JP5446639B2 - Toner production method - Google Patents

Description

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

  Conventionally, the pulverization method has been the only production method for electrophotographic toners used in copiers, printers, fax machines, and composite machines based on the electrophotographic recording method. However, in recent years, a method of forming a toner in an aqueous medium called a polymerization method has been widely adopted and has a tendency to surpass the pulverization method (see, for example, Patent Document 1). The toner produced by the polymerization method is called “polymerized toner” or “chemical toner” in some countries, but the polymerization method includes a production method that does not necessarily involve a polymerization process for convenience. The polymerization methods currently in practical use 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 a toner manufacturing method that replaces the polymerization method, a so-called spray drying method in which the toner composition liquid is formed into droplets in the gas phase without using water and then solidified has been proposed, but there is a problem that the particle size distribution is wide. is there.
As an attempt to make the toner composition liquid droplets in the gas phase and narrow the particle size distribution, a manufacturing method has been proposed in which fine droplets are formed using piezoelectric pulses, which are then dried and solidified to become toners ( Patent Document 2). In addition, a manufacturing method has been proposed in which fine droplets are formed using thermal expansion in a nozzle, and this is dried and solidified into a toner (see Patent Document 3). Furthermore, a manufacturing method has been proposed in which an acoustic lens is used and the same processing as in Patent Document 3 is performed (see Patent Document 4). Further, in a droplet discharge device that discharges droplets from nozzles provided on a nozzle plate, a droplet discharge device in which the nozzle outlet shape is non-axisymmetric (see Patent Document 5), and a discharge port for discharging a liquid material are provided. A liquid droplet ejection head including a first through hole having a second through hole having an injection port for injecting the liquid material and having a protrusion on the surface of the second through hole (see Patent Document 6) Has been proposed.
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.
On the other hand, productivity can be improved by forming microdroplets using high-frequency vibrations. Moreover, productivity can be further improved by discharging with a plurality of nozzles. However, if high-frequency vibration is used, liquid oozes easily from the nozzle, which deteriorates ejection stability and dispersibility of microdroplets. In the case of a plurality of nozzles, it has been found that the liquid oozes more easily and tends to worsen the discharge. In addition, in the case of a plurality of nozzles, the directionality of the ejected fine droplets is poor, coalescence of the droplets occurs, the coarse powder in the dried particles increases, and there is a problem that the single dispersibility is poor. .

  Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide a toner manufacturing method using a nozzle in which bleeding of the toner composition liquid is reduced.

The features of the present invention, which is a means for solving the above problems, are listed below.
1. In the toner production method of the present invention, a toner composition liquid in which a toner material containing at least a resin liquid and a colorant is dissolved or dispersed in a solvent is periodically discharged as droplets from a plurality of nozzles into a gas phase by vibration means. then the toner production method including a step of solidifying drying the droplets, the nozzle has a convex shape to the droplet discharge side, wherein the convex shape is a cylinder formed on the inner wall around the nozzle hole, the nozzle When the diameter of the hole is a, the outer diameter of the cylinder is b, and the height of the cylinder is h, the relationship of (1/2) a ≦ h ≦ 2a and a <b ≦ 3a is satisfied. Features.
2. In the toner production method of the present invention, a toner composition liquid in which a toner material containing at least a resin liquid and a colorant is dissolved or dispersed in a solvent is periodically discharged as droplets from a plurality of nozzles into a gas phase by vibration means. Next, in the toner manufacturing method including the step of solidifying and drying the droplets, the nozzle has a convex shape on the droplet discharge side, and the cross section of the convex shape parallel to the liquid discharge direction is tangent to the inner wall of the nozzle hole. When the diameter of the nozzle hole is a and the curvature radius of the curve is r, the relationship of (1/2) a ≦ r ≦ 2a is satisfied. It is characterized by.
3. The toner manufacturing method of the present invention is further characterized in that the vibration means is composed of lead zirconate titanate (PZT) .
4). The toner manufacturing method of the present invention is further characterized in that the nozzle is made of a metal plate .
5. The toner manufacturing method of the present invention is further characterized in that the nozzle is made of silicon .
6). The toner manufacturing method of the present invention is further characterized in that the nozzle is made of nickel .
7). Toner production method of the present invention, further, the nozzle, characterized in that consists of stainless steel.

  According to the present invention, it is possible to provide a toner manufacturing method using a nozzle in which bleeding of the toner composition liquid is reduced.

FIG. 3 is a schematic configuration diagram illustrating an example of a toner manufacturing apparatus according to the present invention. FIG. 2 is an enlarged explanatory view for explaining a droplet ejecting unit in the toner manufacturing apparatus shown in FIG. 1. FIG. 3 is an explanatory bottom view of the droplet ejecting unit shown in FIG. 2 as viewed from below. FIG. 2 is a schematic explanatory view showing an example of a step-type horn-type vibrator constituting vibration generation means of a droplet ejecting unit in the toner manufacturing apparatus shown in FIG. 1. FIG. 2 is a schematic explanatory diagram illustrating an example of an exponential horn-type vibrator constituting vibration generation means of a droplet jetting unit in the toner manufacturing apparatus shown in FIG. 1. FIG. 2 is a schematic explanatory view illustrating an example of a conical horn-type vibrator constituting vibration generation means of a droplet ejecting unit in the toner manufacturing apparatus shown in FIG. 1. FIG. 2 is an enlarged explanatory view for explaining an example of a droplet ejecting unit in the toner manufacturing apparatus shown in FIG. 1. FIG. 2 is an enlarged explanatory view for explaining an example of a droplet ejecting unit in the toner manufacturing apparatus shown in FIG. 1. FIG. 2 is an enlarged explanatory view for explaining an example of a droplet ejecting unit in the toner manufacturing apparatus shown in FIG. 1. FIG. 10 is an explanatory diagram for explaining an example in which a plurality of droplet ejection units shown in FIG. 9 are arranged. 1 is a schematic configuration diagram illustrating an embodiment of a toner manufacturing apparatus according to the present invention. FIG. 12 is an enlarged explanatory view for explaining a droplet jetting unit of the toner manufacturing apparatus shown in FIG. 11. It is bottom explanatory drawing which looked at the droplet ejection unit shown in FIG. 12 from the lower side. FIG. 13 is a schematic cross-sectional explanatory view of droplet forming means in the droplet ejecting unit shown in FIG. 12. It is expansion sectional explanatory drawing of the droplet formation means which concerns on a comparative example structure. It is principal part explanatory drawing with which it uses for description of the specific application of the droplet ejection unit shown in FIG. It is typical explanatory drawing of the thin film with which it uses for description of the operation principle of droplet formation by the droplet jetting unit which concerns on this invention. It is explanatory drawing with which it uses for description of the fundamental vibration mode of the thin film in the droplet ejection unit which concerns on this invention. It is explanatory drawing with which it uses for description of the secondary vibration mode of the thin film in the droplet injection unit which concerns on this invention. It is explanatory drawing with which it uses for description of the 3rd vibration mode of the thin film in the droplet jetting unit which concerns on this invention. It is explanatory drawing at the time of forming a convex part in the center part of the thin film in the droplet jetting unit which concerns on this invention. 1 is a schematic configuration diagram illustrating an example of a liquid resonance type toner manufacturing apparatus according to the present invention. FIG. 23 is an enlarged explanatory view for explaining a droplet ejecting unit of the toner manufacturing apparatus shown in FIG. 22. FIG. 4 is an explanatory diagram showing an embodiment of a film vibration type toner manufacturing apparatus according to the present invention for collecting toner. It is a schematic sectional drawing which shows the shape of the nozzle which concerns on this invention. It is a schematic sectional drawing which shows the shape of the nozzle which concerns on this invention. 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.

