JP2012141441A - Apparatus and method for manufacturing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus and a method for efficiently manufacturing a very versatile toner whose droplets may be simultaneously discharged from a plurality of discharge holes, may be discharged with high single dispersibility over a large area and may be discharged in a large number per unit time.SOLUTION: An apparatus for manufacturing a toner comprises: droplet forming means for forming droplets by discharging a toner composition liquid including at least a resin and a coloring agent from a plurality of discharge holes; and particle forming means for forming particles by solidifying the droplets of the toner composition liquid. The droplet forming means includes a discharging structure fixed in a center portion and an outermost peripheral portion thereof and having the plurality of discharge holes in a portion not fixed; and a vibration generating body in a disk or ring shape. The plurality of discharge holes of the discharging structure are provided around the vibration generating body.

Description

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

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

Conventionally, dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like are so-called pulverized toners in which a toner binder such as a styrene resin or a polyester resin is melt-kneaded with a colorant and finely pulverized. Is widely used. Recently, a polymerization type toner produced by a toner production method using a suspension polymerization method or an emulsion polymerization aggregation method has been proposed.
However, the suspension polymerization method and the emulsion polymerization aggregation method have a problem that versatility of usable resins is low.

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

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

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

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

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

Therefore, the thin film formed with a plurality of discharge holes connected to the flow path is directly vibrated by the electromechanical conversion means arranged around the thin film to discharge the toner composition liquid to form droplets (film vibration type) (Discharge means) and a toner particle manufacturing method and apparatus for manufacturing toner particles by solidifying the droplets have been proposed (see, for example, Patent Documents 6 to 7). According to the toner particle manufacturing method and apparatus, since the thin film in which the ejection holes are formed can be directly vibrated, it is possible to obtain a toner having a monodispersity in particle size.
However, in the case of a method in which a wave is generated in a direction parallel to the thin film in which a plurality of ejection holes are formed and the toner composition liquid is ejected into droplets as in the toner particle manufacturing method and apparatus, the toner particle is parallel to the thin film. Since the vibration velocity distribution can be made in any direction, a distribution is generated in the sound pressure applied to the meniscus of the toner composition liquid in the discharge holes, and thus in the discharge speed of the toner composition liquid. As a result, the area where the monodisperse liquid droplets can be ejected is limited to the above-mentioned thin film (ejection structure) because the liquid droplets are not ejected at a place where the sound pressure applied to the meniscus is small and the liquid droplets are likely to coalesce even if ejected. Body, nozzle plate). If the area where monodisperse droplets can be ejected is small, not only will it be necessary to widen the equipment required for production, but also the energy efficiency of the manufacturing equipment will be reduced, so the area needs to be expanded. Is the current situation.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention can eject droplets simultaneously from a plurality of ejection holes, has a wide area capable of ejecting highly monodisperse droplets, has a large number of droplets that can be ejected per unit time, and has high versatility. It is an object of the present invention to provide a toner manufacturing apparatus and a method for manufacturing the same.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies and as a result, obtained the following findings. That is, a toner composition liquid containing at least a resin and a colorant is ejected from a plurality of ejection holes to form droplets, and the dropletized toner composition liquid is solidified to form particles. In the toner manufacturing apparatus having the particle forming means, the droplet forming means includes a discharge structure in which the central portion and the outermost peripheral portion are fixed and the discharge holes are provided in the non-fixed portion, and a disk shape. And a ring-shaped vibration generator, and a plurality of discharge holes of the discharge structure are provided around the vibration generator so that droplets can be simultaneously discharged from the plurality of discharge holes. Has found that it has a wide area for ejecting highly monodisperse droplets, has a large number of droplets that can be ejected per unit time, and can efficiently produce highly versatile toner. It came.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> Droplet forming means for forming a droplet by discharging a toner composition liquid containing at least a resin and a colorant from a plurality of discharge holes, and forming particles by solidifying the dropletized toner composition liquid A droplet forming means, wherein the droplet forming means has a central portion and an outermost peripheral portion fixed, and a plurality of discharge holes are provided in a non-fixed portion; and And a vibration generator having a disk-like shape or an annular shape, and a plurality of discharge holes of the discharge structure are provided around the vibration generator. Device.
<2> The toner manufacturing apparatus according to <1>, wherein the plurality of discharge holes of the discharge structure are provided in an annular shape around the vibration generator.
<3> The vibration generator according to any one of <1> to <2>, wherein the vibration generating body has an annular shape, and includes a transport airflow generation unit that generates a transport airflow for transporting the discharged droplets inside the ring. This is a toner manufacturing apparatus.
<4> The toner production apparatus according to <3>, wherein an outlet flow velocity of the conveying airflow is 10 m / second to 50 m / second.
<5> A method for producing toner using the toner production apparatus according to any one of <1> to <4>, wherein a toner composition liquid containing at least a resin and a colorant A droplet forming step of forming droplets by discharging from the plurality of discharge holes of a discharge structure having a fixed portion and a plurality of discharge holes provided in a non-fixed portion; and And a particle forming step of solidifying the particles to form a toner.

