounding gas ";
(4) “The cleaning liquid droplet discharge means uses a warmed solvent as the cleaning solvent so that the temperature becomes higher than the ambient temperature at the time of discharge of the toner composition liquid discharge head. “Method for producing toner according to item 3)”.

  As will be understood from the following detailed and specific description, according to the present invention, a liquid formed by a droplet forming unit that discharges a toner composition liquid containing a resin and a colorant from a nozzle to form droplets. In toner manufacturing technology using a toner manufacturing apparatus having particle forming means for solidifying droplets to form toner particles, wiping is performed by providing cleaning liquid discharging means for discharging liquid for cleaning nozzles in a specific arrangement. This eliminates the deterioration of the nozzle surface due to the nozzle, smoothes and ensures the cleaning of the nozzle, and solves the problem that the liquid ooze from the nozzle and the coalescence of the liquid droplets deteriorate the particle size distribution of the toner. Toner production technology for stably producing toner is provided, and further, by discharging a specific nozzle cleaning liquid in a specific manner from such nozzle cleaning liquid discharge means Extremely excellent effect that aspects technology more excellent nozzle cleaning is provided is exhibited.

FIG. 3 is a schematic configuration diagram illustrating an example of a toner manufacturing apparatus according to the present invention. FIG. 6 is an enlarged explanatory diagram for explaining a droplet ejecting unit of the toner manufacturing apparatus. Example (a) of step type horn type vibrator constituting vibration generating means of liquid droplet ejecting unit, example (b) of exponential type horn type vibrator, and example of conical type horn type vibrator It is a typical explanatory view showing (c). FIG. 6 is an enlarged explanatory diagram for explaining two other examples of the droplet ejecting unit of the toner manufacturing apparatus. FIG. 10 is an enlarged explanatory view for explaining still another example of the droplet ejecting unit of the toner manufacturing apparatus. FIG. 6 is an explanatory diagram for explaining an example in which a plurality of droplet ejection units in FIG. 5 are arranged. 1 is a schematic configuration diagram illustrating an embodiment of a toner manufacturing apparatus according to the present invention. FIG. 6 is an enlarged explanatory diagram for explaining a droplet ejecting unit of the toner manufacturing apparatus. It is bottom explanatory drawing which looked at FIG. 8 from the lower side. It is expansion sectional explanatory drawing of the droplet formation means of the droplet ejection unit. It is expansion sectional explanatory drawing of the droplet formation means which concerns on a comparative example structure. FIG. 3 is a main part explanatory diagram for explaining a specific application of the toner manufacturing apparatus. It is a typical explanatory view of a thin film used for explanation of an operation principle of droplet formation by the droplet ejection unit. It is explanatory drawing similarly used for description of a fundamental vibration mode. It is explanatory drawing similarly used for description of secondary vibration mode. It is explanatory drawing similarly used for description of a tertiary vibration mode. It is explanatory drawing at the time of forming a convex part in the center part of a thin film similarly. 1 is a schematic configuration diagram illustrating an example of a liquid resonance type toner manufacturing apparatus according to the present invention. FIG. 19 is an enlarged explanatory diagram for explaining a droplet ejecting unit of the toner manufacturing apparatus of FIG. 18. It is explanatory drawing of the method of making the cross-sectional shape of the nozzle in the manufacturing apparatus of the liquid resonance type toner which concerns on this invention into a two-stage type. 5 is an embodiment of the film vibration type toner manufacturing apparatus according to the toner repair of the present invention;

(Toner production method)
The present invention will be described in detail and specifically below.
First, in order to facilitate understanding of the present invention, a conventional pulverization method that is a toner production method and a spray method and a vibration injection method that are the production methods of the present invention will be described.

<Crushing method>
This is a method for producing a general toner that is not subject to the present invention and has been conventionally performed. The toner composition is melt-kneaded with a two-roll or twin-screw extruder, cooled, and then coarsely pulverized. , Fine pulverization, classification, and mixing of external additives such as fluidizing agents with a Henschel mixer, etc., if necessary. Known manufacturing apparatuses such as elbow jets and various air classifiers can be used.

<Spraying method>
On the other hand, the spraying method includes a one-fluid nozzle (pressurizing nozzle) sprayer that pressurizes liquid and sprays from the nozzle, a multi-fluid spray nozzle sprayer that mixes and sprays liquid and compressed gas, and a rotating disk. In this method, the toner composition liquid is formed into droplets in a gas phase by using a rotary disk type sprayer or the like that forms liquid droplets by centrifugal force. 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>
In addition, the vibration injection method mechanically vibrates a thin film having a plurality of nozzles having the same opening diameter, thereby periodically discharging a toner composition liquid from the nozzles to generate droplets having a uniform particle diameter. In this method, toner particles are obtained by drying. The mechanical vibration means may be arranged in any way as long as it vibrates in the direction perpendicular to the film having the nozzle. 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 nozzles 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 the area where the thin film nozzle having the nozzles 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 the schematic configuration diagram of FIG.
The toner production apparatus (1) periodically discharges the toner composition liquid from a plurality of nozzles having the same opening diameter to form droplets (toner composition liquid) in a periodic droplet formation process in which droplets are formed in the gas phase. A droplet ejecting unit (2) as a means, and the droplet ejecting unit (2) is disposed above, and solidifies the droplets of the toner composition liquid that has been formed into droplets discharged from the droplet ejecting unit (2). Then, a particle forming part (3) as a particle forming means in a particle forming step for forming toner particles T, and a toner collecting part (4) for collecting toner particles (T) formed by the particle forming part (3) ) And toner particles (T) collected by the toner collection unit (4) are transferred through the tube (5), and a toner storage unit as a toner storage unit that stores the transferred toner particles (T) (6) and a raw material container (10) containing the toner composition liquid (10) ), A pipe (liquid feeding pipe) (8) for feeding the toner composition liquid (10) from the inside of the raw material container (7) to the droplet jetting unit (2), and a toner composition liquid during operation, etc. And a pump (9) for pumping and supplying (10).
The toner composition liquid (10) 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). For example, as described above, the liquid is supplied supplementarily using the pump (9).

Next, the droplet ejecting unit (2) will be described with reference to FIG.
FIG. 2 is a schematic cross-sectional explanatory view of the liquid droplet ejecting unit (2).
The droplet ejecting unit (2) includes a thin film (12) having a plurality of nozzles (discharge ports) (11) and mechanical vibration means (hereinafter referred to as “vibration means”) that vibrates the thin film (12). 13) and a flow path member (15) forming a reservoir (liquid flow path) (14) for supplying the toner composition liquid (10) between the thin film (12) and the vibration means (13). Yes.

  The thin film (12) having the plurality of nozzles (11) is installed in parallel to the vibration surface (13a) of the vibration means (13), and a part of the thin film (12) is solder or toner composition liquid. It is bonded and fixed to the flow path member (15) with a resin binding material that does not dissolve in, and is in a position substantially perpendicular to the vibration direction of the vibration means (13). The gist of the present invention is also in the shape of the nozzle, which will be described separately. A 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) is mechanically transmitted. It can be converted into vibration. As a communication means for providing an electrical signal, a lead wire whose surface is insulated is suitable. For the vibration means (13), it is preferable to use an element with a large vibration amplitude, such as various horn type vibrators and bolted Langevin type vibrators described later, for efficient and stable toner production.

