JP5754315B2 - Production method of resin fine particles and toner, and production apparatus thereof - Google Patents

Description

  The present invention relates to a resin fine particle, a toner manufacturing method for developing an electrostatic image in a copying machine, electrostatic printing, printer, facsimile, electrostatic recording, and the like, and a manufacturing apparatus thereof.

  The developer used to develop the electrostatic image in electrophotography, electrostatic recording, electrostatic printing, etc. is, for example, once attached to the electrostatic latent image carrier on which the electrostatic image is formed, After being transferred from the electrostatic latent image carrier to a recording medium such as transfer paper, it is fixed on the paper surface. In this case, as a developer for developing an electrostatic charge image formed on the electrostatic latent image carrier, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier ( Magnetic toner and non-magnetic toner) are known.

  Conventionally, dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like are so-called pulverized toners in which a toner binder such as a styrene resin or a polyester resin is melt-kneaded with a colorant and finely pulverized. Is widely used.

Recently, a polymerization type toner produced by a toner production method using a suspension polymerization method or an emulsion polymerization aggregation method has been proposed.
However, the suspension polymerization method and the emulsion polymerization aggregation method have a problem that versatility of usable resins is low.

Therefore, a polymerization type toner produced by a method involving volume shrinkage called a polymer dissolution suspension method has been proposed (for example, see Patent Document 1). In the polymer dissolution suspension method, the toner material is dispersed or dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified in an aqueous medium containing a dispersant to form droplets, and then the volatile solvent is removed. To do. Unlike the suspension polymerization method and the emulsion polymerization aggregation method, the polymer dissolution suspension method has high versatility of usable resins, and in particular, transparency and smoothness of the image area after fixing are required. It is excellent in that a polyester resin useful for a full color process can be used.
However, since the polymer dissolution suspension method is based on the premise that a dispersant is used in an aqueous medium, a dispersant that impairs the charging characteristics of the toner remains on the toner surface, thereby impairing environmental stability. There arises a problem that a large amount of washing water is required to remove this problem.

Therefore, a spray granulation method has been proposed for a long time as a method for producing toner without using an aqueous medium (see, for example, Patent Document 2). The spray granulation method is a problem due to the use of an aqueous medium in order to obtain a particle by discharging a molten liquid of a toner composition or a liquid in which a toner composition liquid is dissolved using various atomizers, and then discharging and drying. Does not occur.
However, the particles obtained by the conventional spray granulation method are relatively coarse and large and have a wide particle size distribution, which causes a problem of deteriorating the characteristics of the toner itself.

Therefore, a toner manufacturing method and a manufacturing apparatus have been proposed in which fine droplets are formed from a nozzle using a piezoelectric pulse, and this is dried and solidified to manufacture toner (see, for example, Patent Document 3).
However, in the toner manufacturing method and manufacturing apparatus, only one droplet can be ejected from one nozzle using one piezoelectric body, and the number of droplets that can be ejected per unit time is small. There is a problem that the nature is bad.

In addition, a toner manufacturing method in which a piezoelectric pulse is converged by an acoustic lens, and a toner composition is ejected from a nozzle to a solidified portion by the converged acoustic pulse to form a fine droplet, which is dried and solidified to produce a toner; and A manufacturing apparatus has been proposed (see, for example, Patent Document 4).
However, even with the toner manufacturing method and manufacturing apparatus, only one droplet can be ejected from one nozzle using one piezoelectric body, and the number of droplets that can be ejected per unit time is small. There is a problem that the nature is bad.

Therefore, the vibration surface facing the thin film in which a plurality of discharge holes (nozzles) are formed is vibrated by the expansion and contraction of the piezoelectric body, and droplets of the toner composition fluid are ejected at a constant frequency, and the liquid is solidified to form a toner. A toner manufacturing method for manufacturing particles has been proposed (see, for example, Patent Document 5).
However, in the toner manufacturing method, when a plurality of ejection holes are provided for one piezoelectric body, the speed at which the vibration of the piezoelectric body is transmitted to each ejection hole differs depending on the distance from the piezoelectric body. There is a problem that a time lag occurs in the discharged liquid droplets, and the discharge amount varies between the discharge holes.

Therefore, the thin film with a plurality of discharge holes connected to the liquid chamber is directly vibrated by the electromechanical conversion means arranged around the thin film, and the toner composition liquid is discharged to form droplets (film vibration). (Mold ejection means), a toner particle manufacturing method and a manufacturing apparatus for manufacturing toner particles by solidifying the droplets have been proposed (see, for example, Patent Document 6). According to the method and apparatus for producing toner particles, since the thin film in which the ejection holes are formed can be directly vibrated, it is possible to obtain a toner having a monodispersibility in particle size.
However, in the case of the method of generating a wave in a direction parallel to the thin film in which a plurality of ejection holes are formed and discharging the toner composition liquid into droplets as in the toner particle manufacturing method and manufacturing apparatus, the thin film Can be distributed in the direction parallel to the sound pressure, the distribution of the sound pressure applied to the meniscus of the toner composition liquid in the discharge holes, and thus the discharge speed of the toner composition liquid. As a result, the area where the monodisperse liquid droplets can be ejected is limited to the above-mentioned thin film (ejection structure) because the liquid droplets are not ejected at a place where the sound pressure applied to the meniscus is small and the liquid droplets are likely to coalesce even if ejected. Body, nozzle plate). If the area where monodisperse droplets can be ejected is small, not only will it be necessary to widen the equipment required for production, but also the energy efficiency of the manufacturing equipment will be reduced, so the area needs to be expanded. Is the current situation.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, according to the present invention, the number of droplets that can be discharged simultaneously from a plurality of discharge holes, the droplets discharged from the plurality of discharge holes can be discharged in uniform amounts without being united, and can be discharged per unit time. It is an object of the present invention to provide a toner manufacturing method and a manufacturing apparatus therefor, which can efficiently manufacture a toner having high versatility and high monodispersibility.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies and as a result, obtained the following findings. That is, a droplet forming means for discharging a toner composition liquid containing at least a resin and a colorant from a plurality of discharge holes including those having different shapes at a uniform discharge speed, and the droplet formation And a particle forming means for solidifying the toner composition liquid to form particles, whereby droplets can be discharged simultaneously from a plurality of discharge holes, and the droplets discharged from the plurality of discharge holes can be discharged together. The inventors have found that a toner that can be ejected in a uniform amount, can be ejected per unit time, can be efficiently produced, and has high versatility and monodispersibility. Thus, the present invention has been completed.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> A droplet forming unit that discharges a toner composition liquid containing at least a resin and a colorant from a plurality of discharge holes including different shapes at a uniform discharge speed, and the droplet And a particle forming means for forming particles by solidifying the solidified toner composition liquid.
<2> The droplet forming means has a discharge structure in which a plurality of discharge holes including those having different shapes are formed, and the shape of the plurality of discharge holes has an opening diameter of the plurality of discharge holes. The toner manufacturing apparatus according to <1>, wherein the toner composition apparatus has a tapered shape that decreases in a discharge direction of the toner composition liquid, and the plurality of discharge holes have different taper angles depending on positions in the discharge structure.
<3> The toner manufacturing apparatus according to <2>, wherein the droplet forming unit further includes a vibration generator that generates vibration, and the vibration generator is provided in an annular shape around the discharge structure. It is.
<4> The toner production apparatus according to <3>, wherein a taper angle of a discharge hole located on a vibration generator side in the discharge structure is larger than a taper angle of a discharge hole located in a central portion.
<5> The droplet forming means includes a liquid chamber in which discharge holes are opened, and a vibration generator that applies vibration to the toner composition liquid in the liquid chamber, and vibration is applied by the vibration generator. In addition, the toner composition liquid in the liquid chamber forms a pressure standing wave by liquid column resonance, and the toner composition liquid is ejected from the ejection hole formed in the region that becomes the antinode of the pressure standing wave. The toner production apparatus according to any one of <1> to <2>, wherein the toner is a unit for converting the toner into a toner.
<6> Any one of the items <1> to <5>, wherein the particle forming unit includes a carrier airflow passage that circulates a carrier airflow that conveys at least one of the dropletized toner composition liquid and the solidified particles. The toner manufacturing apparatus according to claim 1.
<7> The transport airflow passage according to <6>, wherein the transport airflow passage is provided so as to form a transport airflow in a direction substantially orthogonal to the direction of the initial discharge speed of the droplets discharged by the droplet forming unit. This is a toner manufacturing apparatus.
<8> A method for producing toner using the toner production apparatus according to any one of <1> to <7>, wherein toner composition liquids containing at least a resin and a colorant are formed in different shapes. A droplet forming step of forming droplets by discharging at a uniform discharge speed from a plurality of discharge holes including a certain one, and a particle forming step of solidifying the dropletized toner composition liquid to form particles A method for producing a toner.
<9> In the droplet forming step, a vibration generator provided in an annular shape around a discharge structure having a plurality of discharge holes imparts vibrations to the discharge structure to discharge the toner composition liquid to drop The method for producing a toner according to <8>, wherein the toner is a step of forming a toner.
<10> The droplet forming step imparts vibration to the toner composition liquid in the liquid chamber having a plurality of ejection holes, forms a pressure standing wave by liquid column resonance in the toner composition liquid, and The method for producing a toner according to <8>, wherein the toner composition liquid is ejected from the ejection holes formed in an antinode region.
<11> The particle forming step further includes a step of transporting at least a droplet in a range of 2 mm from the discharge opening of the discharge hole by a transport airflow in a direction substantially orthogonal to the direction of the initial discharge speed of the droplet. The toner production method according to any one of <8> to <10>.
<12> A toner manufactured using the toner manufacturing apparatus according to any one of <1> to <7>.
<13> The toner according to <12>, wherein the particle size distribution (weight average particle size / number average particle size) is 1.00 to 1.10.
<14> Droplet forming means for discharging a resin composition liquid containing at least a resin from a plurality of discharge holes including those having different shapes at a uniform discharge speed, and the dropletized resin An apparatus for producing resin fine particles, comprising at least particle forming means for solidifying a composition liquid to form particles.
<15> A method for producing resin fine particles using the resin fine particle production apparatus according to <14>, wherein a plurality of discharge holes including at least a resin composition liquid containing a resin having different shapes A resin fine particle characterized in that it has at least a droplet forming step for forming droplets by discharging at a uniform discharge speed from a particle, and a particle forming step for forming particles by solidifying the dropletized resin composition liquid It is a manufacturing method.

  According to the present invention, the conventional problems can be solved, the object can be achieved, droplets can be discharged simultaneously from a plurality of discharge holes, and the droplets discharged from the plurality of discharge holes can be united. There can be provided a toner manufacturing method and a manufacturing apparatus thereof capable of efficiently manufacturing a toner that can be discharged in a uniform amount, has a large number of droplets that can be discharged per unit time, and has high versatility and monodispersibility. .

FIG. 1 is a schematic sectional view showing an example of a toner manufacturing apparatus according to the present invention. FIG. 2 is a cross-sectional view showing an example of a droplet discharge section in the droplet formation unit of FIG. FIG. 3 is a cross-sectional view taken along the line A-A ′ showing the droplet forming unit of FIG. 1. FIG. 4A is a schematic diagram illustrating an example of a state of a liquid column resonance phenomenon in a liquid chamber. FIG. 4B is a schematic diagram illustrating an example of a liquid column resonance phenomenon in the liquid chamber. FIG. 4C is a schematic diagram illustrating an example of a liquid column resonance phenomenon in the liquid chamber. FIG. 4D is a schematic diagram illustrating an example of a liquid column resonance phenomenon in the liquid chamber. FIG. 4E is a schematic diagram illustrating an example of a liquid column resonance phenomenon in the liquid chamber. FIG. 5 is a schematic cross-sectional view showing an example of a toner manufacturing apparatus according to the present invention. FIG. 6 is an enlarged view showing an example of a droplet discharge unit of the toner manufacturing apparatus of FIG. FIG. 7 is a bottom view of FIG. 6 viewed from below. FIG. 8 is an enlarged cross-sectional view illustrating an example of a droplet discharge unit of the droplet discharge unit. FIG. 9A is a schematic cross-sectional view for explaining an example of the shape of the discharge hole for making the discharge speed of the toner composition liquid uniform. FIG. 9B is a schematic cross-sectional view for explaining an example of the shape of the ejection holes for making the ejection speed of the toner composition liquid uniform. FIG. 9C is a schematic cross-sectional view for explaining an example of the shape of the ejection holes for making the ejection speed of the toner composition liquid uniform. FIG. 10 is an enlarged cross-sectional view showing an example of a conventional droplet discharge unit. FIG. 11 is a schematic cross-sectional view showing an example in which a plurality of droplet discharge units are arranged. FIG. 12A is a schematic diagram for explaining an example of an operation principle of droplet formation by the droplet discharge unit. FIG. 12B is a schematic diagram for explaining an example of an operation principle of droplet formation by the droplet discharge unit. FIG. 13 is a diagram for explaining an example of the fundamental vibration mode. FIG. 14 is a diagram for explaining an example of the secondary vibration mode. FIG. 15 is a diagram for explaining an example of the tertiary vibration mode. FIG. 16 is a diagram illustrating an example in which a convex portion is formed at the center of the ejection structure (thin film, nozzle plate). FIG. 17 is a schematic bottom view for explaining the taper angle of the ejection structure used in Examples 1 to 4. FIG. 18A is a schematic explanatory diagram showing a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is one side fixed end and N = 1. FIG. 18B is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is fixed on both sides and N = 2. FIG. 18C is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is open at both sides and N = 2. FIG. 18D is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is one side fixed end and N = 3. FIG. 18E is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is fixed on both sides and N = 4. FIG. 18F is a schematic explanatory diagram illustrating a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is open at both sides and N = 4. FIG. 18G is a schematic explanatory diagram showing a standing wave of velocity and pressure fluctuation when the liquid column resonance liquid chamber is one side fixed end and N = 5. FIG. 19 is a schematic cross-sectional view and a schematic bottom view for explaining the discharge structure used in Examples 5-9. FIG. 20 is a diagram illustrating an example of the direction of the conveying airflow. FIG. 21 is a diagram illustrating another example of the direction of the conveyance airflow. FIG. 22A is a diagram illustrating an example of a state of the toner composition liquid ejected from the ejection holes. FIG. 22B is an enlarged view of a broken line part of FIG. 22A.

(Production apparatus and production method for resin fine particles)
The apparatus for producing resin fine particles of the present invention includes at least a droplet forming unit and a particle forming unit, and further includes other units as necessary.
The method for producing resin fine particles of the present invention includes at least a droplet forming step and a particle forming step, and further includes other steps as necessary.
The droplet forming step is a step of discharging a resin composition liquid containing at least a resin from a plurality of discharge holes including those having different shapes at a uniform discharge speed into droplets. Therefore, the resin fine particles need only contain at least a resin, and further contain other components as necessary.
Hereinafter, the resin fine particle production method and production apparatus of the present invention will be described in detail, taking toner as an example of resin fine particles as an example.
The toner manufacturing apparatus of the present invention includes at least a droplet forming unit and a particle forming unit, and further includes other units as necessary.
The toner production method of the present invention includes at least a droplet forming step and a particle forming step, and further includes other steps as necessary. The toner production method of the present invention is preferably performed by the toner production apparatus.
Hereinafter, the toner manufacturing method of the present invention will be described in detail together with the description of the toner manufacturing apparatus of the present invention.