  According to the present invention, the conventional problems can be solved, the object can be achieved, droplets can be ejected simultaneously from a plurality of ejection holes, and a large area capable of ejecting highly monodisperse droplets is wide. Therefore, it is possible to provide a toner manufacturing apparatus and a manufacturing method thereof that can efficiently manufacture a highly versatile toner with a large number of droplets that can be ejected per unit time.

FIG. 1 is a schematic sectional view showing an example of a toner manufacturing apparatus according to the present invention. FIG. 2 is a cross-sectional view showing an example of droplet forming means in the droplet forming unit of FIG. FIG. 3 is an enlarged cross-sectional view of the discharge structure and vibration generator of FIG. 2 and a bottom view of the discharge structure and vibration generator viewed from below. FIG. 4 is a bottom view of the discharge structure and the vibration generator of FIG. 2 as viewed from below, and is a diagram illustrating an example of the arrangement of a plurality of discharge holes. FIG. 5 is an enlarged cross-sectional view showing an example of a discharge structure and a vibration generator in a conventional droplet forming means, and a bottom view of the discharge structure and the vibration generator as viewed from below. 6A is a cross-sectional view showing another example of the droplet forming means in the droplet forming unit of FIG. 6B is a cross-sectional view showing still another example of droplet forming means in the droplet forming unit of FIG. FIG. 7 is a schematic cross-sectional view showing an example in which a plurality of droplet discharge units are arranged. FIG. 8A is a schematic diagram for explaining an example of an operation principle of droplet formation by the droplet discharge unit. FIG. 8B is a schematic diagram for explaining an example of an operation principle of droplet formation by the droplet discharge unit. FIG. 9 is a diagram for explaining an example of the fundamental vibration mode. FIG. 10 is a diagram for explaining an example of the secondary vibration mode. FIG. 11A is a schematic cross-sectional view of a discharge hole in the discharge structure. FIG. 11B is a schematic cross-sectional view of a discharge hole in the discharge structure. FIG. 12 is a diagram for explaining the arrangement of the discharge holes in Comparative Example 3.

(Toner production apparatus and production method)
The toner manufacturing apparatus of the present invention includes at least a droplet forming unit and a particle forming unit, and further includes other units as necessary.
The toner production method of the present invention includes at least a droplet forming step and a particle forming step, and further includes other steps as necessary. The toner production method of the present invention is preferably performed by the toner production apparatus.
Hereinafter, the toner manufacturing method of the present invention will be described in detail together with the description of the toner manufacturing apparatus of the present invention.

<Droplet formation process, droplet formation means>
The droplet forming step is a step of forming a droplet by discharging a toner composition liquid from a plurality of discharge holes, and is preferably performed by the droplet forming means.

<< Droplet formation means >>
The droplet forming means includes at least a discharge structure provided with the plurality of discharge holes, and a vibration generator, and further, if necessary, a fixing portion or a bonding portion for fixing the discharge structure, and toner It has a composition liquid channel and other members.

  The droplet forming means is not particularly limited as long as it is a means having the discharge structure and the vibration generator, and can be appropriately selected according to the purpose. It is preferable to use a plurality of discharge holes in the discharge structure to discharge a toner composition liquid described later in droplets. In this case, if the resonance frequency of the toner composition liquid flow path (also referred to as a reservoir or a liquid chamber) overlaps with the resonance frequency of the vibration generator, the toner composition liquid cannot be given a desired vibration. Therefore, it is more preferable that the resonance frequency of the vibration generator is lower than the resonance frequency of the liquid chamber because the pressure of the toner composition liquid in the liquid chamber can be increased uniformly and droplets can be formed at a uniform discharge speed. .