  The vibration means (13) includes a vibration generation means (21) that generates vibration and a vibration amplification means (22) that amplifies the vibration generated by the vibration generation means (21). By applying a drive voltage (drive signal) having a required frequency from the source (23) between the electrodes (21a, 21b) of the vibration generating means (21), vibration is excited in the vibration generating means (21). The vibration is amplified by the vibration amplifying means (22), and the vibration surface (13a) arranged in parallel with the thin film (12) vibrates periodically, and the thin film (13a) is vibrated by the periodic pressure due to the vibration of the vibration surface (13a). 12) vibrates at the required frequency.

  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. Since (12) is vibrated, the vibration generating means (21) is preferably a piezoelectric body (21A) excited by a bimorph-type flexural vibration. The piezoelectric body (21A) has a function of converting electrical energy into mechanical energy. Specifically, by applying a voltage, flexural vibration is excited and the thin film (12) can be vibrated.

Examples of the piezoelectric body (21A) that constitutes the vibration generating means (21) include piezoelectric ceramics such as lead zirconate titanate (PZT). There are many. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO ₃ , and the like can be given.
The vibration means (13) may be arranged in any way as long as it gives vibration in the vertical direction to the thin film (12) having the nozzle (11), but the vibration surface (13a) and the thin film (12) Are arranged in parallel.
In the illustrated example, a horn type vibrator is used as the vibration means (13) constituted by the vibration generation means (21) and the vibration amplification means (22), and this horn type vibrator is a vibration generation means such as a piezoelectric element. Since the amplitude of (21) can be amplified by the horn (22A) as the vibration amplifying means (22), the vibration generating means (21) itself for generating mechanical vibration may be a small vibration and the mechanical load is reduced. Therefore, it will lead to longer life as a production device.

As the horn type vibrator, a known typical horn shape may be used. For example, a step type as shown in FIG. 3A, an exponential type as shown in FIG. Conical type as shown. In these horn type vibrators, the piezoelectric body (21A) is arranged on the surface of the horn (22A) having a large area, and the piezoelectric body (21A) uses the longitudinal vibration to induce the efficient vibration of the horn (22A). The horn (22A) is designed so that the surface having a small area is the vibration surface (13a), and this vibration surface (13a) is the maximum vibration surface. Lead wires (24) are disposed above and below the piezoelectric body (21), and an AC voltage signal is applied from the drive circuit (23). The shape of the maximum vibration surface of these horn vibrators is designed so as to be (13a).
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.

  The configuration of the reservoir, the mechanical vibration means, and the thin film will be described in detail with reference to the schematic diagram of FIG. The reservoir (14) is provided with at least one liquid supply tube (18), and as shown in a partial cross-sectional view, the liquid is introduced into the liquid reservoir through the flow path. It is also possible to provide a bubble discharge tube (19) as required. The droplet ejection unit (2) is installed and held on the top surface portion of the particle forming portion (3) by a support member (not shown) attached to the flow path member (15). In addition, although demonstrated here in the example which has arrange | positioned the droplet jetting unit (2) in the top | upper surface part of a particle formation part (3), it is in the drying part side wall used as a particle formation part (3), or a bottom part. It can also be set as the structure which installs a droplet jetting unit (2).

The size of the vibration means (13) that generates mechanical vibration is generally increased with a decrease in the oscillation frequency, and according to the required frequency, the vibration means is directly perforated appropriately to store the storage section. Can be provided. It is also possible to vibrate the entire storage part efficiently.
In this case, the vibration surface is defined as a surface on which the thin films having the plurality of nozzles are bonded.

A different example of the droplet ejecting unit (2) having such a configuration will be described with reference to FIG.
In the example shown in FIG. 4A, a horn type vibrator (80) composed of a piezoelectric body (81) as a vibration generating part and a horn (82) as a vibration amplifying part as vibration means (80 (13)). ), A reservoir (flow path) (14) is formed in a part of the horn (82). This droplet jetting unit (2) is fixed to the wall surface of the particle forming part (3) (drying means) by a fixing part (flange part) (83) formed integrally with the horn (82) of the horn type vibrator (80). From the viewpoint of preventing vibration loss, which is preferably performed, an elastic body (not shown) may be used for fixing.

  In the example shown in FIG. 4B, as the vibration means (90 (13)), the piezoelectric bodies (91A, 91B) and the horns (92A, 92B) as the vibration generating portions are mechanically firmly fixed with bolts. A storage part (flow path 14) is formed in a horn (92A) using a bolted Langevin type vibrator (90) that is configured. Depending on the frequency condition, the element may be large, and as shown in the drawing, the fluid introduction / discharge path and the reservoir can be processed in a part of the vibrator, and a metal thin film having a plurality of thin films can be attached.

  Although FIG. 1 shows an example in which only one droplet ejecting unit 2 is attached to the particle forming unit (3), a plurality of droplet ejecting units (2) are connected to the particle forming unit (3). (Drying tower) Parallel to the upper part is preferable from the viewpoint of productivity improvement, and the number thereof 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 configuration. The toner composition liquid (10) may be configured to be supplied in a self-contained manner along with droplet formation, or may be configured to supply the liquid supplementarily using the pump (9) during operation of the apparatus. It can also be.

Another example of the droplet ejecting unit will be described with reference to FIG. FIG. 5 is a schematic cross-sectional explanatory view of the liquid droplet ejecting unit.
In the liquid droplet ejecting unit (2), similarly to the above-described example, the horn-type vibrator is surrounded by the vibration generating means (13) and the toner composition liquid (10) is surrounded by the vibration generating means (13). A flow path member (15) to be supplied is disposed, and a reservoir (14) is formed in a portion of the horn (22) of the vibration generating means (13) facing the thin film (12). Further, an air flow path forming member (36) is formed around the flow path member (15) to form an air flow path (37) through which an air flow (35) flows with a predetermined interval. In addition, in order to simplify illustration, although the nozzle (11) of the thin film (12) is shown as one piece, as described above, a plurality of nozzles are provided.
Also, as shown in FIG. 6, from the viewpoint of controllability, a plurality of, for example, 100 to 1,000 droplet ejection units (2) are arranged side by side on the top of the drying tower constituting the particle forming unit (3). To do. Thereby, productivity can be further improved.

(Annular mechanical vibration means)
FIG. 7 shows the apparatus shown in FIG. 1 in which the droplet ejecting unit is replaced with a ring type.
The ring type droplet ejecting unit (2) will be described with reference to FIGS. 8 is a cross-sectional explanatory view of the liquid droplet ejecting unit 2, FIG. 9 is a main surface bottom explanatory view of FIG. 8 viewed from the lower side, and FIG. 10 is a schematic cross-sectional explanatory view of droplet forming means.
The liquid droplet ejecting unit (2) supplies at least the toner composition liquid (10) into liquid droplet forming means (16) and supplies the toner composition liquid (10) to the liquid droplet forming means (16). And a flow path member (15) in which a reservoir (liquid flow path) (14) is formed.

  The droplet forming means (16) includes a thin film (12) in which a plurality of nozzles (discharge ports) (11) are formed, and an annular vibration generating means (electromechanical conversion means) that vibrates the thin film (12) ( 17). 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 shown by hatching in FIG. 10). The vibration generating means (17) is arranged around the area where the nozzle is provided in the deformable area (16A) of the thin film (12) (area not fixed to the flow path member (15)). As shown in FIG. 8, a drive voltage (drive signal) having a required frequency is applied to the vibration generating means (17) from the drive circuit (drive signal generating source) (23) through the lead wire (24). For example, bending vibration is generated.

