JP2012093644A - Apparatus for producing toner, production method of toner, and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus for producing a toner, which can achieve continuous discharging of droplets by continuous driving at a high frequency, has extremely high productivity, and can stably produce a toner having a sharp grain size distribution while preventing unification of droplets in an initial stage.SOLUTION: The apparatus for producing a toner includes: droplet discharging means, which imparts vibrations to a toner composition liquid in a liquid column resonance liquid chamber having at least one discharge hole opened therein, by a vibration generating unit to form pressure stationary waves by liquid column resonance, and discharges the toner composition liquid into droplets through the discharge hole formed in a region corresponding to an antinode of the pressure stationary waves; and droplet solidifying means conveying the droplets by an air flow and solidifying the droplets. The droplet solidifying means includes an air flow guide aperture, which is disposed in a downstream side along the discharging direction of the droplets and which guides the air flow to the downstream side. The air flow guide aperture includes an entrance portion and a diaphragm portion where the aperture diameter reaches the minimum, and has a tapered shape at the entrance portion where an aperture plane in the air flow guide aperture gradually decreases from a plane including the surface of the discharge hole to the diaphragm portion.

Description

  The present invention relates to a toner manufacturing apparatus, a toner manufacturing method, and a toner.

  The resin fine particles that require uniformity are used in various applications such as toner fine particles for electrophotography, spacer particles for liquid crystal panels, colored fine particles for electronic paper, and fine particles as a drug carrier for pharmaceuticals. As a method for producing uniform fine particles, a method of inducing a reaction in a liquid to obtain resin fine particles having a uniform particle diameter, such as a soap-free polymerization method, is known. Since it is difficult to reuse the aqueous solution as a reaction solution due to by-products that are not contained in the product but are produced in the aqueous solution, the production method has a high environmental load. In addition, as an example of the metal fine particles, ball solder particles and other solar cells using uniform silicone fine particles have attracted attention in recent years.

  Conventionally, a pulverization method is known as a general method for producing toner. In this pulverization method, the toner composition is first melt-kneaded with two rolls, a twin screw extruder, etc., cooled, and then coarsely pulverized, finely pulverized, and classified. If necessary, external additives such as a fluidizing agent are mixed with a Henschel mixer or the like. In the coarse pulverization process, a rotoplex, a pulverizer, or the like is used. In the fine pulverization process, a jet mill, a turbo mill, or the like is used. In the classification process, a known manufacturing apparatus such as an elbow jet or various air classifiers is used.

  As a toner production method other than the pulverization method, a spray method is known. The spray method includes a one-fluid discharge hole (pressure discharge hole) sprayer that pressurizes liquid and sprays from the discharge hole, a multi-fluid spray discharge hole sprayer that mixes and sprays liquid and compressed gas, and a rotating disk. In this method, the toner composition liquid is formed into droplets in a gas phase by using a rotary disk type sprayer or the like that forms liquid droplets by centrifugal force. In such a spraying method, a commercially available apparatus called a spray drying system that performs spraying and drying simultaneously can be used. If sufficient drying is not possible using this spray drying system, secondary drying such as fluidized bed drying is performed, and external additives such as a fluidizing agent are mixed with a Henschel mixer as necessary.

  However, when a toner having a small particle diameter is produced by the pulverization method or the spraying method, there is a disadvantage that the fine powder content becomes very large. The fine powder tends to contaminate the carrier and the developing device and must be removed in the classification step. However, since many fine powders are removed, there are problems that productivity is lowered and manufacturing cost is increased.

  As yet another toner manufacturing method, a discharge granulation method is known. In this discharge granulation method, the portion where liquid is dropped and solidified as in the spray method is the same, but the portion where liquid droplets are discharged from discharge holes having the same diameter as the toner using vibration generating means It is different. As one of the discharge granulation methods, the pressure chamber is pressurized in one direction to generate a liquid column from the nozzle, and the liquid column is divided into droplets by weak ultrasonic vibration, which is dried and solidified. There has been proposed a toner manufacturing method and apparatus for converting it into a toner (see Patent Document 1). Such a toner manufacturing apparatus includes a toner composition liquid container that contains a toner composition liquid to be supplied to the pressurizing chamber of the droplet discharge unit, and the toner composition liquid container is used to agitate the toner composition liquid contained therein. In general, a stirring member that generates a flow is disposed. In the toner composition container, the material is uniformly dispersed in the toner composition liquid by causing the flow to be generated by the agitating member, and each material is non-uniformly dispersed in the toner composition liquid. It is possible to prevent the material from becoming non-uniformly dispersed. A liquid column is formed from the through hole by applying pressure to the toner composition liquid in one direction. Then, minute vibrations are applied to the formed liquid column by the vibration generating means to induce Rayleigh splitting to form uniform droplets. The droplets are solidified to produce toner base particles. Such a Rayleigh splitting method has a merit that it is only necessary to generate a weak vibration by the vibration generating means because the liquid is pressurized and discharged, and it is possible to form particles with a low voltage.

  However, in the toner manufacturing method, in order to use Rayleigh splitting, it is necessary to form droplets having a particle size that is about twice the inner diameter of the discharge hole. In addition, there is a problem that the inner diameter of the toner needs to be reduced, and the liquid is unidirectionally pressurized in the reservoir, and the toner composition is clogged inside the ejection hole due to the toner composition.

  Furthermore, as another conventional example using the discharge granulation method, a pressure pulse operation is performed in which the entire raw material stored in the raw material storage unit storing the toner raw material is uniformly pressurized and discharged in the head unit, A droplet discharge method is known in which a toner material is discharged from an discharge hole (see Patent Document 2). Hereinafter, the principle of droplet discharge disclosed in this document will be outlined with reference to FIG. FIG. 17 also shows the pressure value in the raw material reservoir. This droplet discharge method is a method of intermittently forming droplets by performing an operation of repeating the following three states in the raw material reservoir. As shown in FIG. 17 (a), the head portion is in a first state where no discharge signal is input. That is, as shown in FIG. 17A, the piezoelectric body is not deformed and the volume of the raw material storage portion is not changed. The raw material liquid is not discharged from the hole. Next, as a second state, a discharge signal is input, and as shown in FIGS. 17B and 17C, the piezoelectric body is displaced to the inside of the raw material reservoir, and the volume of the raw material reservoir is reduced. . At this time, the pressure in the entire raw material reservoir is uniformly and instantaneously increased, and droplets are ejected from the ejection holes. At this time, the raw material flows also to the raw material storage part (not shown) called a feeder which communicates with the raw material storage part and stores the raw material liquid. Next, as a third state, after the discharge of the raw material of one droplet is completed, as shown in FIGS. 17D and 17E, the application of voltage is stopped, and the piezoelectric element is almost in its original shape. Return to. At this time, a negative pressure acts on the raw material liquid in the raw material storage part, and an amount of the raw material liquid corresponding to the discharge amount flows from the raw material storage part to the raw material storage part.

However, the droplet discharge method is a method in which the raw material liquid is intermittently discharged by performing an operation of repeating three states in the raw material reservoir, and the raw material liquid reduced by the discharge in this operation is supplied into the raw material reservoir. Thereafter, it is necessary to go through a first state in which the raw material liquid is not discharged. Therefore, in the droplet discharge method, a time loss occurs in view of the entire manufacturing process time by the amount corresponding to the time of the first state, and the toner production efficiency corresponding to the time loss There is a problem of lowering.
In addition, in this droplet discharge method, generally large droplets are formed. Therefore, in order to obtain dry toner particles, it is necessary to use a discharge portion with a small diameter or dilute the raw material. However, if the size of the discharge part is reduced, the probability that the solid dispersion such as a pigment that is essential as a toner component and a release agent added as necessary is clogged dramatically increases. There's a problem.
Furthermore, when the raw material is diluted, there is a problem that the energy for drying and solidifying the diluted solution is increased, and thus the production efficiency is greatly reduced. Further, since the production efficiency is lowered, it takes a long time to store the raw material liquid in the raw material storage part, and thus the raw material liquid is retained, and the toner raw material is stuck in the long-term production. There is also.

  Further, as another conventional example using the discharge granulation method, the toner composition liquid supplied to and stored in the storage unit by vibrating a thin film in which a plurality of discharge holes are formed in the head unit is supplied to a plurality of discharge units. By providing an airflow forming means for forming an airflow that discharges from the hole and flows in the liquid droplet discharge direction through the throttle portion corresponding to the discharge hole formation region disposed on the downstream side in the liquid droplet discharge direction, There has been disclosed a toner manufacturing method and a manufacturing apparatus for manufacturing toner base particles by solidifying droplets while widening the interval between droplets and preventing droplet coalescence (see Patent Document 3).

  However, the toner manufacturing method includes an air flow path forming member that forms an air flow that flows in the droplet discharge direction through the throttle portion corresponding to the discharge hole formation region disposed on the downstream side in the droplet discharge direction. Although it is possible to produce a toner having a sharp particle size distribution by expanding the interval between the droplets, the prevention of coalescence at the initial stage, that is, immediately after droplet ejection, is not sufficient and there is room for further study. is there.

  An object of the present invention is to solve the conventional problems and achieve the following objects. In other words, the present invention can realize continuous droplet discharge by continuous driving at a high frequency, has a very high productivity, and stabilizes a toner having a sharp particle size distribution without initial droplet coalescence. It is an object of the present invention to provide a toner manufacturing method, a toner manufacturing apparatus, and a toner that can be manufactured automatically.

Means for solving the problems are as follows. That is,
<1> A toner manufacturing apparatus comprising: a droplet discharge unit that discharges a toner composition liquid in droplets from at least one discharge hole; and a droplet solidification unit that transports and solidifies the droplets by an air flow.
The toner composition liquid is obtained by dissolving or dispersing the toner composition in an organic solvent,
The droplet discharge means includes a liquid column resonance liquid chamber in which the discharge hole is opened, and a vibration generation unit that applies vibration to the toner composition liquid in the liquid column resonance liquid chamber. A vibration is imparted to the toner composition liquid in the liquid column resonance liquid chamber to form a pressure standing wave due to the liquid column resonance, and the toner composition is formed from the discharge hole formed in a region that is antinode of the pressure standing wave. Discharge the liquid into droplets,
The droplet solidifying means is disposed on the downstream side in the droplet discharge direction, and has an airflow guide hole for guiding the airflow downstream.
The airflow guide hole has a throttle portion having a minimum opening diameter, and an inlet portion,
An opening surface of the airflow guide hole that is perpendicular to the opening axis of the discharge hole has a tapered shape that gradually decreases from the surface of the discharge hole toward the throttle portion at the inlet portion. It is a manufacturing device.
<2> The airflow guide hole further has an outlet portion,
The opening surface perpendicular to the opening axis of the discharge hole in the airflow guide hole has a tapered shape that gradually expands toward the downstream side in the droplet transport direction from the throttle portion at the outlet portion. This is a toner manufacturing apparatus.
<3> The liquid droplet solidifying means further includes an air flow channel for circulating the air flow from the outer periphery of the liquid column resonance liquid chamber to the air flow guide hole, and the air flow channel has a uniform velocity distribution in the droplet discharge direction. The toner production apparatus according to any one of <1> to <2>, wherein the toner has an airflow.
<4> The toner production apparatus according to any one of <1> to <3>, wherein a plurality of ejection holes are formed in one liquid column resonance liquid chamber.
<5> The toner production apparatus according to any one of <1> to <4>, wherein reflection wall surfaces are provided at least partially at both ends of the liquid column resonance liquid chamber in the longitudinal direction.
<6> The toner production apparatus according to any one of <1> to <5>, wherein the toner composition liquid is vibrated at a frequency f that satisfies the following expression (1).
f = N × c / (4L) (1)
(Wherein, L represents the length of the liquid column resonance liquid chamber in the longitudinal direction, c represents the speed of sound waves of the toner composition liquid, and N represents an integer.)
<7> The toner production apparatus according to any one of <1> to <6>, wherein the toner composition liquid is vibrated at a frequency f that satisfies the following expression (2).
N × c / (4L) ≦ f ≦ N × c / (4Le) (2)
(Where, L is the length in the longitudinal direction of the liquid column resonance liquid chamber, Le is the distance between the end on the liquid supply path side and the center of the discharge hole closest to the end, and c is (Sound wave velocity of toner composition liquid, N represents an integer, respectively)
<8> The toner manufacturing apparatus according to any one of <1> to <7>, wherein the toner composition liquid is vibrated at a frequency f that satisfies the following expression (3).
N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le) (3)
(Where, L is the length in the longitudinal direction of the liquid column resonance liquid chamber, Le is the distance between the end on the liquid supply path side and the center of the discharge hole closest to the end, and c is (Sound wave velocity of toner composition liquid, N represents an integer, respectively)
<9> The toner production apparatus according to any one of <7> to <8>, wherein Le / L> 0.6.
<10> The toner production apparatus according to any one of <1> to <9>, wherein the vibration frequency is high-frequency vibration of 300 kHz or more.
<11> A toner manufacturing method including a droplet discharge step of discharging a toner composition liquid into droplets from at least one discharge hole, and a droplet solidification step of transporting and solidifying the droplets by an air flow,
The toner composition liquid is obtained by dissolving or dispersing the toner composition in an organic solvent,
In the liquid droplet ejection step, vibration is applied to the toner composition in the liquid column resonance liquid chamber in which the discharge hole is opened to form a pressure standing wave by liquid column resonance, The toner composition is ejected in droplets from the ejection holes formed in the region,
The droplet solidifying step includes conveying the droplets by an airflow through an airflow guide hole that is disposed on the downstream side in the discharge direction of the droplets and guides the airflow to the downstream side,
The airflow guide hole has a throttle portion having a minimum opening diameter, and an inlet portion,
An opening surface of the airflow guide hole that is perpendicular to the opening axis of the discharge hole has a tapered shape that gradually decreases from the surface of the discharge hole toward the throttle portion at the inlet portion. It is a manufacturing method.
<12> The airflow guide hole further has an outlet portion,
The opening surface perpendicular to the opening axis of the discharge hole in the airflow guide hole has a tapered shape that gradually expands from the throttle portion toward the downstream side in the droplet transport direction at the outlet portion. A toner manufacturing method.
<13> The liquid droplet solidifying step further includes flowing an air flow from the outer periphery of the liquid column resonance liquid chamber to the air flow guide hole, and the air flow has a uniform velocity distribution in a droplet discharge direction. To <12>.
<14> A toner obtained by the toner production method according to any one of <11> to <13>.