-Discharge structure-
The discharge structure has a central portion and an outermost peripheral portion fixed, has a plurality of discharge holes in a non-fixed portion, and further has other portions as necessary.
The discharge structure is not particularly limited as long as it has a central portion and an outermost peripheral portion and a plurality of discharge holes in the non-fixed portion, and can be appropriately selected according to the purpose. In this respect, a thin film or a plate is preferred.
Moreover, there is no restriction | limiting in particular as a material of the said discharge structure, Although it can select suitably according to the objective, A metal plate is preferable.

There is no restriction | limiting in particular as thickness of the said discharge structure, Although it can select suitably according to the objective, 5 micrometers-500 micrometers are preferable, and 20 micrometers-100 micrometers are more preferable.
The shape of the discharge structure is not particularly limited and may be appropriately selected depending on the intended purpose. Etc. Among these, the discharge structure is preferably circular and more preferably a perfect circle.
There is no restriction | limiting in particular as an outer diameter of the said discharge structure, Although it can select suitably according to the objective, 5 mm-100 mm are preferable, and 10 mm-50 mm are more preferable. The outer diameter means a diameter if the discharge structure is a perfect circle, and means an average diameter if the discharge structure is a polygon such as an ellipse, a rectangle, a hexagon, an octagon, or a regular polygon.
In the case where the toner manufacturing apparatus includes a carrier airflow generation unit, which will be described later, the discharge structure is preferably annular, and more preferably annular.

The discharge structure may have an insulating liquid repellent film, which will be described later, formed on the entire exposed surface.
There is no restriction | limiting in particular as said discharge structure, Although it can select suitably according to the objective, It is preferable that it is provided so that bending may generate | occur | produce in the said discharge structure when it vibrates. The method for generating the deflection in the discharge structure is not particularly limited and can be appropriately selected according to the purpose. For example, the fixing portion for fixing the central portion and the outermost peripheral portion of the discharge structure or the vibration For example, a method of bonding and fixing the generator through a bonding portion may be used.

-Fixed part-
The said fixing | fixed part is a member which fixes the center part and outermost periphery part of the said discharge structure. There is no restriction | limiting in particular as said fixing | fixed part, According to the objective, it can select suitably, For example, a flame | frame etc. are mentioned.
The shape of the fixing portion that fixes the outermost peripheral portion of the discharge structure is not particularly limited and can be appropriately selected according to the purpose, but is the same shape as the outer diameter of the discharge structure. Is preferred.
Moreover, there is no restriction | limiting in particular as a shape of the fixing | fixed part which fixes the center part of the said discharge structure body, Although it can select suitably according to the objective, It is preferable that it is cylindrical.
There is no restriction | limiting in particular as a material of the said fixing | fixed part, According to the objective, it can select suitably, For example, steel, stainless steel, nickel, copper, brass, or these mixtures etc. are mentioned.

The width of the region where the discharge structure is in contact with the fixing portion that fixes the outermost periphery of the discharge structure is not particularly limited and can be appropriately selected according to the dimensions of the discharge structure. 0.5 mm to 10 mm is preferable, and 0.5 mm to 5 mm is more preferable. When the width is less than 0.5 mm, the discharge structure is not sufficiently fixed to the fixed portion, and the fixed portion vibrates together with the discharge structure, or the fixed portion and the discharge structure are May peel off.
Here, the width of the region where the discharge structure is in contact with the fixing portion that fixes the outermost peripheral portion of the discharge structure is determined on one side of the discharge structure as viewed from the cross section passing through the center of the discharge structure. The width. For example, when the discharge structure is a perfect circle, it refers to the length of the area where the discharge structure is in contact with the fixing portion for fixing the outermost peripheral portion of the discharge structure on the radius of the discharge structure. .