  The droplet forming means (16) includes a thin film having a plurality of nozzles (11) facing the storage section (14) (an annular vibration generating means 17 is provided around a region in which the nozzles in the deformable region 16A of 12 are provided. As a result, the displacement of the thin film (12) is relatively less than that of the structure in which the vibration generating means (17A) holds the periphery of the thin film (12) as in the comparative example structure shown in FIG. A plurality of nozzles (11) can be arranged in a region of a relatively large area (φ1 mm or more) where the amount increases and this large amount of displacement can be obtained, and more droplets than the plurality of nozzles (11) at a time. Can be stably formed and released.

  FIG. 7 shows an example in which one droplet ejecting unit (2) is arranged, but preferably, as shown in FIG. 12, a plurality of, for example, 100 to 1,000 from the viewpoint of controllability. Individual droplet ejecting units (2) (only four are shown in FIG. 12) are arranged side by side on the top surface portion (3A) of the particle forming unit (3), and each droplet ejecting unit (2) has a pipe (8A). ) Through the raw material container (7) (common liquid reservoir) to supply the toner composition liquid (10). As a result, more droplets can be discharged at a time, and the production efficiency can be improved.

(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 vibration generated by the vibrating means (13), which is a mechanical vibrating means, on the thin film (12) having the plurality of nozzles (11) facing the storage section (14). Propagating and periodically vibrating the thin film (12), disposing a plurality of nozzles (11) in a relatively large area (φ1 mm or more), and periodically dropping droplets from the plurality of nozzles (11). , Can be stably formed and released.

When the peripheral portion (12A) of the simple circular membrane (12) as shown in FIG. 13 is fixed, the periphery of the basic vibration becomes a node, and as shown in FIG. 14, the displacement (ΔL) occurs at the center (O) of the thin film. Becomes the maximum (ΔLmax) cross-sectional shape, and periodically vibrates in the vibration direction.
Further, it is known that higher order modes as shown in FIGS. 15 and 16 exist.
These modes have one or more concentric nodes in a circular membrane, and are substantially axisymmetric deformation shapes. In addition, as shown in FIG. 17, the central portion has a convex shape (12c), so that the traveling direction of the liquid droplet can be controlled and the vibration amplitude can be adjusted.

Due to the vibration of the circular thin film, a sound pressure (P _ac ) proportional to the vibration speed (V _m ) of the film is generated in the liquid in the vicinity of the nozzles provided in the circular film. It is known that the sound pressure is generated as a reaction of the radiation impedance (Z _r ) of the medium (toner composition liquid), and the sound pressure is a product of the radiation impedance and the membrane vibration velocity (V _m ), which is expressed by the following formula (1). It is expressed using the following equation.
P _ac (r, t) = Z _r · V _m (r, t) Equation (1)

Since the vibration velocity (V _m ) of the film periodically varies with time, it is a function of time (t), and various periodic variations such as a sine waveform and a rectangular waveform can be formed.
Further, as described above, the vibration displacement in the vibration direction is different in each part of the film, and (V _m ) is also a function of the position coordinates on the film. The vibration mode of the film used in the present invention is an axial object as described above. Therefore, it is substantially a function of the radius (r) coordinate.

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

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

  Here, the diameter of the formed droplet tends to increase as the vibration displacement in the vicinity of the nozzle of the film increases. When the vibration displacement is small, a droplet is formed or does not become a droplet. In order to reduce such a variation in droplet size at each nozzle site, it is necessary to define the nozzle arrangement at an optimum position of the membrane vibration displacement.

In the present invention, as will be described with reference to FIGS. 14 to 16, the ratio of the maximum value (ΔLmax) to the minimum value (ΔLmin) of the vibration direction displacement (ΔL) of the film in the vicinity of the nozzle generated by the mechanical vibration means ( By disposing the nozzle at a site where R (= ΔLmax / ΔLmin)) is 2.0 or less, the variation in the droplet size described above is applied to a region necessary as a toner fine particle capable of providing a high-quality image. I found that I could keep it.
The conditions of the toner composition liquid were changed, and since the satellite generation start region was the same in the region of the viscosity of 20 mPa · s or less and the surface tension of 20 to 75 mN / m, the displacement amount of the sound pressure was 500 kPa or less. More preferably, it is 100 kPa or less.

(Thin film with multiple nozzles)
As described above, the thin film having the nozzle is a member that discharges a solution or dispersion of the toner composition into droplets.
The material of the thin film (12) and the shape of the nozzle (11) are the gist of the present invention and will be described separately.

(Liquid resonance method)
An example of a liquid resonance type toner manufacturing apparatus is shown in FIG. 18, and an example of a droplet ejection unit is shown in FIG. Its basic configuration is almost the same as the mechanical longitudinal vibration method, but the mechanical longitudinal vibration method oscillates a thin film with a nozzle by means of vibration generation to form droplets, whereas in the liquid resonance method The difference is that the droplets are not formed by the vibration of the thin film having the nozzles but by the resonance of the liquid.

  Therefore, the strength of the thin film is increased to the extent that it does not vibrate. As the material, silicon, silicon oxide, or the like is used, and it is desirable to use a silicon substrate, particularly an SOI (Silicon on Insulator) substrate in terms of nozzle formation. The nozzle shape is the gist of the present invention and will be described separately. FIG. 19B is a schematic cross-sectional explanatory view of the droplet ejecting unit (2), FIG. 19A is an assembly view for explaining in more detail, and FIG. 19C is FIG. 19A. It is explanatory drawing of droplet formation by the droplet ejection unit shown to (b).

The droplet jet unit (2) includes a thin film (12) having a plurality of nozzles (discharge ports) (11), a vibrating means (13), and between the thin film (12) and the vibrating means (13). And a storage portion constituting member (15) for forming a storage portion (liquid flow path) (14) for supplying a toner composition liquid (10) containing at least a resin, a colorant, and a specific phenol-based resin. . A configuration in which the position is fixed between the vibration means and the reservoir wall by a vibration separating member (26) so as not to transmit vibration is desirable. ) May be directly fixed to the wall via The toner composition liquid (10) is supplied to the liquid storage section (14) through a pipe (18) used for liquid supply and liquid circulation.
As the vibration means (13) and the vibration amplification means (22), those described in the description of the membrane vibration system using the mechanical longitudinal vibration means can be used.

The members constituting the partition of the liquid storage part are made of a common material such as metal, ceramics, and plastic that does not dissolve in the spray liquid and does not cause modification of the spray liquid.
The liquid storage part (14) is divided into a plurality of liquid storage areas (29) by a plurality of partition walls. By dividing the partition wall in this way, the vibration pressure distribution in the liquid chamber becomes uniform in the drive of several tens of kHz, so that uniform discharge can be performed and the effect of increasing the resonance frequency can be expected.