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

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

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

<Vibration injection method>
By mechanically vibrating a thin film having a plurality of nozzles having the same opening diameter, a toner composition liquid is periodically discharged from the nozzles, thereby generating droplets having a uniform particle diameter and drying to obtain toner particles. Is the method. 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 a schematic configuration diagram shown in FIG.
The toner manufacturing apparatus 1 periodically discharges a toner composition liquid from a plurality of nozzles having the same opening diameter, and a droplet ejecting unit 2 as a droplet forming unit in a periodic droplet forming process for forming droplets in a gas phase. The droplet jetting unit 2 is disposed above, and the droplets of the toner composition liquid droplets discharged from the droplet jetting unit 2 are solidified to form toner particles T in the particle forming step. A particle forming part (solvent removing part) 3 as a means, a toner collecting part 4 for collecting toner particles T formed by the particle forming part 3, and a toner particle T collected by the toner collecting part 4 A toner storage unit 6 serving as a toner storage unit that stores the toner particles T transferred through the tube 5, a raw material storage unit 7 that stores the toner composition liquid 10, and droplets from the raw material storage unit 7. Toner composition for jet unit 2 10 and liquid feed piping (liquid feed pipe) 8, and a pump 9 for pumping supplying toner composition liquid 10, such as during operation.
Further, the toner composition liquid 10 delivered from the raw material container 7 is supplied to the droplet ejection unit 2 in a self-sufficient manner due to the droplet formation phenomenon by the droplet ejection unit 2, but as described above when the apparatus is in operation, etc. In addition, the liquid is supplied by using the pump 9 as an auxiliary. In FIG. 1, reference numeral 31 denotes a droplet, 35 denotes a dry gas, 41 denotes a tapered surface of the toner collecting unit 4, 42 denotes an air flow (vortex), and 43 denotes a charge removing unit that neutralizes the charge of the toner particles.

Next, the droplet ejecting unit 2 will be described with reference to FIGS. FIG. 2 is a schematic cross-sectional explanatory view of the droplet jetting unit 2, and FIG.
The droplet ejection unit 2 includes a thin film 12 in which a plurality of nozzles (discharge ports) 11 are formed, a mechanical vibration means (hereinafter referred to as “vibration means”) 13 that vibrates the thin film 12, a thin film 12 and vibration means. 13 and a flow path member 15 that forms a reservoir (liquid flow path) 14 for supplying the toner composition liquid 10.
The thin film 12 having the plurality of nozzles 11 is disposed in parallel to the vibration surface 13a of the vibration means 13, and the flow path member is made of a resin binding material in which a part of the thin film 12 is not dissolved in the solder or the toner composition liquid. 15 and is in a positional relationship substantially perpendicular to the vibration direction of the vibration means 13. The gist of the present invention is the shape of the nozzle, which will be described later. 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 can be converted into mechanical vibration. As a communication means for providing an electrical signal, a lead wire whose surface is insulated is suitable. In addition, it is suitable for efficient and stable toner production that the vibration means 13 uses elements having a large vibration amplitude such as various horn type vibrators and bolted Langevin type vibrators described later.

The vibration unit 13 includes a vibration generation unit 21 that generates vibrations and a vibration amplification unit 22 that amplifies the vibrations generated by the vibration generation unit 21. The drive unit (drive signal generation source) 23 drives a required frequency. When a voltage (drive signal) is applied between the electrodes 21 a and 21 b of the vibration generating means 21, vibration is excited in the vibration generating means 21, and this vibration is amplified by the vibration amplifying means 22 and arranged in parallel with the thin film 12. The vibrating surface 13a is periodically vibrated, and the thin film 12 is vibrated at a required frequency by the periodic pressure caused by the vibration of the vibrating surface 13a.
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. Therefore, the vibration generating means 21 is preferably a piezoelectric body that is excited by a bimorph-type flexural vibration. The piezoelectric body has a function of converting electrical energy into mechanical energy. When a piezoelectric body is used as the vibration generating means, a flexural vibration is excited by applying a voltage to the piezoelectric body, and the thin film 12 can be vibrated.

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

As the horn type vibrator as the vibration means 13, a known typical horn shape may be used. For example, a step type horn type vibrator as shown in FIG. 4 or an exponential horn type as shown in FIG. Examples thereof include a vibrator and a conical horn vibrator as shown in FIG.
In these horn type vibrators, as shown in FIG. 2, a piezoelectric body (vibration generating means 21) is arranged on the surface of the horn (vibration amplifying means 22) having a large area, and the piezoelectric body (vibration generating means 21) is longitudinal. The vibration is induced to induce efficient vibration of the horn (vibration amplifying means 22), and the surface of the horn (vibration amplifying means 22) having a small area is defined as the vibration surface 13a, so that the vibration surface 13a becomes the maximum vibration surface. Designed to. Communication means (lead wire) 24 is disposed above and below the piezoelectric body (vibration generating means 21), and an AC voltage signal is applied from the drive circuit 23. The maximum vibration surface of these horn vibrators is designed to be the vibration surface 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.

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

In general, the size of the vibration means 13 that generates mechanical vibration increases as the oscillation frequency decreases. Can be provided. It is also possible to vibrate the entire storage unit 14 efficiently.
In this case, the vibration surface is defined as a surface on which the thin films having the plurality of nozzles are bonded.
Different examples of the droplet ejecting unit having such a configuration will be described with reference to FIGS.
A droplet ejecting unit 204 shown in FIG. 7 uses a horn-type vibrator 134 composed of a piezoelectric body 81 as a vibration generating unit and a horn 82 as a vibration amplifying unit as a vibrating unit, and a part of the horn 82. A reservoir (flow path) 144 is formed. The droplet ejecting unit 204 is fixed to the wall surface of the particle forming unit 3 (drying unit) shown in FIG. 1 by a fixing unit (flange unit) 83 formed integrally with the horn 82 of the horn type vibrator 134. From the viewpoint of preventing vibration loss, it may be fixed using an elastic body (not shown). In FIG. 7, 134a is a vibration surface, 114 is a nozzle, 124 is a thin film, 184 is a liquid supply tube, and 194 is a bubble discharge tube.