Further, the width of the fixing portion for fixing the outermost peripheral portion of the discharge structure is not particularly limited and can be appropriately selected according to the dimensions of the discharge structure, etc., from the viewpoint of securing rigidity, 1.5 mm to 11 mm are preferable, and 1.5 mm to 6 mm are more preferable. If the width of the fixed portion is less than 1.5 mm, the discharge structure is not sufficiently fixed to the fixed portion, and the fixed portion vibrates together with the discharge structure, thereby imparting desired vibration to the discharge hole. There are things that cannot be done.
Here, the width of the fixed portion refers to a width on one side of the discharge structure as viewed from a cross section passing through the center of the discharge structure. For example, when the discharge structure is a perfect circle, it refers to the length of the fixing portion that fixes the outermost peripheral portion of the discharge structure on the radius of the discharge structure.

Inside the fixed portion, a toner composition liquid channel that is stored before the toner composition liquid is ejected from ejection holes in the ejection structure, and the toner composition liquid is supplied to the toner composition liquid channel A liquid supply tube (liquid supply hole) and a bubble discharge tube (bubble discharge hole) for discharging bubbles in the toner composition liquid may be provided.
The toner composition liquid flow path is preferably arranged so as to correspond to the discharge hole. For example, when the discharge hole is provided in an annular shape around the vibration generator, the toner composition is similarly formed. The liquid flow path is also preferably provided in an annular shape.

For example, when the toner composition liquid channel is provided in an annular shape, the fixing portion that fixes the central portion of the ejection structure has a columnar shape. Therefore, when the toner composition liquid channel is provided in an annular shape, the outer diameter of the fixing portion (column portion) that fixes the central portion of the discharge structure is approximately equal to the inner diameter of the annular toner composition liquid channel. Are the same. In the case where the toner composition liquid flow path has a circular shape made of a perfect circle, the outer diameter of the column portion (cylindrical portion) is a diameter, which is a polygon such as an ellipse, a quadrangle, a hexagon, an octagon, or the like. In the case of a regular polygon, it means the average diameter.
The outer diameter of the column part is not particularly limited, and can be appropriately selected according to the size of the vibration generator, the width of a vibration region to be described later, and the like with respect to the outer diameter of the vibration generator. It is preferable that the thickness is less than 0.5 mm. That is, it is preferable that the outer diameter of the vibration generating body is larger than the outer diameter of the column portion by 0.5 mm or more. If the outer diameter of the vibration generator is not larger than 0.5 mm with respect to the outer diameter of the column portion, the vibration generation cannot sufficiently excite the discharge structure, and the liquid droplets may not be discharged. is there.

  Further, when the droplet forming unit has a carrier airflow generation unit, which will be described later, and a carrier air flow path in the carrier airflow generation unit is provided from the fixed part (column part) to the discharge structure, the column The part is annular. Therefore, the inner diameter of the annular fixed portion at the center of the discharge structure and the outer diameter of the carrier air flow path are substantially the same.

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

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

-Vibration region-
In the present invention, a region where a large strain for droplet discharge in the discharge structure is generated is a vibration region. For example, the center and outermost peripheral portion of the discharge structure and the fixed portion are bonded and fixed by the bonding portion, and a vibration generator described later on the surface opposite to the surface bonded to the fixed portion of the discharge structure Indicates a region that is not fixed to both. In this case, the entire area where the discharge structure and the fixing portion are not fixedly bonded is the deformable area. Of the deformable area, the discharge structure and the vibration generator are bonded. The fixed region has a very small vibration compared to the vibration region, and hardly contributes as a distortion (deflection) for discharging the droplet.
When a disc-like or annular vibration generator is fixed around the center of the discharge structure, the vibration region is an annular region around the vibration generator.

The width of the vibration region is not particularly limited and may be appropriately selected according to the magnitude of vibration applied by the vibration generator, but is preferably 20 mm or less, and more preferably 5 mm or less. If the width of the vibration region exceeds 20 mm, it may be difficult to obtain the effect when the coalescence prevention means is provided.
The width of the vibration region is the shortest width on one side of the region of the discharge structure that is not fixed to both the fixed portion and the vibration generator, as viewed from the cross section passing through the center of the discharge structure. Say. For example, when the discharge structure is a perfect circle, it means the length of the vibration region of the discharge structure on the radius of the discharge structure.