Next, the mechanism of droplet formation by the droplet ejecting unit (2) as the droplet forming means will be described with reference to FIG. The vibration generated on the vibration surface (13a) by the vibration means is transmitted to the liquid in the reservoir, and the liquid in the reservoir causes a liquid resonance phenomenon. In a plurality of nozzles provided in the thin film (12), the liquid is discharged to the gas side in a state of being uniformly pressurized. By the action of resonance of the entire liquid, the liquid is uniformly ejected from all the nozzles, and further, the dispersed fine particles contained in the toner composition liquid are suspended in the storage part without being deposited on the storage part surface of the thin film. Therefore, the liquid can be stably ejected stably.
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 does n’t matter.

The vibration generated by the vibration means is transmitted to the liquid in the reservoir, and the liquid in the reservoir causes a liquid resonance phenomenon. In a plurality of nozzles provided in the thin film, the liquid is discharged to the gas side in a state of being uniformly pressurized. By the action of resonance of the entire liquid, the liquid is uniformly ejected from all the nozzles, and further, the dispersed fine particles contained in the toner composition liquid are suspended in the storage part without being deposited on the storage part surface of the thin film. Therefore, the liquid can be stably ejected stably.
When a thin film provided with a plurality of nozzles is vibrated mechanically, there is an advantage that nozzle clogging is difficult to occur. However, if the thin film area is large, uniform vibrations may not be obtained and the droplet size distribution may be obtained.
On the other hand, in the liquid resonance method, a substantially equal vibration pressure is applied to each nozzle, so that droplets with a narrow particle size distribution are easily obtained even with a wide thin film.

(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 all injection methods, a representative explanation will be given with an annular mechanical vibration means.
FIG. 21 shows an embodiment of the toner production apparatus of the present invention. In the present embodiment, the discharge unit has a shroud and has a transport airflow around the toner flow, and the transport airflow increases the group speed of the discharged toner group, and the initial discharge speed. If the value is high, decrease it. As a result, it is possible to efficiently prevent coalescence caused by colliding with each other during the drying process until the discharged toner is solidified, and the resulting toner group has very little coalescence, improving productivity including yield. Can be made.
Also in this embodiment, a droplet ejecting unit is provided in the upper part of the apparatus, and a chamber portion (18) for ejecting and drying droplets, and a guide tube for sending toner obtained in the chamber portion (18) to the toner storage portion. And is configured.

As described above, in the droplet jetting unit (2), a 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 is dropletized and released. A droplet forming means (11) to be formed and a container (13) in which a reservoir (12) for supplying the toner composition liquid (10) to the droplet forming means (11) is formed.
The droplet forming means (11) is the same as the membrane vibration method. A liquid supply hole (20) and a discharge hole (21) for supplying the toner composition liquid (10) to the reservoir (12) are connected to the toner container (13), respectively. The droplet (23) is discharged from the nozzle (15) by the droplet forming means (11). The outer side of the container (13) has an opening (30a) having an opening facing the nozzle (15), and flows along the direction in which the toner composition liquid (10) is discharged from the nozzle (15). A shroud portion (30) that forms an air flow path for the gas carrying the droplet (23) is attached. The shroud portion (30) is composed of a double hook-like wall (30b, 30c) having an open nozzle portion, which are coupled to each other by a lid portion (31). A gas blowing pipe (91) is fitted on the side surface of the shroud portion (30). Of the double walls, the inner wall (30c) ends near the lower end of the container (13). Out of the double walls, the outer wall (30b) extends to the lower part of the nozzle (15) and ends with a lower circular opening (30a) facing the nozzle (15). The diameter of the opening (30a) is (D), and the inner wall of the bottom (30d) of the outer wall (30b) and the lower end of the nozzle (15) maintain a clearance (G). Since (G) is smaller in size than (D), (G) is the main factor that determines the flow velocity of the carrier airflow.

The stream (23a) containing droplets (23) is then directed into a large volume shroud section (30) with a shroud section (30) and container (13) attached to the top. In the chamber portion (18), a downward air flow (96) shown in FIG. 20 is formed by a chamber portion outlet (93) described later. The air flow (96) is a uniform laminar flow, and the flow (23a) including the droplets (23) is 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). Sent to the guide tube (92). The guide tube (92) is connected to a cyclone (not shown), collected while being dried, and fed to the toner reservoir (5). On the upper side surface of the shroud portion (30), a gas blowing pipe (91) is fitted in an airtight manner.
A pressure gauge (PG1) is inserted on the opposite side surface of the chamber portion (18). Moreover, the pressure gauge (PG2) is also inserted in the side surface of the blowing pipe of the shroud part (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 and driven at 100 kHz, for example, by a driving device (not shown) while the toner composition liquid (10) is accommodated in the container (13) with an appropriate pressure. Vibration is propagated to the discharge plate (16), and the toner composition liquid (10) is discharged from the plurality of nozzles (15) at a discharge frequency that matches the vibration drive frequency. The released initial velocity (v0) tends to decelerate due to resistance due to the viscosity of the gas in the shroud portion (30).
On the other hand, in the shroud part (30), gas is blown out by the blowing pipe (91) to form a carrier airflow (95) through the shroud part (30), and from the opening (30a) to the chamber part (18 ). The air flow (95) formed is uniform and downward in the circumferential direction, and the lower end of the wall (30b) of the shroud (30) is rounded so that the air flow smoothly changes sideways, (15) It merges below and is further discharged from the opening (30a). If the airflow at this time is turbulent, the droplets (23) are likely to coalesce with each other.

  The discharged droplet (23) rides on the carrier airflow (95) and is released from the opening (30a) into the chamber portion (18) where it rides on the laminar airflow (96) and coalesces. Without being sent to the toner collecting section (4).

In this example, the flow velocity (v1) of the carrier airflow (95) is larger than the initial velocity (v0) of the droplet (23), and the droplet (23) is accelerated and then sent on the carrier airflow (95). Is shown. (V1) may be higher than the free fall speed, and may be lower than the initial speed (v0). An air flow (96) having a flow velocity (v2) faster than (v1) is formed in the chamber. The larger the flow velocity (v2) of the air flow (96), the more preferable in terms of preventing coalescence. The air flow (96) in the chamber part (18) is blown out of the gas from the blow-out pipe (93) to form a uniform and uniform air flow in the circumferential direction as in the shroud part (30). Laminar flow is preferred in the chamber part (18). Since the flow (23a (the flow rate is v1)) of the droplet including the droplet (23) immediately after being discharged into the chamber portion (18) does not cause turbulent flow and flows down smoothly, the chamber portion (18 It is preferable that [v2 ≧ v1] with respect to the flow velocity (v2) of the air flow (96) in ().
The flow rates of the carrier airflow (95) in the shroud part (30) and the airflow (96) in the chamber part (18) 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 (23) and the liquid flows backward.

As described above, since it is [D> G] that determines the flow velocity of the conveying airflow (95) of the shroud portion (30), (G), that is, the wall (30b) and the head (2a). And clearance.
The above is the air flow (95) in the shroud portion (30) and the air flow (96) in the chamber portion (18), and the blowing pipe (91) and the chamber portion outlet (93) in the upper portion of the chamber portion (18). However, the air flow may be formed by suction from a pipe (92) provided at the lower portion of the chamber (18).
The cross section of the opening (30a) of the wall (30b) of the shroud (30) has a diameter that increases along the gas discharge direction, that is, a taper (30e) in the direction in which the outer diameter increases. It is preferable. Thus, by forming the taper (30e) in the opening (30a), when the droplet (23) passes through the opening (30a), the droplet (23) becomes a wall surface of the opening (30a). It is possible to avoid contact with and adhere to.
In this embodiment, nitrogen gas is used for the shroud part (30) and the chamber part (18) as the gas to be blown out. However, it may be a gas, and may be air or other gas. In FIG. 21, the shroud portion (30) is configured with a double pot-shaped wall, but the inner (30c) wall may be shared with the outer peripheral wall constituting the flow path member (13). Further, the production efficiency of the toner can be further increased by arranging a plurality of droplet ejecting units (2) and a shroud portion (30) in a single chamber portion (18).
The discharged droplets (23) are removed by the solvent while passing through the particle forming unit (3), and are collected in the toner storage unit (5) in a solid form.