The droplet ejecting unit 205 shown in FIG. 8 vibrates a bolt-clamped Langevin type vibrator 135 configured by mechanically and firmly fixing piezoelectric bodies 911 and 912 and horns 921 and 922 as vibration generation units with bolts. In this case, a storage part (flow path) 145 is formed in the horn 921. Depending on the frequency conditions, the horn 921 may become large, and a metal thin film having a plurality of thin films by processing the liquid supply tube 185 (fluid introduction / discharge path) and the reservoir 145 in a part of the horn 921 as shown in the figure. Can be pasted. In FIG. 8, 135a is a vibrating surface, 115 is a nozzle, 125 is a thin film, and 195 is a bubble discharge tube.
FIG. 1 shows an example in which only one droplet ejecting unit 2 is attached to the particle forming unit 3, but a plurality of droplet ejecting units 2 are arranged above the particle forming unit 3 (drying tower). Paralleling is preferable from the viewpoint of improving productivity. The number of droplet ejection units is preferably in the range of 100 to 1000 from the viewpoint of controllability. In this case, the toner composition liquid 10 is supplied to each storage section 14 of the droplet ejection unit 2 through the pipe 8 to the raw material storage section (common liquid reservoir) 7. The toner composition liquid 10 can be configured to be supplied in a self-contained manner along with droplet formation, or can be configured to supply the liquid supplementarily using the pump 9 during operation of the apparatus. You can also.

Another example of the droplet ejecting unit will be described with reference to FIG. FIG. 9 is a schematic cross-sectional explanatory view of the liquid droplet ejecting unit.
The droplet ejecting unit 206 shown in FIG. 9 uses a horn-type vibrator 136 as a vibrating means. A flow path member 156 for supplying the toner composition liquid 10 is disposed so as to surround the horn type vibrator 136, and a storage portion 146 is formed on the horn 226 of the horn type vibrator 136 at a portion facing the thin film 126. Yes. Further, an air flow path forming member 36 that forms an air flow path 37 through which the air flow 35 flows is disposed around the flow path member 156 at a required interval. In order to simplify the illustration, only one nozzle 116 of the thin film 126 is shown, but a plurality of nozzles 116 are provided as described above. In FIG. 9, 186 is a liquid supply tube and 216 is a piezoelectric body.
As shown in FIG. 10, from the viewpoint of controllability, a plurality of, for example, 100 to 1000 droplet ejection units 206 are arranged side by side on the top of the drying tower constituting the particle forming unit 3 shown in FIG. Thereby, productivity can be further improved.

(Annular mechanical vibration means)
FIG. 11 shows an example in which the liquid droplet ejecting unit is replaced with a ring type in the toner manufacturing apparatus shown in FIG.
The ring type droplet ejecting unit 207 will be described with reference to FIGS. 12 is a cross-sectional explanatory view of the liquid droplet ejecting unit 2, FIG. 13 is a main surface bottom explanatory view of FIG. 12 viewed from the lower side, and FIG. It is.
As shown in FIG. 12, the droplet ejecting unit 207 includes at least a droplet forming unit 16 that discharges the toner composition liquid 10 into droplets, and a storage unit that supplies the toner composition liquid 10 to the droplet forming unit 16. (Liquid flow path) 147 having a flow path member 147 formed thereon.

  The droplet forming means 16 includes a thin film 127 in which a plurality of nozzles (discharge ports) 117 are formed, and an annular vibration generating means (electromechanical conversion means) 17 that vibrates the thin film 127. Here, the thin film 127 is bonded and fixed to the flow path member 157 with a resin binding material that does not dissolve in the solder or the toner composition liquid at the outermost peripheral portion (region shown by hatching in FIG. 13). The vibration generating means 17 is arranged around a region provided with nozzles in the deformable region 16A (region not fixed to the flow path member 157) of the thin film 127 shown in FIG. As shown in FIG. 12, a drive voltage (drive signal) having a required frequency is applied to the vibration generating means 17 from a drive circuit (drive signal generating source) 23 through a communication means (lead wire) 24. Generates flexural vibration. In FIG. 12, 20 is a support member, 187 is a liquid supply tube, and 197 is a bubble discharge tube.

  The droplet forming means 16 has an annular vibration generating means 17 arranged around the area where the nozzles are provided in the deformable area 16A of the thin film 127 having a plurality of nozzles 117 facing the storage portion 147. For example, as compared with the configuration in which the vibration generating means 171 holds the periphery of the thin film 127 as in the comparative example configuration shown in FIG. 15, the displacement amount of the thin film 127 is relatively large, and this large displacement amount is obtained. A plurality of nozzles 117 can be arranged in a region having a large area (φ1 mm or more), and more droplets can be stably formed and discharged at a time than the plurality of nozzles 117.

  FIG. 11 shows an example in which one droplet ejecting unit 207 is arranged, but preferably, as shown in FIG. 16, a plurality of, for example, 100 to 1000 (for example, from the viewpoint of controllability) 4 droplet jetting units 207 are arranged side by side on the top surface portion 301 of the particle forming unit 3, and each droplet jetting unit 2 has a pipe 801 connected to the raw material storage unit (common liquid reservoir) 7. The toner composition liquid 10 is supplied. 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 thin film 12 having the plurality of nozzles 11 facing the storage unit 14 to propagate the vibration generated by the vibration means 13 that is a mechanical vibration means, thereby periodically causing the thin film 12 to move. By vibrating, a plurality of nozzles 11 are arranged in a relatively large area (φ1 mm or more), and droplets can be periodically and stably formed and discharged from the plurality of nozzles 11.

As shown in FIGS. 17A and 17B, when the peripheral portion 12A of the simple circular film 12 is fixed, the periphery of the fundamental vibration is a node, and as shown in FIG. 18, the displacement ΔL at the center O of the thin film. Becomes the maximum (ΔLmax) cross-sectional shape, and periodically oscillates in the vibration direction.
Further, it is known that higher order modes as shown in FIGS. 19 and 20 exist. These vibration modes have one or a plurality of nodes concentrically in a circular film and are substantially axisymmetric deformation shapes. In addition, as shown in FIG. 21, by making the central portion of the thin film have a convex shape 12C, it is possible to control the traveling direction of the droplet and adjust the vibration amplitude.

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. Sound pressure, medium are known to occur as a reaction of the radiation impedance Z _r of (toner constituent liquid), sound pressure, using Equation (1) below the product of the radiation impedance and film vibration velocity Vm Table Is done.
P _ac (r, t) = Z _r · V _m (r, t) (1)
Is a function of time (t) since the vibration speed V _m of the film fluctuates periodically with time, for example a sine wave, such as a rectangular waveform, it is possible to form various periodic variations. Further, as described above, the vibration displacement in the vibration direction is different in each part of the 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 thin film that enables droplet formation, a range 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, and when the vibration displacement is small, a small droplet is formed or is not formed into 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. 18 to 20, the ratio R (= ΔLmax / ΔLmin) between the maximum value ΔLmax and 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. However, by arranging the nozzle at a site within 2.0, the variation in the droplet size can be maintained in a necessary region as toner fine particles capable of providing a high-quality image.
The conditions of the toner composition liquid were changed, and the satellite generation start region was the same in the region where the viscosity was 20 mPa · s or less and the surface tension was 20 to 75 mN / m. Therefore, the displacement of the sound pressure was 500 kPa or less. It will be necessary. More preferably, it is 100 kPa or less.