<Droplet formation process, droplet formation means>
The droplet forming step is a step of discharging a toner composition liquid from a plurality of discharge holes including those having different shapes into droplets at a uniform discharge speed, and is performed by the droplet forming means.
The droplet forming means is not particularly limited as long as it can be ejected at a uniform ejection speed from a plurality of ejection holes including those having different shapes, and can be appropriately selected according to the purpose. It is preferable to have a liquid chamber and a droplet discharge portion.
The type of the droplet forming means is not particularly limited as long as the droplets can be formed, and can be appropriately selected according to the purpose. For example, a film vibration type droplet forming means, a liquid column resonance type, or the like And a droplet forming means.

<< Membrane vibration type >>
When the discharge structure having a plurality of discharge holes, which will be described later, is a film, the film vibration type droplet forming means imparts vibration to the film from a vibration generator, which will be described later, and supplies the toner composition liquid from the discharge holes. Means for discharging into droplets.

-Liquid chamber-
The liquid chamber is provided in the toner composition liquid flow path and stores a toner composition liquid described later.
There is no restriction | limiting in particular as a shape of the said liquid chamber, According to the objective, it can select suitably, For example, cylindrical shape, square shape, truncated cone shape etc. are mentioned.
The structure of the liquid chamber is not particularly limited and may be appropriately selected depending on the purpose. For example, a single layer structure including only a container, a double structure including a container body and a surface layer, a laminated structure, and the like. Can be mentioned.
The material of the container and the material of the surface layer in contact with the toner composition liquid may be the same or different.
The material for the surface layer in contact with the toner composition liquid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include metals, ceramics, plastics, and silicones. Among these, those which do not dissolve in the toner composition liquid and do not cause modification of the toner composition liquid are preferable.
There is no restriction | limiting in particular as a magnitude | size of the said liquid chamber, According to the objective, it can select suitably.

-Droplet ejection unit-
The droplet discharge section includes at least a discharge structure having a plurality of discharge holes including those having different shapes, and a vibration generator, and further includes other portions as necessary. The droplet discharge unit applies vibrations by the vibration generator and discharges the toner composition liquid in droplets from the plurality of discharge holes including those having different shapes at a uniform discharge speed.
The droplet discharge unit is not particularly limited and may be appropriately selected depending on the purpose. However, the resonance phenomenon of the liquid existing in the liquid chamber (sometimes referred to as “reservoir”) is used. Thus, the liquid droplets are preferred. In this case, if the resonance frequency of the liquid chamber overlaps with the resonance frequency of the toner composition liquid, the toner composition liquid cannot be given a desired vibration. Therefore, the resonance frequency of the toner composition liquid in the liquid chamber is equal to the resonance frequency of the liquid chamber. It is more preferable that the pressure of the toner composition liquid in the liquid chamber is increased evenly and droplets can be formed at a uniform discharge speed.

--Discharge structure--
The discharge structure includes a plurality of discharge holes including at least different shapes provided for discharging the toner composition liquid, and further includes other portions as necessary.
As the ejection structure, when the droplet forming means is a film vibration type, a thin film or a plate is preferable in terms of vibration.

The area of the surface having the plurality of discharge holes of the discharge structure (the surface having the opening surface of the discharge holes in the discharge structure) is not particularly limited, and the magnitude of vibration added by the vibration generator, etc. 1 mm ^{2 to} 80 mm ² is preferable, and 3 mm ^{2 to} 20 mm ^{2 is} more preferable. When the area is less than 1 mm ² , when a conveying airflow passage is provided in the particle forming means described later, the area of the ejection holes occupying the entire area of the ejection structure is reduced, and the toner production efficiency is deteriorated. In some cases, if it exceeds 80 mm ² , the production apparatus becomes too large, and it is difficult to obtain the effect of preventing droplets from being coalesced when the carrier airflow passage is provided.
Moreover, there is no restriction | limiting in particular as a material of the said discharge structure, Although it can select suitably according to the objective, A metal plate is preferable.

There is no restriction | limiting in particular as thickness of the said discharge structure, Although it can select suitably according to the objective, 5 micrometers-500 micrometers are preferable.
The shape of the discharge structure is not particularly limited and may be appropriately selected depending on the purpose. However, when the droplet forming unit is a membrane vibration type, a circular shape is preferable in that it can be vibrated uniformly. . In addition, when viewed from a cross section in the thickness direction of the discharge structure, the central portion of the surface having the plurality of discharge holes of the discharge structure is formed in a convex shape in the direction in which droplets are discharged. It is preferable in that the discharge direction (traveling direction) of the droplets can be controlled, and the entire discharge structure can be vibrated more uniformly, thereby forming the droplets uniformly.

  In the case where the droplet forming means is a membrane vibration type, it is preferable that the discharge structure is provided so that the discharge structure is deflected when vibrated. A method for generating deflection in the discharge structure is not particularly limited and may be appropriately selected depending on the purpose.For example, a frame provided on the outermost peripheral portion of the discharge structure and a joint portion may be provided. The method of joining and fixing via is mentioned.

The elastic modulus of the joint member is not particularly limited and can be selected according to the purpose. However, a concentric uniform vibration state in the discharge hole is obtained, and the droplet discharge state is stabilized and uniform. 10 ⁸ Pa or more is preferable in that a toner having a uniform particle size distribution can be obtained.
Use of a material having a high elastic modulus as the member of the joint is advantageous in that the outermost peripheral portion of the discharge structure and the discharge structure can be firmly fixed. Thereby, vibration is efficiently propagated to the discharge structure. In particular, it is preferable in that vibration is efficiently propagated when the discharge structure (film) is circular (film).
The elastic modulus can be measured by, for example, an ultrasonic method.

  The discharge structure and the frame, and / or the discharge structure and the vibration generator are electrically insulated from each other by the liquid repellent film of the insulator or the bonding agent of the insulator. It is preferable.

The material used for the liquid repellent film or the bonding agent is not particularly limited as long as it is an insulator, and can be appropriately selected according to the purpose. For example, polytetrafluoroethylene (PTFE), tetrafluoroethylene -Fluorocarbon resins such as perfluoroalkyl vinyl ether copolymer (PFA), fluorinated ethylene propylene (FEP), and polyvinylidene fluoride; epoxy resins such as bisphenol A and bisphenol F; SiO _{2 and the} like. These may be used alone or in combination of two or more. Further, described in JP-A-2010-107904, it has a perfluoroalkyl group on the SiO ₂ film, and liquid-repellent film made of a compound having a siloxane bond group at the terminal can also be suitably used.

---- Discharge hole ---
A plurality of the discharge holes (sometimes referred to as “nozzles” or “through holes”) are formed in the discharge structure. The plurality of ejection holes include those having different shapes.
The number of the discharge holes is not particularly limited and may be appropriately selected depending on the purpose. However, when the droplet forming unit is a film vibration type, the number of discharge holes formed in one discharge structure is not limited. The number is preferably 2 to 3,000.

  There is no restriction | limiting in particular as the shortest space | interval (pitch) between the center part of the said adjacent discharge hole, Although it can select suitably according to the objective, An equal space | interval is preferable at the point which discharges a uniform particle.

The opening diameter of the discharge opening (the end of the discharge hole in the discharge direction) of the discharge hole is not particularly limited and may be appropriately selected depending on the volume of the target discharge droplet, but is 3 μm to 30 μm. However, it is preferable in that the droplets of the toner composition liquid are ejected (ejected) from the ejection holes so that micro droplets having a very uniform particle diameter are generated. Since the volume of the ejected droplet is substantially determined by the opening diameter of the ejection opening of the ejection hole, for example, when the solidified toner has a particle diameter of about 6 μm, the opening diameter of the ejection hole is 8 μm to 12 μm. Is preferred.
The opening diameter of the discharge hole means a diameter if it is a perfect circle, and an average diameter if it is a polygon such as an ellipse, a quadrangle, a hexagon, an octagon, or a regular polygon.

The arrangement of the plurality of ejection holes in the ejection structure is not particularly limited and may be appropriately selected according to the purpose. However, when the droplet forming means is a membrane vibration type, the ejection structure It is preferable to be provided at the central portion (hereinafter, sometimes referred to as “the central portion of the discharge structure”) in a plane perpendicular to the thickness direction of the body.
When the toner manufacturing apparatus has a vibration generator to be described later around the discharge structure, the shortest distance between the plurality of discharge holes and the vibration generator is not particularly limited, and the discharge structure However, the plurality of discharge holes may be provided at a position where the vibration displacement of the discharge structure is not zero. preferable. In the ejection hole where the vibration displacement is 0, the toner composition liquid may ooze out.

The shape of the plurality of ejection holes is not particularly limited as long as the toner composition liquid can be uniformly ejected between the plurality of ejection holes, including shapes different from each other, and is appropriately selected according to the purpose. can do.
As the shape of such a discharge hole, for example, a tapered shape or a round shape in which the opening diameter of the discharge hole becomes smaller in the discharge direction of the droplet (toner composition liquid) is preferable. When the shape of the discharge hole is a taper shape, the plurality of discharge holes preferably have different taper angles depending on the position in the discharge structure, and when the shape of the discharge hole is a round shape, the plurality of the discharge holes It is preferable that the discharge hole has a different radius of curvature depending on the position in the discharge structure. As described above, the plurality of ejection holes have different taper angles and curvature radii depending on positions in the ejection structure, so that the toner composition liquid can be ejected uniformly. That is, by changing the taper angle and the radius of curvature of the plurality of discharge holes according to the position in the discharge structure, the pressure loss due to the position of the discharge hole in the discharge structure is changed, and the discharge speed in the plurality of discharge holes The toner composition liquid can be discharged at a uniform speed through the plurality of discharge holes. This is preferable in that the speed of the discharge liquid has the same distribution in each discharge hole and the toner can be processed with high accuracy.
Here, the taper angle refers to a perpendicular (opening axis) to the opening surface of the discharge hole (surface perpendicular to the thickness direction of the discharge structure) and the discharge hole in a cross section in the thickness direction of the discharge structure. The angle formed with the side surface of the cross-sectional shape. The radius of curvature is a radius of curvature in a round shape from the opening surface of the discharge hole (a surface perpendicular to the thickness direction of the discharge structure) toward the thickness direction of the discharge structure. The taper angle and the radius of curvature can be measured by observing with a confocal microscope, for example.

  There is no restriction | limiting in particular as a method of forming the said discharge hole in the said discharge structure, It can select suitably according to the objective, For example, the method of processing by electroforming, the method of processing by electric discharge, etc. are mentioned. Moreover, there is no restriction | limiting in particular as a method of processing an ejection hole into arbitrary taper angles or curvature radii, According to the objective, it can select suitably, For example, when processing by electroforming, it is LIGA process, by discharge In the case of processing, there is a method of controlling with an electrode.

--- Vibration generator--
The vibration generator is not particularly limited as long as it can generate vibration, and can be appropriately selected according to the purpose. As a result, vibration is applied to the discharge structure, and the toner composition liquid in the discharge hole of the discharge structure is discharged in the form of droplets.
Specific examples of the vibration generator include an ultrasonic generator that generates mechanical vibration by a piezoelectric effect or a magnetostriction effect. Among these, those capable of converting electricity into mechanical vibration by the piezoelectric effect are preferable in that vibration can be efficiently generated at a higher frequency, and examples thereof include a piezoelectric body.
There is no restriction | limiting in particular as a material of the said piezoelectric material, According to the objective, it can select suitably, For example, piezoelectric polymers, such as piezoelectric ceramics, such as lead zirconate titanate (PZT), polyvinylidene fluoride (PVDF), etc. Crystal, LiNbO ₃ , LiTaO ₃ , KNbO _{3 and} other single crystals. Among these, lead zirconate titanate (PZT) is preferable in terms of vibration controllability.

The arrangement of the vibration generator is not particularly limited as long as vibration can be efficiently propagated to the toner composition liquid, and can be appropriately selected according to the purpose. In the case of a mold, it is preferably provided around the region where the discharge holes of the discharge structure are formed, and more preferably provided in an annular shape around the region where the discharge holes of the discharge structure are formed. preferable.
The method of providing the vibration generator around the region where the discharge holes of the discharge structure are formed is not particularly limited and can be appropriately selected depending on the purpose. For example, the vibration generator, For example, a method of bonding and fixing the discharge structure through a bonding portion may be used. In this case, the vibration generating body is formed with a discharge hole in a region (hereinafter sometimes referred to as “deformable region”) that is not fixed to a frame provided on the outermost peripheral portion of the discharge structure. It is particularly preferable to provide an annular shape around the region.

-Droplet formation-
Next, a mechanism for periodically discharging the toner composition liquid in the form of droplets when the droplet forming means is a film vibration type in the droplet forming step will be described.

  When the discharge structure is a film, the vibration generated by the vibration generator is propagated to the discharge structure (film) having a plurality of discharge holes facing the liquid chamber to periodically vibrate the discharge structure. Therefore, a plurality of discharge holes can be arranged in a relatively large area (diameter of 1 mm or more), and droplets can be periodically and stably formed and discharged from the plurality of discharge holes.

When the peripheral portion 12A of the discharge structure 16 which is a simple circular film as shown in FIGS. 12A and 12B is fixed, the periphery of the basic vibration is a node, and the center O of the discharge structure 16 is shown in FIG. The vibration displacement ΔL is maximum (ΔLmax) at the discharge hole located in the center of the discharge structure, and the vibration displacement ΔL is minimum (ΔLmin) at the outermost discharge hole (discharge hole located on the vibration generator side). It has a cross-sectional shape and periodically vibrates up and down in the vibration direction. In addition, it is preferable to provide the discharge hole which is ΔLmin in a range where the liquid droplets discharged from the discharge hole do not adhere to the vibration generator.
Further, it is known that higher order modes such as a secondary vibration mode as shown in FIG. 14 and a tertiary vibration mode as shown in FIG. 15 exist. These modes have one or more concentric nodes in a circular membrane, and are substantially axisymmetric deformation shapes. In addition, as shown in FIG. 16, it is possible to control the traveling direction of the liquid droplet and adjust the vibration amplitude amount to some extent by making the central portion of the ejection structure 16 have a convex shape 12C.
The vibration displacement can be measured by, for example, a laser Doppler vibrometer.

When the discharge structure 16 vibrates, a sound pressure Pac proportional to the vibration speed Vm of the discharge structure is generated in the liquid near the discharge hole provided at each position of the circular film (discharge structure). It is known that the sound pressure is generated as a reaction of the radiation impedance Zr of the medium (toner composition liquid). The sound pressure is the product of the radiation impedance and the vibration velocity Vm of the ejection structure, and the following equation (1) is obtained. It is expressed using.
Pac (r, t) = Zr · Vm (r, t) (1)
Since the vibration velocity Vm of the discharge structure varies periodically with time, it is a function of time (t). For example, various periodic variations such as a sine waveform and a rectangular waveform can be formed. Further, the vibration displacement in the vibration direction is different at each position of the discharge structure, and Vm is also a function of position coordinates on the discharge structure. The vibration form of the discharge structure used in the present invention is an axial object. Therefore, it is substantially a function of the radius (r) coordinate.