(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.

<Nozzle shape>
As described above, there are various droplet discharge means that are applied in the present invention. In the droplet discharge means as described above, if the nozzle and the thin film do not deal with the bleeding of the toner liquid, the toner liquid oozes in an unexpected state during the ejection, and as a result, the entire nozzle covers the toner liquid, It has become clear that it falls into a situation that prevents injection. Even if the toner liquid does not interfere with the ejection, the toner liquid will eventually dry, and the dry matter will cause the nozzle to become clogged or change in shape, causing the ejection to drop or stop the ejection.
For this reason, it is necessary to apply measures to prevent the nozzle from seeping out.
Since the nozzle plate is subjected to a soot treatment, and the nozzle surface is a flat discharge surface as in the prior art, the toner surface can be exuded by changing the discharge surface to a convex shape. Can be reduced.
The nozzle shape of the present invention is not particularly limited. The shape of the nozzle which the convex process is given to the injection outlet side may be sufficient.
The nozzle material of the present invention 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 them, silicon, stainless steel, or nickel is particularly desirable in order to ensure processing accuracy and filter strength.

  The actual size of the nozzle of the present invention is determined by the intended droplet size. The thin film (12) described in FIGS. 1, 2, 4, 5, 6, 7, 8, 9, 10, 11, and 13 is formed of a metal plate having a thickness of 5 to 500 μm, and the opening diameter of the nozzle (11). Is preferably 3 to 30 μm from the viewpoint of generating fine droplets having a very uniform particle diameter when the droplets of the toner composition liquid (10) are ejected from the nozzle (11). The opening diameter of the nozzle (11) means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse. The number of the plurality of nozzles (11) is preferably 2 to 3000.

  When the film thickness is very large with respect to the opening diameter of the nozzle, the discharge performance is improved by making the cross-sectional shape of the nozzle two-stage. Next, a method of making the cross-sectional shape of the nozzle into a two-stage type will be described with reference to FIG. Resist (111) is coated on both sides of the silicon substrate (11a), covered with a photomask on which a nozzle pattern is formed, and exposed to ultraviolet rays to form resist (111) as a nozzle pattern (11b). Anisotropic dry etching using ICP discharge is performed from the support layer (112) surface side to form a first nozzle hole (115), and the same anisotropic dry etching is performed on the active layer (114) surface side. The second nozzle (116) is formed (11c), and finally the dielectric layer (113) is removed with a hydrofluoric acid-based etchant to obtain a two-stage through hole (11d). Most preferable for uniform formation. Although not shown, the nozzle can be formed by a similar method even when the silicon substrate is not an SOI substrate but a single layer silicon substrate. In that case, the depth of the first nozzle hole and the depth of the second nozzle hole can be adjusted by adjusting the etching time.

<Cleaning the nozzle>
As described above, when the toner composition liquid is ejected, the toner composition liquid adheres to the surface of the nozzle plate around the nozzle due to exudation, etc. In addition, it has been experimentally observed that the number of nozzles in which such a phenomenon occurs increases. When such a situation occurs, the ejection of droplets is disturbed, leading to a deterioration in the particle size distribution of the collected toner particles. Further, when such a state continues, one of the nozzles is blocked and the ejection is stopped. Therefore, it is necessary to periodically clean the nozzle surface.

  The present invention proposes a non-contact nozzle cleaning method using a pure solvent. By cleaning the nozzles in a non-contact manner, the deformation of the nozzle shape due to the reduction or deterioration of the surface treatment effect can be minimized, and the above-described problems caused by wiping can be solved.

  During nozzle cleaning, the drive signal of the ejection head that forms toner droplets is stopped, and the head is removed from the solvent removal unit. A separate droplet ejection head is used for cleaning. The cleaning liquid droplet ejecting head is placed toward the nozzle plate of the toner composition liquid ejecting head, and using a high frequency and a plurality of nozzles, droplets of pure solvent are directed toward the nozzle plate of the toner liquid ejecting head. Discharge. Although the nozzle is cleaned with the pure solvent, using the high frequency has the same effect as the ultrasonic cleaning, the cleaning effect is high, and the cleaning time is not so long.

  When cleaning the nozzle, the pressure of the toner composition liquid needs to be kept at the same value as the pressure of the surrounding gas or slightly higher than that. However, when the pressure is slightly increased, it is necessary to reduce the pressure to the same value as the pressure of the surrounding gas before the cleaning is completed so that the toner composition liquid does not exude. This pressure condition is to prevent dirt from entering the nozzle and at the same time to prevent the cleaning solvent from entering the nozzle and diluting the toner composition liquid or changing its composition.

The solvent used for cleaning needs to be a solvent that can easily dissolve the toner composition.
This is to improve the cleaning effect. Further, it is necessary that the solvent does not cause a great change in the toner composition liquid, such as a chemical reaction with the toner composition liquid. The same solvent used in the toner composition liquid is preferably used for nozzle cleaning, but is not limited thereto. Another solvent that easily volatilizes can be used for cleaning as long as the above-described conditions are satisfied. In the examples described at the back of the present invention, the solvent used in the toner composition liquid is ethyl acetate, which is used for cleaning. Acetone).

  In the present invention, the cleaning effect can be further improved by raising the temperature of the solvent used for cleaning. The higher the temperature, the higher the cleaning effect, but when the temperature is higher than the boiling point of the solvent used in the toner composition liquid, heat is transferred into the toner composition liquid discharge head, and the solvent in the toner composition liquid boils. It may happen that air bubbles do not resume after cleaning. In addition, if the temperature of the cleaning solvent is higher than the melting point of wax or the like dispersed in the toner composition liquid, the dispersed particles coalesce and the characteristics of the toner composition liquid change, which adversely affects subsequent ejection. There is a fear. Therefore, it is necessary to be within a temperature range that does not adversely affect the toner composition liquid in the toner composition liquid discharge head.

  As for the liquid to be discharged, the speed immediately after the discharge is the fastest and the speed gradually decreases. Therefore, in order to improve the cleaning effect, it is necessary to bring the cleaning head as close as possible to the nozzle plate of the toner liquid jet head. The cleaning head is placed in a direction opposite to the toner liquid ejecting head. If the cleaning head is directed in the direction opposite to the liquid ejection direction of the toner liquid ejecting head, the cleaning solvent is placed in the nozzle. The possibility of getting into is high. Therefore, it is necessary to tilt. The larger the inclination angle θ, the lower the possibility that the cleaning liquid will enter the nozzle. Therefore, it is necessary to satisfy θ> 0 °, and preferably θ> 45 °.

  Note that θ = 0 is a state in which the ejection direction of the cleaning head and the ejection direction of the toner liquid ejection head are not slightly deviated and are completely opposite to each other. When the ejection direction of the cleaning head is parallel to the nozzle plate surface of the toner liquid ejection head, θ = 90 °, which is the maximum value of θ.