(Thin film with multiple nozzles)
As described above, the thin film having the nozzle is a member in which a solution or dispersion of the toner composition is discharged to form 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 later.

(Liquid resonance method)
An example of a liquid resonance type toner manufacturing apparatus is shown in FIG. 22, and an example of a droplet ejection unit is shown in FIG. The basic structure of the liquid resonance system is almost the same as that of the mechanical longitudinal vibration system. However, the mechanical longitudinal vibration system vibrates the thin film having the nozzles by the vibration generating means to form liquid droplets. The resonance method is different in that it is not formed by vibration of a thin film having a nozzle but is formed into droplets by resonance of the liquid.
Therefore, the strength of the thin film is increased to the extent that it does not vibrate. As the material of the thin film, silicon, silicon oxide, or the like is used, and it is desirable in terms of nozzle formation to use a silicon substrate, particularly an SOI (Silicon on Insulator) substrate. The nozzle shape is the gist of the present invention and will be described later.

FIG. 23B is a schematic cross-sectional explanatory view of the droplet ejecting unit 2, FIG. 23A is an assembly diagram for explaining in more detail, and FIG. 23C is FIGS. It is explanatory drawing of the droplet formation by the droplet ejection unit shown to b).
The droplet ejecting unit 208 includes at least a resin, a colorant, and a specific phenol between the thin film 128 in which a plurality of nozzles (discharge ports) 118 are formed, the vibration unit 138, and the thin film 128 and the vibration unit 138. And a reservoir constituting member 158 that forms a reservoir (liquid channel) 148 for supplying the toner composition liquid 10 containing a resin. A configuration in which the position is fixed between the vibration means 138 and the wall of the storage portion 148 by the vibration separating member 26 so as not to transmit vibration is desirable. It may be configured to be fixed directly to the wall via 27. The toner composition liquid 10 is supplied to the liquid reservoir 148 through a pipe 808 used for liquid supply and liquid circulation.
As the vibration means 138, the vibration generation means 218, and the vibration amplification means 228, those exemplified in the description of the membrane vibration method using the mechanical longitudinal vibration means described above can be similarly used.

The partition wall of the reservoir 148 is made of a material that does not dissolve in the spray liquid and does not cause modification of the spray liquid among common materials such as metal, ceramics, and plastic. Further, the liquid storage part 148 is divided into a plurality of liquid storage regions 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. In FIG. 23 (a), A is the length of the liquid chamber, B is the width of the liquid chamber, and in FIG. 23 (b), H is the height of the liquid chamber.
Next, the mechanism of droplet formation by the droplet ejecting unit 208 as droplet forming means will be described with reference to FIG.
The vibration generated on the vibration surface 138a by the vibration means 138 is transmitted to the liquid in the reservoir 148, and the liquid in the reservoir 148 causes a liquid resonance phenomenon. In the plurality of nozzles provided in the thin film 128, the liquid is discharged to the gas side in a state of being uniformly pressurized. By the action of resonance of the entire liquid in the storage unit 148, the liquid is uniformly ejected from all the nozzles, and further, the dispersed fine particles contained in the toner composition liquid are not deposited on the storage unit surface of the thin film. Since the reservoir is floated, the liquid can be stably ejected stably.

Any vibration means 138 can be used as long as it can apply mechanical ultrasonic vibration to the liquid at a high amplitude, such as a laminated PZT or a combination of an ultrasonic vibrator and an ultrasonic horn described later. It doesn't matter.
When 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, since substantially equal vibration pressure is applied to each nozzle, it is easy to obtain droplets having a narrow particle size distribution 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 any injection method, an explanation will be given with an annular mechanical vibration means as a representative.
FIG. 24 is an explanatory view showing 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, the apparatus has a droplet jetting unit at the top of the apparatus, and has a chamber part 180 for jetting and drying droplets, and a guide tube for sending the toner obtained in the chamber part 180 to the toner storage part. Configured.
The droplet ejecting unit 209 includes droplet forming means 161 that discharges the toner composition liquid 10 in which a toner composition containing at least a resin and a colorant is dispersed or dissolved in an organic solvent into droplets. A container 130 having a reservoir 149 for supplying the toner composition liquid 10 to the means 161.

The droplet forming means 161 is the same as the membrane vibration method. A liquid supply hole 200 and a discharge hole 210 for supplying the toner composition liquid 10 to the reservoir 149 are connected to the toner container 130, respectively. A droplet 31 is discharged from the nozzle 119 by the droplet forming means 161.
Further, on the outside of the container 130, there is an opening 30 a that opens at a portion facing the nozzle 119, and an air flow path for gas that conveys the droplet 31 that flows along the discharge direction of the toner composition liquid 10 from the nozzle 119. A shroud portion 30 is attached. The shroud portion 30 is composed of double pot-shaped walls 30b and 30c having an open nozzle portion, and the shroud portion 30 is coupled to each other by a lid portion 310. A gas blowing pipe 91 is fitted into the side surface of the shroud portion 30. Of the double walls, the inner wall 30 c ends near the lower end of the container 130. Out of the double walls, the outer wall 30 b extends to the lower part of the nozzle 119 and ends with a lower circular opening 30 a facing the nozzle 119. The diameter of the opening 30 a is “D”, and a clearance G is maintained between the inner wall of the bottom 30 d of the outer wall 30 b and the lower end of the nozzle 119. Since G is smaller than D, G is the main factor that determines the flow velocity of the carrier airflow.

  The flow 31a containing the droplets 31 is then guided into the large volume shroud 30 with the shroud 30 and container 130 attached to the top. A downward air flow 96 shown in FIG. 24 is formed in the chamber portion 180 by a chamber portion outlet 93 described later. This air flow 96 is a uniform laminar flow, and the flow 31 a containing the droplets 31 is sent to a guide tube 92 connected to the toner collecting unit 401 at the bottom while being dried and solidified in a laminar flow state by the air flow 96. . The guide tube 92 is connected to a cyclone (not shown), collected while being dried, and fed to the toner storage unit 601. On the upper side surface of the shroud portion 30, a gas blowing pipe 91 is fitted in an airtight manner. A pressure gauge PG <b> 1 is inserted on the opposite side surface of the chamber portion 180. A pressure gauge PG <b> 2 is also inserted into the side surface of the blowing pipe of the shroud portion 30.

Next, the operation of the toner manufacturing apparatus according to this embodiment will be described. Here, the case where the toner composition liquid 10 is circulated will be described. When the annular vibration means 170, which is a vibration means, is vibrated at, for example, 100 kHz by a driving device (not shown) while the toner composition liquid 10 is stored in the container 130 at an appropriate pressure, the thin film 129 is vibrated. Propagating, and the toner composition liquid 10 is ejected from the plurality of nozzles 119 at a discharge frequency that matches the frequency of vibration drive. The released initial velocity V ₀ tends to decelerate due to resistance due to the viscosity of the gas in the shroud portion 30.
On the other hand, gas is blown out into the shroud portion 30 by the blowout pipe 91, forms a carrier airflow 95 through the shroud portion 30, and is discharged from the opening 30 a to the chamber portion 180. The formed conveying airflow 95 is uniform and downward in the circumferential direction, and since the lower end of the wall 30b of the shroud portion 30 is rounded, the airflow smoothly changes its direction horizontally and merges under the nozzle 15, Furthermore, it discharges | emits from the opening part 30a. If the airflow at this time is a turbulent flow, the droplets 31 are likely to coalesce with each other.