The product of the sound pressure Pac (r, t) and the sectional area Sn on the toner composition liquid supply side of the discharge hole is applied to the toner composition liquid in each discharge hole as a force Fn by vibration. The force Fn is represented by the following formula (2).
Fn = Pac (r, t) · Sn Equation (2)
The sound pressure Pac is not constant over the entire cross section of the ejection hole on the toner composition liquid supply side, but is regarded as having a sufficiently small cross-sectional area and approximated by a function of the radius (r) coordinate. The subscript n indicates the nth discharge hole from the center of the discharge structure. From the above formula (2), it can be seen that the force Fn increases as Sn is increased, and the magnitude of the force Fn can be made uniform by adjusting Sn. Actually, a local loss and a pipe loss occur with respect to this force Fn, and the resultant resultant force becomes the discharge speed of the toner composition liquid. The discharge speed can be adjusted including these pressure losses. is there.

  The discharge speed of the toner composition liquid is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 8 m / second to 20 m / second, and more preferably 12 m / second to 16 m / second. When the discharge speed is less than 8 m / second, droplets discharged from the plurality of discharge holes may be united. When the discharge speed exceeds 20 m / second, satellites may be generated or toner composition liquid may be discharged. Permeation from the holes may occur. The satellite is a discharge droplet having a diameter approximately one-half of a droplet formed mainly.

  The discharge speed is preferably uniform in all the discharge holes. Therefore, the ratio of the discharge speed at the discharge hole where the vibration displacement ΔL is maximum (ΔLmax) and the discharge speed at the discharge hole where the vibration displacement ΔL of the discharge structure is minimum (ΔLmin) (the discharge hole whose ΔLmin is (Discharge speed / discharge speed of discharge holes of ΔLmax) is preferably 0.5 to 1.0, more preferably 0.8 to 1.0.

The method for measuring the ejection speed is not particularly limited and can be appropriately selected depending on the purpose. For example, the ejected toner composition dispersion is irradiated with LED light, and the ejected toner composition dispersion is sandwiched between them. Observation is performed by taking a picture with a CCD camera installed facing the LED, and the driving frequency of the LED is synchronized with the frequency of the droplet discharge unit (timing of vibration generation by the vibration generator and voltage applied to the LED to emit light). By adjusting the timing of the toner discharge, it is possible to confirm the discharge of the toner composition liquid from the discharge holes.
FIG. 22A shows the state of the toner composition dispersion discharged from the discharge hole (not shown), and FIG. 22B shows an enlarged view of the broken line part of FIG. 22A. The liquid column of the toner composition dispersion liquid ejected from the ejection holes due to the constant vibration causes the constriction p of the liquid column at a constant interval (hereinafter sometimes referred to as “liquid column constriction”). By splitting into a certain amount of droplets at the tip of the liquid column, toner particles having a certain particle diameter are continuously generated (FIG. 22A). From the discharged liquid column constriction p and the vibration frequency, it can be estimated by calculation of discharge speed (m / second) = constriction wavelength (μm) / frequency (kHz). Here, the constriction wavelength is the maximum from the liquid column constriction p (liquid column constriction p closest to the ejection opening) first appearing in the liquid column made of the toner composition dispersion liquid ejected from the ejection hole opening (not shown). It means length.

The toner composition liquid periodically discharged from the discharge side end portions of the plurality of discharge holes to the outside (gas phase) of the discharge holes is discharged at the discharge side end portions of the plurality of discharge holes. Since the sphere is formed by the difference in surface tension between the inside (liquid phase) and the gas phase, droplet-like ejection occurs periodically.
The vibration frequency of the discharge structure that enables droplet formation is not particularly limited and can be appropriately selected according to the area of the discharge structure, but generally a region of 20 kHz to 2.0 MHz is used. It is done. Among these, the range of 50 kHz to 500 kHz is preferable. 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.
There is no restriction | limiting in particular as said sound pressure, Although it can select suitably according to the objective, 10 kPa or more is preferable at the point which the microparticle dispersion | distribution promotion effect generate | occur | produces more suitably. Further, as the conditions of the toner composition liquid, in the region where the viscosity is 20 mPa · s or less and the interfacial tension is 20 mN / m to 75 mN / m, the sound generation pressure is 500 kPa or less in that the satellite generation start region is the same. It will be necessary. Among these, 100 kPa or less is preferable.

<< Liquid column resonance type >>
The liquid column resonance type droplet forming unit is described later on the toner composition liquid in the liquid chamber when a discharge structure having a plurality of discharge holes, which will be described later, is one wall surface forming the liquid chamber. A means for applying vibration by a vibration generator to form a pressure standing wave by liquid column resonance, and forming the toner composition liquid into droplets from the ejection holes formed in the region that becomes the antinode of the pressure standing wave. is there.
The “region that becomes the antinode of the pressure standing wave” is a region where the amplitude in the pressure wave of the liquid column resonance standing wave is large and the pressure fluctuation is large, and is large enough to eject a droplet. This is a region having pressure fluctuation. There is no particular limitation on the region that becomes the antinode of such a pressure standing wave, and it can be appropriately selected according to the purpose. However, the position where the amplitude of the pressure standing wave becomes a maximum (as a velocity standing wave) ± 1/3 wavelength is preferable from the section of (1) to the position where it becomes the minimum, and ± 1/4 wavelength is more preferable.
When the discharge hole is formed in a region that becomes the antinode of the pressure standing wave, even if a plurality of discharge holes are opened, a substantially uniform droplet can be formed from each discharge hole. Furthermore, it is preferable in that the droplets can be efficiently discharged and the discharge holes are not easily clogged.

-Liquid chamber-
In the case of the liquid column resonance type, the shape, structure, and size of the liquid chamber are not particularly limited and can be appropriately selected according to the purpose. And so on.
Also, the material of the liquid chamber may be the same as that of the membrane vibration type.

When the droplet forming means is a liquid column resonance type, the liquid chamber (liquid column resonance liquid chamber) generates a pressure standing wave by vibration applied by the vibration generator according to the principle of the liquid column resonance phenomenon described later. A liquid chamber that can be formed, a discharge hole is formed in a region that becomes the antinode of the pressure standing wave, and a communication port for supplying the toner composition liquid (at the longitudinal end of the liquid column resonance liquid chamber) If necessary, a reflection wall surface (perpendicular to the longitudinal axis) is provided at least at one end or both ends in the longitudinal direction of the liquid column resonance liquid chamber.
Here, the “reflective wall surface” refers to a wall surface formed by a member that is hard enough to reflect the sound wave of the liquid, for example, a metal member such as aluminum or stainless steel, a member such as silicone, or the like.

  The length L between the wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber as shown in FIG. 2 is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably determined based on the column resonance principle. Further, as shown in FIG. 3, the width W of the liquid column resonance liquid chamber is not particularly limited and can be appropriately selected according to the purpose. However, in order not to give an extra frequency to the liquid column resonance, It is preferable that the length is less than half of the length L of the liquid column resonance liquid chamber.

  The number of the liquid chambers is not particularly limited and may be appropriately selected depending on the purpose. However, when the droplet forming means is a liquid column resonance type, the operability and the productivity can be compatible with each other. The number is preferably 2,000 to 2,000, more preferably 100 to 1,000, and particularly preferably 100 to 400.

-Droplet ejection unit-
The droplet discharge unit includes at least a discharge structure and a vibration generator, and further includes other parts as necessary. The droplet discharge unit applies vibrations by the vibration generator and discharges the toner composition liquid in droplets from the plurality of discharge holes including those having different shapes at a uniform discharge speed.
The droplet discharge unit is not particularly limited and may be appropriately selected depending on the purpose. However, it is preferable that the droplet discharge unit is formed into a droplet using the resonance phenomenon of the liquid existing in the liquid chamber. In this case, if the resonance frequency of the liquid chamber overlaps with the resonance frequency of the toner composition liquid, the toner composition liquid cannot be given a desired vibration. Therefore, the resonance frequency of the toner composition liquid in the liquid chamber is equal to the resonance frequency of the liquid chamber. It is more preferable that the pressure of the toner composition liquid in the liquid chamber is increased evenly and droplets can be formed at a uniform discharge speed.

--Discharge structure--
The discharge structure includes a plurality of discharge holes including at least different shapes provided for discharging the toner composition liquid, and further includes other portions as necessary.
Examples of the ejection structure include a wall surface that forms the liquid column resonance liquid chamber when the droplet forming unit is a liquid column resonance type.

  The area, thickness, and shape of the surface having the plurality of discharge holes of the discharge structure (the surface having the opening surface of the discharge holes in the discharge structure) are not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include those similar to the membrane vibration type.

The material of the discharge structure is not particularly limited and may be appropriately selected depending on the purpose. For example, the same material as the membrane vibration type may be used, but based on the liquid column resonance principle described later. In order to form a pressure standing wave in the toner composition liquid in the liquid column resonance liquid chamber, and to drop the toner composition liquid into droplets from the ejection holes formed in the antinode region of the pressure standing wave, the ejection structure The body is preferably formed by joining frames formed of a material having a high rigidity that does not affect the resonance frequency of the toner composition liquid. Examples of such materials include metals, ceramics, and silicone.
The discharge structure may have an insulating liquid repellent film, which will be described later, formed on the entire exposed surface.
There is no restriction | limiting in particular as said liquid repellent film, According to the objective, it can select suitably, For example, the same thing as the said film vibration type etc. are mentioned.

---- Discharge hole ---
A plurality of the discharge holes are formed in the discharge structure. The plurality of ejection holes include those having different shapes.
The number of the discharge holes is not particularly limited and can be appropriately selected according to the purpose. When the droplet forming means is a liquid column resonance type, the discharge formed in one liquid column resonance liquid chamber Although the number of holes may be one, it is preferable to arrange a plurality of holes from the viewpoint of productivity, preferably 2 to 100, more preferably 4 to 60, and particularly 4 to 20 preferable. If the number of ejection holes formed in one liquid column resonance liquid chamber exceeds 100, the voltage applied to the vibration generator when droplets of a desired toner composition liquid are formed from the 100 ejection holes. May need to be set high, and the behavior of the vibration generator may become unstable. In the case of 4 to 20, the pressure standing wave is stable and the productivity is maintained.
Further, when the droplet forming means is a liquid column resonance type, the number of ejection holes formed in at least one of the regions that become the antinodes of the pressure standing wave is not particularly limited. 1 to 20 is preferable, 4 to 15 is more preferable, and 4 to 10 is particularly preferable. The productivity increases as the number of the ejection holes increases, but when the number exceeds 20, the ejection holes become too dense and the ejected droplets may coalesce into coarse particles, which may adversely affect image quality. .

  There is no particular limitation on the shortest interval (pitch) between the central portions of the adjacent discharge holes, and the opening diameter of the discharge openings (end portions in the discharge direction of the discharge holes) of the discharge holes. Although it can select suitably according to a volume etc., the pitch and opening diameter similar to the said membrane vibration type are preferable.

In the case where the droplet forming means is a liquid column resonance type, the position of the plurality of discharge holes in the discharge structure is not particularly limited as long as it is formed in a region that becomes an antinode of the pressure standing wave. There is no limitation, and it can be appropriately selected according to the length L between both ends in the longitudinal direction of the liquid column resonance liquid chamber, the width W of the liquid column resonance liquid chamber, and the like.
The distance ratio (Le / L) between the length L between both ends in the longitudinal direction of the liquid column resonance liquid chamber and the distance Le between the center of the discharge hole closest to the end of the liquid column resonance liquid chamber There is no particular limitation, and it can be appropriately selected according to the purpose, but it is preferably larger than 0.6.

  The shape of the plurality of ejection holes is not particularly limited as long as the toner composition liquid can be uniformly ejected between the plurality of ejection holes, including shapes different from each other, and is appropriately selected according to the purpose. However, the same shape as the membrane vibration type is preferable.

--- Vibration generator--
The vibration generator is not particularly limited as long as vibration can be generated, and can be appropriately selected according to the purpose. Examples thereof include the same as the membrane vibration type.

When the droplet forming means is a liquid column resonance type, the arrangement of the vibration generator is not particularly limited and can be appropriately selected according to the purpose. However, the liquid in which a plurality of discharge holes are formed is used. It is preferably formed on a wall facing one wall surface (longitudinal surface) of the columnar resonance liquid chamber.
The vibration generator is preferably bonded to an elastic plate, and the elastic plate may form a part of the wall of the liquid column resonance liquid chamber so that the vibration generator does not come into contact with the liquid. preferable.
Furthermore, it is preferable that the vibration generator is arranged so that it can be individually controlled for each liquid column resonance liquid chamber. In addition, it is preferable to arrange a vibration generating body such as a block-like piezoelectric body through an elastic plate in accordance with the arrangement of the liquid column resonance liquid chambers from the viewpoint of individually controlling each liquid column resonance liquid chamber.

-Droplet formation-
Next, a mechanism for periodically discharging the toner composition liquid in the form of droplets when the droplet forming means is a liquid column resonance type in the droplet forming step will be described.

When the sound velocity of the toner composition liquid in the liquid column resonance liquid chamber is c and the driving frequency applied to the toner composition liquid as a medium from the vibration generator is f, the wavelength λ at which the liquid resonance occurs is expressed by the following formula ( 3).
λ = c / f Formula (3)

FIG. 2 is a cross-sectional view illustrating an example of a droplet discharge unit. In the liquid column resonance liquid chamber 12 of FIG. 2, the length from the end 54 of the frame on the fixed end side to the end 55 on the liquid common supply path 52 side is L, and further, the end of the frame on the liquid common supply path 52 side And the height of the communication port is h2 (= about 40 μm).
In the case of a both-side fixed end that is equivalent to a closed fixed end on the liquid common supply path 52 side, resonance occurs when the length L coincides with an even multiple of a quarter of the wavelength λ. Most efficiently formed. That is, it is expressed by the following formula (4).
L = (N / 4) λ (4)
(However, N represents an even number.)
The case where it is equivalent to the fixed end is a case where it can be considered that there is no pressure relief portion at a certain end. For example, the height of the reflection wall surface at a certain end is the communication for supplying the toner composition liquid. This refers to the case where the height of the mouth is twice or more, or the case where the area of the reflection wall surface at a certain end is twice or more the area of the opening of the communication port for supplying the toner composition liquid.

Further, the above formula (4) is also established in the case of a double-sided open end where both ends are completely open or equivalent to a double-sided open end.
Similarly, when one side is equivalent to an open end with a pressure relief portion and the other side is closed (fixed end), that is, one side fixed end or one side open end, the length L is the wavelength λ. Resonance is most efficiently formed when it matches an odd multiple of a quarter. That is, N in the above formula (4) is expressed as an odd number. In the case of the open ends on both sides, L corresponds to an even multiple of a quarter of the wavelength, and in the case of one side fixed end, L corresponds to an odd multiple of a quarter of the wavelength.

For the drive frequency f with the highest efficiency, the following equation (5) is derived from the above equations (3) and (4).
f = N × c / (4L) (5)
(However, L is the length of the liquid column resonance liquid chamber in the longitudinal direction, c is the velocity of the sound wave of the toner composition liquid, and N is an integer.)
Therefore, in the method for producing a toner of the present invention, it is preferable to apply a vibration having a frequency f that satisfies the above formula (5) to the toner composition liquid. However, in reality, since the liquid has a viscosity that attenuates resonance, the vibration is not amplified infinitely, and has a Q value. As shown in equations (6) and (7) described later, Resonance also occurs at frequencies in the vicinity of the most efficient drive frequency f shown in (5).