  Since the cleaning ejection head ejects droplets from a plurality of nozzles at a high frequency, the operation principle is the same as that of the toner liquid ejection head. Therefore, the operation and illustration are the same as those of the toner liquid ejecting head. There are various types of toner liquid jet heads described above. The toner liquid ejecting head and the nozzle cleaning ejecting head need not all be the same type.

  After cleaning, the droplets that are ejected early may have a lower solid content, so the toner particles that are formed may be smaller than the target particle size, so do not collect them or use another container It is necessary to confirm the particle size distribution.

(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 thus a toner having a monodispersed particle size distribution can be obtained.
Specifically, the particle size distribution (weight average particle diameter / number average particle diameter) of the toner is preferably in the range of 1.00 to 1.15. More preferably, it is 1.00 to 1.05. Moreover, as a weight average particle diameter, it is preferable to exist in the range of 1-20 micrometers, More preferably, it is 3-10 micrometers.

Next, the toner material (toner composition liquid) that can be used in the present invention will be described. First, a toner composition liquid in which a toner composition is dispersed and dissolved in a solvent as described above will be described.
As the toner material, the same material as that of a conventional electrophotographic toner can be used. That is, a toner binder such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin is dissolved in various organic solvents, a colorant is dispersed, and a release agent is dispersed or dissolved. The target toner particles can be produced by drying and solidifying into fine droplets by the toner production method. 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, a styrene monomer, an acrylic monomer, a methacrylic monomer, etc. Vinyl polymers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins , Coumarone indene resin, polycarbonate resin, petroleum resin, and the like.
Examples of the styrene monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-amyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, Examples thereof include styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof.

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

  The following (1)-(18) is mentioned as an example of the other monomer which forms the said vinyl polymer or a copolymer. (1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8), vinyl naphthalenes; (9) acrylonitrile, Such as methacrylonitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic anhydride and alkenyl succinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid, etc. (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; 16) Monomers having a carboxyl group such as anhydrides of the α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof; ) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1 -Hydroxy-1-methylhexyl) monomers having a hydroxy group such as styrene.

In the toner according to the present invention, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic vinyl vinyl compounds such as divinylbenzene and divinylnaphthalene. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6. And xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of these compounds with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.
Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).
Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds in place of methacrylate, triallyl cyanide. Examples include nurate and triallyl trimellitate.

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

Examples of the polymerization initiator used in the production of the vinyl polymer or copolymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1 , 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2 ′ , 4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone Ketone peroxides such as oxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di -Tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexyl Sulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexarate, tert-butyl peroxylaurate, tert-butyl-oxybenzoate, tert-butyl Peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-tert-butyl Kisa Hydro terephthalate to Rupaokishi, tert- butylperoxy azelate, and the like.
When the binder resin is a styrene-acrylic resin, the molecular weight distribution by GPC soluble in the resin component tetrahydrofuran (THF) has at least one peak in the region of molecular weight 3,000 to 50,000 (in terms of number average molecular weight). A resin which is present and has at least one peak in a region having a molecular weight of 100,000 or more is preferable in terms of fixing property, offset property and storage property. Further, as the THF soluble component, a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50 to 90% is preferable, and a binder resin having a main peak in a molecular weight region of 5,000 to 30,000 is more preferable. A binder resin having a main peak in the region of 5,000 to 20,000 is most preferable.
The acid value when the binder resin is a vinyl polymer such as styrene-acrylic resin is preferably 0.1 mgKOH / g to 100 mgKOH / g, and preferably 0.1 mgKOH / g to 70 mgKOH / g. More preferably, it is most preferably 0.1 mgKOH / g to 50 mgKOH / g.

The following are mentioned as a monomer which comprises a polyester-type polymer.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned.
In order to crosslink the polyester resin, it is preferable to use a trivalent or higher alcohol together.
Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, such as dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene , Etc.

  Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And unsaturated dibasic acid anhydrides. Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like.

When the binder resin is a polyester resin, the toner has fixability and offset resistance because at least one peak exists in the molecular weight range of 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component. In addition, as a THF soluble component, a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100% is preferable, and at least one peak exists in a region having a molecular weight of 5,000 to 20,000. More preferable is a binder resin.
When the binder resin is a polyester resin, the acid value is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / g. Most preferably, it is g-50 mgKOH / g.
In the present invention, the molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.

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

In the present invention, the acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation conforms to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. 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 a mixed solution 150 (ml) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The amount of use of the KOH solution at this time is S (ml), a blank is measured at the same time, the amount of use of the KOH solution at this time is B (ml), and the following formula is used. 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 mixtures thereof are used.
Specific examples of magnetic materials include Fe3O4, γ-Fe2O3, ZnFe2O4, Y3Fe5O12, CdFe2O4, Gd3Fe5O12, CuFe2O4, PbFe12O, NiFe2O4, NdFe2O, BaFe12O19, MgFe2O4, LaCoO powder, LaFeO3 powder, Can be mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of triiron tetroxide and γ-iron trioxide are particularly preferable.
Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used. Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, And gallium. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may be present on the surface as an oxide or hydroxide. Is preferably contained as an oxide.
The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grain 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, respectively.
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 with respect to the toner.

The colorant used in the toner according to the present invention can also be used as a master batch combined with a resin. As the binder resin kneaded together with the production of the master batch or the master batch, in addition to the above-mentioned modified and unmodified polyester resins, for example, polystyrene, poly p-chlorostyrene, polyvinyltoluene and other styrene and its substitutes Polymer: Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate Copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene -Α-Chloromethyl methacrylate Polymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, Styrene copolymers such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl Examples include butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. There is also a method of removing 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 dispersant is preferably blended in the toner at a ratio of 0.1 to 10% by mass with respect to the colorant. When the blending ratio is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it is more than 10% by mass, the chargeability under high humidity may be deteriorated.
The weight average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene conversion weight in gel permeation chromatography, preferably 500 to 100,000, and more preferably 3000 to 100,000 from the viewpoint of pigment dispersibility. In particular, 5000 to 50000 is preferable, and 5000 to 30000 is most preferable. When the molecular weight is less than 500, the polarity becomes high and the dispersibility of the colorant may be lowered. When the molecular weight exceeds 100,000, the affinity with the solvent is increased and the dispersibility of the colorant is lowered. There is.
The addition amount of the dispersant is preferably 1 to 200 parts by mass, more preferably 5 to 80 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 1 part by mass, the dispersibility may be lowered, and if it exceeds 200 parts by mass, the chargeability may be lowered.