  According to the present invention, the conventional problems can be solved, the object can be achieved, continuous droplet discharge by continuous driving at a high frequency can be realized, and the productivity is very high. It is possible to provide a toner manufacturing method, a toner manufacturing apparatus, and a toner capable of stably manufacturing a toner having a sharp particle size distribution without initial droplet coalescence.

FIG. 1 is a cross-sectional view showing the overall configuration of a toner manufacturing apparatus according to an embodiment of the present invention. FIG. 2 is a cross-sectional view showing a configuration of a droplet discharge head in the droplet discharge means of FIG. FIG. 3 is a cross-sectional view taken along line A-A ′ showing the configuration of the droplet discharge means in FIG. 1. FIG. 4A is a schematic diagram illustrating an example of an airflow guide hole of a toner manufacturing apparatus according to an embodiment of the present invention. FIG. 4B is a schematic diagram illustrating another example of the airflow guide hole of the toner manufacturing apparatus according to the embodiment of the present disclosure. FIG. 5 is a diagram illustrating an example of a main part of the toner manufacturing apparatus according to the embodiment of the present invention. FIG. 6 is a diagram illustrating another example of the main part of the toner manufacturing apparatus according to the embodiment of the present invention. FIG. 7 is a schematic diagram showing the state of the liquid column resonance phenomenon in the liquid column resonance chamber of the droplet discharge head. FIG. 8 is a schematic diagram showing standing waves of velocity and pressure fluctuations when N = 1, 2, and 3. FIG. 9 is a schematic diagram showing standing waves of velocity and pressure fluctuations when N = 4 and 5. FIG. 10 is a schematic view showing the state of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber in the droplet discharge head in the droplet discharge means. FIG. 11 is a diagram showing a state of actual droplet discharge. FIG. 12 is a characteristic diagram showing drive frequency and droplet discharge speed frequency characteristics. FIG. 13 is a diagram illustrating an example of a droplet discharge head of a toner manufacturing apparatus according to an embodiment of the present invention. FIG. 14 is a view showing another example of a droplet discharge head of a toner manufacturing apparatus according to an embodiment of the present invention. FIG. 15 is a diagram illustrating another example of a droplet discharge head of a toner manufacturing apparatus according to an embodiment of the present invention. FIG. 16 is a diagram showing a comparative example of the droplet discharge means. FIG. 17 is a cross-sectional view showing a droplet operation of a toner droplet head in a conventional toner manufacturing apparatus.

(Toner manufacturing method and toner manufacturing apparatus)
The toner manufacturing method of the present invention includes at least a droplet discharge step and a droplet solidification step, and further includes other steps as necessary.
The toner manufacturing apparatus of the present invention includes at least a droplet discharge unit and a droplet solidification unit, and further includes other units as necessary.

<Droplet discharge process and droplet discharge means>
The droplet discharge step is a step of discharging the toner composition liquid in droplets from at least one discharge hole. In the present invention, in the droplet discharge step, a vibration is imparted to the toner composition liquid in the liquid column resonance liquid chamber in which the discharge hole is opened to form a pressure standing wave by liquid column resonance, and the pressure control is performed. The toner composition liquid needs to be ejected in droplets from the ejection holes formed in the region where the wave is present, and the droplet ejection step can be performed by the droplet ejection means.

  The droplet discharge means includes a liquid column resonance liquid chamber in which the discharge hole is opened, and a vibration generation unit that applies vibration to the toner composition liquid in the liquid column resonance liquid chamber. A vibration is imparted to the toner composition liquid in the liquid column resonance liquid chamber to form a pressure standing wave due to the liquid column resonance, and the toner composition is formed from the discharge hole formed in a region that is antinode of the pressure standing wave. It is necessary to discharge the liquid into droplets.

<< Discharge hole >>
The discharge hole is not particularly limited as long as it is formed in a region that becomes the antinode of the pressure standing wave, and can be appropriately selected according to the purpose. It is preferable that a plurality of regions are formed in at least one of the regions, and that a plurality of regions are formed in one liquid column resonance liquid chamber.

  The region that becomes the antinode of the pressure standing wave is a region where the amplitude of the pressure wave of the liquid column resonance standing wave is large and the pressure fluctuation is large, and the pressure fluctuation is large enough to discharge a droplet. It is an area | region which has. 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) The wavelength is preferably ± 1/3 wavelength and more preferably ± 1/4 wavelength (see FIG. 7). 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, driven at a low voltage, and clogging of the discharge holes is less likely to occur.

  The number of discharge holes formed in the one liquid column resonance liquid chamber is not particularly limited and may be appropriately selected according to the purpose. In view of the above, 2 to 100 are preferable, and 4 to 60 are more preferable. When the number of the ejection holes exceeds 100, it is necessary to set a high voltage to the vibration generating unit when forming droplets of a desired toner composition liquid from the 100 ejection holes. The behavior of the generating part may become unstable.

There is no restriction | limiting in particular as an opening diameter of the said discharge hole, Although it can select suitably according to the objective, 1 micrometer-40 micrometers are preferable, 2 micrometers-15 micrometers are more preferable, and 6 micrometers-12 micrometers are especially preferable. If the opening diameter is less than 1 μm, the formed droplets are very small, and toner may not be obtained. Further, when solid fine particles such as a pigment are contained as a component of the toner composition liquid, there is a possibility that the ejection holes are frequently blocked and the productivity is lowered. In addition, when the opening diameter exceeds 40 μm, the diameter of the toner droplet is large, and when it is dried and solidified to obtain a desired toner particle diameter, it is necessary to dilute the toner composition with an organic solvent to a very dilute liquid. In some cases, a large amount of drying energy is required to obtain a certain amount of toner, which is inconvenient. On the other hand, when the opening diameter is 6 μm to 12 μm, when manufacturing a member in which the discharge holes are opened, it is possible to keep small variations in the diameters of the many discharge holes, and the discharge holes are concentrated to increase productivity. This is advantageous because it can be maintained.
The opening diameter of the discharge hole is the diameter of the opening located on the side of the discharge hole where the droplets are discharged. If it is a perfect circle, it means the diameter, and it is an ellipse, square, hexagon, If it is a polygon such as a square or a regular polygon, it means the average diameter.

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 having a taper angle in which the opening diameter of the discharge hole becomes smaller in the discharge direction of the droplet (toner composition liquid) is preferable.
Here, the “taper angle” refers to an angle formed by the opening axis of the discharge hole and the side surface of the cross-sectional shape of the discharge hole in the cross section in the thickness direction of the formation surface of the discharge hole. The “opening axis” means a perpendicular to the opening surface of the discharge hole (a surface perpendicular to the thickness direction of the discharge hole forming surface). Examples of the “taper” include a linear taper, an exponential taper, a parabolic taper, and a combination thereof.

When a plurality of discharge holes are formed, the pitch between the discharge holes (the shortest distance between the central portions of the adjacent discharge holes) in one of the regions that become the antinodes of the pressure standing wave is 20 μm to 200 μm. Preferably, 30 μm to 135 μm is more preferable. If the pitch between the ejection holes is less than 20 μm, there is a high probability that droplets discharged from adjacent ejection holes collide with each other to form large droplets, leading to a deterioration in toner particle size distribution.
The pitch between the discharge holes may be equal at all intervals between the plurality of discharge holes, or at least one pitch may be different. It is preferable in that it can be obtained.

<< Liquid column resonance liquid chamber >>
The liquid column resonance liquid chamber is a liquid chamber capable of forming a pressure standing wave by vibration applied by the vibration generating unit in accordance with the principle of the liquid column resonance phenomenon described later. A discharge hole is formed in the region, and a communication port for supplying the toner composition liquid is provided at the longitudinal end of the liquid column resonance liquid chamber. A reflection wall surface perpendicular to the longitudinal axis is provided at least at a part of one end or both ends. The liquid column resonance liquid chamber preferably has a vibration generating portion disposed on one of the walls parallel to the longitudinal direction of the liquid column resonance liquid chamber, and the wall on which the vibration generating portion is disposed It is preferable that the discharge hole is formed in the facing wall.
The shape of the liquid column resonance liquid chamber is not particularly limited as long as a pressure standing wave can be formed by the vibration, and can be selected as appropriate. For example, a quadrangular column (a rectangular parallelepiped), a cylinder, a truncated cone, etc. Can be mentioned.
It is preferable that a reflection wall surface is provided on at least a part of 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.
Further, as shown in FIG. 2, the length L between the wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber is determined based on the liquid column resonance principle as described later. Further, as shown in FIG. 3, the width W of the liquid column resonance liquid chamber is less than half the length L of the liquid column resonance liquid chamber so as not to give an extra frequency to the liquid column resonance. Small is preferable.

  Further, the liquid column resonance liquid chamber is formed by joining frames formed of a material having high rigidity that does not affect the resonance frequency of the toner composition liquid at the vibration drive frequency. Preferably, examples of such a material include metals, ceramics, and silicone.

Further, it is preferable that a plurality of the liquid column resonance liquid chambers are arranged with respect to one droplet discharge means in order to dramatically improve productivity. The number of liquid column resonance liquid chambers installed for one droplet discharge means is not particularly limited and can be appropriately selected according to the purpose. However, in terms of achieving both operability and productivity, 100 to 2,000 are preferable, 100 to 1,000 are more preferable, and 100 to 400 are particularly preferable.
Here, each of the liquid column resonance liquid chambers is connected to a flow path for supplying a liquid from a common liquid supply path, and the common liquid supply path communicates with a plurality of the liquid column resonance liquid chambers. is doing.

<< Vibration generator >>
The vibration generator is not particularly limited as long as it can be driven at a predetermined frequency and imparts vibration to the toner composition liquid in the liquid column resonance liquid chamber, and can be appropriately selected according to the purpose. Examples thereof include a piezoelectric body and an ultrasonic vibration generator.
The piezoelectric body is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include piezoelectric ceramics such as lead zirconate titanate (PZT), piezoelectric polymers such as polyvinylidene fluoride (PVDF), and crystals. , A piezoelectric body formed of a material such as single crystal such as LiNbO ₃ , LiTaO ₃ , KNbO _3, or the like. Since the piezoelectric ceramics generally have a small displacement, they are often used by being laminated. There is no restriction | limiting in particular as said ultrasonic vibration generator, According to the objective, it can select suitably, For example, a magnetostriction element etc. are mentioned.
The vibration generating part is preferably bonded to an elastic plate, and the elastic plate preferably forms part of the wall of the liquid column resonance liquid chamber so that the vibration generating part does not come into contact with the liquid.
Furthermore, it is preferable that the vibration generating unit is arranged so that it can be individually controlled for each liquid column resonance liquid chamber. In addition, it is preferable to dispose a vibration generating unit such as a block-like piezoelectric body via 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.

First, the mechanism of droplet formation by the droplet discharge means in the toner manufacturing apparatus of the present invention will be described.
The principle of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber (for example, the liquid column resonance liquid chamber 18 in the droplet discharge head 11 in FIGS. 1 and 2) will be described. When the sound velocity of the liquid is c and the driving frequency applied to the toner composition liquid as a medium from the vibration generating section (for example, the vibration generating section 20 in FIG. 2) is f, resonance of the toner composition liquid occurs. The wavelength λ to be
λ = c / f Formula (A)
Are in a relationship.

Here, in the case where the liquid column resonance liquid chamber is fixed on both sides or equivalent to both side fixed ends, the length between the reflection wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber is expressed as liquid column resonance. The length L in the longitudinal direction of the liquid chamber is used. In this case, resonance is formed most efficiently when the length L matches an even multiple of one-fourth of the wavelength λ. That is, it is represented by the following formula (B).
L = (N / 4) λ Formula (B)
(However, N is 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, and 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.
In FIG. 2, the length from the end of the liquid column resonance liquid chamber 18 on the fixed end side to the end on the liquid common supply path 17 side corresponds to the length L. Further, the height h1 (= about 80 μm) of the end of the frame on the liquid common supply path 17 side is about twice the height h2 (= about 40 μm) of the communication port, and the both ends are fixed. Can be considered equivalent to.