18A to 18G show the shape of the standing wave of the velocity and pressure fluctuation (resonance mode) when N = 1, 2, 3, 4, and 5. FIG.
Although it is originally a sparse / dense wave (longitudinal wave), it is generally expressed as shown in FIGS. 18A-G, the solid line is the velocity standing wave, and the dotted line is the pressure standing wave.
For example, as can be seen from FIG. 18A showing the case of one-side fixed end where N = 1, the velocity distribution has an amplitude of zero at the closed end and a maximum amplitude at the open end in the case of the velocity distribution.
When the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is L, the wavelength at which the liquid resonates is λ, and the standing wave is most efficiently generated when the integer N is 1 to 5. . In addition, since the standing wave pattern varies depending on the open / closed state of both ends, they are also shown. As will be described later, the condition of the end is determined by the state of the opening of the discharge hole and the opening of the supply side.
In acoustics, the open end is an end at which the moving speed of the medium (liquid) in the longitudinal direction becomes zero, and conversely, the pressure becomes maximum. Conversely, the closed end is defined as an end where the moving speed of the medium becomes zero. The closed end is considered as an acoustically hard wall and wave reflection occurs. When ideally completely closed or opened, a resonant standing wave having a form as shown in FIGS. 18A to 18G is generated by superposition of waves, but the standing wave also depends on the number of ejection holes and the opening position of the ejection holes. The pattern fluctuates, and the resonance frequency appears at a position deviated from the position obtained from the above equation. However, a stable ejection condition can be created by appropriately adjusting the driving frequency.

For example, the sound velocity c of the liquid is 1,200 m / s, the length L of the liquid column resonance liquid chamber is 1.85 mm, wall surfaces exist at both ends, and N = 2 resonance that is completely equivalent to the fixed ends on both sides. When the mode is used, the most efficient resonance frequency is derived as 324 kHz from the above equation (4).
In another example, the sound velocity c of the liquid is 1,200 m / s, the length L of the liquid column resonance liquid chamber is 1.85 mm, and the same conditions as described above are used. When the equivalent N = 4 resonance mode is used, the most efficient resonance frequency is derived from the above equation (4) as 648 kHz. Even in the liquid column resonance liquid chamber having the same structure, higher order resonance frequency is obtained. Resonance can be used.

Further, the numerical aperture of the discharge holes 15, the opening arrangement position, and the cross-sectional shape of the discharge holes are factors that determine the drive frequency, and the drive frequency can be appropriately determined according to this.
For example, when the number of discharge holes 15 is increased, the restriction at the tip of the liquid column resonance liquid chamber 12 that has been a fixed end gradually becomes loose, a resonance standing wave that is almost close to the open end is generated, and the drive frequency increases. . Furthermore, if the opening position of the discharge hole 15 existing closest to the liquid common supply path 52 is a loose starting condition, and if the volume of the discharge hole varies depending on the thickness of the discharge structure, the actual standing The wave has a short wavelength and is higher than the drive frequency. When a voltage is applied to the vibration generator at the drive frequency determined in this way, the vibration generator 17 is deformed, and the resonance standing wave is generated most efficiently at the drive frequency. Further, the liquid column resonance standing wave is generated even at a frequency in the vicinity of the drive frequency at which the resonance standing wave is generated most efficiently. That is, when the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is L, and the distance to the center of the discharge hole 15 closest to the end 55 on the liquid common supply path 52 side is Le, L and Le The vibration generator is vibrated using a drive waveform whose main component is the drive frequency f in the range determined by the following formulas (6) and (7) using both the lengths of Thus, it is possible to discharge droplets from the discharge holes.

N × c / (4L) ≦ f ≦ N × c / (4Le) (6)
N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le) (7)
(However, L is the length of the liquid column resonance liquid chamber in the longitudinal direction, Le is the distance to the discharge hole closest to the end on the liquid supply path side, c is the velocity of the sound wave of the toner composition liquid, and N is an integer. )

  The liquid column resonance pressure standing wave is formed in the liquid column resonance liquid chamber 12 of FIG. 2 using the principle of the liquid column resonance phenomenon described above, and the discharge holes 15 arranged in a part of the liquid column resonance liquid chamber 12. In this case, droplet discharge occurs continuously. Note that it is preferable to dispose the discharge hole 15 at a position where the standing wave pressure fluctuates the most, because the discharge efficiency is increased and the device can be driven at a low voltage.

Next, the state of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber in the droplet discharge unit in the droplet forming unit will be described with reference to FIGS.
4A to E, the solid line written in the liquid column resonance liquid chamber plots the speed at each arbitrary measurement position from the fixed end side in the liquid column resonance liquid chamber to the end on the liquid common supply path side. The velocity distribution is shown, and the direction from the liquid common supply path side to the liquid column resonance liquid chamber is +, and the opposite direction is-.
4A to 4E, the dotted lines marked in the liquid column resonance liquid chamber plot the pressure values at arbitrary measurement positions from the fixed end side to the end of the liquid common supply path side in the liquid column resonance liquid chamber. The positive pressure is + and the negative pressure is-with respect to the atmospheric pressure.
Moreover, if it is a positive pressure, a pressure will be applied to the downward direction in the figure, and if it is a negative pressure, a pressure will be applied to the upward direction in the figure.
4A to 4E, the liquid common supply path side is opened as described above, but the height of the opening where the liquid common supply path 52 communicates with the liquid column resonance liquid chamber 12 (height h2 shown in FIG. 2). 2), the height of the frame serving as the fixed end (height h1 shown in FIG. 2) is preferably about twice or more, so that the liquid column resonance liquid chamber 12 is approximately the fixed end on both sides. Each change over time of the velocity distribution and the pressure distribution under the condition is shown.

  FIG. 4A shows a pressure waveform and a velocity waveform in the liquid column resonance liquid chamber 12 during droplet discharge. In FIG. 4B, the meniscus pressure increases again after the liquid is drawn immediately after the droplet is discharged. As shown in FIGS. 4A and 4B, the pressure in the liquid column resonance liquid chamber in which the discharge hole 15 in the liquid column resonance liquid chamber 12 is provided is maximum. Thereafter, as shown in FIG. 4C, the positive pressure in the vicinity of the discharge hole 15 decreases, and the liquid droplet 23 is discharged in a negative pressure direction.

And as shown to FIG. 4D, the pressure of the discharge hole 15 vicinity becomes the minimum. From this time, the filling of the toner composition liquid 10 into the liquid column resonance liquid chamber 12 starts. Thereafter, as shown in FIG. 4E, the negative pressure in the vicinity of the discharge hole 15 becomes smaller and shifts to the positive pressure direction. At this point, the filling of the toner composition liquid 10 is completed. Then, again, as shown in FIG. 4A, the positive pressure in the droplet discharge region of the liquid column resonance liquid chamber 12 becomes maximum, and the droplet 23 is discharged from the discharge hole 15. In this way, a pressure standing wave due to liquid column resonance is generated in the liquid column resonance liquid chamber by high-frequency driving of the vibration generator, and the pressure standing wave caused by liquid column resonance is the position where the pressure fluctuates the most. Since the discharge holes 15 are arranged in the droplet discharge region corresponding to the above, the droplets 23 are continuously discharged from the discharge holes 15 according to the antinode period.
The discharge speed in the case of the liquid column resonance type is preferably the same as that of the membrane vibration type, and the method of measuring the discharge speed in the case of the liquid column resonance type is also the same method as that of the film vibration type. Can be measured.

<< Toner Composition Liquid >>
The toner composition liquid contains at least a resin and a colorant and, if necessary, further disperses or dissolves a toner material containing other components such as a magnetic material, a wax, and a fluidity improver in an organic solvent. Is preferred.

  As the toner composition liquid, the same toner as a conventional electrophotographic toner can be used. That is, the toner particles of interest are prepared by dissolving the resin in various organic solvents, dispersing the colorant, and dispersing or dissolving the release agent in the form of fine droplets that are dried and solidified. Is possible. 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-melt kneading the above materials in various solvents as fine droplets.

The viscosity of the toner composition liquid is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 Pa · s to 15 mPa · s, and is preferably 0.5 Pa · s to 1.5 mPa · s. More preferred. If the viscosity exceeds 15 mPa · s, the viscous resistance may not be discharged significantly.
The viscosity of the toner composition liquid can be measured by, for example, a conical plate type rotational viscometer.

-Resin-
The resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, vinyl resins, polyester resins, polyol resins, phenols composed of styrene monomers, acrylic monomers, methacrylic monomers, etc. Examples thereof include resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins, coumarone indene resins, polycarbonate resins, and petroleum resins. These may be used alone or in combination of two or more.

-Colorant-
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 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 Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phisa red, para Lortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment 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, Quinacridone Red, Lazolone 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, Indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Grits Enlake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon, and mixtures thereof. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
There is no restriction | limiting in particular as content with respect to the toner of the said coloring agent, Although it can select suitably according to the objective, 1 mass%-15 mass% are preferable, and 3 mass%-10 mass% are more preferable.

  When a pigment is used as the colorant, it is preferable to include a pigment dispersant having high compatibility with the resin in terms of pigment dispersibility. Examples of commercially available pigment dispersants include “Ajisper PB821”, “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.), “Disperbyk-2001” (manufactured by BYK Chemie), and “EFKA-4010” (EFKA Corporation). Manufactured).

There is no restriction | limiting in particular as addition amount with respect to the coloring agent of the said dispersing agent, Although it can select suitably according to the objective, 1 mass%-200 mass% are preferable with respect to a coloring agent, 5 mass%-80 The mass% is more preferable. When the addition amount is less than 1% by mass, the dispersibility may be lowered, and when it exceeds 200% by mass, the chargeability may be lowered.
Further, the dispersing agent for dispersing the colorant is not particularly limited and can be appropriately selected according to the purpose, but may be blended at a ratio of 0.1% by mass to 10% by mass. preferable. When the content is less than 0.1% by mass, the pigment dispersibility may be insufficient. When the content exceeds 10% by mass, the chargeability under high humidity may be deteriorated.

  The weight average molecular weight of the dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. However, the molecular weight of the maximum value of the main peak in terms of styrene conversion weight in measurement using GPC is 500 to 100,000 is preferable, 3,000 to 100,000 is more preferable, 5,000 to 50,000 is further preferable, and 5,000 to 30,000 is particularly preferable. When the weight average molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the weight average molecular weight exceeds 100,000, the affinity with the solvent increases, Dispersibility may decrease.

  The colorant can also be used in the form of a master batch combined with a resin. There is no restriction | limiting in particular as binder resin kneaded with manufacture of a masterbatch or a masterbatch, According to the objective, it can select suitably, For example, in addition to a modified polyester resin or an unmodified polyester resin, for example, polystyrene , Resins of styrene such as poly-p-chlorostyrene and polyvinyltoluene, or substitutes thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer Polymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-methacrylic acid Ethyl acetate copolymer, styrene Butyl crylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene -Styrene resins such as acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester , Epoxy resin, epoxy polyol resin, polyurethane, 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.

There is no restriction | limiting in particular as the acid value of resin for the said masterbatch, Although it can select suitably according to the objective, 30 mgKOH / g or less is preferable and 20 mgKOH / g or less is more preferable. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered and the pigment dispersibility may be insufficient. The acid value can be measured by the method described in JIS K0070.
There is no restriction | limiting in particular as an amine value of resin for the said masterbatch, Although it can select suitably according to the objective, 1-100 are preferable and 10-50 are more preferable. When the amine value is less than 1 or more than 100, pigment dispersibility may be insufficient. The amine value can be measured by the method described in JIS K7237.

The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant with a high shear force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin.
The master batch may be manufactured using a flushing method. The flushing method is a method of mixing and kneading an aqueous paste containing a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing water and organic solvent components. In this case, since the wet cake of the colorant can be used as it is, there is no need to dry it.
For mixing and kneading, a high shearing dispersion device such as a three-roll mill can be used.

  There is no restriction | limiting in particular as the usage-amount with respect to resin to which the said masterbatch was attached, Although it can select suitably according to the objective, 0.1 mass%-20 mass% are preferable.

-Organic solvent-
The organic solvent is not particularly limited as long as the organic solvent can disperse or dissolve the resin and the colorant, and can be appropriately selected according to the purpose. For example, water; methanol, ethanol, isopropanol, n- Alcohols such as butanol and methyl isocarbinol; Ketones such as acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone and cyclohexanone; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide Ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4-dihydro-2H-pyran; glycols such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether A Glycol ether acetates such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate and 2-butoxyethyl acetate; esters such as methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, ethyl lactate and ethylene carbonate; benzene Aromatic hydrocarbons such as toluene, xylene; aliphatic hydrocarbons such as hexane, heptane, iso-octane, cyclohexane; halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, dichloropropane, chlorobenzene, etc. Sulfoxides such as dimethyl sulfoxide; pyrrolidones such as N-methyl-2-pyrrolidone and N-octyl-2-pyrrolidone; These may be used individually by 1 type and may use 2 or more types together.

-Magnetic material-
As the magnetic member is not particularly limited and may be appropriately selected depending on the purpose, for _{example, 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 Examples thereof include powder and nickel powder. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of iron trioxide and γ-iron trioxide are preferable.

In addition, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used as the magnetic material. The heterogeneous element is not particularly limited and can be appropriately selected depending on the purpose. For example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, Examples include titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, and gallium. Among these, magnesium, aluminum, silicon, phosphorus, or zirconium is particularly preferable.
The heterogeneous 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. Although it is good, it is preferably contained as an oxide.
The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grains production | generation, or adding salt of each element and adjusting pH.

There is no restriction | limiting in particular as usage-amount of the said magnetic body, Although it can select suitably according to the objective, 10 mass%-200 mass% are preferable with respect to resin, and 20 mass%-150 mass% are more. preferable.
The number average particle size of the magnetic material is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 μm to 2 μm, more preferably 0.1 μm to 0.5 μm.
The number average diameter can be obtained by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.
The magnetic properties of the magnetic material are not particularly limited and can be appropriately selected according to the purpose. The magnetic properties at 10K oersted application are coercive force of 20 oersted to 150 oersted and saturation magnetization is 50 emu / g to 200 emu / g, and the residual magnetization is preferably 2 emu / g to 20 emu / g.
The magnetic material can also be used as a colorant.

-Wax-
The wax is not particularly limited and may be appropriately selected depending on the intended purpose. For example, aliphatic hydrocarbons 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 oxidized polyethylene wax or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax; beeswax, lanolin, whale wax, etc. Animal waxes; mineral waxes such as ozokerite, ceresin and petrolatum; waxes based on fatty acid esters such as montanic acid ester wax and castor wax; partially or all fatty acid esters such as deoxidized carnauba wax Deoxidation Such as the ones and the like.