--Discharge hole--
A plurality of the discharge holes (sometimes referred to as “nozzles” or “through holes”) are formed around the vibration generator.
The number of the discharge holes is not particularly limited and may be appropriately selected depending on the purpose. However, it is preferably 2 to 5,000, and preferably 50 to 4,000 for one discharge structure. More preferably.
There is no restriction | limiting in particular as the shortest space | interval (pitch) between the center part of the said adjacent discharge hole, Although it can select suitably according to the objective, 10 micrometers-1,000 micrometers are preferable, and 50 micrometers-300 micrometers are more preferable. If the pitch is less than 10 μm, the droplets may coalesce, and if it exceeds 1,000 μm, the productivity may be significantly reduced.
Moreover, it is preferable that the said pitch is equal intervals at the point which discharges a uniform droplet. In the case where the pitches of the adjacent discharge holes are equally spaced and the plurality of discharge holes are formed in two or more rows from the vibration generator side, as a result, the plurality of discharge holes are alternately arranged for each row. It becomes a staggered arrangement. Further, the plurality of discharge holes may have an equal interval between all the discharge holes.

The opening diameter of the discharge opening (the end of the discharge hole in the discharge direction) of the discharge hole is not particularly limited and may be appropriately selected depending on the volume of the target discharge droplet, but is 3 μm to 30 μm. However, it is preferable in that the droplets of the toner composition liquid are ejected (ejected) from the ejection holes in order to generate micro droplets having a very uniform particle diameter. Since the volume of the ejected droplets is substantially determined by the diameter of the ejection opening of the ejection hole, for example, when the toner particle size obtained by solidifying the toner composition dispersion having a solid content of 10% by mass is about 6 μm, The opening diameter of the discharge holes is preferably 8 μm to 12 μm.
The opening diameter of the discharge hole means a diameter if it is a perfect circle, and an average diameter if it is a polygon such as an ellipse, a quadrangle, a hexagon, an octagon, or a regular polygon.
The opening diameters of the discharge holes may be the same in the plurality of discharge holes or may be different in the two or more discharge holes, but all preferably have the same opening diameter. Here, the same opening diameter means a range of ± 0.3 μm.

The position of the plurality of discharge holes in the discharge structure is not particularly limited as long as it is around the vibration generator, and can be appropriately selected according to the purpose, but a vibration region in which flexural vibration occurs. It is preferable to provide in the center of the vibration region.
When a vibration generator to be described later is provided around the center of the discharge structure, the shortest distance between the plurality of discharge holes and the vibration generator is not particularly limited, and the width of the vibration region and the generation of vibration are not particularly limited. Although it can select suitably according to the magnitude | size etc. of the vibration added by a body, it is preferable to provide the said several discharge hole in the position where the vibration displacement of the said discharge structure is not zero. In the ejection hole where the vibration displacement is 0, the toner composition liquid may ooze out.

The arrangement of the plurality of discharge holes when the discharge structure is viewed from the bottom is not particularly limited as long as it is provided around the vibration generator, and can be appropriately selected according to the purpose. An annular shape may be sufficient, and the shape which does not have a discharge hole in a part of annular shape may be sufficient.
The arrangement shape in the case of the annular shape is not particularly limited and may be appropriately selected depending on the purpose. For example, a circular shape such as a perfect circle or an ellipse; Examples include squares.
Examples of the shape having no discharge hole in a part of the annular shape include a semicircular shape and a shape having no discharge hole in a part of a polygon.
Among these, the arrangement of the plurality of discharge holes when the discharge structure is viewed from the bottom is preferably annular, and the arrangement shape is more preferably a perfect circle or a regular polygon. When the arrangement shape is a regular polygon, it is more preferable that the number of corners is larger.

  There is no restriction | limiting in particular as a method of forming the said discharge hole in the said discharge structure, It can select suitably according to the objective, For example, the method of processing by electroforming, the method of processing by electric discharge, etc. are mentioned.

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

  The arrangement of the vibration generator is not particularly limited as long as vibration can be efficiently propagated to the toner composition liquid, and can be appropriately selected according to the purpose. It is preferable that the discharge structure (film) is circular (film), and it is more preferable that the discharge structure (film) is provided in a disk shape or an annular shape inside the vibration region. It is particularly preferable that the ring is provided in an annular shape.