The discharged liquid droplet 23 rides on the carrier airflow 95 and is released from the opening 30a into the chamber portion 180, where it rides on the airflow 96 which is a laminar flow and is sent to the toner collecting portion 401 without being attached.
In this example, the flow velocity V ₁ of the carrier airflow 95 is larger than the initial velocity V _{0 of} the droplet 31, and the droplet 31 is accelerated and then sent along the carrier airflow 95. V ₁ may be higher than the free fall speed, and may be lower than the initial speed V ₀ . An air flow 96 having a flow velocity V ₂ faster than V ₁ is formed in the chamber. As the flow velocity V ₂ of the air flow 96 is large, preferable in terms of preventing coalescence. As the air flow 96 in the chamber portion 180 is blown out from the blowing pipe 93, a uniform and uniform air flow is formed in the circumferential direction as in the shroud portion 30. A laminar flow is preferable in the chamber portion 180. Since the flow 31a (flow velocity is V ₁ ) of the droplet including the droplet 31 immediately after being discharged into the chamber portion 180 does not cause turbulent flow and flows down smoothly, the flow velocity of the air flow 96 in the chamber portion 180 to V _2, it is preferable that _{V 2} ≧ _{V 1.}

The flow rates of the carrier airflow 95 in the shroud section 30 and the airflow 96 in the chamber section 180 are managed by pressure gauges PG1 and PG2. It is preferable that the pressure P1 in the shroud part 30 and the pressure P2 in the chamber part 18 have a relationship of P1 ≧ P2. If this relationship is not satisfied, there is a possibility that a negative pressure acts on the droplet 31 and the liquid flows backward.
As described above, it is G> that is the clearance between the wall 30b and the head 2a that determines the flow rate of the conveying airflow 95 of the shroud 30 because D> G.
The carrier airflow 95 in the shroud portion 30 and the airflow 96 in the chamber portion 180 are formed by blowing gas from the blowing pipe 91 and the chamber portion outlet 93 at the top of the chamber portion 18. An air flow may be formed by suction from a pipe 92 provided at the lower part of the pipe.

The cross section of the opening 30a of the wall 30b of the shroud 30 preferably has a taper 30e in the direction in which the diameter increases along the gas discharge direction, that is, the outer diameter increases. Thus, by forming the taper 30e in the opening 30a, when the droplet 31 passes through the opening 30a, it can be avoided that the droplet 31 contacts and adheres to the wall surface of the opening 30a.
In the present embodiment, nitrogen gas is used for the shroud portion 30 and the chamber portion 180 as the gas to be blown out. However, the gas may be any gas, and may be air or other gases. In FIG. 24, the shroud portion 30 is configured by the double pot-shaped walls 30 b and 30 c, but the inner wall 30 c may be used as the outer peripheral wall constituting the container 130. Further, by using a configuration in which a plurality of droplet ejection units 209 and a shroud portion 30 are arranged in one chamber portion 180, the toner production efficiency can be further increased.
The discharged droplets 31 are removed by the solvent while passing through the particle forming unit 301 and are collected in the toner storage unit 601 in a solid form. In FIG. 24, 25 is a head, 32 is a valve, 70 is a liquid feed pipe, 71 is a drain pipe, 100 is a pump, and 701 is a raw material container.

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

<Nozzle shape>
As described above, there are various types of droplet discharge means applied in the present invention. In the droplet discharge means as described above, if no countermeasure is taken against the seepage of the toner composition liquid in the nozzle and the thin film, the toner composition liquid exudes unexpectedly during ejection, and as a result, the entire nozzle covers the nozzle composition liquid. As a result, it has become clear that the situation of injection is hindered. Further, even when the toner composition liquid itself does not hinder the ejection, the toner composition liquid eventually dries, and the dry matter also causes the nozzle to be clogged or the shape change to cause a decrease in ejection or stop of the ejection. For this reason, it is necessary to take measures to prevent the nozzle from bleeding.
In the present invention, it has been found that since the discharge surface is a flat plate that has been implemented in the past, the discharge of the toner composition liquid can be remarkably reduced by changing the discharge surface to a shape that is convex. Invented.
In the present invention, a nozzle having an octopus shape on the droplet discharge side is used. Here, the octopus shape means a shape having a convex shape on the droplet discharge side, and the convex shape is a cylindrical object formed around the inner wall of the nozzle hole. Examples of the cross section of the cylindrical object include circles, ellipses, triangles, quadrangles, hexagons, octagons, and other polygons.
As shown in FIGS. 25 and 26, the shape of the nozzle of the present invention is convex on the injection outlet side. The nozzle shown in FIG. 25 satisfies the relationship of the following formulas (1) and (2), where a is the diameter of the nozzle A, b is the diameter of the convex portion B, and h is the convex portion height.
a <b ≦ 3a (1)
1 / 2a ≦ h ≦ 2a (2)

In the nozzle shape shown in FIG. 25, as shown in the equation (1), when the diameter of the nozzle A is equal to or larger than the diameter of the convex portion B (a ≧ b), the convex B cannot substantially exist. The diameter b of the convex B is 3 times or less (b ≦ 3a) of the diameter a of the nozzle A, and preferably 2 times or less (b ≦ 2a). When the diameter b of the convex B exceeds three times the diameter a of the nozzle A, the meniscus diameter of the nozzle becomes too large and the convex B does not exist, and the droplet diameter is not stabilized and the particle size distribution is not changed. Is not preferable because it becomes wider.
In the nozzle shape shown in FIG. 25, the height h of the protrusion B needs to be 1/2 or more of the nozzle A diameter, as shown in Expression (2). If it is less than ½, the meniscus is substantially unchanged due to vibration of the meniscus and turbulence of the airflow, and the meniscus spreads and the droplet discharge directionality does not become stable and the droplet size distribution is wide. Become. The height h of the convex B needs to be not more than twice the diameter of the nozzle A, and is preferably 1.5 times. If it exceeds twice, the nozzle plate is thick, so the ratio between the height L in the hole of the nozzle A and the diameter a (L / a) is substantially increased, which makes it difficult to process the nozzle. Pressure loss during discharge increases and discharge voltage increases. This makes it impossible to save energy in the production of toner.

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

  In the present invention, the actual size of the nozzle is determined by the intended droplet size. The thin film 12 described in FIGS. 1, 2, 3, 7, 8, 9, 10, 11, 12, 13, 14, 15, 17 is formed of a metal plate having a thickness of 5 to 500 μm, and the opening diameter of the nozzle 11 Is preferably from 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.