Furthermore, the wax is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include palmitic acid, stearic acid, montanic acid, and linear alkylcarboxylic acids having a linear alkyl group. Saturated linear fatty acids; Unsaturated fatty acids such as prandidic acid, eleostearic acid, valinalic acid; stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesyl alcohol, or long chain alkyl alcohol Saturated alcohol; polyhydric alcohol such as sorbitol; fatty acid amide such as linoleic acid amide, olefinic acid amide, lauric acid amide; saturated fatty acid bis such as methylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bisstearic acid amide Mid; Unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasinic acid amide; m-xylene bisstearic acid Aromatic bisamides such as amide and N, N-distearylisophthalic acid amide; Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate; aliphatic hydrocarbon wax such as styrene and acrylic acid Examples thereof include waxes grafted with vinyl monomers; partial ester compounds of fatty acids such as behenic monoglyceride and polyhydric alcohols, and methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats.
Among these, 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, polyolefins polymerized using catalysts such as Ziegler catalysts and metallocene catalysts under low pressure, radiation , Synthesized by electromagnetic waves or light, synthesized by thermal decomposition of high molecular weight polyolefin, low molecular weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method, age method, etc. Synthetic hydrocarbon wax, synthetic wax using a compound having one carbon atom as a monomer, hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group, hydrocarbon wax and hydrocarbon wax having a functional group A mixture of styrene these waxes as a matrix, maleic acid esters, acrylates, methacrylates, wax graft-modified with a vinyl monomer such as maleic anhydride is preferred.

  There is no restriction | limiting in particular as content with respect to the resin of the said wax, Although it can select suitably according to the objective, 0.2 mass%-20 mass% are preferable, and 0.5 mass%-10 mass% are more. preferable.

<Particle forming step, particle forming means>
The particle forming step is a step of solidifying the droplets (toner composition liquid) formed in the droplet forming step to form particles, and is performed by particle forming means. It is preferable that the particle forming step further includes a step of transporting the droplets ejected in the droplet forming step by a transport air current. The transporting step is preferably performed by a transport airflow passage.

  The transporting step is not particularly limited as long as the droplets ejected in the droplet forming step can be transported, and can be appropriately selected according to the purpose, but at least 2 mm from the ejection opening of the ejection hole. It is preferable to transport droplets in the range, more preferably transport droplets in the range of 1.5 mm from the discharge opening, more preferably transport droplets in the range of 1.0 mm from the discharge opening, It is particularly preferable to transport droplets in the range of 0.5 mm from the opening. If the droplets are transported after exceeding a range of 2 mm from the discharge opening of the discharge hole, the droplets may be united.

  The particle forming means is means for forming particles by solidifying the liquid toner composition. The particle forming means is not particularly limited as long as particles can be formed, and can be appropriately selected according to the purpose. However, the particle forming means has members such as a drying unit, the transport airflow passage, and a collection unit. preferable.

<< Dry section >>
The drying unit is a member that removes the organic solvent in the droplets by heating or the like.

<< Carrying airflow passage >>
The said conveyance airflow path is a member which distribute | circulates a conveyance airflow inside. As a result, at least one of the droplet-formed toner composition liquid and the solidified particles can be transported by the transport airflow.
The member that forms the carrier airflow passage is not particularly limited as long as the carrier airflow can be circulated therein, and can be appropriately selected according to the purpose. For example, a shroud (sheath portion or covering portion) Is mentioned.

It is preferable that the transport airflow passage is provided outside the droplet forming unit, particularly around the discharge hole from which the droplet is discharged so as not to prevent the discharge of the droplet from the discharge hole. In the present invention, the outside of the droplet forming means means the outside (gas phase) of the ejection hole.
By creating a gas flow in the inside of the carrier airflow passage, the carrier airflow is circulated around at least one of the liquid toner composition liquid and the solidified particles, and the toner discharged by the carrier airflow is discharged. In order to increase the group speed of the group consisting of at least one of the composition liquid and solidified particles, and when the initial discharge speed of at least one of the toner composition liquid and solidified particles is high, the speed is reversed. Can be decelerated.

There is no restriction | limiting in particular as a shape of the said conveyance airflow flow path, According to the objective, it can select suitably. The transport airflow passage may be provided so that the direction of the transport airflow flows in a direction parallel to the direction of the initial discharge speed of the droplets discharged by the droplet forming means, The direction of the conveying airflow may be provided so as to circulate in a direction that changes the direction of the discharged droplets.
The direction in which the direction of the discharged droplet is changed is not particularly limited and can be appropriately selected according to the purpose. For example, in the direction of the initial discharge speed of the droplet discharged by the droplet forming means. For example, a direction substantially orthogonal to the direction may be used.
Among these, the transport airflow passage is provided so that the direction of the transport airflow circulates in a direction that changes the direction of the ejected droplets. Is preferable in that the component is uniform, that is, a monodispersed droplet, and the direction of the air flow is substantially perpendicular to the direction of the initial discharge velocity of the droplet discharged by the droplet forming means It is more preferable that it is provided so as to be distributed. At this time, as described in the transporting step, at least a droplet in a range of 2 mm from the discharge opening of the discharge hole is transported by a transport airflow in a direction substantially orthogonal to the direction of the initial discharge speed of the droplet. It is particularly preferable.
As a result, the obtained toner group has very little coalescence, and productivity including yield can be improved. In addition, it is preferable that the particle forming unit has the conveying airflow passage in that it can efficiently prevent coalescence due to collision with each other during the drying process until the discharged toner composition liquid is solidified.

  There is no restriction | limiting in particular as gas used for the said conveyance airflow, According to the objective, it can select suitably, For example, nonflammable gas, such as air and nitrogen, etc. are mentioned. Moreover, the temperature of the gas used for the conveyance airflow can be adjusted as appropriate, and it is desirable that there is no fluctuation during production.

The air velocity of the carrier airflow is not particularly limited, and can be appropriately selected according to the droplet ejection speed, the opening diameter of the ejection holes, the angle of the carrier airflow with respect to the droplet ejection direction, and the like.
The air flow velocity can be adjusted by adjusting the pressure of the air flow with a regulator.

The toner dried by the drying unit or the conveying airflow may be further subjected to secondary drying. If the organic solvent remains in the toner, not only the toner characteristics such as heat-resistant storage stability, fixability, and charging characteristics will change over time, but the organic solvent will volatilize during fixing by heating, which will adversely affect users and peripheral devices. Therefore, it is necessary to carry out sufficient drying. Therefore, secondary drying is advantageous in that the organic solvent in the toner composition liquid can be sufficiently dried.
There is no restriction | limiting in particular as the method of performing said secondary drying, According to the objective, it can select suitably, For example, a fluid bed drying method, a vacuum drying method, etc. are mentioned.

An external additive may be further added to the toner thus obtained.
There is no restriction | limiting in particular as said external additive, According to the objective which assists fluidity | liquidity, developability, and electrification property, it can select suitably, For example, an inorganic fine particle, polymeric fine particle, etc. are mentioned. Among these, inorganic fine particles are preferable.

The inorganic fine particles are not particularly limited and can be appropriately selected depending on the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, oxide Tin, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. Can be mentioned.
There is no restriction | limiting in particular as a primary particle diameter of the said inorganic fine particle, Although it can select suitably according to the objective, 5 nm-2 micrometers are preferable, and 5 nm-500 nm are more preferable.
The specific surface area by the BET method, not particularly limited and may be appropriately selected depending on the intended ^purpose, 20m ² / ^g~500m 2 / g are preferred.
The amount of the inorganic fine particles added to the toner particles is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 0.01% by mass to 5% by mass, and 0.01% by mass to 2% by mass. More preferred.

  The polymer fine particles are not particularly limited and can be appropriately selected depending on the purpose. For example, polystyrene, methacrylic acid ester or acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization can be used. Examples thereof include polymer, polycondensation systems such as silicone, benzoguanamine, and nylon, and polymer particles made of thermosetting resin.

The external additive is surface treated with a surface treatment agent to increase hydrophobicity and prevent deterioration of the external additive itself even under high humidity.
The surface treatment agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, and an organic titanate coupling agent. , Aluminum coupling agents, silicone oils, modified silicone oils, and the like.

  When the external additive is added, there is no particular limitation, and a general powder mixer can be appropriately selected and used. However, a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter A mixer such as a mixer or a Henschel mixer can be used. At this time, the mixer is preferably equipped with a jacket or the like to adjust the internal temperature. In order to change the history of the load applied to the external additive, the external additive may be added in the middle or gradually, or the rotational speed, rolling speed, time, temperature, etc. of the mixer may be changed. . Further, after applying a strong load to the external additive, a weak load may be applied, or vice versa.

Next, the toner manufacturing apparatus of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an example of a toner production apparatus of the present invention having liquid column resonance type droplet forming means, and FIG. 5 is a toner of the present invention having film vibration type droplet forming means. It is a schematic sectional drawing which shows an example of this manufacturing apparatus.
The toner manufacturing apparatus (1 and 200) includes a droplet discharge unit 2 that periodically discharges a toner composition liquid 10 from a plurality of discharge holes 15 having a uniform opening diameter to form droplets in a gas phase, and a droplet A particle forming unit 3 serving as a particle forming unit that forms a toner particle T by solidifying the droplet 23 of the toner composition liquid that has been formed into a droplet, which is disposed above, and discharged from the droplet discharge unit 2; The neutralizing device 43 (not shown in FIG. 1) for neutralizing the toner particles T formed by the particle forming unit 3, the toner collecting unit 4 for collecting the toner particles T, and the toner collecting unit 4 The collected toner particles T are transferred through the air flow path 42 (not shown in FIG. 1) and the tube 7, and the toner storage section 5 as toner storage means for storing the transferred toner particles T, and the toner composition A raw material container 6 for storing the liquid 10; A liquid supply pipe (pipe) 8 for supplying the toner composition liquid 10 from the container 6 to the droplet discharge unit 2 and a pump 100 for supplying the toner composition liquid 10 by pressure during operation and the like are provided. Yes.

  In addition, the toner composition liquid 10 from the raw material container 6 is supplied to the droplet discharge unit 2 in a self-sufficient manner due to the droplet formation phenomenon by the droplet discharge unit 2, but assists as described above when the apparatus is in operation. In particular, liquid supply is performed using the pump 100. The toner composition liquid 10 uses a toner composition liquid in which at least a resin and a colorant are dissolved or dispersed in a solvent. It is most preferable to construct a circulation system.

-Membrane vibration type-
Hereinafter, a droplet discharge unit using an annular vibration generator and including a liquid chamber and a discharge structure (when the droplet forming means is a membrane vibration type) will be described with reference to FIGS. The present invention is not limited to this.
6 is an enlarged view of the droplet discharge unit 2 of the toner manufacturing apparatus of FIG. 5, FIG. 7 is a bottom view of FIG. 6 viewed from below, and FIG. It is an expanded sectional view of a droplet discharge part.

  The droplet discharge unit 2 includes a liquid supply tube (liquid supply hole) 20 that supplies a toner composition liquid 10 containing at least a resin and a colorant, and a bubble discharge tube (discharge hole) 21 that discharges bubbles of the toner composition liquid 10. A droplet discharge section 11 that discharges the toner composition liquid 10 into droplets, and a frame (liquid chamber member) 14 in which a liquid chamber 24 that supplies the toner composition liquid 10 to the droplet discharge section 11 is formed. ing. In the droplet discharge unit 2, the droplet discharge unit 2 is installed and held on the top surface portion 3 </ b> A of the particle forming unit 3 by a support member 19 attached to the frame 14.

The droplet discharge unit 11 includes a discharge structure (thin film, nozzle plate, discharge plate) 16 in which a plurality of discharge holes (nozzles, through-holes) 15 including different shapes are formed, and the discharge structure 16. And an annular vibration generator (electromechanical conversion means) 17 that vibrates.
The discharge structure 16 is bonded and fixed to the frame 14 through the discharge structure joint portion 13a at the outermost peripheral portion (region shown by hatching in FIG. 8). In addition, the discharge structure 16 is bonded and fixed via the vibration generator 17 and the vibration generator joint portion 13b.

  Here, the shape of the discharge hole 15 is a tapered shape in which the opening diameter decreases toward the discharge direction of the toner composition liquid 10 as shown in FIG. 9A, and the shape of the discharge hole 15 opens toward the discharge direction of the toner composition liquid 10 as shown in FIG. 9B. Either a tapered shape with a small diameter, a shape in which the tip of the discharge hole in the discharge direction is a straight portion, or a round shape having a radius of curvature toward the discharge direction of the toner composition liquid 10 as shown in FIG. 9C. Also good.

The taper angle of the plurality of discharge holes 15 is represented by “θ _n ”, and the radius of curvature of the plurality of discharge holes 15 is represented by “R _n ”. Here, “n” is an integer. When n = 1, the taper angle or the radius of curvature of the discharge hole 15 at the center of the discharge structure 16 is expressed, and as the distance from the discharge hole 15 at the center of the discharge structure 16 increases. It is preferable that the number of n becomes large.
There is no restriction | limiting in particular as the number of n, Although it can select suitably according to the area of a discharge structure, etc., the number of n is so preferable that it is large. A large number of n is preferable in that the taper angle or the radius of curvature can be finely set in the plurality of discharge holes 15 and the droplets can be discharged at a uniform discharge speed over the plurality of discharge holes 15 as a whole. .

The plurality of discharge holes are not particularly limited as long as they include ones having different shapes, and can be appropriately selected according to the purpose. However, the taper angle (θ _{n>) of} the discharge holes located on the vibration generator side is not limited. ₁ ) or the radius of curvature (R _{n> 1} ) is preferably larger than the taper angle (θ ₁ ) or the radius of curvature (R ₁ ) of the discharge hole located at the center. That is, it is preferable that the taper angle or the radius of curvature is larger as the vibration displacement of the discharge structure 16 is closer to ΔLmin. For example, when a plurality of discharge holes 15 are provided as shown in FIG. 7, the taper angle of each discharge hole is such that the number of n increases in a concentric regular hexagonal shape with the discharge hole having θ ₁ as the center. It is preferable. At this time, the taper angle may increase continuously as the number of n increases, or may increase stepwise. The same applies to the radius of curvature.

The taper angle is not particularly limited and can be appropriately selected depending on the area of the discharge structure, the position of the discharge hole in the discharge structure, the magnitude of vibration applied by the vibration generator, and the like. ° to 60 ° is preferable, and 10 ° to 30 ° is more preferable.
The curvature radius is not particularly limited and can be appropriately selected according to the area of the discharge structure, the position of the discharge hole in the discharge structure, the magnitude of vibration added by the vibration generator, 40 micrometers-100 micrometers are preferable, and 40 micrometers-80 micrometers are more preferable.

  The vibration generator 17 is provided around a region provided with the discharge holes 15 in the deformable region 16 </ b> A (region not fixed to the frame 14) of the discharge structure 16. A drive voltage (drive signal) having a required frequency is applied to the vibration generator 17 from a drive circuit (drive signal generation source) 51 through a lead wire 50, for example, bending vibration is generated.

  In the droplet discharge section 11, an annular vibration generator 17 is arranged around a region provided with the discharge holes 15 in the deformable region 16 </ b> A of the discharge structure 16 having a plurality of discharge holes 15 facing the liquid chamber 24. Therefore, for example, as shown in FIG. 10, the displacement amount of the discharge structure 16 is relatively larger than that in the case where the vibration generating body 17A holds the periphery of the discharge structure 16, and this large amount. A plurality of discharge holes 15 can be arranged in a relatively large area (diameter of 1 mm or more) where a displacement amount can be obtained, and more liquid droplets can be stably formed at a time than the plurality of discharge holes 15. Can be discharged.