<Wax>
In the present invention, a wax can be contained together with the binder resin and the colorant.
The wax is not particularly limited and can be appropriately selected from those usually used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sazol wax, etc. Of aliphatic hydrocarbon waxes, oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof, plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax, beeswax, Waxes mainly composed of animal waxes such as lanolin and whale wax, mineral waxes such as ozokerite, ceresin, and petrolatum, and fatty acid esters such as montanic acid ester wax and castor wax. Deoxidized carnauba wax and other fatty acid esters that have been partially or wholly deoxidized are included.
Examples of the wax further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group, prandidic acid, eleostearic acid, and valinal acid. Unsaturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnupyl alcohol, seryl alcohol, mesyl alcohol, or long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acids Fatty acid amides such as amide and lauric acid amide, methylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide and other saturated fatty acid bisamides, ethylene bis oleic acid amide, hexamethylene bis Unsaturated fatty acid amides such as oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasinic acid amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Grafted onto aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate, and aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid. Examples thereof include waxes, partial ester compounds of polyhydric alcohols such as behenic acid monoglycerides, and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.
More preferable examples include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, and polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure. Polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fitzscher Tropsch wax, Jintole method, hydrocol method, age method Synthetic hydrocarbon waxes synthesized by the above, synthetic waxes having a compound having one carbon atom, hydrocarbon waxes having functional groups such as hydroxyl groups or carboxyl groups, hydrocarbon waxes and hydrocarbons having functional groups Mixture of system wax, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.
In addition, these waxes have a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.
The melting point of the wax is preferably 70 to 140 ° C., and more preferably 70 to 120 ° C., in order to balance the fixability and the offset resistance. If it is less than 70 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 melting point difference of 10 ° C. to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.
When selecting two types of wax, in the case of a wax having the same structure, a wax having a relatively low melting point exhibits a plasticizing action, and a wax having a high melting point exhibits a releasing action. At this time, when the difference in melting point is 10 to 100 ° C., functional separation is effectively expressed. If it is less than 10 ° C., the function separation effect may be difficult to appear, and if it exceeds 100 ° C., the function may not be emphasized by interaction. At this time, the melting point of at least one of the waxes is preferably 70 to 120 ° C, and more preferably 70 to 100 ° C, because the function separation effect tends to be easily exhibited.
As for the wax, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exhibit a plastic action, and those having a more linear structure or functional group Nonpolar or non-denatured straight materials that do not have a mold exhibit a releasing action. Preferred combinations include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene, polyolefins and graft modified polyolefins, alcohol waxes, fatty acid waxes or ester waxes. And hydrocarbon wax combinations, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax combination, Fischer-Tropsch wax and polyolefin wax combination, paraffin wax and microcrystal wax combination, Carnauba Wax, Can Delila wax, rice wax or montan wax and hydrocarbon wax Combinations thereof.
In any case, since it becomes easy to balance the toner storage stability and the fixing property, the peak 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 raising and lowering the temperature once and taking a previous history.

<Fluidity improver>
A fluidity improver may be added to the toner according to the present invention. The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface.
Examples of the fluidity improver include, for example, carbon black, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder unoxidized titanium, Fine powder non-alumina, treated silica obtained by subjecting them to surface treatment with a silane coupling agent, titanium coupling agent or silicone oil, treated titanium oxide, treated alumina, and the like can be mentioned. Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.
The particle size of the fluidity improver is preferably 0.001 to 2 μm, and 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, dimethylvinylchlorosilane, Divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α -Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane , Triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, Examples include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to Si. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The number average particle diameter of the fluidity improver is preferably 5 to 100 nm, more preferably 5 to 50 nm.
The specific surface area by measuring nitrogen adsorption by the BET method, preferably at least ^{30m 2 / g, 60~400m 2 /} g is more preferable.
The surface-treated fine powder, 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 an electrostatic latent image carrier / carrier, improvement of cleaning property, adjustment of thermal characteristics / electrical characteristics / physical characteristics, resistance adjustment, softening point adjustment, fixing rate For the purpose of improvement, various metal soaps, fluorosurfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, and inorganic such as titanium oxide, aluminum oxide, alumina A fine powder or the like can be added as necessary. These inorganic fine powders may be hydrophobized as necessary. In addition, lubricants such as polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, strontium titanate, anti-caking agents, white particles and black particles having opposite polarity to the toner particles, Can also be used in small amounts as a developability improver.
These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control and the like. It is also preferable to treat with a treating agent or various treating agents.

In preparing the developer, inorganic fine particles such as the hydrophobic silica fine powder mentioned above may be added and mixed in order to improve the fluidity, storage stability, developability and transferability of the developer. For mixing external additives, a general powder mixer can be appropriately selected and used. However, it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually, and the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. The load may then be given a relatively weak load and vice versa.
Examples of the mixer that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like.
A method for further adjusting the shape of the obtained toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner material composed of a binder resin and a colorant is melt-kneaded and then finely pulverized. Using a hybridizer, mechano-fusion, etc., the resulting material is mechanically adjusted, or the so-called spray-drying method is used to dissolve and disperse the toner material in a solvent in which the toner binder is soluble, and then using a spray-drying device. Examples thereof include a method of removing a solvent to obtain a spherical toner and a method of forming a spherical toner by heating in an aqueous medium.
As the external additive, inorganic fine particles can be preferably used.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like.
The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, more preferably 5 mμ to 500 mμ.
The specific surface area according to the BET method is preferably 20 to 500 m ² / g.
The proportion of the inorganic fine particles used is preferably 0.01 to 5% by mass of the toner, and more preferably 0.01 to 2.0% by mass.
In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation system such as silicone, benzoguanamine and nylon, thermosetting resin And polymer particles.
Such an external additive can be made hydrophobic by the surface treatment agent and prevent deterioration of the external additive itself even under high humidity.
Examples of the surface treatment agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, a modified silicone oil, Etc. are preferable.
The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and more preferably 5 mμ to 500 mμ. Moreover, as a specific surface area by BET method, it is preferable that it is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by weight of the toner, and more preferably 0.01 to 2.0% by weight.
Examples of the cleaning property improver for removing the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymethyl methacrylate. There may be mentioned polymer fine particles produced by soap-free emulsion polymerization such as fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a 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.

-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, 30 parts by weight of the wax dispersion, 840 parts by weight of ethyl acetate, and stirring for 10 minutes using a mixer having stirring blades, Evenly dispersed. Pigments and wax particles did not aggregate due to shock due to solvent dilution.

-Preparation of toner-
The obtained toner composition liquid (500 ml) was supplied to the nozzle (11) of the droplet forming means (16) of the toner production apparatus shown in FIG. The thin film used (16 (nozzle plate)) is a nickel plate having an outer diameter of 15.0 mm and a thickness of 50 μm shown in the nozzle specification 1 of Table 1. A perfectly circular discharge hole (nozzle) having a diameter of 10 μm (11) Was produced 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 liquid (toner composition liquid) was prepared, droplets were discharged under the following toner production conditions, and then the toner base particles were produced by drying and solidifying the droplets.

[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
Nozzle vibration frequency: 98 kHz
Nozzle applied voltage sine wave peak value: 10.5V

(Discharge head specifications)
Thin film (nozzle plate) thickness: 50 μm
Nozzle diameter: 10 μm
Nozzle shape: Follows an octopus shape (a shape provided with convex portions) (convex height: 10 μm, convex diameter b: 20 μm)
The toner composition liquid discharge head and the nozzle cleaning head have the same specifications.
The “nozzle frequency” means “frequency of the thin film (16)”. Under this condition, the toner composition liquid was stably discharged without causing nozzle clogging (clogging). The dried and solidified toner particles 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. The weight average particle size (D4) was 5.3 μm, and the number average 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, nonion in 10 ml of water having a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) in 10-3 cm ³ of water. A few drops of a surfactant (preferably Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.) is added, and 5 mg of a measurement sample is further added, and the condition is 20 kHz, 50 W / 10 cm ^{3 with} a UH-50 manufactured by an ultrasonic disperser STM. Dispersion treatment is performed for 5 minutes, and further, dispersion treatment is performed for a total of 5 minutes, and a sample dispersion liquid in which the particle concentration of the measurement sample is 4000 to 8000 pieces / 10 −3 cm ³ (for particles in the equivalent circle diameter range). The particle size distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is measured.
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 the toner production in Example 1 can be stably performed over a long period of time by performing regular one minute maintenance once every 40 minutes.