In the present invention, it is possible to select the convex processing of the nozzle as shown in FIG. The nozzle shown in FIG. 26 satisfies the relationship of the following formula (3) when the diameter of the nozzle A is a and the curvature radius of the convex portion is r.
1 / 2a ≦ r ≦ 2a (3)
In the case of a convex shape having a curvature radius r on the droplet discharge side in the shape of the nozzle shown in FIG. 26, the curvature radius r of the convex portion can be said to be the same as the height h shown in the above equation (2). The radius r can be regarded as the height h in the above equation (2). Therefore, as shown in Equation (3), the radius of curvature r needs to be 1/2 or more of the diameter a of the nozzle A. When the radius of curvature r is less than ½ of the diameter a of the nozzle A, the meniscus spreads and the droplet discharge directionality is substantially unchanged from the state without the convex B due to vibration of the meniscus or turbulence of the airflow. Does not become stable and the droplet size distribution becomes wide. Further, the curvature radius r needs to be not more than twice the diameter a of the nozzle A, and is preferably 1.5 times. If it exceeds twice, the nozzle plate is thick, so the ratio between the height L in the hole of the nozzle A and the diameter a (L / a) is substantially increased, which makes it difficult to process the nozzle. Pressure loss during discharge increases and discharge voltage increases. This makes it impossible to save energy in the production of toner.
Even when the shape shown in FIG. 26 is selected, the optimum nozzle material and nozzle diameter are applied in FIG.

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 1110 is coated on both surfaces of the silicon substrate (11a), covered with a photomask on which a nozzle pattern is formed, and exposed to ultraviolet rays to form resist 1110 as a nozzle pattern (11b). Anisotropic dry etching using ICP discharge (inductively coupled plasma discharge) is performed from the support layer 1120 surface side to form a first nozzle hole 1150, and the same anisotropic dry etching is performed on the active layer 1140 surface side. Then, the second nozzle 1160 is formed (11c), and finally the dielectric layer 1130 is removed with a hydrofluoric acid etching solution to obtain a two-stage through hole (11d). This method is the most preferable method for uniformly forming the deep nozzle shape. Although not shown, even when a single-layer silicon substrate is used as the silicon substrate, the nozzle can be formed by the same method as that for the SOI 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.

(toner)
Next, the toner according to the present invention will be described. The toner according to the present invention is a toner manufactured by a toner manufacturing method using the above-described toner manufacturing apparatus, and a monodispersed particle size distribution is obtained by this manufacturing method.
Specifically, the particle size distribution (volume average particle diameter (Dv) / number average particle diameter (Dn)) of the toner is preferably in the range of 1.00 to 1.15. More preferably, it is 1.00 to 1.05. Moreover, as a volume average particle diameter, it is preferable to exist in the range of 1-20 micrometers, More preferably, it is 3-10 micrometers.
Next, the toner material (toner composition liquid) used in the present invention will be described. First, a toner composition liquid in which a toner composition is dispersed and dissolved in a solvent as described above will be described.
As the toner material, the same material as that of a conventional electrophotographic toner can be used. That is, a toner binder such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin is dissolved in various organic solvents, a colorant is dispersed, and a release agent is dispersed or dissolved. The target toner particles can be produced by drying and solidifying into fine droplets by the toner production method. It is also possible to obtain a target toner by drying and solidifying a liquid obtained by dissolving or dispersing a kneaded material obtained by hot-melting and kneading the above materials in various solvents into fine droplets by the toner production method. is there.

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

〔resin〕
Examples of the resin include at least a binder resin.
The binder resin is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, vinyl such as styrene monomer, acrylic monomer, methacrylic monomer, etc. Polymers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins, Coumarone indene resin, polycarbonate resin, petroleum resin and the like can be mentioned.
Examples of the styrene monomer include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, and pn-amyl styrene. , P-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene such as chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or derivatives thereof.
Examples of the acrylic monomer include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic acid 2 -Acrylic acid such as ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate, or esters thereof.
Examples of the methacrylic monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid 2 -Methacrylic acid such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, or esters thereof.

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

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

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

  Examples of the polymerization initiator used in the production of the vinyl polymer or vinyl copolymer used in the present invention include 2,2′-azobisisobutyronitrile and 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, cycl Ketone peroxides such as hexanone peroxide; 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydro Peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl Peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxide Dicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohex Xylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaurate, tert-butyl-oxybenzoate, tert- Butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di- ert- butyl peroxy the hexa hydro terephthalate, etc. tert- butylperoxy azelate, and the like.

When the binder resin is a styrene-acrylic resin, the molecular weight distribution measured by gel permeation chromatography (GPC) of the soluble component in tetrahydrofuran (THF) as a resin component has a molecular weight of 3000 to 50000 (in terms of number average molecular weight). A resin having at least one peak in a region and at least one peak in a region having a molecular weight of 100,000 or more is preferable in terms of fixing property, offset property and storage property. Further, as the THF-soluble component, a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50 to 90% is preferable, and a binder resin having a main peak in a molecular weight region of 5000 to 30000 is more preferable. A binder resin having a main peak in the 20000 region is most preferred.
The acid value when the binder resin is a vinyl polymer such as styrene-acrylic resin is preferably 0.1 to 100 mgKOH / g, more preferably 0.1 to 70 mgKOH / g, and 0 More preferably, it is 1-50 mgKOH / g.

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

  Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, 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 the like, and the like. Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, anhydrides thereof, partial lower alkyl esters and the like.

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

As the binder resin that can be used in the toner according to the present invention, it is also possible to use a resin containing a monomer component capable of reacting with both of these resin components in at least one of the vinyl polymer component and the polyester resin component. it can. Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin is 0.1-50 mgKOH / g is preferable.
In the present invention, the acid value of the binder resin component of the toner composition can be determined by the following method, and the basic operation conforms to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as W (g). For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 ml beaker, and 150 ml of a mixed solution of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with an ethanol solution of 0.1 mol / L KOH using a potentiometric titrator.
(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, (2) metals such as iron, cobalt, nickel, or Alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, (3) and these And the like.
Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , _{PbFe 12 O, NiFe 2 O 4} , NdFe 2 O, BaFe 12 O 19, MgFe 2 O 4, MnFe 2 O 4, LaFeO 3, iron powder, cobalt powder, nickel powder, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of Fe ₃ O ₄ (triiron tetroxide) and γ-Fe ₂ O ₃ (γ-iron trioxide) are particularly suitable.
Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used. Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, Examples include gallium. As a preferable different element, it is an element selected from magnesium, aluminum, silicon, phosphorus and zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may 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.
The magnetic material can also be used as a colorant.

[Colorant]
The colorant is not particularly limited and may be appropriately selected from commonly used resins. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fu Issey Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Nacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide , Pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green , Malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.
The content of the colorant is preferably 1 to 15% by mass and more preferably 3 to 10% by mass based on the total amount of toner.