  FIG. 5 shows an example in which one droplet discharge unit 2 is arranged. However, as shown in FIG. 11, a plurality of droplet discharge units 2 are arranged on the top surface portion 3A of the particle forming unit 3. It is preferable to arrange them side by side. Among these, it is preferable from the viewpoint of controllability that the number of the droplet discharge units 2 is 100 to 1,000 (only four are shown in FIG. 11). In this case, the toner composition liquid 10 is supplied to each droplet discharge unit 2 by connecting a pipe (liquid feeding pipe) 8A to the raw material container 6 (common liquid reservoir). As a result, more droplets can be ejected at a time, and the production efficiency can be improved.

In FIG. 5, the droplets 23 of the toner composition liquid discharged from the droplet discharge unit 2 are dried and solidified to form toner particles T when transported downward by gravity in the particle forming unit 3. . At this time, it is possible to generate a transport air flow 40 from the upper side to the lower side of the particle forming unit 3 and to transport the droplets 23 by the transport air flow 40 not only by gravity but also outside the droplet discharge unit 2. This is preferable in that coalescence between the formed droplets can be prevented and a toner with higher monodispersibility can be obtained. By generating these transport airflows, it is possible to prevent the discharged droplets 23 from being decelerated due to air resistance. When the droplets 23 are continuously discharged, before the droplets 23 are dried before By decelerating by the air resistance, the droplets 23 ejected later catch up with the droplets 23 ejected before, so that the droplets 23 coalesce and become one, and the particle size of the droplets 23 increases. Can be suppressed.
The toner particles T that have been dried and solidified are neutralized by the neutralization device 43, collected by the toner collecting unit 4, and transferred through the air flow path 42 and the tube 7 in the air flow path forming member 41, and the toner storage section. 5 is stored.

-Liquid column resonance type-
Next, the case where the droplet forming means is a liquid column resonance type will be described with reference to FIG. 2, but the present invention is not limited to this.
FIG. 2 is an enlarged cross-sectional view of the droplet discharge section 11 having the discharge holes 15 of the toner manufacturing apparatus of FIG. The droplet discharge unit 11 stores therein the toner composition liquid 10 containing at least a resin and a colorant, and is disposed on the liquid common supply path 52 side from the end 54 of the frame on the fixed end side in the liquid column resonance liquid chamber 12. The length to the end 55 corresponds to the length L. The vibration generator 17 is bonded to the elastic plate 56 on the wall surface opposite to the wall surface on which the discharge holes 15 of the droplet discharge section 11 are provided, and the vibration generator 17 is in contact with the toner composition liquid 10. The liquid column resonance liquid chamber 12 is provided in a state where a part of the wall is formed.
The shapes of the plurality of ejection holes 15 are simplified in FIGS. 2 and 4A to E, but have a tapered shape as shown in FIGS. 9A and 9B.

When the droplet forming means is a liquid column resonance type, when the taper angle θ _n or the radius of curvature R _n is defined in the same manner as in the case of the membrane vibration type, n = 1 is a pressure standing wave due to the liquid column resonance. It is preferable that the number of n increases as the distance from the discharge hole at the position where the amplitude of the pressure standing wave due to the liquid column resonance becomes maximum is represented.
There is no restriction | limiting in particular as the number of n, Although it can select suitably according to the area of a discharge structure, etc., the number of n is so preferable that it is large. A large number of n is preferable in that the taper angle or the radius of curvature can be finely set in the plurality of discharge holes 15 and the droplets can be discharged at a uniform discharge speed over the plurality of discharge holes 15 as a whole. .

The plurality of discharge holes are not particularly limited as long as they include ones having different shapes, and can be appropriately selected according to the purpose, but the discharge holes at positions where the amplitude of the pressure standing wave is minimized The taper angle (θ _{n> 1} ) is preferably larger than the taper angle (θ ₁ ) of the discharge hole corresponding to the antinode of the pressure standing wave due to the liquid column resonance. For example, when a plurality of discharge holes 15 are provided as shown in FIG. 4C, the taper angle of each discharge hole 15 is a position where the amplitude of the pressure standing wave due to the liquid column resonance is maximum (the pressure is maximum). The taper angle of the corresponding discharge hole is θ ₁ , and the number of n is toward the end 54 direction of the frame on the fixed end side and the liquid common supply path 52 direction around the discharge hole 15 having the θ _1. It is preferable to make it large. At this time, the taper angle may increase continuously as the number of n increases, or may increase stepwise. The same applies to the radius of curvature.

The taper angle is not particularly limited and can be appropriately selected depending on the area of the discharge structure, the position of the discharge hole in the discharge structure, the magnitude of vibration applied by the vibration generator, and the like. ° to 60 ° is preferable, and 10 ° to 30 ° is more preferable.
The curvature radius is not particularly limited and can be appropriately selected according to the area of the discharge structure, the position of the discharge hole in the discharge structure, the magnitude of vibration added by the vibration generator, 40 micrometers-100 micrometers are preferable, and 40 micrometers-80 micrometers are more preferable.

In FIG. 1, a droplet 23 of toner composition liquid discharged from the droplet discharge unit 2 is dried and solidified to form toner particles T when being transported downward by gravity in the particle forming unit 3. . At this time, conveying the droplets 23 not only by gravity but also by the conveying airflow 40 prevents coalescence between the ejected droplets, and a toner with higher monodispersibility can be obtained. preferable. There is no restriction | limiting in particular as the direction of a conveyance airflow path, and the direction of the conveyance airflow 40, According to the objective, it can select suitably. For example, the direction may be a direction parallel to the direction of the initial ejection speed of the ejected droplet, or may be a direction in which the direction of the ejected droplet 23 is changed.
FIG. 2 is a diagram illustrating an example in which the carrier airflow passage 53 is provided in a direction parallel to the direction of the initial discharge speed of the droplets 23 discharged, and according to this aspect, A carrier air flow 40 is generated downward.
FIG. 20 is a diagram illustrating an example in which the conveying airflow passage 53 is provided in a direction substantially orthogonal to the direction of the initial discharge speed of the droplet 23 discharged. The direction of the carrier airflow passage 53 in FIG. 20 is the direction to the gas phase in the particle forming unit 3.
Further, FIG. 21 shows that the carrier airflow passage 53 communicates with the first carrier airflow passage 53-1 and the first carrier airflow passage 53-1, and leads to the gas phase of the particle forming unit 3. 2, the direction of the first carrier airflow passage 53-1 is substantially perpendicular to the droplet discharge direction, and the second carrier airflow passage 53-1. Is a direction substantially orthogonal to the direction of the first carrier airflow passage 53-1 and the same direction as the droplet discharge direction.

  By generating these transport airflows, it is possible to prevent the discharged droplets 23 from being decelerated due to the air resistance, and when the droplets 23 are continuously discharged, the air resistance is reduced before the droplets 23 are dried. The droplet 23 discharged later catches up with the previously discharged droplet 23, so that the droplets 23 are joined and integrated, and the particle size of the droplet 23 is prevented from increasing. be able to. The dried and solidified toner particles T are collected by the toner collecting unit 4 and stored in the toner storing unit 5.

<Toner>
The toner produced by the method and apparatus for producing toner according to the present invention in which a toner composition liquid is formed into droplets, and the formed toner composition liquid is solidified into particles, has a single particle size distribution. This is advantageous in that a dispersion can be obtained.

The particle size distribution (weight average particle size / number average particle size) of the toner particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1.00 to 1.15, and preferably 1.00. -1.07 is more preferable. When the particle size distribution exceeds 1.15, there is a large variation in the particle system, the chargeability between the particles becomes non-uniform, and abnormal images such as background stains are generated, and image quality such as granularity is deteriorated. There is.
The weight average particle diameter of the toner particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 μm to 20 μm, and more preferably 3 μm to 10 μm. If the mass average particle size is less than 1 μm, the number of finely charged particles increases, and the charge site of the carrier is deprived by, for example, firmly adhering to the carrier, resulting in a decrease in developability, that is, generation of abnormal images In addition to causing it, inhalation may affect the human body.
The method for measuring the particle size distribution of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method of measuring with a flow particle image analyzer (Flow Particle Image Analyzer).

The toner manufacturing method and manufacturing apparatus of the present invention can simultaneously discharge liquid droplets from a plurality of discharge holes at a uniform speed, and therefore the liquid droplets discharged from the plurality of discharge holes can be discharged in uniform amounts without being united. Since the number of droplets that can be discharged and discharged per unit time is large, toner can be produced efficiently.
Further, since the toner obtained by the toner production method and production apparatus of the present invention has high versatility and high monodispersibility of the toner, an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc. Can be suitably used as a developer for developing the toner. As the developer, any electrostatic latent image carrier used in conventional electrophotography can be used. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image carrier, and a selenium electrostatic latent image are used. An image carrier, a zinc oxide electrostatic latent image carrier and the like can be preferably used.

EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but the present invention is not limited to these examples.

Example 1
<Preparation of colorant dispersion>
Using a mixer having a stirring blade, 17 parts by mass of carbon black (Regal 400, manufactured by Cabot), 3 parts by mass of a pigment dispersant (Ajisper PB821, manufactured by Ajinomoto Fine Techno Co., Ltd.), and 80 parts by mass of ethyl acetate are primarily dispersed. It was. The obtained primary dispersion is secondarily dispersed using a dyno mill (NPM-PILOT, manufactured by Willy et Bacofen) to completely remove aggregates having a particle size of 5 μm or more, and a colorant dispersion Was prepared.

<Preparation of wax dispersion>
Next, using a mixer having a stirring blade, 18 parts by mass of carnauba wax, 2 parts by mass of a wax dispersant, and 80 parts by mass of ethyl acetate were primarily dispersed. The wax dispersant used was a polyethylene wax grafted with a styrene-butyl acrylate copolymer. The obtained primary dispersion was heated to 80 ° C. with stirring to dissolve the carnauba wax, and then cooled to room temperature to precipitate the carnauba wax so that the maximum diameter was 3 μm or less. Further, a wax dispersion was prepared by secondary dispersion using a dyno mill so that the maximum diameter was 1 μm or less.

<Preparation of toner composition dispersion>
Next, using a mixer having a stirring blade, 100 parts by mass of a polyester resin as a binder resin, 30 parts by mass of the colorant dispersion, 30 parts by mass of the wax dispersion, and 840 parts by mass of ethyl acetate are added for 10 minutes. The mixture was stirred and dispersed uniformly to prepare a toner composition liquid (dispersion). The pigment and wax particles did not aggregate due to solvent dilution.

<Production of toner>
Next, a plurality of ejection holes (nozzles) of the obtained toner composition dispersion liquid 500 mL are used in the droplet ejection section 11 of the toner manufacturing apparatus shown in FIG. 15 was supplied.
The used discharge structure (thin film, nozzle plate) 16 is a nickel plate having an outer diameter of 20.0 mm and a thickness of 40 μm, and a discharge opening diameter having a circular shape at the end of the discharge hole on the discharge side (gas phase side). A discharge hole 15 (diameter) of 10 μm was produced by processing by electroforming.
The discharge hole draws a perpendicular (opening axis) to the center of the surface (opening surface of the discharge hole) perpendicular to the thickness direction of the discharge structure (the center of the discharge structure), and this perpendicular is the center. In the direction of the opening surface, 21 discharge holes were provided in a range of 3 mm in diameter. The distance between the discharge holes is such that the shortest distance between the center portions of the discharge holes is about 100 μm pitch, and the discharge holes 15 are indicated by the black circles in the region surrounded by the rectangle (solid line) in FIG. The discharge holes located at the center of the structure are provided in a line so as to be symmetric with respect to the center.
In the present invention, it is preferable to provide a plurality of concentric regular hexagonal discharge holes 15 at the center of the discharge structure 16 like the discharge holes 15 indicated by black circles and gray circles in FIG. In order to make it easier to observe the discharge of the toner composition liquid, the discharge holes 15 are provided in a row for convenience. In the toner manufacturing apparatus according to the present invention, the discharge hole and the range in which the discharge hole is provided are small and do not affect the propagation of the resonance frequency and vibration of the toner composition liquid. The result is substantially the same as when it is provided in a regular hexagonal shape.

Each discharge hole has a tapered shape with an opening diameter that decreases in the discharge direction of the toner composition liquid. That is, the taper angle of the discharge hole located at the center of the discharge structure and the first to third taper angles on both sides of the central discharge hole are θ ₁ = 13 °, and the fourth to sixth The taper angle up to the individual is θ ₂ = 15 °, the taper angle from the seventh to the ninth is θ ₃ = 17 °, and the tenth taper angle is θ ₄ = 19 °. Here, the taper angle refers to an angle formed by the side surface of the discharge hole with respect to the perpendicular (opening axis).
When a plurality of discharge holes 15 are provided in the center of the discharge structure 16 in a concentric regular hexagon shape, the discharge holes in the regular hexagonal region surrounded by each broken line in FIG. 17 have the same taper angle.

Further, a SiO ₂ film was formed on the entire exposed surface of the discharge structure by RF sputtering, and a fluorine-based compound (OPTOOL, manufactured by Daikin Industries, Ltd.) was deposited on the SiO ₂ film to form a liquid repellent film. The film thickness of the liquid repellent film was 50 nm as measured using a non-contact type film thickness measuring device (ellipsometer, manufactured by Mizoji Optical Co., Ltd.). The contact angle of the liquid repellent film was measured using a contact angle meter (DM500, manufactured by Kyowa Interface Science Co., Ltd.), and the contact angle of the toner composition dispersion was 58 °.
In FIG. 8, the vibration generator 17 is lead zirconate titanate (PZT) having an inner diameter of 4 mm, a diameter of 15 mm, and a thickness of 2.0 mm. Both the joining surfaces 13a with the frame 14 produced in the above were joined using an epoxy resin (elastic modulus 1.3 × 10 ⁸ Pa) under heating conditions of 170 ° C. × 5 minutes.

After preparing the toner composition dispersion, the droplets were discharged under the toner production conditions shown below, and then the droplets were dried and solidified in the particle forming unit 3 to produce toner base particles. In Example 1, an apparatus having no carrier airflow passage in the particle forming unit was used.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Temperature inside the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 125.0 kHz
Applied voltage to PZT Sin wave pp value: 43.5V
The “ejection hole frequency” is an input vibration frequency to the vibration means 17 by the electric drive device 51 shown in FIG.

The state of ejection was observed by shining LED light on the toner composition dispersion liquid droplets and photographing with a CCD camera placed opposite the LEDs with the droplets sandwiched therebetween. By synchronizing the driving frequency of this LED with the frequency of the droplet discharge section 11, it was confirmed that the toner composition liquid was discharged from the discharge holes. Out of 21 discharge holes, the discharge was made from all 21 discharge holes.
From the discharged liquid column constriction and the vibration frequency, the discharge speed can be estimated by calculation of discharge speed (m / second) = neck wavelength (μm) / frequency (kHz).
The maximum discharge speed is the sixth discharge hole from the center discharge hole, 16.5 m / sec, and the minimum discharge speed is the ninth discharge hole from the center discharge hole, 14.1 m / sec. The minimum discharge speed / maximum discharge speed was 0.85.
The discharge amount was 1.35 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 0.13 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour from the operation was measured by a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) by the following measurement method, the weight average particle size (D4) Was 7.19 μm, the number average particle diameter (Dn) was 5.8 μm, and D4 / Dn was 1.24.