There is no restriction | limiting in particular as an outer diameter, an internal diameter, and thickness of the said vibration generating body, According to the objective, it can select suitably.
The outer diameter of the vibration generator is not particularly limited and can be appropriately selected according to the type of the vibration generator and the dimensions of the discharge structure, but is preferably 2 mm to 97 mm, more preferably 2 mm to 47 mm. preferable. If the outer diameter of the vibration generator is less than 2 mm, sufficient vibration may not be applied to the discharge structure, and droplets may not be discharged. If it exceeds 97 mm, a discharge hole is formed around the vibration member. The area that can be provided is reduced, and the number of droplets that can be ejected per unit time may be reduced.
When the vibration generator is an annular shape, the width of the annular vibration generator is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 mm or more. When the width of the annular vibration generator is less than 2 mm, sufficient vibration may not be applied to the discharge structure, and droplets may not be discharged.
The width of the annular vibration generator refers to the length of one side of the vibration generator (the length on the radius of the vibration generator) as viewed from the cross section passing through the center of the vibration generator. .
The thickness of the vibration generator is not particularly limited and may be appropriately selected depending on the purpose. However, the ratio of the thickness of the vibration generator to the outer diameter (the thickness of the vibration generator / the outside of the vibration generator) (Diameter) is 1/3 or more, and the thickness of the vibration generator is preferably 0.5 mm or more. If the ratio of the thickness of the vibration generating body to the outer diameter is less than 1/3, coupled vibration may occur and desired vibration may not be obtained. Further, if the thickness of the vibration generator is less than 0.5 mm, sufficient vibration may not be applied to the discharge structure, and droplets may not be discharged.

--- Conveyance airflow generation part--
In the case where the vibration generator is an annular shape, it is preferable to have a transport air flow generation unit that generates a transport air flow for transporting the discharged droplets inside the ring. As a result, it is possible to prevent coalescence between the ejected droplets and to obtain a toner with higher monodispersibility.
There is no restriction | limiting in particular as said conveyance air flow generation | occurrence | production part, According to the objective, it can select suitably, For example, the conveyance air flow path formed in the said flame | frame and / or the said discharge structure is shroud (sheath part or covering part) ) And flowing a gas in the carrier air flow path to introduce a carrier air flow around the droplets (toner flow) ejected from the ejection holes, and the group velocity of the ejected toner group is reduced by this carrier air stream. For example, there may be a member that increases the discharge speed or decreases the discharge initial speed when the discharge initial speed is high.

The shape of the carrier air channel is not particularly limited as long as the carrier air flow can be generated inside the annular vibration generator, and can be appropriately selected according to the purpose. For example, it may be provided so as to penetrate from the fixing part (column part) that fixes the central part of the ejection structure toward the ejection structure, or may not penetrate.
There is no restriction | limiting in particular as an opening diameter of the exit of the said conveyance air flow path, Although it can select suitably according to the objective, 0.5 mm or more is preferable. When the opening diameter is less than 0.5 mm, the carrier airflow becomes a laminar flow, the airflow does not spread from the outlet of the carrier air flow path, and the discharged droplets may not be entrained. There is no restriction | limiting in particular as an upper limit of the said opening diameter, According to the dimension of the said discharge structure, etc., it can select suitably.
The opening diameter of the outlet of the carrier air channel means a diameter if the cross section of the carrier air channel is a perfect circle, and may be an ellipse, a polygon such as a rectangle, a hexagon, an octagon, or a regular polygon. Mean diameter.
There is no restriction | limiting in particular as gas used for the said conveyance airflow, According to the objective, it can select suitably, For example, nitrogen gas, air, etc. are mentioned.

There is no restriction | limiting in particular as exit flow velocity of the said conveyance airflow, Although it can select suitably according to the objective, 10 m / sec-50 m / sec are preferable, and 15 m / sec-30 m / sec are more preferable. When the outlet flow velocity is less than 10 m / second, the droplets may not be accelerated by the carrier air flow, and the toner particle size distribution may increase. Therefore, it may be difficult to spread over the entire area where the discharge holes are formed, and the discharged droplets may not be involved.
In the present invention, the outlet flow velocity means the flow velocity at the opening surface of the carrier air flow path on the side in contact with the vibration generator of the discharge structure located inside the annular vibration generator.
The carrier airflow generation unit may include an adjustment unit such as a pressure adjustment valve for adjusting the outlet flow velocity.