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

The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, there is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.
As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.
The resin for the masterbatch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and a colorant dispersed therein. The acid value is 20 mgKOH / g or less and the amine value is 10 It is more preferable that the colorant is dispersed and used at ˜50. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered, and the pigment dispersibility may be insufficient. Also, when the amine value is less than 1 and when the amine value exceeds 100, the pigment dispersibility may be insufficient. The acid value can be measured by the method described in JIS K0070, and the amine value can be measured by the method described in JIS K7237.

The dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific examples of commercially available products include “Ajisper PB821” and “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.). , “Disperbyk-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like.
The weight average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene 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. When the addition amount is less than 1 part by mass, the dispersibility of the colorant may be lowered, and when it exceeds 200 parts by mass, the chargeability may be lowered.

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

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

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

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

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

<Fluidity improver>
A fluidity improver may be added to the toner according to the present invention. The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface.
Examples of the fluidity improver include, for example, carbon black, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder titanium oxide, fine powder. Examples include non-alumina, treated silica obtained by subjecting them to a surface treatment with a silane coupling agent, a titanium coupling agent, or silicone oil, treated titanium oxide, and treated alumina. Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.
The particle size of the fluidity improver is preferably 0.001 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, and dimethylvinylchlorosilane. , Divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchloro Silane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, Examples include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to Si. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The number average particle diameter of the fluidity improver is preferably 5 to 100 nm, more preferably 5 to 50 nm.
The specific surface area by measuring nitrogen adsorption by the BET method of fluidity improving agent, preferably at least ^{30m 2 / g, 60~400m 2 /} g is more preferable. Specific surface area of the surface-treated fine powder is preferably at least ^{20m 2 / g, 40~300m 2 /} g is more preferable.
The application amount of these fine powders is preferably 0.03 to 8 parts by mass with respect to 100 parts by mass of the toner particles.
In the toner according to the present invention, as other additives, protection of the electrostatic latent image carrier / carrier, improvement of cleaning properties, adjustment of thermal characteristics / electrical characteristics / physical characteristics, resistance adjustment, softening point adjustment, fixing rate For the purpose of improvement, various metal soaps, fluorosurfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, and inorganic such as titanium oxide, aluminum oxide, alumina A fine powder or the like can be added as necessary. These inorganic fine powders may be hydrophobized as necessary. In addition, lubricants such as polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, strontium titanate, anti-caking agents, white particles and black particles having opposite polarity to the toner particles, Can also be used in small amounts as a developability improver.
These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control and the like. It is also preferable to treat with a treating agent or various treating agents.

When preparing the toner, an external additive such as the above-mentioned hydrophobic silica fine powder may be added and mixed in order to improve the fluidity, storage stability, developability and transferability of the toner. For mixing external additives, a general powder mixer can be appropriately selected and used. However, it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually, and the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. The load may then be given a relatively weak load and vice versa.
Examples of the mixer that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like.
A method for further adjusting the shape of the obtained toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner material composed of a binder resin and a colorant is melt-kneaded and then finely pulverized. The material is mechanically adjusted using a hybridizer, mechano-fusion, etc., or the so-called spray drying method is used to dissolve and disperse the toner material in a solvent in which the toner binder is soluble, and then removed using a spray drying device. Examples thereof include a method of obtaining a spherical toner by forming a solvent, and a method of forming a spherical toner by heating in an aqueous medium.

As the external additive, inorganic fine particles can be preferably used. Examples of inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth, Examples thereof include chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 to 500 nm.
The specific surface area of the inorganic fine particles by the BET method is preferably 20 to 500 m ² / g.
The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass and more preferably 0.01 to 2.0% by mass in the total amount of the toner.

In addition, polymer fine particles, such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylate esters, acrylate copolymers, polycondensation systems such as silicone, benzoguanamine, and nylon, thermosetting Examples thereof include polymer particles made of a resin.
Such an external additive can be made hydrophobic by the surface treatment agent and prevent deterioration of the external additive itself even under high humidity.
Examples of the surface treatment agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. Preferably mentioned.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, more preferably 5 to 500 nm. Moreover, as a specific surface area by BET method, it is preferable that it is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and more preferably 0.01 to 2.0% by mass.

Examples of the cleaning property improver for removing the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymethyl methacrylate. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.
The developing method using the toner according to the present invention can use all of the electrostatic latent image carriers used in the conventional electrophotography. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image, and the like. A carrier, a selenium electrostatic latent image carrier, a zinc oxide electrostatic latent image carrier, and the like can be suitably used.

Next, specific examples in the above embodiment will be described. In addition, this invention is not limited to the following Example at all.
Example 1
-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
First, 17 parts by mass of carbon black (Regal 400; manufactured by Cabot) and 3 parts by mass of a pigment dispersant (Ajisper PB821; manufactured by Ajinomoto Fine Techno Co., Ltd.) are dispersed in 80 parts by mass of ethyl acetate using a mixer having stirring blades. It was. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion in which aggregates having a diameter of 5 μm or more were completely removed.

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

-Preparation of toner composition liquid-
Next, a toner composition liquid having the following composition to which a resin as a binder resin, the colorant dispersion liquid, and the wax dispersion liquid were added was prepared.
100 parts by mass of a polyester resin as a binder resin, 30 parts by mass of the colorant dispersion, and 30 parts by mass of the wax dispersion are put into 840 parts by mass of ethyl acetate, and are stirred for 10 minutes using a mixer having stirring blades. And uniformly 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 119 of the droplet forming means 161 of the toner manufacturing apparatus 103 (FIG. 24). The used thin film (hereinafter, also referred to as “nozzle plate”) 129 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, and has a perfect circular shape with a diameter of 10 μm. The discharge hole (nozzle) 119 was produced by processing by an electroforming method. The discharge holes were provided only in a range of about 5 mmφ at the center of the thin film 129 in a staggered pattern so that the distance between the discharge holes was 100 μm pitch. In this case, the number of effective discharge holes in calculation is 1000.
After the dispersion was prepared, the droplets were discharged under the following toner production conditions, and then the droplets were dried and solidified to produce toner base particles.

[Toner preparation conditions]
Dispersion density: 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

“Nozzle frequency” means “frequency of thin film 129”. 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. When the particle size distribution of the collected particles was measured with a flow particle image analyzer (FPIA-2000) under the following measurement conditions, the volume average particle size (Dv) was 5.2 μm and the number average particle size (Dn) was Toner base particles having a diameter of 4.9 μm and a Dv / Dn of 1.06 were obtained.
When the stability of the discharge was tested, the change in the discharge amount when continuously operated for 1 hour did not change after 1 hour with respect to the initial 1.02 g / min. The particle size distribution of the toner collected after the continuous operation for 1 hour was measured and found to be 0.91 g / min. This was evaluated as follows as the continuous ejection property after 1 hour. As a result, the continuous dischargeability was calculated as 89%. It means that continuous discharge property is excellent, so that this figure is high.
Continuous discharge property after 1 hour = toner composition liquid discharge amount after 1 hour / initial toner composition liquid discharge amount × 100 (%)