The above formula (B) 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 Resonance is most efficiently formed when it matches an odd multiple of a quarter of the wavelength λ. That is, this corresponds to the case where N in the above formula (B) is represented by 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.

From the above formula (A) and the above formula (B), the most efficient drive frequency f is
f = N × c / (4L) (1)
(L: length of liquid column resonance liquid chamber in longitudinal direction, c: velocity of sound wave of toner composition liquid, N: integer)
It is guided.
Therefore, in the toner manufacturing method and manufacturing apparatus according to the present invention, it is preferable to apply a vibration having a frequency f at which the above formula (1) is established to the toner composition liquid. However, in actuality, since the toner composition liquid has a viscosity that attenuates resonance, the vibration is not amplified infinitely, and has a Q value, as shown in equations (2) and (3) described later. In addition, resonance occurs at a frequency in the vicinity of the drive frequency f with the highest efficiency shown in the equation (1).

FIG. 8 shows the shape of the standing wave of the velocity and pressure fluctuation (resonance mode) when N = 1, 2, and 3. FIG. 9 shows the standing wave of the velocity and pressure fluctuation when N = 4, 5. The shape (resonance mode) is shown. The standing wave is a sparse / dense wave (longitudinal wave), but is generally expressed as shown in FIGS. The solid line indicates the velocity standing wave, and the dotted line indicates the pressure standing wave. For example, as can be seen from FIG. 8A showing the case of one-side fixed end with N = 1, the amplitude of the velocity distribution becomes zero at the closed end and the amplitude of the velocity distribution becomes maximum at the open end. When the length between both ends in the longitudinal direction of the liquid column resonance liquid chamber is L, and the wavelength at which the toner composition liquid resonates is λ, the standing wave is most efficient when the integer N is 1 to 5. appear. 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 where the moving speed of the medium (liquid) in the longitudinal direction becomes maximum, and conversely, the pressure becomes zero. 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. 8 and 9 is generated by superposition of waves. However, the standing wave pattern also varies depending on the number of ejection holes and the opening position of the ejection holes. Although the resonance frequency appears at a position deviated from the position obtained from the above equation (1), a stable ejection condition can be created by appropriately adjusting the driving frequency. For example, the sound velocity c of the toner composition liquid is 1,200 m / s, the length L of the liquid column resonance liquid chamber is 1.85 mm, wall surfaces are present at both ends, and N = 2 resonance that is completely equivalent to both fixed ends. When the mode is used, the most efficient resonance frequency is derived as 324 kHz from the above formula (B). In another example, the sound velocity c of the toner composition 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 = 4 equivalent to the fixed ends on both sides. When the resonance mode is used, the most efficient resonance frequency is derived from the above formula (B) as 648 kHz. Therefore, even in a liquid column resonance liquid chamber having the same shape, higher-order resonance can be used by adjusting the drive frequency.
The frequency of the vibration can be appropriately set according to the shape of the liquid column resonance liquid chamber and the like and is not uniquely selected, but is preferably a high frequency vibration of 300 kHz or more, 000 kHz is more preferable.

  The liquid column resonance liquid chamber in the liquid droplet ejection head of the liquid droplet ejection means of this embodiment shown in FIGS. 1 and 2 is acoustically affected by the fact that both ends are equivalent to the closed end state or the influence of the opening of the ejection holes. In order to increase the frequency, an end portion that can be described as a soft wall is preferable in order to increase the frequency. The influence of the opening of the discharge hole here means that the acoustic impedance is reduced, and in particular, the compliance component is increased. Therefore, the configuration in which the wall surfaces are formed at both ends in the longitudinal direction of the liquid column resonance liquid chamber as shown in FIG. 8B and FIG. 9A is regarded as the resonance mode at both fixed ends and the discharge hole side as an opening. This is preferable because all resonance modes of the open end on one side can be used.

Further, the numerical aperture of the ejection holes, the opening arrangement position, and the cross-sectional shape of the ejection holes are factors that determine the driving frequency, and the driving frequency can be appropriately determined according to this. For example, when the number of ejection holes is increased, the restriction at the tip of the liquid column resonance liquid chamber, which has been the fixed end, gradually loosens, a resonance standing wave that is almost close to the open end is generated, and the drive frequency increases. Furthermore, a loose constraint condition is established starting from the opening arrangement position of the discharge hole that is present on the most liquid supply path side. In addition, the cross-sectional shape of the discharge hole becomes a round shape, the volume of the discharge hole varies depending on the thickness of the frame, the actual standing wave has a short wavelength, and is higher than the drive frequency. When a voltage is applied to the vibration generating unit at the drive frequency determined in this way, the vibration generating unit is deformed, and a resonant standing wave is generated most efficiently at the drive frequency. Further, a 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 between the end on the liquid supply path side and the center of the discharge hole closest to the end is Le, L and Le The vibration generating unit is vibrated using a drive waveform whose main component is a drive frequency f in a range determined by the following formulas (2) and (3) using both of the lengths. Then, it is possible to eject liquid droplets from the ejection holes by inducing liquid column resonance.
Therefore, in the toner manufacturing method and manufacturing apparatus of the present invention, it is preferable to apply vibrations having a frequency f that satisfies either of the following formulas (2) and (3) to the toner composition liquid.

N × c / (4L) ≦ f ≦ N × c / (4Le) (2)
N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le) (3)
(L: length in the longitudinal direction of the liquid column resonance liquid chamber, Le: distance between the end on the liquid supply path side and the center of the ejection hole closest to the end, c: velocity of sound waves of the toner composition liquid, N: integer)

  The ratio of the distance Le between the length L between both ends in the longitudinal direction of the liquid column resonance liquid chamber, the end on the liquid supply path side, and the center of the discharge hole closest to the end is Le / L> 0. .6 is preferred.

  Based on the principle of the liquid column resonance phenomenon described above, a pressure standing wave is formed in the liquid column resonance liquid chamber, and a discharge hole is formed in a region that becomes an antinode of the pressure standing wave of the liquid column resonance liquid chamber. In this case, droplet discharge occurs continuously.

<Droplet solidification step and droplet solidification means>
The droplet solidification step is a step of transporting and solidifying the droplets by an air current, and can be performed by the droplet solidification means. The droplet solidifying means is a means for conveying and solidifying the droplets by an air flow.
The droplet solidification step in the present invention includes conveying the droplets by an airflow through an airflow guide hole that is arranged on the downstream side in the droplet discharge direction and guides the airflow downstream. The guide hole has a narrowed portion having a minimum opening diameter and an inlet portion, and an opening surface perpendicular to the opening axis of the discharge hole in the airflow guide hole extends from the surface of the discharge hole in the inlet portion. The taper shape needs to be gradually reduced as it goes to the throttle portion.
Further, the droplet solidifying means in the present invention is disposed on the downstream side in the droplet discharge direction and has an airflow guide hole for guiding the airflow downstream, and the airflow guide hole has a minimum opening diameter. An opening surface that has a throttle portion and an inlet portion and that is perpendicular to the opening axis of the discharge hole in the airflow guide hole gradually decreases in the inlet portion as it goes from the surface of the discharge hole toward the throttle portion. It needs to be tapered.

<< Airflow guide hole >>
The airflow guide hole has a throttle portion having an opening diameter that is minimum and an inlet portion, and is provided on the downstream side in the droplet discharge direction to guide the airflow downstream.
In the present invention, the opening surface of the airflow guide hole that is perpendicular to the opening axis of the discharge hole gradually decreases at the inlet portion from the surface of the discharge hole toward the throttle portion (inlet portion taper shape). Need to be.
Since the opening surface of the airflow guide hole has a tapered shape at the inlet portion, in the droplets passing through the inlet portion, the velocity of the droplets located outside contacting the airflow and the droplets located inside Since the difference is smaller and the difference in kinetic energy of each droplet is reduced, contact between droplets due to the difference in velocity of droplets discharged from multiple discharge holes is prevented, and coalescence immediately after droplet discharge is prevented. Is done.
By providing the throttle part, the velocity of the airflow increases, the velocity of the droplets increases, and the droplet interval between the droplets ejected before and after the droplets increases, The coalescence of the drops is prevented.
In addition, the airflow guide hole further includes an outlet portion, and an opening surface perpendicular to the opening axis of the discharge hole in the airflow guide hole is downstream in the transport direction of the droplet from the throttle portion in the outlet portion. It is preferable that it is a taper shape (exit part taper shape) which expands gradually as it goes to.
Since the opening surface of the airflow guide hole is tapered at the outlet portion, the airflow passage at the outlet portion is widened, the airflow is accelerated, and the interval between the droplets is widened to prevent the droplets from coalescing. Is done.
Here, the “opening surface” means a surface on which an opening of the airflow guide hole located on a plane perpendicular to the opening axis of the discharge hole is formed. The “opening diameter” means the opening diameter (opening width) of the airflow guide hole in the section of the discharge hole in the opening axial direction.
Further, the “tapered shape” means that the opening axis of the discharge hole and the side surface of the cross-sectional shape of the airflow guide hole have a taper angle in the section in the opening axis direction of the discharge hole. For example, a linear taper, an exponential taper, a parabolic taper, and a combination thereof can be used.

  4A and 4B are schematic views showing an example of an airflow guide hole of a toner manufacturing apparatus according to an embodiment of the present invention, each of (A) a first form having only the inlet portion taper shape, and ( B) The 2nd form which has the said entrance part taper shape and the said exit part taper shape is shown.

In the first and second embodiments, “the tapered shape that gradually decreases in the inlet portion as it goes from the surface of the discharge hole to the throttle portion” is from a surface that includes the surface of the discharge hole on the horizontal axis. When the distance x (corresponding to the position on the opening axis of the discharge hole) is taken and the opening diameter D of the airflow guide hole is taken on the vertical axis, this means that the graph is drawn with one continuous line. The graph from the surface including the surface of the discharge hole (x = 0) to the opening surface (x = x ₁ ) including the inlet side end of the restricting portion is only in a negative slope region (dD / dx <0). Alternatively, a region having a negative slope and a region having a zero slope (dD / dx = 0) may be mixed. Among these, those consisting only of a negative slope region (dD / dx <0) are preferable.

  In the region where the slope is negative (dD / dx <0), the slope may be always constant (linear taper) or different. For example, when the opening diameter of the airflow guide hole of the present invention is composed of only a negative slope region (dD / dx <0), the opening diameter gradually increases from the surface of the discharge hole toward the inlet side end of the throttle portion. In addition, it is possible to adopt a mode in which dD / dx increases (a mode in which the absolute value decreases).

In the second embodiment, “in the outlet portion, a tapered shape that gradually expands from the throttle portion toward the downstream side in the droplet conveyance direction” is a distance from a surface that includes the surface of the discharge hole on the horizontal axis. When x (corresponding to the position on the opening axis of the discharge hole) is taken and the opening diameter D of the airflow guide hole is taken on the vertical axis, it means that the graph is drawn with one continuous line. The graph from the opening surface (x = x ₂ ) including the inlet side end portion of the throttle portion to the opening surface (x = x ₃ ) including the downstream end portion in the droplet transport direction is a positive slope region It may be composed only of (dD / dx> 0), or may be a mixture of a positive slope area and a zero slope area (dD / dx = 0). Among these, those composed only of regions having a positive inclination (dD / dx> 0) are preferable.

  In a region where the slope is positive (dD / dx> 0), the slope may be always constant (linear taper) or different. For example, when the opening surface of the airflow guide hole of the present invention is composed only of a positive slope region (dD / dx> 0), the outlet side end of the throttle part is located downstream of the droplet transport direction. A mode in which dD / dx gradually increases toward the head (a mode in which the absolute value increases) can be taken.

The shape of the airflow guide hole is not particularly limited as long as the above conditions are satisfied, and can be selected as appropriate. For example, when the inlet part or outlet part of the exhaust hole has a linear taper, various parameters shown in FIG. Can be defined by
FIG. 5 is a diagram illustrating an example of a main part of the toner manufacturing apparatus according to the embodiment of the present invention. FIG. 5A is a cross-sectional view showing the droplet discharge means and the airflow guide hole, and FIG. 5B is a bottom view showing the arrangement of the discharge holes and the throttle portion.
When the airflow guide hole inlet portion angle β is an angle formed by the opening axis of the discharge hole and the cross-sectional side surface of the inlet portion of the airflow guide hole in the cross section of the discharge hole in the opening axis direction, The guide hole inlet portion angle β is preferably 15 ° to 85 °, and more preferably 30 ° to 80 °. In addition, a plurality of the airflow guide hole inlet portion angles β may be provided.
Moreover, the corner which forms the said airflow guide hole entrance part angle (beta) may have a corner radius, As such a corner radius, 1 mm-50 mm are preferable and 2 mm-20 mm are more preferable.