  Thereby, the obtained toner group is preferable in that it is possible to obtain a toner having a very small unity and higher monodispersibility. In addition, it is preferable that a particle forming unit described later has a drying unit because it is possible to efficiently prevent adhesion due to collision with each other during the drying process until the discharged toner is solidified.

-Toner composition liquid flow path-
The toner composition liquid channel is a channel for storing the toner composition liquid.
There is no restriction | limiting in particular as a shape of the said toner composition liquid flow path, According to the objective, it can select suitably, For example, cylindrical shape, square shape, truncated cone shape etc. are mentioned.
The structure of the toner composition liquid channel is not particularly limited and may be appropriately selected depending on the intended purpose. Examples include the structure.
The material of the container and the material of the surface layer in contact with the toner composition liquid may be the same or different.
The material for the surface layer in contact with the toner composition liquid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include metals, ceramics, plastics, and silicones. Among these, those which do not dissolve in the toner composition liquid and do not cause modification of the toner composition liquid are preferable.
There is no restriction | limiting in particular as a dimension of the said toner composition liquid channel, According to the objective, it can select suitably.

<< Droplet formation >>
Next, the droplet forming step will be described with reference to the drawings, but the present invention is not limited to this.

FIG. 1 is a schematic cross-sectional view showing an example of the toner production apparatus of the present invention.
The toner manufacturing apparatus 1 includes a raw material storage unit 6, a liquid feed pipe (pipe) 8, a pump 100, a droplet discharge unit 2 as the droplet formation unit, a particle formation unit 3, and a charge removal device 43. The toner collecting unit 4, the air flow path 42, and the toner storage unit 5 are included.
In the droplet forming step, the toner composition liquid 10 stored in the raw material storage unit 6 is supplied by pressure by a pump 100 during operation or the like, and above the particle forming unit 3 via a liquid supply pipe (pipe) 8. The liquid is delivered to the arranged droplet discharge unit 2. The toner composition liquid 10 sent to the droplet discharge unit 2 is periodically discharged from the discharge holes of the droplet forming means 11 via the toner composition liquid flow path 12 and outside the discharge holes (in the gas phase). A droplet 23 is formed.
In addition, the toner composition liquid 10 from the raw material container 6 is supplied to the droplet discharge unit 2 in a self-sufficient manner due to the droplet formation phenomenon by the droplet discharge unit 2, but assists as described above when the apparatus is in operation. In particular, liquid supply is performed using a pump 100. The toner composition liquid 10 uses a toner composition liquid in which at least a resin and a colorant are dissolved or dispersed in a solvent. It is particularly preferable to construct a circulation system.

Hereinafter, an example of a droplet discharge unit including a discharge structure using an annular vibration generator will be described with reference to FIGS. 2 to 3, but the present invention is not limited to this.
FIG. 2 is a cross-sectional view (enlarged view) showing an example of droplet forming means in the droplet discharge unit 2 of the toner manufacturing apparatus of FIG. 1, and FIG. It is the expanded sectional view and the bottom view which looked at this discharge structure and this vibration generating body from the lower side.

  In FIG. 2, the droplet discharge unit 2 includes a liquid supply tube (liquid supply hole) 20 for supplying a toner composition liquid 10 containing at least a resin and a colorant, and a bubble discharge tube (for discharging bubbles of the toner composition liquid 10). Discharge hole) 21, a droplet forming unit 11 for forming and discharging the toner composition liquid 10 as a droplet, and a frame formed with a toner composition liquid channel 12 for supplying the toner composition liquid 10 to the droplet forming unit 11. (Channel member) 14. The droplet discharge unit 2 is installed and held on the top surface portion 3A of the particle forming unit 3 by a support member 19 attached to the frame 14 as shown in FIG.

As shown in FIG. 3, the droplet forming unit 11 includes a discharge structure (thin film, nozzle plate, discharge plate) 16 in which a plurality of discharge holes (nozzles, through holes) 15 are formed, and the discharge structure 16. It comprises a vibration generator (electromechanical conversion means) 17 that vibrates.
The discharge structure 16 has the central portion and the outermost peripheral portion bonded and fixed to the frame 14 via the discharge structure joint portion 13a. In addition, the discharge structure 16 is bonded and fixed via the vibration generator 17 and the vibration generator joint portion 13b.
In FIG. 3, the discharge holes 15 are provided in the shape of a regular hexagonal ring around the vibration generator 17 for the sake of convenience. However, the present invention is not limited to this and may be provided as shown in FIG. In addition, although two rows are provided from the center of the discharge structure, any number of rows may be provided, and can be appropriately selected according to the number, pitch, and the like of the discharge structures.