[Examples 2 to 16]
The results of Examples 2 to 16 evaluated in the same manner as Example 1 using the nozzle specifications shown in Table 1 are shown in Table 2. Note that the same toner liquid and peripheral devices are used.

[Comparative Examples 1-4]
Similarly to the example, the results of Comparative Examples 1 to 4 evaluated in the same manner as in Example 1 using the nozzle specifications shown in Table 1 are also shown in Table 2. Note that the same toner liquid and peripheral devices are used.
Comparative Examples 1 and 2 show the results when the cleaning head is not tilted (θ = 0).
Comparative Examples 3 and 4 show that when the nozzle is cleaned with a solvent that does not easily volatilize, the surface remains painted after cleaning, resulting in unstable ejection.
From the above results, it was shown that high quality toner can be stably produced by using the nozzle cleaning method of the present invention.

(Explanation of evaluation items)
Nozzle surface condition after cleaning: The amount of toner composition adhering to the periphery of the nozzle due to exudation, etc. remaining around the nozzle after cleaning. Expressed as a percentage of nozzles that are still dirty around.
Discharge recovery rate: Ratio of nozzles that discharge normally after cleaning.
Toner average particle size distribution: The particle size distribution of the toner collected in each of Examples and Comparative Examples. In each example, the continuous discharge time is 40 minutes and the cleaning is performed three times, so the total discharge time is 160 minutes.
Cleaning effect evaluation: represents the lowest evaluation of any of the above three items.

＊ノズル周辺にトナーが付着しているノズルの割合

* Percentage of nozzles with toner around them

(About FIGS. 1-17)
DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet jet unit 3 Particle formation part (solvent removal part)
DESCRIPTION OF SYMBOLS 4 Toner collection part 5 Tube 6 Toner collection part 7 Raw material accommodating part 8 Piping 9 Pump 10 Toner composition liquid 11 Nozzle 12 Thin film 13 Vibrating means 13a Vibrating surface 14 Storage part 15 Flow path member 16 Droplet forming means 17 Vibration generating means (Electromechanical conversion means)
18 liquid supply tube 19 bubble discharge tube 20 support member 21 vibration generating means 21A piezoelectric body 22 vibration amplifying means 22A horn 23 drive circuit (drive signal generation source)
24 communication means 31 droplet 35 air flow 36 air flow path forming member 37 air flow path 80 horn type vibrator 81 piezoelectric body 82 horn 83 fixing portion 90 Langevin type vibrator 91 piezoelectric body 92 horn T toner particles (about FIGS. 18 to 20)
DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet jet unit 3 Particle formation part (solvent removal part)
DESCRIPTION OF SYMBOLS 4 Toner collection part 5 Tube 6 Toner storage part 7 Raw material storage part 8 Piping 9 Pump 10 Toner composition liquid 11 Nozzle 12 Thin film 13 Vibration means 13a Vibrating surface 14 Storage part 15 Storage part component 16 Droplet formation means 16A Deformable area 17 Vibration generating means (electromechanical conversion means)
18 liquid supply tube 19 bubble discharge tube 20 support member 21 vibration generating means 21A piezoelectric body 21a, 21b electrode 22 vibration amplifying means 22A horn 23 drive circuit (drive signal generation source)
24 Communication means 26 Vibration separating member 27 Node portion of vibration means having small vibration amplitude 29 Liquid storage area 31 Liquid droplet 35 Air flow 36 Air flow path forming member 37 Air flow path 80 Horn type vibrator 81 Piezoelectric element 82 Horn 83 Fixing part 90 Langevin type vibrator 91 piezoelectric body 92 horn 111 resist 112 support layer 113 dielectric layer 114 active layer 115 first nozzle hole 116 second nozzle hole T toner particles (about FIG. 21)
DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet jet unit 2a Head 3 Chamber area (particle solidification area)
4 Toner Collection Unit 5 Toner Storage Unit 6 Raw Material Storage Unit 7 Liquid Supply Pipe 8 Carrying Airflow 9 Drainage Pipe 10 Toner Composition Liquid (Material Liquid)
11 Droplet Means 12 Reservoir 13 Liquid Chamber (Container)
DESCRIPTION OF SYMBOLS 14 Supply path 15 Nozzle 16 Discharge plate 17 Vibrating means 18 Chamber part 20 Liquid supply hole 21 Discharge hole 23 Droplet 23a Droplet flow 30 Shroud part 30a Opening part 30b Wall 30c Wall 30d Bottom part 30e Taper 31 Lid part 32 Valve 40 Means 42 Arm control device 51 Vibrator 52 Pipe 53 Deaeration hole 54 Ultrasonic liquid chamber 91 Spout pipe 92 Guide pipe 93 Spout 95 Transport airflow 96 Airflow PG1 Pressure gauge PG2 Pressure gauge 100 Pump

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

Claims (4)

Droplet forming means for discharging a toner composition liquid containing a resin and a colorant from a plurality of nozzles to form droplets, and particle formation for solidifying the droplets formed by the droplet forming means to form toner particles And a cleaning liquid discharging means for discharging a liquid for cleaning the nozzle opposite to the nozzle of the droplet forming means , wherein the cleaning liquid discharging means A solvent that is more volatile than the solvent used in the toner composition liquid, or the same solvent as the solvent used in the toner composition liquid is used as a cleaning solvent, and the discharge direction of the cleaning solvent is set to the toner The angle θ with respect to the composition droplet discharge direction satisfies θ> 0 °, and the pressure of the toner composition liquid is the same as that of the surrounding gas at the nozzle outlet when the nozzle is cleaned, or Higher pressure Toner production apparatus, characterized in that kept value. According to claim 1 wherein the cleaning liquid droplet discharge means, wherein said to temperature than the ambient temperature during discharge of the toner composition liquid discharge head is increased, the use of warmed solvent as a solvent for cleaning Toner manufacturing device. A step of forming droplets by a droplet forming unit that discharges a toner composition liquid containing a resin and a colorant from a plurality of nozzles to form droplets; and particles that solidify the formed droplets to form toner particles A cleaning liquid discharging step of discharging a liquid for cleaning the nozzle opposite to the nozzle of the droplet forming means between the execution of the droplet forming step only contains, in the cleaning solution discharge step, using easily volatile or solvent than the solvent used in the toner composition solution, or the same solvent as used in the toner composition liquid as a solvent for cleaning, The cleaning solvent discharge direction has an angle θ with respect to the toner composition droplet discharge direction, and the angle θ satisfies θ> 0 °, and the pressure of the toner composition liquid during nozzle cleaning is Ambient gas at the outlet Method for producing a toner, characterized in that kept the same pressure value or higher pressure value.   4. The warmed solvent is used as a cleaning solvent so that the cleaning droplet discharge means has a temperature higher than an ambient temperature at the time of discharge of the toner composition liquid discharge head. Toner manufacturing method.

Images