The throttle portion position H, and the surface of the discharge hole, if the distance between the inlet end of the narrowed portion (corresponding to x ₁ in FIG. 4A and B), examples of the narrowed portion position H, any restriction However, 1 mm to 20 mm is preferable, and 3 mm to 15 mm is more preferable.
Further, when the throttle portion length L is the distance between the inlet side end portion of the throttle portion and the outlet side end portion of the throttle portion (corresponding to x ₂ -x ₁ in FIGS. 4A and 4B), the throttle portion length The length L varies depending on other various parameters that define the shape of the airflow guide hole, and cannot be generally defined, but is preferably 1 mm to 100 mm, and more preferably 2 mm to 80 mm.
The opening width B of the throttle portion is not particularly limited as long as it is the same as or wider than the arrangement width of the discharge holes, and other various types that define the shape of the liquid column resonance liquid chamber, the discharge holes, and the airflow guide holes to be used It can be appropriately selected according to the parameters. Here, the “arrangement width of the discharge holes” is surrounded by a straight line or a curve connecting the outer edges of the discharge holes located on the outer peripheral portion in the plurality of discharge holes arranged in one or more liquid column resonance chambers. It means the opening diameter (opening width) of the cross section in the opening axis direction in the arrangement area of the discharge holes.

When the airflow guide hole outlet portion angle γ is an angle formed by the opening axis of the discharge hole and the side surface of the cross-sectional shape of the outlet portion of the airflow guide hole in the cross section of the discharge hole in the opening axial direction. The hole exit portion angle γ is preferably 2.5 ° to 80 °, more preferably 2.5 ° to 60 °.
The air flow velocity V in the throttle portion is preferably faster than the initial velocity of the droplets ejected from the ejection holes, and such a velocity differs depending on the initial velocity and cannot be generally defined. 5 m / s to 100 m / s is preferable, and 5 m / s to 50 m / s is more preferable.

Further, in addition to the embodiment shown in FIG. 5 in which a linear taper is provided at the inlet portion or outlet portion of the airflow guide hole, an exponential function taper is provided in the inlet portion or outlet portion of the airflow guide hole as shown in FIG. The form can also be preferably used.
FIG. 6 is a diagram illustrating another example of the main part of the toner manufacturing apparatus according to the embodiment of the present invention. 6A is a cross-sectional view showing the droplet discharge means and the airflow guide hole, and FIG. 6B is a bottom view showing the arrangement of the discharge holes and the throttle portion.

<< Airflow channel >>
In the method for producing a toner of the present invention, the droplet discharge step further includes flowing an air flow from an outer periphery of the liquid column resonance liquid chamber to the air flow guide hole, and the air flow is in the droplet discharge direction. It is preferable to have a uniform velocity distribution. Here, this can be carried out by an air flow channel described later.
In the toner manufacturing apparatus according to the aspect of the invention, it is preferable that the droplet discharge unit further includes an air flow channel for flowing an air flow from an outer periphery of the liquid column resonance liquid chamber to the air flow guide hole.
The air flow channel is a flow channel for allowing an air flow to flow from the outer periphery of the liquid column resonance liquid chamber to the air flow guide hole, and the air flow is controlled by the tapered shape of the inlet portion, so that the droplet discharge direction is increased. An air flow having a uniform velocity distribution is formed. The air flow can suppress deceleration of the droplet due to air resistance and the like, thereby preventing droplets from contacting and coalescing to increase the particle size of the droplet. Moreover, the turbulence of the airflow can be prevented and the pressure loss of the airflow can be suppressed.
The shape of the air flow channel is not particularly limited as long as the above conditions are satisfied, and can be appropriately selected according to the purpose.

The droplet discharge means may include an air flow channel forming container that covers an outer periphery of the liquid column resonance liquid chamber and has an outer peripheral portion that forms the air flow channel and the air flow guide hole. When the air flow channel forming container is provided, it is preferable that the air flow channel forming container has a shape corresponding to the shape of the liquid column resonance liquid chamber.
More preferably, an air flow control member is provided on the outer periphery of the liquid column resonance liquid chamber so as to correspond to the shape of the air flow channel forming container. By further providing the air flow control member, the air flow channel can be freely changed, and by forming an air flow having a uniform velocity distribution in the discharge direction of the droplets, the droplets can be decelerated due to air resistance or the like. Therefore, it is possible to prevent the droplets from coming into contact with each other and coalescing to increase the particle size of the droplets. Further, it is possible to prevent the airflow from being disturbed and to suppress the pressure loss of the conveying airflow.
When the airflow control member angle α is an angle formed by the opening axis of the discharge hole and the side surface of the cross-sectional shape of the airflow control member in the cross section in the opening axis direction of the discharge hole, this is a linear taper (FIG. 5). Reference), the airflow control member angle α is preferably 10 ° to 85 °, and more preferably 30 ° to 80 °.

  The method for solidifying the droplets is not particularly limited as long as the droplets can be solidified into particles, and a known method can be appropriately selected according to the purpose. For example, the organic solvent contained in the droplets is dried. Examples include a method of evaporating into a gas and performing shrinkage solidification by drying.

Hereinafter, an embodiment of a toner manufacturing apparatus for carrying out the toner manufacturing method of the present invention will be described with reference to schematic configuration diagrams of FIGS.
FIG. 1 is a cross-sectional view showing the overall configuration of a toner manufacturing apparatus according to an embodiment of the present invention. FIG. 2 is a cross-sectional view showing a configuration of a droplet discharge head in the droplet discharge means of FIG. 3 is a cross-sectional view taken along the line AA ′ showing the configuration of the droplet discharge means of FIG. A toner manufacturing apparatus 1 according to the present embodiment illustrated in FIG. 1 includes a droplet discharge unit 10 and a dry collection unit 30 that is a part of the droplet solidification unit.

The droplet discharge means 10 is a liquid chamber having a droplet discharge region communicating with the outside through the discharge hole, and the liquid in which a pressure standing wave due to the liquid column resonance is generated under the conditions described later. A plurality of droplet discharge heads 11 for discharging the toner composition liquid in the columnar resonance liquid chamber as droplets from the discharge holes are arranged.
Further, the droplet discharge means 10 includes a raw material storage portion 13 that stores a toner composition liquid 14 that is a toner raw material, and a droplet discharge head 11 that passes the toner composition liquid 14 stored in the raw material storage portion 13 through a liquid supply pipe 16. And a liquid circulation pump 15 that pumps the toner composition liquid 14 in the liquid supply pipe 16 so as to be supplied to the liquid common supply path 17 (described later) and returned to the raw material container 13 through the liquid return pipe 22. . Further, as shown in FIG. 2, the droplet discharge head 11 includes a liquid common supply path 17 and a liquid column resonance liquid chamber 18. The liquid column resonance liquid chamber 18 communicates with a liquid common supply path 17 provided on one of the wall surfaces at both ends in the longitudinal direction. The liquid column resonance liquid chamber 18 is provided on a wall surface facing the discharge hole 19 and a discharge hole 19 that discharges the toner droplet 21 to one wall surface of the wall surfaces connected to both ends. In order to form a standing wave, it has a vibration generator 20 that generates high-frequency vibration. The vibration generator 20 is connected to a high frequency power source (not shown).

  An airflow channel 12 including an airflow control member 36 and an airflow channel forming container 37 is provided on the outer periphery of the droplet discharge head 11, and toner droplets of the toner composition liquid discharged from the droplet discharge head 11 are provided. 21 is conveyed to the dry collection unit 30 side by flowing the conveyance airflow 33 pumped from the airflow generation part which is not illustrated to the airflow flow path 12. FIG. Since the toner droplet 21 is forcibly conveyed not only by gravity but also by the conveying airflow 33, it is possible to suppress the discharged toner droplet 21 from being decelerated due to air resistance. Accordingly, when the toner droplets 21 are continuously ejected, the toner droplets 21 ejected before are decelerated by the air resistance, and the toner droplets 21 ejected later are the toner droplets 21 ejected before. By catching up with the toner droplets 21, it is possible to prevent the toner droplets 21 from coming into contact with each other, and the toner droplets 21 from becoming larger in particle size. Furthermore, the airflow flow path forming container 37 includes an airflow guide hole having the throttle portion 40, and the conveyance airflow speed increases at the throttle portion 40. As a result, the toner droplet velocity is increased, and the interval between the previously ejected toner droplet 21 and the later ejected toner droplet 21 is increased, thereby preventing the toner droplets 21 from being coalesced. .

  Here, the airflow control member 36 is formed so as to freely change the airflow passage 12, adjust the airflow introduction path, prevent disturbance of the transport airflow 33, and suppress the pressure loss of the transport airflow 33. The shape of the airflow control member 36 is not particularly limited as long as the above conditions are satisfied. For example, as shown in FIGS. 5 and 6, the airflow control member 36 has a shape corresponding to the shape of the airflow channel formation container 37. Is preferable from the viewpoint of controlling the airflow. With such a configuration, the transport air flow 33 can be efficiently converted into a transport direction air flow, and uniform kinetic energy can be obtained for each toner droplet 21 by making the velocity distribution of the transport air flow 33 uniform. Therefore, it is possible to prevent the droplets from coming into contact with each other due to the difference in velocity of the droplets ejected from the plurality of ejection holes.

The diaphragm portion 40 the inlet side of the air flow passage formed container 37 opening diameter (the airflow guide hole entry section, corresponding to 0 ≦ x ≦ x ₁ portion in FIGS. 4A and B) are squeezed from the opening surface of the discharge hole 19 portion Accordingly, the velocity of the air flow 33 of the toner droplets 21 is formed to be uniform while preventing the air flow 33 from being disturbed. Here, the turbulence of gas means generation of stagnation, vortex flow, and the like. Further, the shape of the inlet side of the air flow channel forming container 37 is not particularly limited as long as the above conditions are satisfied. For example, in addition to the linear tapered shape shown in FIG. 5, as shown in FIG. Alternatively, an exponential taper shape may be used.
By making the velocity distribution of the conveying air flow 33 of the toner droplets 21 uniform on the inlet side of the restricting portion 40 of the air flow channel forming container 37, as described above, the droplets come into contact with each other and coalesce. Can be prevented.

Further, the opening diameter of the air flow passage forming container 37 on the outlet side of the throttle portion 40 (the air flow guide hole outlet portion, corresponding to the portion x ₂ ≦ x ≦ x ₃ in FIGS. 4A and B) is from the throttle portion 40 to the toner droplet 21. Accordingly, the air flow path 12 is widened at the outlet, so that the transport air flow 33 flows in the outer peripheral direction, and the interval between the droplets can be increased. Can be prevented. Further, the shape of the airflow passage forming container 37 on the outlet side of the throttle portion 40 is not particularly limited as long as the above conditions are satisfied. For example, in addition to the linear tapered shape shown in FIG. 5, as shown in FIG. It may be an exponential taper shape.
It is possible to prevent the droplets from coming into contact with each other by accelerating the conveyance air flow 33 of the toner droplets 21 on the outlet side of the throttle portion 40 of the air flow channel forming container 37 and expanding the droplet interval.

  The dry collection unit 30 shown in FIG. 1 includes a chamber 31 and a toner collection unit 32. In the chamber 31, a large downdraft 39 is formed in which the dry airflow 38 generated by an airflow generator (not shown) and the transport airflow 33 are merged. As the air flow generation unit, either a method in which an air blower is provided in the upstream portion for pressurization or a method in which the air is sucked from the toner collection unit 32 and the pressure is reduced can be employed. In addition, a rotating airflow generator (not shown) that generates a rotating airflow that rotates around an axis parallel to the vertical direction is disposed in the toner collecting unit 32. Further, the toner collecting section 32 has a toner storing section 35 for storing the dried and solidified toner particles that have passed through the toner collecting tube 34 communicating with the chamber 31.

Next, a toner manufacturing process in the toner manufacturing apparatus of this embodiment will be described.
The toner composition liquid 14 accommodated in the raw material container 13 shown in FIG. 1 is passed through the liquid supply pipe 16 by a liquid circulation pump 15 for circulating the toner composition liquid 14, and the droplet discharge means 10 shown in FIG. 3. Into the liquid common supply path 17 and supplied to the liquid column resonance liquid chamber 18 of the droplet discharge head 11 shown in FIG. A pressure distribution is formed in the liquid column resonance liquid chamber 18 filled with the toner composition liquid 14 by the liquid column resonance standing wave generated by the vibration generating unit 20. Then, the toner droplet 21 is discharged from the discharge hole 19 formed in the region where the pressure standing wave becomes antinode.

  The toner composition liquid 14 that has passed through the common liquid supply path 17 flows through the liquid return pipe 22 and is returned to the raw material container 13. When the amount of the toner composition liquid 14 in the liquid column resonance liquid chamber 18 decreases due to the ejection of the toner droplets 21, a suction force due to the action of the liquid column resonance standing wave in the liquid column resonance liquid chamber 18 acts, and the liquid common The flow rate of the toner composition liquid 14 supplied from the supply path 17 increases. Then, the toner composition liquid 14 is replenished in the liquid column resonance liquid chamber 18. When the toner composition liquid 14 is replenished into the liquid column resonance liquid chamber 18, the flow rate of the toner composition liquid 14 passing through the liquid common supply path 17 is restored. Then, the liquid supply pipe 16 and the liquid return pipe 22 are in a state where the flow of the toner composition liquid 14 circulating in the apparatus is formed again.