-Measuring method of toner particle size distribution-
A measurement method using a flow particle image analyzer (Flow Particle Image Analyzer) will be described below.
The particle size distribution of the toner, toner particles, and external additives was measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation).
The measurement is performed by removing fine dust through a filter, and as a result, in ^10-3 water of 10 ⁻³ cm ³ of water having a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) of 20 or less particles. Add a few drops of nonionic surfactant (Contaminone N; manufactured by Wako Pure Chemical Industries, Ltd.), add 5 mg of the measurement sample, and 20 kHz, 50 W / 10 cm with an ultrasonic disperser (UH-50; manufactured by STM). ^3. Dispersion treatment is performed for 1 minute under the conditions of ³ , and further, dispersion treatment is performed for a total of 5 minutes, and the particle concentration of the measurement sample is 4,000 / 10 ⁻³ cm ^{3 to} 8,000 / 10 ⁻³ cm ³ (measurement The particle size distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm was measured using the sample dispersion liquid (for particles in the equivalent circle diameter range).
The sample dispersion was allowed to pass through a flow path (spread 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. Taken as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area was calculated as the equivalent circle diameter.
In about 1 minute, the equivalent circle diameter of 1,200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 μm 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.

<External processing>
After drying and solidifying the toner base particles, cyclone is collected, and 1.0 mass% of hydrophobic silica (H2000; manufactured by Clariant Japan) is externally added using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). A toner was prepared.

<Creation of carrier>
After a silicone resin as a coating layer material is dispersed in toluene to prepare a coating layer dispersion, the core material (spherical ferrite particles having an average particle size of 50 μm) is spray-coated, heated and cooled in a heated state. Thereafter, a carrier having an average thickness of the coating layer of 0.2 μm was prepared.

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

(Example 2)
In Example 1, a toner and a developer were prepared in the same manner as in Example 1 except that an apparatus having a conveying airflow passage in the particle forming unit was used and the toner preparation conditions were changed to the conditions shown below.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Transport air flow rate: Dry nitrogen gas in the apparatus 30.0 L / min Direction of the transport air flow: Same direction as the direction of the initial discharge speed of the ejected droplets Transport air flow speed: 15 m / sec Temperature in the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 125.0 kHz
Applied voltage to PZT Sin wave pp value: 43.5V

The state of discharge was observed with an LED and a CCD camera in the same manner as in Example 1. In the same manner as in Example 1, out of 21 discharge holes, the discharge was made from all 21 discharge holes.
The maximum discharge speed is the sixth discharge hole from the center discharge hole, 16.5 m / sec, and the minimum discharge speed is the ninth discharge hole from the center discharge hole, 14.1 m / sec. The minimum discharge speed / maximum discharge speed was 0.85.
The discharge amount was 1.35 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 0.13 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour from the operation was measured by a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) by the following measurement method, the weight average particle size (D4) Was 5.6 μm, the number average particle diameter (Dn) was 5.3 μm, and D4 / Dn was 1.06.

(Example 3)
In Example 2, a toner and a developer were produced in the same manner as in Example 2 except that the toner production conditions were changed to the following conditions.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Transport airflow rate: Dry nitrogen gas in the apparatus 30.0 L / min Direction of transport airflow: Direction substantially orthogonal to the direction of the initial discharge velocity of the discharged droplets Transport airflow velocity: 15 m / sec Temperature in the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 125.0 kHz
Applied voltage to PZT Sin wave pp value: 37.5V

The state of discharge was observed with an LED and a CCD camera in the same manner as in Example 1. In the same manner as in Example 1, out of 21 discharge holes, the discharge was made from all 21 discharge holes.
The maximum discharge speed is the 6th discharge hole from the center discharge hole, 16.7 m / sec, and the minimum discharge speed is the 9th discharge hole from the center discharge hole, 14.7 m / sec. The minimum discharge speed / maximum discharge speed was 0.88.
The discharge rate was 1.39 g / min based on the toner composition dispersion. The toner standard after drying was about 0.13 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour has elapsed after the operation was measured with a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) in the same manner as in Example 1, The weight average particle diameter (D4) was 5.41 μm, the number average particle diameter (Dn) was 5.2 μm, and D4 / Dn was 1.04.

Example 4
In Example 2, a toner and a developer were produced in the same manner as in Example 2 except that the shape of the ejection holes and the toner production conditions were changed to the following conditions.
The shape of each discharge hole was a round shape in which the opening diameter becomes smaller in the toner composition liquid discharge direction. That is, the radius of curvature of the ejection hole located at the center of the ejection structure and the first to third curvature radii on both sides of the central ejection hole are R ₁ = 80 μm, and the fourth to sixth The radius of curvature up to the eyes was R ₂ = 60 μm, the radius of curvature from the seventh to the ninth was R ₃ = 45 μm, and the radius of curvature of the tenth was R ₄ = 40 μm. Here, the radius of curvature is a radius of curvature in a round shape from the opening surface of the discharge hole (a surface perpendicular to the thickness direction of the discharge structure) toward the thickness direction of the discharge structure.
When a plurality of discharge holes 15 are provided in the center of the discharge structure 16 in a concentric regular hexagon shape, the discharge holes in the regular hexagonal region surrounded by each broken line in FIG. 17 have the same radius of curvature.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Transport airflow rate: Dry nitrogen gas in the apparatus 30.0 L / min Direction of transport airflow: Direction substantially orthogonal to the direction of the initial discharge velocity of the discharged droplets Transport airflow velocity: 15 m / sec Temperature in the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 120.2 kHz
Applied voltage to PZT Sin wave pp value: 36.0V

The state of discharge was observed with an LED and a CCD camera in the same manner as in Example 1. In the same manner as in Example 1, out of 21 discharge holes, the discharge was made from all 21 discharge holes.
The maximum discharge speed is the sixth discharge hole from the center discharge hole, 14.0 m / sec, and the minimum discharge speed is the ninth discharge hole from the center discharge hole, 12.35 m / sec. The minimum discharge speed / maximum discharge speed was 0.88.
The discharge rate was 1.39 g / min based on the toner composition dispersion. The toner standard after drying was about 0.12 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour has elapsed after the operation was measured with a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) in the same manner as in Example 1, The weight average particle diameter (D4) was 5.36 μm, the number average particle diameter (Dn) was 5.1 μm, and D4 / Dn was 1.05.

(Comparative Example 1)
In Example 1, a toner and a developer were produced in the same manner as in Example 1 except that the toner production conditions were changed to the following conditions.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Temperature inside the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 122.4 kHz
Applied voltage to PZT Sin wave pp value: 45.0V
Discharge hole shape: Tapered shape (taper angle: 15 ° for all)

The state of discharge was observed with an LED and a CCD camera in the same manner as in Example 1. Out of the 21 discharge holes, the discharge was made from 13 discharge holes near the center of the discharge structure. The narrowing wavelength of the discharge was distributed with respect to the position of the discharge hole.
The maximum discharge speed is the central discharge hole, 21.6 m / second, the minimum discharge speed is the sixth discharge hole from the central discharge hole, 6.3 m / second, the minimum discharge speed / maximum discharge The speed was 0.29.
The discharge amount was 0.97 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 0.09 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour has elapsed after the operation was measured with a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) in the same manner as in Example 1, The weight average particle diameter (D4) was 9.31 μm, the number average particle diameter (Dn) was 6.7 μm, and D4 / Dn was 1.39.

(Comparative Example 2)
In Example 2, a toner and a developer were produced in the same manner as in Example 2 except that the toner production conditions were changed to the following conditions.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Transport air flow rate: Dry nitrogen gas in the apparatus 30.0 L / min Direction of the transport air flow: Same direction as the direction of the initial discharge speed of the ejected droplets Transport air flow speed: 15 m / sec Temperature in the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 122.4 kHz
Applied voltage to PZT Sin wave pp value: 45.0V
Discharge hole shape: Tapered shape (taper angle: 15 ° for all)

The state of discharge was observed with an LED and a CCD camera in the same manner as in Example 1. Out of the 21 discharge holes, the discharge was made from 13 discharge holes near the center of the discharge structure. The narrowing wavelength of the discharge was distributed with respect to the position of the discharge hole.
The maximum discharge speed is the central discharge hole, 21.6 m / second, the minimum discharge speed is the sixth discharge hole from the central discharge hole, 6.3 m / second, the minimum discharge speed / maximum discharge The speed was 0.29.
The discharge amount was 0.97 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 0.09 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour has elapsed after the operation was measured with a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) in the same manner as in Example 1, The weight average particle diameter (D4) was 7.1 μm, the number average particle diameter (Dn) was 6.0 μm, and D4 / Dn was 1.18.

(Comparative Example 3)
In Example 2, a toner and a developer were produced in the same manner as in Example 2 except that the toner production conditions were changed to the following conditions.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Transport air flow rate: Dry nitrogen gas in the apparatus 30.0 L / min Direction of the transport air flow: Same direction as the direction of the initial discharge speed of the ejected droplets Transport air flow speed: 15 m / sec Temperature in the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 115.9 kHz
Applied voltage to PZT Sin wave pp value: 37.5V
Discharge hole shape: Round shape (curvature radius: all 40μm)

The state of discharge was observed with an LED and a CCD camera in the same manner as in Example 1. Out of the 21 discharge holes, the discharge was made from 15 discharge holes near the center. The narrowing wavelength of the discharge was distributed with respect to the position of the discharge hole.
The maximum discharge speed is the central discharge hole, 15.9 m / second, the minimum discharge speed is the seventh discharge hole from the central discharge hole, which is 7.3 m / second, the minimum discharge speed / maximum discharge The speed was 0.46.
The discharge rate was 1.03 g / min based on the toner composition dispersion. The toner standard after drying was about 0.10 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour has elapsed after the operation was measured with a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) in the same manner as in Example 1, The weight average particle diameter (D4) was 6.8 μm, the number average particle diameter (Dn) was 5.6 μm, and D4 / Dn was 1.21.

(Example 5)
Example 1 is the same as Example 1 except that the droplet forming step and the particle forming step are changed to the toner manufacturing apparatus shown in FIG. 1 in which the droplet forming unit is a liquid column resonance type shown in FIG. Similarly, a toner and a developer were prepared. In Example 5, an apparatus having no carrier airflow passage in the particle forming unit was used.
FIG. 19 is a view showing the droplet forming means used in the fifth embodiment. Twenty-four discharge holes 15 are opened at the end 54 of the frame on the fixed end side in the liquid column resonance liquid chamber 12 and reflected to the end 55 on the liquid common supply channel (not shown) side of the liquid column resonance liquid chamber 12. It is an example of the standing wave at the time of providing a wall. Since the discharge hole 15 is provided in the vicinity of the end portion 54, the end portion 54 side is a slightly loose fixed end, and the end portion 55 side on the liquid common supply path side is a fixed end N = 2 resonance mode. Can be regarded as standing waves. The drive frequency was 420 kHz which is a resonance frequency. The solid line in the liquid column resonance liquid chamber 12 in FIG. 19 represents the velocity standing wave, and the dotted line represents the pressure standing wave.
The length L between the wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber 12 is 1.85 mm, and the width W of the liquid column resonance liquid chamber (the length in the direction perpendicular to L) is 0.12 mm. A frame including all wall surfaces other than the wall surface provided with the discharge holes of the liquid chamber 12 was produced by stainless punching, and the discharge structure provided with the discharge holes was bonded to the frame with a joining member.
The discharge structure used was formed on a nickel plate having a thickness of 40 μm with discharge holes 15 having a perfect circular discharge opening diameter (diameter) of 8.2 μm at the discharge side (gas phase side) end of the discharge holes. It was produced by casting.
As shown in FIG. 19, 24 discharge holes were provided in a staggered arrangement of 13 rows in the longitudinal direction in a range from the end 54 of the frame on the fixed end side of the discharge structure to 0.6 μm in the longitudinal direction. The distance between the discharge holes was set such that the shortest distance between the center portions of the discharge holes was about 100 μm pitch.
In Example 5, since the arrangement of the ejection holes may affect the resonance frequency and vibration propagation of the toner composition liquid, as an efficient condition, the ejection holes are arranged in the longitudinal direction of the liquid column resonance. This was carried out in a multi-row arrangement provided in 13 rows.

Each discharge hole has a tapered shape with an opening diameter that decreases in the discharge direction of the toner composition liquid. That is, the discharge holes at the end of the frame on the fixed end side (end 54 side) are the first row, the taper angles of all the discharge holes from the first row to the third row are θ ₁ = 20 °, 4 The taper angle from the fifth row to the fifth row is θ ₂ = 18 °, the taper angle from the sixth row to the eighth row is θ ₃ = 16 °, and the taper angle from the ninth row to the eleventh row is θ ₄ = 14 °, and the taper angle of the 12th to 13th rows was θ ₅ = 12 °. Here, the taper angle refers to an angle formed by the side surface of the discharge hole with respect to the perpendicular (opening axis).

-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Temperature inside the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 420.0 kHz
Applied voltage to PZT Sin wave pp value: 15.6V

In the same manner as in Example 1, the state of ejection was observed for each row of ejection holes using an LED and a CCD camera while shifting the focus of the CCD camera. Out of 24 discharge holes, the discharge was made from all 24 discharge holes.
The maximum discharge speed was 16.4 m / second, the minimum discharge speed was 14.7 m / second, and the minimum discharge speed / maximum discharge speed was 0.90.
The discharge rate was 4.72 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 0.45 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour has elapsed after the operation was measured with a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) in the same manner as in Example 1, The weight average particle diameter (D4) was 6.55 μm, the number average particle diameter (Dn) was 5.5 μm, and D4 / Dn was 1.19.

(Example 6)
In Example 5, a toner and a developer were prepared in the same manner as in Example 5 except that an apparatus having a conveying airflow passage in the particle forming unit was used and the toner preparation conditions were changed to the conditions shown below.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Transport air flow rate: Dry nitrogen gas in the apparatus 30.0 L / min Direction of the transport air flow: Same direction as the direction of the initial discharge speed of the ejected droplets Transport air flow speed: 15 m / sec Temperature in the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 420.0 kHz
Applied voltage to PZT Sin wave pp value: 15.6V

In the same manner as in Example 1, the state of ejection was observed for each row of ejection holes using an LED and a CCD camera while shifting the focus of the CCD camera. Out of 24 discharge holes, the discharge was made from all 24 discharge holes.
The maximum discharge speed was 16.4 m / second, the minimum discharge speed was 14.7 m / second, and the minimum discharge speed / maximum discharge speed was 0.90.
The discharge rate was 4.72 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 0.45 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour has elapsed after the operation was measured with a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) in the same manner as in Example 1, The weight average particle diameter (D4) was 5.41 μm, the number average particle diameter (Dn) was 5.2 μm, and D4 / Dn was 1.04.