Flow-type particle image analyzer (Flow
The measurement method using the Particle Image Analyzer will be described below. The measurement of toner, toner particles and external additives using a flow type particle image analyzer can be performed using, for example, a flow type particle image analyzer FPIA-2000 manufactured by Toa Medical Electronics.
The measurement removes fine dust through a filter, and as a result, the number of particles in a predetermined measurement range (here, a circle equivalent diameter of 0.60 μm or more and less than 159.21 μm) is 20 or less in water having a density of 10 ⁻³ cm ^3. A few drops of nonionic surfactant (Contaminone N, manufactured by Wako Pure Chemical Industries, Ltd.) are added to 10 ml of water, and 5 mg of a measurement sample is added, and 20 kHz is obtained using an ultrasonic dispersing device (SH, UH-50). , 50 W / 10 cm ³ for 1 minute dispersion treatment, further dispersion treatment is performed for a total of 5 minutes dispersion treatment, the measurement sample particle concentration is 4000-8000 pieces / 10 ⁻³ cm ³ (equivalent to measurement circle) The particle size distribution of particles having a circle-equivalent diameter of 0.60 μm or more and less than 159.21 μm was measured by the following method using the sample dispersion liquid (for particles in the diameter range).

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.
According to this measurement method, the equivalent circle diameter of 1200 or more particles can be measured in about 1 minute. The number based on the equivalent circle diameter distribution and the ratio of particles having a prescribed equivalent circle diameter (number%) ) Can be measured. As shown in Table 1, the measurement results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels for one octave). In actual measurement, particles were measured in a range where the equivalent circle diameter was 0.60 μm or more and less than 159.21 μm.
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 a regular maintenance for about one hour.

(Examples 2 to 12)
Table 2 shows the results of Examples 2 to 12 evaluated in the same manner as Example 1 using the nozzle specifications shown in Table 1. The toner composition liquid and peripheral devices used are the same as those in Example 1 except that the nozzle specifications are changed.

(Comparative Examples 1-7)
Similar to Example 1, evaluation was performed in the same manner as in Example 1 using nozzles having the specifications shown in Table 1. The results are also shown in Table 2. The toner composition liquid and peripheral devices used were the same as those in Example 1 except that the nozzle specifications were changed.
Comparative Example 1 has no projection and shows the result with a conventional nozzle shape.
Comparative Examples 2 and 3 show that there is no effect even if the height of the convex portion is further increased compared to Examples 7 and 8.
Comparative Examples 4 to 7 indicate that it is difficult to achieve both the particle size distribution and the continuous dischargeability with a nozzle shape outside the range of the present invention.
From the above results, it was shown that high-quality toner can be stably produced by using the ejection device having the nozzle shape of the present invention.

1, 101, 102, 103 Toner manufacturing apparatus 2, 201, 202, 203, 204, 205, 206, 207, 208, 209 Droplet ejecting unit 3, 301 Particle forming part 301 Top surface part 4, 401 Toner collecting part 5 Tube 6, 601 Toner reservoir 7, 701 Raw material container 8, 801, 808 Piping 9 Pump 10 Toner composition liquid 11, 114, 115, 116, 117, 118, 119 Nozzle 12, 124, 125, 126, 127, 128 129 Thin film 13, 131, 132, 133, 138 Vibrating means 13a, 131a, 132a, 133a, 138a Vibrating surface 14, 144, 145, 146, 147, 148, 149 Reservoir 15, 156, 157, 158 Flow path member 16, 161 droplet forming means 17, 171 vibration generating means (electromechanical converting means)
18, 184, 185, 186, 187 Liquid supply tube 19, 194, 195, 197 Bubble discharge tube 20 Support member 21, 218 Vibration generating means 211, 212, 213, 911, 912 Piezoelectric body 21a, 21b Electrode 22, 228 Vibration Amplifying means 221, 222, 223, 921, 922 Horn 23 Drive circuit (drive signal generation source)
24 Communication means 25 Head 26 Vibration separating member 27 Node portion 29 with small vibration amplitude Liquid storage region 30 Shroud portion 30a Opening portion 30b Wall 30c Wall 30d Bottom portion 30e Taper 31 Droplet 31a Droplet flow 32 Valve 35 Dry gas 36 Airflow Path forming member 37 Air flow path 41 Tapered surface 42 Air flow (vortex flow)
43 Static elimination means 70 Liquid supply pipe 71 Drainage pipe 81 Piezoelectric body 82 Horn 83 Fixing part 91 Ejection pipe 92 Guide pipe 93 Outlet 95 Carrying airflow 96 Airflow 100 Pump 130 Container 134 Horn type vibrator 134a Vibration surface 135 Langevin type Vibrator 135a Vibrating surface 136 Horn-shaped vibrator 170 Ring-shaped vibrating means 180 Chamber part 200 Liquid supply hole 210 Discharge hole 216 Piezoelectric body 226 Horn 310 Cover part 1110 Resist 1120 Support layer 1130 Dielectric layer 1140 Active layer 1150 First nozzle Hole 1160 Second nozzle hole PG1 Pressure gauge PG2 Pressure gauge T Toner particle

JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977 JP 2004-314524 A JP 2007-260661 A

Claims (7)

A toner composition solution in which a toner material containing at least a resin liquid and a colorant is dissolved or dispersed in a solvent is periodically ejected as droplets into the gas phase by a vibrating means from a plurality of nozzles, and then the droplets are solidified and dried. In a toner manufacturing method having a process,
The nozzle has a convex shape on the droplet discharge side, and the convex shape is a cylinder formed around the inner wall of the nozzle hole,
When the diameter of the nozzle hole is a, the outer diameter of the cylinder is b, and the height of the cylinder is h, the relationship of (1/2) a ≦ h ≦ 2a and a <b ≦ 3a is satisfied. Toner manufacturing method characterized by the above. A toner composition solution in which a toner material containing at least a resin liquid and a colorant is dissolved or dispersed in a solvent is periodically ejected as droplets into the gas phase by a vibrating means from a plurality of nozzles, and then the droplets are solidified and dried. In a toner manufacturing method having a process,
The nozzle has a convex shape on the liquid droplet ejection side, and a cross section parallel to the liquid ejection direction of the convex shape has a shape formed by a curve tangent to the inner wall of the nozzle hole and the inner wall;
2. A toner manufacturing method, wherein a relationship of (1/2) a ≦ r ≦ 2a is satisfied, where a is a diameter of the nozzle hole and r is a radius of curvature of the curve .   In the toner manufacturing method according to claim 1 or 2,
  The vibration means is composed of lead zirconate titanate (PZT).
  Toner manufacturing method characterized by the above.   In the toner manufacturing method according to any one of claims 1 to 3,
  The nozzle is made of a metal plate
  Toner manufacturing method characterized by the above.   In the toner manufacturing method according to any one of claims 1 to 3,
  The nozzle is made of silicon
  Toner manufacturing method characterized by the above.   In the toner manufacturing method according to claim 4,
  The nozzle is made of nickel
  Toner manufacturing method characterized by the above.   In the toner manufacturing method according to claim 4,
  The nozzle is made of stainless steel
  Toner manufacturing method characterized by the above.

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