On the other hand, as shown in FIG. 1, the toner droplet 21 discharged from the droplet discharge head 11 of the droplet discharge unit 10 enters the air flow channel 12 formed by the air flow control member 36 and the air flow channel forming container 37. The airflow 33 that is pumped from the airflow generation unit (not shown) is forced to be transported to the dry collection unit 30 side by the airflow 33, not only by gravity, and the airflow (not shown) It is conveyed downward by a large descending air flow 39 in which the dry air flow 38 generated by the generation unit and the transport air flow 33 are merged.
Here, on the inlet side of the throttle portion 40 of the airflow flow path forming container 37, the inner area becomes narrower from the opening surface of the discharge hole 19 toward the throttle portion 40, so that the turbulence of the conveying airflow 33 is prevented, and the toner The velocity distribution of the transport airflow 33 of the droplets 21 becomes uniform (that is, an airflow is formed), and as described above, the droplets are prevented from coming into contact with each other.
Further, on the outlet side of the throttle part 40 of the airflow channel forming container 37, the opening diameter increases from the throttle part 40 toward the downstream side in the ejection direction of the toner droplets 21, whereby the conveying airflow 33 is accelerated and the liquid By increasing the droplet interval, contact between the droplets is prevented.

  Next, a spiral airflow is formed along the conical inner wall surface of the toner collecting portion 32 by the rotating airflow and the descending airflow 39 generated by a rotating airflow generator (not shown) in the toner collecting portion 32. . The toner particles are dried and solidified in a laminar flow state on the spiral airflow. The dried and solidified toner particles are stored in the toner storage unit 35 through the toner collecting tube 34.

  Further, as can be seen from FIG. 3, adopting a configuration in which the discharge holes 19 are provided in the width direction in the liquid column resonance liquid chamber 18 can provide a large number of openings of the discharge holes 19, thereby increasing the production efficiency. Therefore, it is preferable. Further, since the liquid column resonance frequency varies depending on the arrangement of the discharge holes 19, it is desirable to appropriately determine the liquid column resonance frequency after confirming the discharge of the droplet.

  Next, the state of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber in the droplet discharge head in the droplet discharge means will be described with reference to FIG. In this figure, the solid line drawn in the liquid column resonance liquid chamber is a velocity distribution in which the velocity at each arbitrary measurement position between the fixed end side and the liquid common supply channel side end in the liquid column resonance liquid chamber is plotted. The direction from the common liquid supply path side to the liquid column resonance liquid chamber is +, and the opposite direction is-. In addition, the dotted line written in the liquid column resonance liquid chamber indicates a pressure distribution in which the pressure value at any measurement position between the fixed end side and the liquid common supply path side end in the liquid column resonance liquid chamber is plotted, Positive pressure is + and negative pressure is-with respect to 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. Furthermore, in the same figure, the liquid common supply path side is opened as described above, but the height of the opening where the liquid common supply path 17 and the liquid column resonance liquid chamber 18 communicate with each other (height h2 shown in FIG. 2). In comparison, the height of the frame serving as the fixed end (height h1 shown in FIG. 2) is about twice or more. Therefore, the liquid column resonance liquid chamber 18 shows respective changes in velocity distribution and pressure distribution over time under an approximate condition that the liquid column resonance liquid chamber 18 is substantially fixed at both sides.

  FIG. 10A shows a pressure waveform and a velocity waveform in the liquid column resonance liquid chamber 18 when droplets are discharged. In FIG. 10B, the meniscus pressure increases again after the liquid is drawn immediately after the droplet is discharged. As shown in (a) and (b) of these figures, the pressure in the flow path provided with the discharge hole 19 in the liquid column resonance liquid chamber 18 is maximum. Thereafter, as shown in FIG. 5C, the positive pressure in the vicinity of the discharge hole 19 decreases, and the liquid droplet 21 is discharged in a negative pressure direction.

  Then, as shown in FIG. 10D, the pressure in the vicinity of the discharge hole 19 is minimized. From this time, the filling of the toner composition liquid 14 into the liquid column resonance liquid chamber 18 starts. Thereafter, as shown in (e) of the figure, the negative pressure in the vicinity of the discharge hole 19 becomes smaller and shifts to the positive pressure direction. At this time, the filling of the toner composition liquid 14 is completed. And again, as shown to (a) of the figure, the positive pressure of the droplet discharge area | region of the liquid column resonance liquid chamber 18 becomes maximum, and the droplet 21 is discharged from the discharge hole 19. FIG. As described above, in the liquid column resonance liquid chamber, a standing wave due to the liquid column resonance is generated by the high-frequency driving of the vibration generating unit, and the standing wave due to the liquid column resonance is located at the position where the pressure fluctuates the most. Since the ejection holes 19 are arranged in the corresponding droplet ejection areas, the toner droplets 21 are continuously ejected from the ejection holes 19 in accordance with the antinode period.

  Next, an example of a configuration in which droplets are actually ejected by the liquid column resonance phenomenon will be described. This example is a resonance mode in which the length L between both ends in the longitudinal direction of the liquid column resonance liquid chamber 18 in FIG. 2 is 1.85 mm and N = 2. In addition, the first to fourth discharge holes were arranged at the antinodes of the N = 2 mode pressure standing wave, and the discharge performed with a sine wave with a driving frequency of 340 kHz was photographed by laser shadowgraphy. The state is shown in FIG. As can be seen from the figure, it is possible to discharge droplets having a uniform diameter and a substantially uniform speed. FIG. 12 is a characteristic diagram showing droplet velocity frequency characteristics when driven by the same amplitude sine wave with a drive frequency of 290 kHz to 395 kHz. As can be seen from the figure, in the first to fourth discharge holes, when the drive frequency is around 340 kHz, the discharge speed from each discharge hole is uniform and the maximum discharge speed. From this characteristic result, it can be seen that uniform discharge is realized at the antinode position of the liquid column resonance standing wave at 340 kHz which is the second mode of the liquid column resonance frequency. Further, from the characteristic results of FIG. 12, a liquid column in which droplets are not ejected between the droplet ejection speed peak at 130 kHz that is the first mode and the droplet ejection speed peak at 340 kHz that is the second mode. It can be seen that the frequency characteristic of the liquid column resonance standing wave, which is characteristic of resonance, is generated in the liquid column resonance liquid chamber.

In addition, by increasing the voltage applied to the piezoelectric body, both the discharge speed and the droplet diameter tend to increase monotonously. By adjusting the applied voltage, depending on the desired discharge speed or the desired toner particle diameter. The droplet diameter can be adjusted.

-Toner composition liquid and toner composition-
The toner composition liquid is obtained by dissolving or dispersing a toner composition in an organic solvent. The toner composition contains at least a resin, a colorant, and a release agent, and, if necessary, a pigment dispersion liquid or the like. Contains other ingredients.
As the toner composition liquid and the toner composition used in the toner production method of the present invention, the same toners as those for conventional electrophotographic toners can be used. That is, a toner material such as a styrene acrylic resin, a polyester resin, a polyol resin, or an epoxy resin dissolved in various organic solvents and finely dispersed, a colorant and a release agent, and if necessary, a charge control agent The target toner (toner base particles) can be produced by drying and solidifying the toner into fine droplets by the toner production method. Furthermore, if necessary, a toner may be obtained by adding a fluidity improver or a cleaning property improver to the surface.

--Resin--
Examples of the resin include at least a binder resin.
The binder resin is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, vinyl such as styrene monomer, acrylic monomer, methacrylic monomer, etc. Polymers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins, Examples include coumarone indene resin, polycarbonate resin, and petroleum resin.

  There is no restriction | limiting in particular as said styrene-type monomer, According to the objective, it can select suitably, For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-amylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, p- Styrene such as n-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or derivatives thereof Etc.

  There is no restriction | limiting in particular as said acrylic monomer, According to the objective, it can select suitably, For example, acrylic acid, esters of acrylic acid, etc. are mentioned. The esters of acrylic acid are not particularly limited and may be appropriately selected depending on the intended purpose. For example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic Examples include n-octyl acid, n-dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate.

  There is no restriction | limiting in particular as said methacrylic monomer, According to the objective, it can select suitably, For example, methacrylic acid, esters of methacrylic acid, etc. are mentioned. The esters of methacrylic acid are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methacrylic acid. Examples include n-octyl acid, n-dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

In the toner according to the present invention, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups.
The crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate, and an alkyl chain such as those obtained by replacing the acrylate of these compounds with methacrylate Diacrylate compounds; diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 Acrylate, dipropylene glycol diacrylate, and diacrylate compounds connected with an alkyl chain containing an ether bond, such as those of acrylates of these compounds is replaced with methacrylate and the like.

Other examples of the crosslinking agent include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond.
Moreover, as said crosslinking agent, polyester type diacrylates, such as brand name MANDA (made by Nippon Kayaku Co., Ltd.), etc. are mentioned, for example.

  Further, as the cross-linking agent, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, and acrylates of the above compounds are replaced with methacrylate, triallyl cyanurate And polyfunctional crosslinking agents such as triallyl trimellitate.

The addition amount of the crosslinking agent is preferably 0.01 parts by mass to 10 parts by mass and more preferably 0.03 parts by mass to 5 parts by mass with respect to 100 parts by mass of the other monomer components. .
Of these cross-linking agents, aromatic divinyl compounds (particularly divinylbenzene), diacrylate compounds linked by a bond chain containing one aromatic group and an ether bond from the viewpoint of fixing properties and offset resistance in toner resins. Are preferred. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

  Examples of the polymerization initiator used for producing the vinyl polymer or copolymer of the present invention include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1 , 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2 ′ , 4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone Ketone peroxides such as oxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di -Tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexyl Sulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexarate, tert-butyl peroxylaurate, tert-butyl-oxybenzoate, tert-butyl Peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-tert-butyl Kisa Hydro terephthalate to Rupaokishi, like tert- butylperoxy azelate.

When the binder resin is a styrene-acrylic resin, it has a molecular weight distribution by GPC that is soluble in the resin component tetrahydrofuran (THF), and has at least one peak in the molecular weight range of 3,000 to 50,000 (in terms of number average molecular weight). Exists. In addition, a resin having at least one peak in a region having a molecular weight of 100,000 or more is preferable from the viewpoint of fixability, offset property, and storage stability.
Further, as the THF soluble component, a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50% to 90% is preferable, and a binder resin having a main peak in a region having a molecular weight of 5,000 to 30,000 is more preferable. A binder resin having a main peak in the region of 5,000 to 20,000 is particularly preferable.

  The acid value when the binder resin is a vinyl polymer such as a styrene-acrylic resin is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 1 mgKOH / g to 50 mgKOH / g is particularly preferable.

The following are mentioned as a monomer which comprises a polyester-type polymer.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, Examples include 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A. It is done.
In order to crosslink the polyester resin, it is preferable to use a trihydric or higher polyhydric alcohol or a trivalent or higher acid in combination.

  Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene Etc.

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

  When the binder resin is a polyester resin, the molecular weight distribution of the THF soluble component of the resin component has at least one peak in the molecular weight region of 3,000 to 50,000. From the viewpoint of sex. In addition, a binder resin in which a component having a molecular weight of 100,000 or less in THF is 70% to 100% is preferable from the viewpoint of ejectability. Furthermore, a binder resin having at least one peak in a region having a molecular weight of 5,000 to 20,000 is more preferable.

  When the binder resin is a polyester resin, the acid value is preferably 0.1 mgKOH / g to 100 mgKOH / g. Moreover, it is more preferable that it is 0.1 mgKOH / g-70 mgKOH / g, and it is especially preferable that it is 0.1 mgKOH / g-50 mgKOH / g.

  In the present invention, the molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.

  As the binder resin, a resin containing a monomer component capable of reacting with both of these resin components in at least one of the vinyl polymer component and the polyester resin component can also be used. Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, and anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid esters or methacrylic acid esters.

  Moreover, when using together a polyester polymer, a vinyl polymer, and other binder resin, the acid value of the whole binder resin should have 60 mass% or more of resin whose 0.1 mgKOH / g-50 mgKOH / g. Is preferred.

In the present invention, the acid value of the binder resin component of the toner composition can be determined by the following method. The basic operation conforms to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. deep. A sample ground product of 0.5 g to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant, magnetic material, etc. are separately measured, and the acid value of the binder resin is determined by calculation.
(2) A sample is put into a 300 ml beaker, and 150 ml of a mixed solution of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The amount of KOH solution used at this time is S (ml), a blank is measured at the same time, the amount of KOH solution used at this time is B (ml), and the following formula (C) is used. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W Formula (C)

The glass transition temperature (Tg) of the binder resin and the composition containing the binder resin is preferably 35 ° C. to 80 ° C., and more preferably 40 ° C. to 70 ° C. from the viewpoint of toner storage stability.
When the glass transition temperature (Tg) is lower than 35 ° C., the toner may be easily deteriorated in a high temperature atmosphere. When the glass transition temperature (Tg) is higher than 80 ° C., the fixability may be lowered.