(Example 7)
In Example 6, a toner and a developer were produced in the same manner as in Example 6 except that the toner production conditions were changed to the following conditions.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Transport airflow rate: Dry nitrogen gas in the apparatus 30.0 L / min Direction of transport airflow: Direction substantially orthogonal to the direction of the initial discharge velocity of the discharged droplets Transport airflow velocity: 15 m / sec Temperature in the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 420.0 kHz
Applied voltage to PZT Sin wave pp value: 15.6V

The state of discharge was observed with an LED and a CCD camera in the same manner as in Example 1. Out of 24 discharge holes, the discharge was made from all 24 discharge holes.
The maximum discharge speed was 16.3 m / second, the minimum discharge speed was 14.5 m / second, and the minimum discharge speed / maximum discharge speed was 0.89.
The discharge rate was 4.70 g / min based on the toner composition dispersion. The toner standard after drying was about 0.45 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour has elapsed after the operation was measured with a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) in the same manner as in Example 1, The weight average particle diameter (D4) was 5.1 μm, the number average particle diameter (Dn) was 5.0 μm, and D4 / Dn was 1.02.

(Example 8)
In Example 6, a toner and a developer were produced in the same manner as in Example 6 except that the shape of the ejection holes and the toner production conditions were changed to the following conditions.
Each discharge hole has a round shape in which the radius of curvature decreases in the discharge direction of the toner composition liquid. That is, the discharge holes at the end of the frame on the fixed end side (end 54 side) are the first row, and the radius of curvature of all the discharge holes from the first row to the third row is R ₁ = 40 μm. The curvature radius from the fifth row to the fifth row is R ₂ = 45 μm, the curvature radius from the sixth row to the eighth row is R ₃ = 50 °, and the curvature radius from the ninth row to the eleventh row is R ₄ = The taper angle in the 12th to 13th rows was R ₅ = 80 °. Here, the radius of curvature is a radius of curvature in a round shape from the opening surface of the discharge hole (a surface perpendicular to the thickness direction of the discharge structure) toward the thickness direction of the discharge structure.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Transport airflow rate: Dry nitrogen gas in the apparatus 30.0 L / min Direction of transport airflow: Direction substantially orthogonal to the direction of the initial discharge velocity of the discharged droplets Transport airflow velocity: 15 m / sec Temperature in the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 420.3 kHz
Applied voltage to PZT Sin wave pp value: 15.2V

The state of discharge was observed with an LED and a CCD camera in the same manner as in Example 1. Out of 24 discharge holes, the discharge was made from all 24 discharge holes.
The maximum discharge speed was 16.0 m / second, the minimum discharge speed was 14.1 m / second, and the minimum discharge speed / maximum discharge speed was 0.88.
The discharge rate was 4.69 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 0.45 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour has elapsed after the operation was measured with a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) in the same manner as in Example 1, The weight average particle diameter (D4) was 5.2 μm, the number average particle diameter (Dn) was 5.1 μm, and D4 / Dn was 1.02.

Example 9
In the preparation of the toner base particles of Example 6, instead of the toner composition liquid, the resin composition liquid prepared in the following resin composition liquid preparation process was used, and the droplet formation process and the particle formation process were changed to the conditions shown below. Except for the above, resin fine particles were produced in the same manner as in Example 6.

<Resin composition liquid preparation process>
Using a mixer having a stirring blade, 110 parts by mass of a polyester resin as a binder resin and 890 parts by mass of ethyl acetate were stirred for 10 minutes and uniformly dispersed to prepare a resin composition liquid.

<Droplet formation process, particle formation process>
In Example 6, resin fine particles were produced in the same manner as in Example 6 except that the toner production conditions were changed to the resin fine particle production conditions shown below.
-Resin fine particle preparation conditions-
Resin composition specific gravity: ρ = 1.19 g / cm ³
Transport airflow rate: Dry nitrogen gas in the apparatus 30.0 L / min Direction of transport airflow: Direction substantially orthogonal to the direction of the initial discharge velocity of the discharged droplets Transport airflow velocity: 15 m / sec Temperature in the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 421.0 kHz
Applied voltage to PZT Sin wave pp value: 15.8V

The state of discharge was observed with an LED and a CCD camera in the same manner as in Example 1. Out of 24 discharge holes, the discharge was made from all 24 discharge holes.
The maximum discharge speed was 16.2 m / second, the minimum discharge speed was 14.5 m / second, and the minimum discharge speed / maximum discharge speed was 0.90.
The discharge rate was 4.73 g / min on the basis of the composition liquid. Based on the particle basis after drying, it was about 0.45 g / min.

  The dried and solidified resin fine particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour has elapsed after the operation was measured with a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) in the same manner as in Example 1, The weight average particle diameter (D4) was 5.1 μm, the number average particle diameter (Dn) was 5.0 μm, and D4 / Dn was 1.02.

(Comparative Example 4)
In Example 5, a toner and a developer were produced in the same manner as in Example 5 except that the toner production conditions were changed to the following conditions.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Transport airflow rate: Dry nitrogen gas in the apparatus 30.0 L / min Direction of transport airflow: Direction substantially orthogonal to the direction of the initial discharge velocity of the discharged droplets Transport airflow velocity: 15 m / sec Temperature in the particle forming part: 27 ° C to 28 ° C
Discharge hole frequency: 423.0 kHz
Applied voltage to PZT Sin wave pp value: 16.0V
Discharge hole shape: Round shape (curvature radius: all 40μm)

The state of discharge was observed with an LED and a CCD camera in the same manner as in Example 1. Out of 24 discharge holes, the discharge was made from all 24 discharge holes. The narrowing wavelength of the discharge was distributed with respect to the position of the discharge hole.
The maximum discharge speed was 21.9 m / second, the minimum discharge speed was 7.3 m / second, and the minimum discharge speed / maximum discharge speed was 0.33.
The discharge rate was 4.36 g / min based on the toner composition dispersion. The toner standard after drying was about 0.42 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour has elapsed after the operation was measured with a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) in the same manner as in Example 1, The weight average particle diameter (D4) was 7.22 μm, the number average particle diameter (Dn) was 5.6 μm, and D4 / Dn was 1.29.

(Comparative Example 5)
In Example 7, toner base particles were prepared in the same manner as in Example 7 except that the toner preparation conditions were changed to the following conditions.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Transport air flow rate: Dry nitrogen gas in the apparatus 30.0 L / min Direction of transport air flow: Direction substantially orthogonal to the direction of initial ejection speed of ejected droplets Transport air flow speed: 15 m / sec Temperature in particle forming part: 27 ° C. to 28 ° C.
Discharge hole frequency: 423.0 kHz
Applied voltage to PZT Sin wave pp value: 16.0V
Discharge hole shape: Round shape (curvature radius: all 40μm)

The state of discharge was observed with an LED and a CCD camera in the same manner as in Example 1. Out of 24 discharge holes, the discharge was made from all 24 discharge holes. The narrowing wavelength of the discharge was distributed with respect to the position of the discharge hole.
The maximum discharge speed was 21.9 m / second, the minimum discharge speed was 7.3 m / second, and the minimum discharge speed / maximum discharge speed was 0.33.
The discharge rate was 4.36 g / min based on the toner composition dispersion. The toner standard after drying was about 0.41 g / min.

  The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. When the particle size distribution of the particles collected after 1 hour has elapsed after the operation was measured with a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) in the same manner as in Example 1, The weight average particle diameter (D4) was 5.8 μm, the number average particle diameter (Dn) was 5.2 μm, and D4 / Dn was 1.12.

  The results of Examples 1-9 and Comparative Examples 1-5 are shown in Table 1 below.

In Examples 1 to 9, the toner composition liquid was discharged from all the discharge holes, but in Comparative Examples 1 to 3, the toner composition liquid was discharged only from 13 or 15 discharge holes, respectively. In Examples 1 to 9, the pressure applied to the toner composition liquid supply side of the plurality of ejection holes is made uniform by adjusting the taper angle or the radius of curvature of the plurality of ejection holes, whereas the comparative example In 1 and 2, the taper angle of the plurality of discharge holes is constant, and in Comparative Example 3, the plurality of discharge holes have a round shape with a constant radius of curvature, so that the pressure applied by the position of the discharge holes in the discharge structure is increased. There is a difference, and it is considered that a sufficient pressure for ejection could not be obtained at the ejection hole on the vibration generator side where the pressure was small.
Further, when the ratio of the minimum discharge speed on the vibration generating body side in the discharge structure and the maximum discharge speed near the center in the discharge structure was taken, Examples 1 to 9 were closer to 1 than Comparative Examples 1 to 5 . This is also considered to be due to the uniform pressure applied to each discharge hole.
As for the weight average particle diameter D4, Examples 1 to 9 were smaller than Comparative Examples 1 to 5. In Comparative Examples 1-5, coalescence between the droplets frequently occurred on the vibration generator having a low discharge speed, whereas in Examples 1-9, there was little coalescence between the droplets. It is thought to be due to. Even in D4 / Dn, which is an index of the size of particles, Examples 1 to 9 were smaller than Comparative Examples 1 to 5 for the same reason. Further, when the toner manufacturing apparatus has a transport air flow path and the ejected liquid droplets are transported by the transport air current, it is closer to 1, and the direction of the transport air flow is the direction of the initial discharge speed of the ejected liquid droplets. When the direction is substantially perpendicular to the angle, it was particularly close to 1.
About the amount of collection, compared with the membrane vibration type of Examples 1-4, there were many liquid column resonance types of Examples 5-9.

The toner manufacturing method and manufacturing apparatus of the present invention can discharge droplets simultaneously from a plurality of discharge holes, and can discharge each droplet in a uniform amount without uniting the droplets discharged from the plurality of discharge holes. Since the number of droplets that can be discharged is large, a toner having high versatility and high monodispersibility can be produced efficiently.
Further, the toner obtained by the toner production method and production apparatus of the present invention has high versatility and high monodispersibility of the toner, so that it can be used in static photography in electrophotography, electrostatic recording, electrostatic printing, and the like. It can be suitably used as a developer for developing a charge image. As the developer, any electrostatic latent image carrier used in conventional electrophotography can be used. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image carrier, and a selenium electrostatic latent image are used. An image carrier, a zinc oxide electrostatic latent image carrier and the like can be preferably used.

DESCRIPTION OF SYMBOLS 1,200 Toner manufacturing apparatus 2 Droplet discharge unit 3 Particle formation part (solvent removal part)
3A Top surface part of particle forming part 4 Toner collecting part 5 Toner storing part 6 Raw material container 7 Tube 8, 8A Liquid feeding pipe (pipe)
9 Liquid return pipe 10 Toner composition liquid 11 Droplet discharge portion 12 Liquid column resonance liquid chamber 12A Peripheral portion of discharge structure O, 12C Center of discharge structure 13a Discharge structure (thin film, nozzle plate, discharge plate) joint 13b Vibration generator joint 14 frame (liquid chamber member)
15 Discharge hole (nozzle, through hole)
16 Discharge structure (thin film, nozzle plate, discharge plate)
16A Deformable region of discharge structure 17, 17A Vibration generator (electromechanical conversion means)
19 support member 20 liquid supply tube (liquid supply hole)
21 Bubble discharge tube (discharge hole)
23 Liquid droplet 24 Liquid chamber 40 Carrying airflow 41 Air flow path forming member 42 Air flow path 43 Static elimination device 50 Lead wire 51 Drive circuit (drive signal generation source)
52 Liquid Common Supply Path 53 Conveying Airflow Flow Path 54 End of Frame on Fixed End Side 55 End on Liquid Common Supply Path 52 Side Elastic Plate 100 Pump T Toner Particles

JP-A-7-152202 JP-A-57-201248 Japanese Patent No. 3786034 Japanese Patent No. 3786035 JP 2008-276146 A JP 2008-281915 A

Claims (13)

  Droplet forming means for discharging a toner composition liquid containing at least a resin and a colorant from a plurality of discharge holes including those having different shapes at a uniform discharge speed, and the dropletized toner And a particle forming means for solidifying the composition liquid to form particles. The droplet forming means has a discharge structure in which a plurality of discharge holes including those having different shapes are formed,
The shape of the plurality of discharge holes is a tapered shape in which the opening diameter of the plurality of discharge holes decreases toward the discharge direction of the toner composition liquid, and the plurality of discharge holes are tapered depending on the position in the discharge structure. The toner manufacturing apparatus according to claim 1, wherein the toner manufacturing apparatus has corners.   The toner manufacturing apparatus according to claim 2, wherein the droplet forming unit further includes a vibration generator that generates vibration, and the vibration generator is provided in an annular shape around the discharge structure.   4. The toner manufacturing apparatus according to claim 3, wherein the taper angle of the discharge hole located on the vibration generating body side in the discharge structure is larger than the taper angle of the discharge hole located in the center portion.   The liquid droplet forming means has a liquid chamber in which discharge holes are opened, and a vibration generator for applying vibration to the toner composition liquid in the liquid chamber, and the liquid to which vibration is applied by the vibration generator The toner composition liquid in the chamber forms a pressure standing wave by liquid column resonance, and the toner composition liquid is discharged into droplets from the discharge holes formed in a region that becomes the antinode of the pressure standing wave. The toner production apparatus according to claim 1, wherein:   6. The toner according to claim 1, wherein the particle forming unit includes a carrier airflow passage for allowing a carrier airflow that conveys at least one of the dropletized toner composition liquid and the solidified particles to flow inside. manufacturing device.   The toner manufacturing apparatus according to claim 6, wherein the transport airflow passage is provided so that a transport airflow is formed in a direction substantially orthogonal to a direction of the initial discharge speed of the droplets discharged by the droplet forming unit. . A method for producing toner using the toner production apparatus according to claim 1, comprising:
A droplet forming step of discharging a toner composition liquid containing at least a resin and a colorant from a plurality of discharge holes including those having different shapes at a uniform discharge speed into droplets; and the dropletized toner And a particle forming step of solidifying the composition liquid to form particles.   In the droplet forming step, a vibration generator provided in an annular shape around a discharge structure having a plurality of discharge holes imparts vibration to the discharge structure and discharges the toner composition liquid to form droplets The method for producing a toner according to claim 8.   The droplet forming step imparts vibration to the toner composition liquid in the liquid chamber having a plurality of ejection holes, forms a pressure standing wave by liquid column resonance in the toner composition liquid, and becomes an antinode of the pressure standing wave. The toner manufacturing method according to claim 8, wherein the toner composition liquid is discharged from the discharge hole formed in the region.   The particle forming step further includes a step of transporting at least a droplet in a range of 2 mm from the discharge opening of the discharge hole by a transport airflow in a direction substantially perpendicular to the direction of the initial discharge speed of the droplet. The method for producing a toner according to any one of the above.   A droplet forming means for discharging a resin composition liquid containing at least a resin from a plurality of discharge holes including those having different shapes at a uniform discharge speed into droplets; and the dropletized resin composition liquid An apparatus for producing resin fine particles, comprising at least particle forming means for solidifying to form particles. A method for producing resin fine particles using the resin fine particle production apparatus according to claim 12,
A droplet forming step of discharging a resin composition liquid containing at least a resin from a plurality of discharge holes including those having different shapes at a uniform discharge speed into droplets; and the dropletized resin composition liquid A method for producing resin fine particles, comprising: a particle forming step of solidifying to form particles.