--Colorant--
There is no restriction | limiting in particular as said coloring agent, Resin normally used can be selected suitably, and can be used, for example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G ), Cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi -Red, Parachlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Kina Redon Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue , Indanthrene Blue (RS, BC), Indigo, Ultramarine, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian , Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake , Malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.

  The content of the colorant is preferably 1% by mass to 15% by mass and more preferably 3% by mass to 10% by mass with respect to the toner.

The colorant can also be used as a master batch combined with a resin.
Examples of the resin kneaded with the master batch include, in addition to the modified and unmodified polyester resins listed above, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, and polymers of substituted products thereof; styrene- p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene -Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethacrylate Methyl acid copolymer, styrene-acrylonitrile Copolymer, Styrene-vinyl methyl ketone copolymer, Styrene-butadiene copolymer, Styrene-isoprene copolymer, Styrene-acrylonitrile-indene copolymer, Styrene-maleic acid copolymer, Styrene-maleic acid ester copolymer Styrene copolymers such as polymers; 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, paraffin wax and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force.
At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, there is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used.
For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

  As the usage-amount of the said masterbatch, 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of said binder resins.

The resin for the masterbatch preferably has an acid value of 30 mgKOH / g or less, an amine value of 1 to 100, and the colorant dispersed therein. The acid value is 20 mgKOH / g or less, the amine value. 10 to 50, and it is more preferable to use the colorant dispersed therein.
When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered and the pigment dispersibility may be insufficient. Also, when the amine value is less than 1 and when the amine value exceeds 100, the pigment dispersibility may be insufficient.
The acid value can be measured, for example, by a method described in JIS K0070, and the amine value can be measured, for example, by a method described in JIS K7237.

--- Pigment dispersion liquid ---
The colorant can also be used as a colorant dispersion dispersed in a pigment dispersion.
The pigment dispersant is not particularly limited and may be appropriately selected according to the purpose. However, in terms of pigment dispersibility, it is preferably highly compatible with the binder resin. Examples of such commercially available products include “Ajisper PB821”, “Azisper PB822” (manufactured by Ajinomoto Fine Techno), “Disperbyk-2001” (manufactured by BYK Chemie), “EFKA-4010” (manufactured by EFKA), and the like. .

  The weight average molecular weight of the pigment dispersant is preferably 500 to 100,000 in terms of the maximum molecular weight of the main peak in terms of styrene equivalent weight in gel permeation chromatography, and among these, from the viewpoint of pigment dispersibility 3000 to 100,000, more preferably 5,000 to 50,000, and most preferably 5,000 to 30,000. When the molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant decreases. There are things to do.

  The mixing ratio of the dispersant in the toner is preferably 0.1% by mass to 10% by mass with respect to the colorant. When the blending ratio is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it exceeds 10% by mass, the chargeability under high humidity may be deteriorated.

--- Mold release agent--
The release agent is not particularly limited and can be appropriately selected from those usually used as waxes. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sasol Aliphatic hydrocarbon waxes such as waxes; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene waxes or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax; Animal waxes such as beeswax, lanolin and whale wax; mineral waxes such as ozokerite, ceresin and petrolatum; waxes based on fatty acid esters such as montanate ester wax and castor wax; deacidified carnauba wax, etc. Fatty acid Such as those deoxidizing part or all Le and the like.

  Other examples of the release agent include palmitic acid, stearic acid, montanic acid, and other saturated straight chain fatty acids such as straight chain alkyl carboxylic acids having a straight chain alkyl group; prundic acid, eleostearic acid, valinaline Unsaturated fatty acids such as acids; stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesilyl alcohol, and other long-chain alkyl alcohols; saturated alcohols such as sorbitol; linoleic acid amides; Fatty acid amides such as olefinic acid amide and lauric acid amide; saturated fatty acid bisamides such as methylene biscapric acid amide, ethylene bislauric acid amide and hexamethylene bisstearic acid amide; ethylene bisoleic acid amide and hexamethylene bisolei Unsaturated fatty acid amides such as acid amides, N, N′-dioleyl adipic acid amides, N, N′-dioleyl sepasic acid amides; A fatty acid metal salt such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate; a wax grafted with an aliphatic hydrocarbon wax using a vinyl monomer such as styrene or acrylic acid; Examples thereof include partial ester compounds of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  More preferable examples of the release agent include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, catalysts such as Ziegler catalysts and metallocene catalysts under low pressures. Polymerized using polyolefin, polyolefin polymerized using radiation, electromagnetic waves, light, etc., low molecular weight polyolefin obtained by pyrolyzing high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydro Synthetic hydrocarbon waxes synthesized by the Cole method, the Age method, etc., synthetic waxes using a compound having one carbon atom as a monomer, hydrocarbon waxes having a functional group such as a hydroxyl group or a carboxyl group, hydrocarbon waxes and functional groups Have Mixture of hydrocarbon wax, styrene these waxes as a matrix, maleic acid esters, acrylates, methacrylates, and graft modified wax with vinyl monomers such as maleic anhydride.

  In addition, these waxes have a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities removed are preferably used as the release agent.

The melting point of the release agent is preferably 70 ° C. to 140 ° C., more preferably 70 ° C. to 120 ° C., in order to balance the fixability and the offset resistance.
When the melting point is less than 70 ° C., the blocking resistance may be lowered, and when it exceeds 140 ° C., the anti-offset effect may be hardly exhibited.

  Further, by using two or more different types of waxes in combination, the plasticizing action and the releasing action which are the actions of the wax can be expressed simultaneously. Examples of the type of wax having a plasticizing action include waxes having a low melting point, those having a branched structure on the molecular structure, and those having a polar group. Examples of the wax having a releasing action include a wax having a high melting point, and the molecular structure includes a linear structure and a non-polar one having no functional group. Examples of use include a combination of two or more different waxes having a difference in melting point of 10 ° C. to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.

  When selecting two types of wax, in the case of a wax having the same structure, a wax having a relatively low melting point exhibits a plasticizing action, and a wax having a high melting point exhibits a releasing action. At this time, when the difference in melting point is 10 ° C. to 100 ° C., functional separation is effectively expressed. If it is less than 10 ° C., the function separation effect may be difficult to appear, and if it exceeds 100 ° C., the function may not be emphasized by interaction. At this time, the melting point of at least one wax is preferably 70 ° C. to 120 ° C., more preferably 70 ° C. to 100 ° C., since it tends to easily exhibit the function separation effect.

  As for the wax, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exhibit a plastic action, and those having a more linear structure or functional group Nonpolar or non-denatured straight materials that do not have a mold exhibit a releasing action. Preferred combinations include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene, polyolefins and graft modified polyolefins, alcohol waxes, fatty acid waxes or the like. Combination of ester wax and hydrocarbon wax, combination of Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax, combination of Fischer-Tropsch wax and polyolefin wax, combination of paraffin wax and microcrystal wax , Carnauba Wax, Candelilla wax, Rice wax or Montan wax and carbonized water A combination of systems waxes.

  In any case, since it becomes easy to balance the toner storage stability and the fixability, the endothermic peak observed in the DSC measurement of the toner has a peak top temperature of the maximum peak in the region of 70 ° C. to 110 ° C. It is more preferable that it has a maximum peak in the region of 70 ° C to 110 ° C.

  The total content of the release agent is preferably 0.2 parts by mass to 20 parts by mass, and more preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the binder resin.

In the present invention, the melting point of the release agent is defined as the peak top temperature of the maximum peak of the endothermic peak of the wax measured by differential scanning calorimetry (DSC).
As the DSC measuring instrument for measuring the melting points of the release agent and the toner, a highly accurate internal heat input compensation type differential scanning calorimeter is preferable. As a measuring method, it carries out according to ASTM D3418-82. The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 ° C./min after raising and lowering the temperature once and taking a previous history.

-Organic solvent-
The organic solvent is not particularly limited as long as it can dissolve or disperse the toner composition, and can be appropriately selected according to the purpose. For example, ethers, ketones, esters, hydrocarbons, Alcohol solvents are preferably used, and in particular, tetrahydrofuran (THF), acetone, methyl ethyl ketone (MEK), ethyl acetate, toluene and the like can be mentioned. These may be used individually by 1 type and may use 2 or more types together.

--- Preparation method of toner composition liquid--
A toner composition liquid can be obtained by dissolving or dispersing the toner composition in an organic solvent.
In preparation of the toner composition liquid, a homomixer, a bead mill, or the like is used so that the dispersion such as the colorant and the release agent is sufficiently fine with respect to the nozzle opening diameter in order to prevent clogging of the discharge holes. It becomes important.
The solid content of the toner composition liquid is preferably 3% by mass to 40% by mass. When the solid content is less than 3% by mass, not only the productivity is lowered, but also dispersions such as colorants and release agent fine particles are liable to settle and aggregate, resulting in non-uniform composition for each toner particle. The toner quality is likely to deteriorate. When the solid content exceeds 40% by mass, a toner having a small particle size may not be obtained.

<Toner>
The toner of the present invention is a toner obtained by the above-described toner manufacturing method of the present invention, whereby a toner having a monodispersed particle size distribution is obtained.
The toner of the present invention can further contain additives such as a fluidity improver, if necessary.

The particle size distribution (weight average particle size / number average particle size) of the toner is preferably 1.00 to 1.15, and more preferably 1.00 to 1.05.
Further, the weight average particle diameter of the toner is preferably 1 μm to 20 μm, and more preferably 3 μm to 10 μm.

  The weight average particle diameter, number average particle diameter, and particle size distribution of the toner can be measured by, for example, a flow type particle image analyzer (Flow Particle Image Analyzer). As the flow type particle image analyzer, for example, a flow type particle image analyzer FPIA-2000 manufactured by Toa Medical Electronics Co., Ltd. can be used. Further, not only toner but also toner particles, additives and the like can be similarly measured by this method.

A measurement method using the flow particle image analyzer will be described below.
First, water from which fine dust is removed through a filter so that the number of particles (for example, particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) existing in a measurement range of 10 ⁻³ cm ³ is 20 or less. A few drops of nonionic surfactant (preferably Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.) is added to 10 ml of the water, and 5 mg of a measurement sample is further added, and 20 kHz with an ultrasonic disperser STM UH-50, Dispersion treatment is performed for 1 minute under the condition of 50 W / 10 cm ³ , and dispersion treatment is further performed for a total of 5 minutes. The particle concentration of the measurement sample is 4,000 to 8,000 particles / 10 ⁻³ cm ³ The particle size distribution of particles having a circle-equivalent diameter of 0.60 μm or more and less than 159.21 μm is measured according to the following procedure using a sample dispersion prepared so as to be a target of

  The prepared sample dispersion is passed through a flow path (expanding 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 opposite sides of the flow cell. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter.

  In about 1 minute, the equivalent circle diameter of 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 are measured in the range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.

-Fluidity improver-
A fluidity improver may be added to the toner according to the present invention. The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface.

  The fluidity improver is not particularly limited and may be appropriately selected depending on the intended purpose. For example, metal such as fine powder silica such as wet process silica and dry process silica, fine powder unoxidized titanium, fine powder unalumina and the like. Oxide fine powder, and treated silica, titanium oxide, treated alumina, surface treated with silane coupling agent, titanium coupling agent, silicone oil, etc .; vinylidene fluoride fine powder, polytetrafluoroethylene fine powder And fluorine resin powders. Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.

  The particle size of the fluidity improver is preferably 0.001 μm to 2 μm, more preferably 0.002 μm to 0.2 μm, as an average primary particle size.

  The fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.

  Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include, for example, AEROSIL (trade name of Nippon Aerosil Co., Ltd., hereinafter the same) -130, -300, -380, -TT600, -MOX170, -MOX80. , -COK84; Ca-O-SiL (trade name of CABOT) -M-5, -MS-7, -MS-75, -HS-5, -EH-5; Wacker HDK (trade name of WACKER-CHEMIE) -N20 V15, -N20E, -T30, -T40; D-CFineSi1ica (trade name of Dow Corning); Franco1 (trade name of Franci1) and the like.

  Furthermore, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is more preferable. In the treated silica fine powder, it is particularly preferred to treat the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is preferably 30% to 80%. Hydrophobization is imparted by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, a method of treating fine silica powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound can be mentioned.

  Examples of the organosilicon compound include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and dimethyl. Vinylchlorosilane, divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethyl Chlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethyl L-chlorosilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxy Silane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, Examples thereof include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to Si. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The number average particle size of the fluidity improver is preferably 5 nm to 100 nm, and more preferably 5 nm to 50 nm.

As the specific surface area of the flowability improving agent, a specific surface area by nitrogen adsorption measured by the BET method, preferably at least ^{30m 2 / g, 60m 2 /} g~400m 2 / g is more preferable.
For fine powder the flowability improver is treated surfaces, the specific surface area is preferably at least ^{20m 2 / g, 40m 2 /} g~300m 2 / g is more preferable.

  The addition amount of the fluidity improver is preferably 0.03 parts by mass to 8 parts by mass with respect to 100 parts by mass of the toner particles.

-Other additives-
In the toner according to the present invention, as other additives, protection of the electrostatic latent image carrier / carrier, improvement of cleaning properties, adjustment of thermal characteristics / electrical characteristics / physical characteristics, resistance adjustment, softening point adjustment, fixing rate Metal soap, fluorosurfactant, dioctyl phthalate, etc. for the purpose of improvement, etc .; tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents; inorganic fine powders such as titanium oxide, aluminum oxide, alumina Etc. can be added as needed. The inorganic fine powder may be hydrophobized as necessary.
Also, lubricants such as polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, strontium titanate, anti-caking agent, white fine particles or black fine particles having opposite polarity to the toner particles, A small amount can be used as a developability improver.

  These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control and the like. It is also preferable to treat with a treating agent or the like.

  In preparing the developer, inorganic fine particles such as the hydrophobic silica fine powder mentioned above may be added and mixed in order to improve the fluidity, storage stability, developability and transferability of the developer. For mixing external additives, a general powder mixer can be appropriately selected and used, but it is preferable to use a mixer equipped with a jacket capable of adjusting 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, and the rotational speed, rolling speed, time, temperature, etc. of the mixer may be changed. A strong load and then a relatively weak load may be applied, and vice versa. Examples of the mixer that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like.

  A method for further adjusting the shape of the obtained toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner material containing a binder resin and a colorant is melt-kneaded and then finely pulverized. A method of mechanically adjusting the shape using a hybridizer, mechano-fusion, etc., so-called spray drying method. After dissolving and dispersing the toner material in a solvent in which the toner binder is soluble, the solvent is removed using a spray drying device. And a method of obtaining a spherical toner, and a method of forming a spherical toner by heating in an aqueous medium.

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm.

The BET specific surface area of the inorganic fine ^particles, 20m ² / ^g~500m 2 / g are preferred. The use ratio of the inorganic fine particles to the toner is preferably 0.01% by mass to 5% by mass, and more preferably 0.01% by mass to 2.0% by mass.

  Other additives include polymer-based fine particles, such as soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, polystyrene, methacrylic ester copolymer, acrylic ester copolymer, silicone, benzoguanamine, nylon, etc. And polycondensation resin, polymer particles of thermosetting resin, and the like.

Such an additive can be treated with a surface treatment agent to increase hydrophobicity and prevent deterioration of the additive itself even under high humidity.
Examples of the surface treatment agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. Are preferable.

  Examples of the cleaning property improver for removing the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymethyl methacrylate. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and the volume average particle size of the polymer fine particles is preferably 0.01 μm to 1 μm.

<< Developer >>
The toner of the present invention may be used as a one-component developer, or may be mixed with a carrier and used as a two-component developer.

-Career-
There is no restriction | limiting in particular as said carrier, According to the objective, it can select suitably, For example, carriers, such as a ferrite and a magnetite, a resin coat carrier, etc. can be mentioned. The resin-coated carrier includes carrier core particles and a coating material that is a resin that coats (coats) the surface of the carrier core particles. Examples of the resin used for the covering material include styrene-acrylic resins such as styrene-acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers; acrylic acid ester copolymers, methacrylic acid ester copolymers. Preferable examples include acrylic resins such as: fluorine-containing resins such as polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride; silicone resins, polyester resins, polyamide resins, polyvinyl butyral, aminoacrylate resins, and the like. In addition to these, resins that can be used as coating materials for carriers such as ionomer resins and polyphenylene sulfide resins can be used. These resins may be used alone or in combination of two or more.

  As the carrier, a binder type carrier core in which magnetic powder is dispersed in a resin can also be used. In the resin-coated carrier, as a method of coating the surface of the carrier core with at least a resin coating agent, for example, a method in which a resin is dissolved or suspended in a solvent and adhered to a coated carrier core, or simply mixed in a powder state The method of doing is mentioned. The ratio of the resin coating material used with respect to the resin-coated carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is 0.01% by mass to 5% by mass with respect to 100 parts by mass of the resin-coated carrier. Preferably, 0.1 mass%-1 mass% are more preferable.

  Examples of use in which the magnetic material is coated with the resin coating material of two or more kinds of mixtures are as follows: (1) Di, methyldichlorosilane and dimethyl silicone oil (mass ratio 1: 5) with respect to 100 parts by mass of fine titanium oxide powder. ) Treated with 12 parts by mass of the mixture, and (2) 100 parts by mass of the fine silica powder with 20 parts by mass of the mixture of dimethyldichlorosilane and dimethyl silicone oil (mass ratio 1: 5). It is done. As the resin coating material, for example, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, a silicone resin, and the like are preferably used, and among these, a silicone resin is particularly preferable.

  Examples of the mixture of the fluororesin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, and a mixture of polytetrafluoroethylene and a styrene-methyl methacrylate copolymer. , Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10), styrene-acrylic acid 2-ethylhexyl copolymer (copolymer mass ratio 10:90 to 90:10) and styrene -A mixture with 2-ethylhexyl acrylate-methyl methacrylate copolymer (copolymer mass ratio 20-60: 5-30: 10: 50) etc. are mentioned. Examples of the silicone resin include modified silicone resins produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with a silicone resin.

  Examples of the magnetic material for the carrier core include oxides such as ferrite, iron-rich ferrite, magnetite and γ-iron oxide, metals such as iron, cobalt and nickel, and alloys thereof. The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done. Among these magnetic materials, copper-zinc-iron-based ferrites mainly composed of copper, zinc and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium and iron components are particularly preferred. It is done.

The volume resistance value of the carrier can be set by appropriately adjusting the degree of unevenness on the surface of the carrier and the amount of the resin to be coated, and is preferably 10 ⁶ Ω · cm to 10 ¹⁰ Ω · cm, for example. There is no restriction | limiting in particular as a particle size of the said carrier, Although it can select suitably according to the objective, 4 micrometers-200 micrometers are preferable, 10 micrometers-150 micrometers are more preferable, and 20 micrometers-100 micrometers are especially preferable. Among these, as the particle diameter of the resin-coated carrier, the 50% particle diameter is most preferably 20 μm to 70 μm. In the two-component developer, the toner of the present invention is preferably used in an amount of 1 part by mass to 200 parts by mass with respect to 100 parts by mass of the carrier, and 2 parts by mass to 50 parts by mass of the toner with respect to 100 parts by mass of the carrier. More preferably it is used.

  In the developing method using the toner of the present invention, all electrostatic latent image carriers used in conventional electrophotography can be used. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image carrier, a selenium electrostatic latent image carrier, a zinc oxide electrostatic latent image carrier, and the like can be suitably used.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not restrict | limited to a following example.

  Examples of the relationship between the number and pattern of the ejection holes of the droplet ejection head and the standing wave and the shape of the airflow control member in the toner production apparatus according to the present embodiment are shown below. In each of the following embodiments, the resonance frequency can be known by experimentally searching for the discharge frequency. In addition, the results of the evaluation of the toner obtained by discharging the toner composition liquid under each condition to obtain toner base particles and then performing the external addition treatment are also shown.

Example 1
A toner composition liquid prepared as described below is used as a droplet discharge means by using the toner manufacturing apparatus shown in FIG. 1 having a droplet discharge head shown in FIG. 13 and an airflow guide hole and an airflow channel shown in FIG. The droplets were discharged under the conditions as described above.

-Preparation of colorant dispersion-
First, a carbon black dispersion was prepared as a colorant.
17 parts by mass of carbon black (Regal 400, manufactured by Cabot) and 3 parts by mass of a pigment dispersant (Ajisper PB821, manufactured by Ajinomoto Fine Techno Co., Ltd.) are primarily dispersed in 80 parts by mass of ethyl acetate using a mixer having stirring blades. I let you. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion in which aggregates of 5 μm or more were completely removed.

-Preparation of wax dispersion-
Next, a wax dispersion was prepared.
18 parts by mass of carnauba wax and 2 parts by mass of a wax dispersant were primarily dispersed in 80 parts by mass of ethyl acetate using a mixer having stirring blades. The primary dispersion was heated to 80 ° C. while stirring to dissolve the carnauba wax, and then the temperature of the liquid was lowered to room temperature to precipitate wax particles so that the maximum particle size was 3 μm or less. As the wax dispersant, a polyethylene wax grafted with a styrene-butyl acrylate copolymer was used. The obtained dispersion was further finely dispersed by a strong shearing force using a dyno mill and adjusted so that the maximum particle size was 1 μm or less.

-Preparation of toner composition liquid-
Next, a toner composition dispersion liquid having the following composition to which a resin as a binder resin, the colorant dispersion liquid, and the wax dispersion liquid were added was prepared.
100 parts by mass of a polyester resin (number average molecular weight: 6,000, weight average molecular weight: 40,000) 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 The mixture was stirred for 10 minutes using a mixer having stirring blades and dispersed uniformly. Aggregation of pigments, wax particles and the like did not occur due to the shock of solvent dilution.

-Preparation of toner-
The obtained toner composition liquid is subjected to the following droplet using the toner manufacturing apparatus of FIG. 1 having the droplet discharge head shown in FIG. 13 as the droplet discharge means and the airflow guide hole and the airflow channel shown in FIG. Droplets were discharged under the discharge conditions and the droplet transport conditions. Thereafter, the droplets were transported, dried and solidified, collected in a cyclone, and further blown and dried at 30 ° C. for 48 hours to produce toner base particles.

FIG. 13A is a cross-sectional view of a droplet discharge head, and FIG. 13B is a cross-sectional view showing the arrangement of discharge holes. The droplet discharge head shown in the figure has two discharge holes 19 on the fixed end side in the liquid column resonance liquid chamber 18 and a reflection wall provided on the liquid common supply path side end of the liquid column resonance liquid chamber 18. A piezoelectric element is provided as the vibration generating unit 20 that applies vibration to the toner composition liquid in the columnar resonance liquid chamber. In the droplet discharge head, the length L in the longitudinal direction of the liquid column resonance liquid chamber is 1.85 mm, and the vibration generating unit 20 causes vibration with a drive frequency of 328 kHz to be applied to the toner composition liquid in the liquid column resonance liquid chamber. As a result, a pressure standing wave is formed by liquid column resonance in a resonance mode of N = 2, which is substantially fixed at both ends. Under this condition, the region that becomes the antinode of the pressure standing wave is a region that becomes ± 1/4 wavelength, and is a region that is 0 mm to 0.46 mm from the end on the liquid supply path side. Two discharge holes 19 having a discharge hole opening of 8.0 μm and a pitch of 130 μm between the discharge holes are opened in this region.
Example 1 shows the result of driving at the resonance peak frequency. The resonance peak is a node of the velocity resonance standing wave in the resonance state, which is the antinode of the liquid column resonance standing wave, that is, a state in which the pressure is highest, and a droplet is experimentally ejected, as shown in FIG. The frequency at which the speed becomes maximum can be determined.
[Droplet discharge conditions]
Toner composition liquid specific gravity: ρ = 1.888 g / cm ³
Number of discharge holes: 2 Drive frequency: 328kHz
Applied voltage sine wave peak value: 8.0V
In-apparatus temperature: 27 to 28 ° C
Droplet diameter formed: 11.4 μm
Note that the droplet diameter is the same as the diameter of a circle having the same area from the area of the two-dimensional image of the formed droplet, as in FIG. Calculated as

In the configuration shown in FIG. 5 with the airflow guide hole and the airflow channel, toner base particles were obtained under the following droplet transport conditions.
[Droplet transport conditions]
Airflow control member angle α: 30 °
Airflow guide hole entrance first angle β1: 30 °
Airflow guide hole entrance second angle β2: 80 °
Aperture position H: 7 mm
Diaphragm length L: 3 mm
Diaphragm opening width B: 5 mm
Airflow guide hole outlet angle γ: 60 °
Constriction part conveyance air velocity V: 25.0 m / s

The toner base particles dried and solidified were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. Particle size of collected particles The particle size distribution of the collected particles was measured with a flow particle image analyzer (FPIA-2000, manufactured by Toa Medical Electronics Co., Ltd.) under the following measurement conditions. ) Was 5.7 μm, the number average particle diameter (Dn) was 5.5 μm, and toner base particles having a sharp particle size distribution with D4 / Dn of 1.04 were obtained.
〔Measurement condition〕
Dispersion condition of sample dispersion: 20 kHz, 50 W / 10 cm ³ ; 1 minute × 6 sets Ultrasonic dispersion device: UH-50 (manufactured by SMT Co., Ltd.)
Particle concentration of sample dispersion: 4000 to 8000 pieces / 10 ⁻³ cm ³
Equivalent circle diameter of particles to be measured: 0.60 μm or more and less than 159.21 μm

-External treatment-
After the dried and solidified toner base particles are collected in a cyclone, 1.0% by mass of hydrophobic silica (H2000, manufactured by Clariant Japan Co.) is added to the toner base particles using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Addition treatment was performed to prepare a toner.

-Fabrication 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.

<Evaluation method>
<< Thin line reproducibility >>
The prepared developer is put in a modified machine with an improved developer part of a commercially available copying machine (Imagiono 271; manufactured by Ricoh Co., Ltd.), and using a 6000 paper manufactured by Ricoh Co., Ltd. with a printing ratio of 7% image occupancy. Running was carried out. The thin line portions of the initial 10th image and the 30,000th image at that time were compared and evaluated with the thin line portion of the document. Specifically, it was magnified and observed at a magnification of 100 using an optical microscope, and evaluated in four stages of ◎, ◯, Δ, and X while comparing the state of missing lines with a stage sample. In addition, it represents that image quality is high in the order of ◎>◯>Δ> ×, and in particular, an evaluation of “X” indicates a level that cannot be adopted as a product. The results are shown in Table 1. Table 1 below also lists the evaluation results of fine line reproducibility of Examples 2 to 10 and Comparative Examples 1 to 3 after Example 1.

(Example 2)
In Example 1, the toner was obtained under the same droplet preparation conditions and droplet transport conditions as in Example 1 except that the airflow control member was removed, that is, the airflow control member angle α was set to 0 °.
The obtained toner was evaluated. The results are shown in Table 1.

(Example 3)
In Example 2, the air flow guide hole outlet angle γ is 90 °, that is, a taper is not provided and a straight shape is used. Obtained.
The obtained toner was evaluated. The results are shown in Table 1.

Example 4
In Example 1, a toner was obtained under the same droplet discharge conditions and droplet transport conditions as in Example 1 except that the droplet discharge head shown in FIG. 14 was used and the following droplet discharge conditions were used.
FIG. 14A is a cross-sectional view of a droplet discharge head, and FIG. 14B is a cross-sectional view showing the arrangement of discharge holes. The droplet discharge head shown in the figure has four discharge holes 19 on the fixed end side in the liquid column resonance liquid chamber 18 and a reflection wall at the liquid common supply path side end of the liquid column resonance liquid chamber 18. A piezoelectric element is provided as the vibration generating unit 20 that applies vibration to the toner composition liquid in the columnar resonance liquid chamber. In the droplet discharge head, the length L in the longitudinal direction of the liquid column resonance liquid chamber is 1.85 mm, and the vibration generating unit 20 causes vibration with a drive frequency of 344 kHz to be applied to the toner composition liquid in the liquid column resonance liquid chamber. As a result, the fixed end side is somewhat loosely restrained by the influence of the opening of the discharge hole as compared with the first embodiment of FIG. 13, but both ends are substantially due to liquid column resonance in a resonance mode of N = 2 at the fixed end. A pressure standing wave is formed. Under this condition, the region that becomes the antinode of the pressure standing wave is a region that becomes ± 1/4 wavelength, and is a region that is 0 mm to 0.46 mm from the end on the liquid supply path side. In this region, four discharge holes 19 having a discharge hole opening of 8.0 μm and a pitch between the discharge holes of 130 μm are opened.
[Droplet discharge conditions]
Number of discharge holes: 4 Drive frequency: 344 kHz
The obtained toner was evaluated. The results are shown in Table 1.

(Example 5)
In Example 4, a toner was obtained under the same droplet discharge conditions and droplet transport conditions as in Example 4 except that the airflow control member was removed, that is, the airflow control member angle α was set to 0 °.
The obtained toner was evaluated. The results are shown in Table 1.

(Example 6)
In Example 5, the airflow guide hole outlet angle γ is 90 °, that is, a taper is not provided and a straight shape is used. Obtained.
The obtained toner was evaluated. The results are shown in Table 1.

(Example 7)
In Example 1, a toner was obtained under the same droplet discharge conditions and droplet transport conditions as in Example 1 except that the droplet discharge head shown in FIG.
FIG. 15A is a cross-sectional view of a droplet discharge head, and FIG. 15B is a cross-sectional view showing the arrangement of discharge holes. The droplet discharge head shown in the figure has 36 discharge holes 19 on the fixed end side in the liquid column resonance liquid chamber 18 and a reflection wall provided at the liquid common supply path side end of the liquid column resonance liquid chamber 18. A piezoelectric element is provided as the vibration generating unit 20 that applies vibration to the toner composition liquid in the columnar resonance liquid chamber. In the droplet discharge head, the length L in the longitudinal direction of the liquid column resonance liquid chamber is 1.85 mm, and vibration with a drive frequency of 468 kHz is applied to the toner composition liquid in the liquid column resonance liquid chamber by the vibration generator 20. As a result, the fixed end side becomes a loosely fixed end, but a pressure standing wave is formed by liquid column resonance in a resonance mode of N = 2 at the both ends. Under this condition, the region that becomes the antinode of the pressure standing wave is a region that becomes ± 1/4 wavelength, and is a region that is 0 mm to 0.46 mm from the end on the liquid supply path side. In this region, there are 36 discharge holes 19 each having a discharge hole opening of 8.0 μm and a pitch of 130 μm between the discharge holes.
The liquid droplet ejection head shown in the figure has 36 ejection holes 19 on the fixed end side in the liquid column resonance liquid chamber 18 so that it is discharged to a range of about one third of the liquid column resonance liquid chamber length L. A hole is provided.
[Droplet discharge conditions]
Number of discharge holes: 36 Drive frequency: 468 kHz
The obtained toner was evaluated. The results are shown in Table 1.

(Example 8)
In Example 7, the toner was obtained under the same droplet discharge conditions and droplet transport conditions as in Example 7 except that the airflow control member was removed, that is, the airflow control member angle α was set to 0 °.
The obtained toner was evaluated. The results are shown in Table 1.

Example 9
In Example 8, the airflow guide hole outlet angle γ is 90 °, that is, a taper is not provided and a straight shape is used, except that the toner is placed under the same droplet discharge conditions and droplet transport conditions as in Example 8. Obtained.
The obtained toner was evaluated. The results are shown in Table 1.

(Example 10)
In Example 1, the airflow guide hole inlet second angle β2 is changed so as to smoothly change from 5 ° to 90 °, and the airflow guide hole outlet angle γ is changed smoothly from 15 ° to 60 °. A toner was obtained under the same droplet discharge conditions and droplet transport conditions as in Example 1 except that the configuration shown in FIG. 6 was changed.
The obtained toner was evaluated. The results are shown in Table 1.

(Comparative Example 1)
In Example 1, except that the airflow guide holes and airflow channels in the configuration shown in FIG. 16 are set to the following droplet transport conditions, the toner is set to the same droplet discharge conditions and droplet transport conditions as in Example 1. Got.
[Droplet transport conditions]
Airflow control member angle α: Airflow control member not used (0 °)
Airflow guide hole entrance first angle β1: 0 °
Airflow guide hole entrance second angle β2: 90 °
Airflow guide hole outlet angle γ: 90 °
The obtained toner was evaluated as described above. The results are shown in Table 1.

(Comparative Example 2)
In Example 4, a toner was obtained under the same droplet discharge conditions as in Example 4 except that the droplet conveyance conditions were the same as in Comparative Example 1.
The obtained toner was evaluated. The results are shown in Table 1.

(Comparative Example 3)
In Example 7, a toner was obtained under the same droplet discharge conditions as in Example 7 except that the droplet conveyance conditions were the same as in Comparative Example 1.
The obtained toner was evaluated. The results are shown in Table 1.

DESCRIPTION OF SYMBOLS 1 Toner production apparatus 10 Droplet discharge means 11 Droplet discharge head 12 Airflow flow path 13 Raw material accommodating part 14 Toner composition liquid 15 Liquid circulation pump 16 Liquid supply pipe 17 Liquid common supply path 18 Liquid column resonance liquid chamber 19 Discharge hole 20 Vibration generating unit 21 Toner droplet 22 Liquid return pipe 30 Dry collection unit 31 Chamber 32 Toner collection unit 33 Conveyance air flow 34 Toner collection tube 35 Toner storage unit 36 Air flow control member 37 Air flow channel forming container 38 Dry air flow 39 Lowering Airflow 40 Restriction part

JP 2007-199463 A Japanese Patent No. 3786034 JP 2008-286947 A

Claims (14)

A toner manufacturing apparatus comprising: a droplet discharge unit that discharges a toner composition liquid in droplets from at least one discharge hole; and a droplet solidification unit that transports and solidifies the droplet by an air flow,
The toner composition liquid is obtained by dissolving or dispersing the toner composition in an organic solvent,
The droplet discharge means includes a liquid column resonance liquid chamber in which the discharge hole is opened, and a vibration generation unit that applies vibration to the toner composition liquid in the liquid column resonance liquid chamber. A vibration is imparted to the toner composition liquid in the liquid column resonance liquid chamber to form a pressure standing wave due to the liquid column resonance, and the toner composition is formed from the discharge hole formed in a region that is antinode of the pressure standing wave. Discharge the liquid into droplets,
The droplet solidifying means is disposed on the downstream side in the droplet discharge direction, and has an airflow guide hole for guiding the airflow downstream.
The airflow guide hole has a throttle portion having a minimum opening diameter, and an inlet portion,
An opening surface of the airflow guide hole that is perpendicular to the opening axis of the discharge hole has a tapered shape that gradually decreases from the surface of the discharge hole toward the throttle portion at the inlet portion. Manufacturing equipment. The airflow guide hole further has an outlet portion;
2. The toner according to claim 1, wherein an opening surface of the airflow guide hole that is perpendicular to the opening axis of the discharge hole has a tapered shape that gradually expands from the throttle portion toward the downstream side in the droplet transport direction at the outlet portion. Manufacturing equipment.   The liquid droplet solidifying means further includes an air flow channel for flowing an air flow from the outer periphery of the liquid column resonance liquid chamber to the air flow guide hole, and the air flow channel generates an air flow having a uniform velocity distribution in the droplet discharge direction. The toner manufacturing apparatus according to claim 1, wherein the toner manufacturing apparatus is formed.   4. The toner manufacturing apparatus according to claim 1, wherein a plurality of ejection holes are formed in one liquid column resonance liquid chamber.   5. The toner manufacturing apparatus according to claim 1, wherein reflection wall surfaces are provided on at least a part of both ends in the longitudinal direction of the liquid column resonance liquid chamber. The toner manufacturing apparatus according to claim 1, wherein a vibration having a frequency f that satisfies the following formula (1) is applied to the toner composition liquid.
f = N × c / (4L) (1)
(Wherein, L represents the length of the liquid column resonance liquid chamber in the longitudinal direction, c represents the speed of sound waves of the toner composition liquid, and N represents an integer.) 7. The toner manufacturing apparatus according to claim 1, wherein a vibration having a frequency f that satisfies the following formula (2) is applied to the toner composition liquid.
N × c / (4L) ≦ f ≦ N × c / (4Le) (2)
(Where, L is the length in the longitudinal direction of the liquid column resonance liquid chamber, Le is the distance between the end on the liquid supply path side and the center of the discharge hole closest to the end, and c is (Sound wave velocity of toner composition liquid, N represents an integer, respectively) The toner manufacturing apparatus according to claim 1, wherein a vibration having a frequency f that satisfies the following expression (3) is applied to the toner composition liquid.
N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le) (3)
(Where, L is the length in the longitudinal direction of the liquid column resonance liquid chamber, Le is the distance between the end on the liquid supply path side and the center of the discharge hole closest to the end, and c is (Sound wave velocity of toner composition liquid, N represents an integer, respectively)   The toner manufacturing apparatus according to claim 7, wherein Le / L> 0.6.   The toner manufacturing apparatus according to claim 1, wherein the vibration frequency is high-frequency vibration of 300 kHz or more. A toner manufacturing method comprising: a droplet discharge step of discharging a toner composition liquid into droplets from at least one discharge hole; and a droplet solidification step of transporting and solidifying the droplets by an air flow,
The toner composition liquid is obtained by dissolving or dispersing the toner composition in an organic solvent,
In the liquid droplet ejection step, vibration is applied to the toner composition in the liquid column resonance liquid chamber in which the discharge hole is opened to form a pressure standing wave by liquid column resonance, The toner composition is ejected in droplets from the ejection holes formed in the region,
The droplet solidifying step includes conveying the droplets by an airflow through an airflow guide hole that is disposed on the downstream side in the discharge direction of the droplets and guides the airflow to the downstream side,
The airflow guide hole has a throttle portion having a minimum opening diameter, and an inlet portion,
An opening surface of the airflow guide hole that is perpendicular to the opening axis of the discharge hole has a tapered shape that gradually decreases from the surface of the discharge hole toward the throttle portion at the inlet portion. Production method. The airflow guide hole further has an outlet portion;
12. The toner according to claim 11, wherein an opening surface of the airflow guide hole that is perpendicular to an opening axis of the discharge hole has a tapered shape that gradually expands from the throttle portion toward the downstream side in the droplet transport direction at the outlet portion. Manufacturing method.   The droplet solidification step further includes circulating an air flow from the outer periphery of the liquid column resonance liquid chamber to the air flow guide hole, and the air flow has a uniform velocity distribution in a droplet discharge direction. A method for producing the toner according to claim 1.   A toner obtained by the toner production method according to claim 11.