  The vibration generator 17 is provided around the deformable region 16 </ b> A of the discharge structure 16. A drive voltage (drive signal) having a required frequency is applied to the vibration generator 17 from a drive circuit (drive signal generation source) 51 through a lead wire 50, for example, flexural vibration is generated, and the vibration region 16B vibrates. Thereby, droplets are ejected from the plurality of ejection holes 15 provided in the deformable region 16A.

  The droplet forming means 11 has not only the outermost peripheral portion of the discharge structure 16 having a plurality of discharge holes 15 facing the toner composition liquid flow path 12 but also the central portion thereof fixed by a frame, so that a distortion suitable for discharge can be obtained. Compared with the case of FIG. 5 in which the central portion of the discharge structure 16 is not fixed by a frame, for example, a relatively large strain area can be obtained. A large number of discharge holes 15 can be arranged in a region having a large area, and a large number of droplets can be stably formed and discharged from these discharge holes 15 at one time.

Next, an example of an aspect having a carrier airflow generation unit inside the annular vibration generator will be described with reference to FIGS. 6A and 6B. 6A and 6B are the same as FIGS. 2 to 3 except that the carrier air flow path 40 is formed. By causing the carrier airflow 44 to flow in the direction of the discharge structure 16 from the carrier air passage inlet 45 into the carrier air passage 40, the carrier airflow 44 flows out from the carrier air passage outlet 46 and is discharged from the discharge holes 15 of the discharge structure 16. The ejected droplets are conveyed by the conveying airflow 44, preventing coalescence of the droplets, and a toner with higher monodispersibility can be obtained.
In FIG. 6A, the carrier air flow path 40 has a constant diameter and is provided at the center of the frame 14 and the discharge structure 16 (the center of the annular vibration generator 17) perpendicular to the discharge structure. However, the shape of the carrier air flow path 40 is not particularly limited as long as the carrier airflow 44 can be generated inside the annular vibration generator 17, and can be appropriately selected according to the purpose. A taper shape may be sufficient. Further, as shown in FIG. 6B, the carrier air flow path 40 may include a bend in the frame 14.
In addition, the carrier airflow 44 can flow in an appropriately selected gas from the carrier air channel inlet 45 using a cylinder or the like.

  In FIG. 1, an example in which one droplet discharge unit 2 is arranged is illustrated. However, as shown in FIG. 7, a plurality of droplet discharge units 2 are arranged on the top surface portion 3 </ b> A of the particle forming unit 3. It is preferable to arrange them side by side. Among these, it is preferable in terms of controllability that the number of the droplet discharge units 2 is 100 to 1,000 (only four are shown in FIG. 7). In this case, the toner composition liquid 10 is supplied to each droplet discharge unit 2 by connecting a pipe (liquid feeding pipe) 8A to the raw material container 6 (common liquid reservoir). As a result, more droplets can be ejected at a time, and the production efficiency can be improved.

Next, a mechanism for forming droplets of the toner composition liquid in the droplet forming means will be described with reference to the drawings.
When the central portion and the outermost peripheral portion 12A of the discharge structure 16 that is a simple circular film as shown in FIGS. 8A and 8B are fixed, the central portion and the outermost peripheral portion are nodes, and as shown in FIG. Furthermore, the cross section shows that the vibration displacement ΔL is approximately the maximum (ΔLmax) between the vibration generator arrangement region of the discharge structure 16 and the outermost peripheral portion (the center of the deformable region 16A), as shown by the broken line in FIG. 8B. Periodically vibrates in the vibration direction. A droplet is discharged from a nozzle arranged in a region where vibration displacement discharged by the droplet is obtained (intervened by ΔLmin). In addition, it is preferable to provide the discharge hole which is ΔLmin in a range where the liquid droplets discharged from the discharge hole do not adhere to the vibration generator.
Further, it is known that higher order modes such as a secondary vibration mode and a tertiary vibration mode as shown in FIG. 10 exist. These modes have a plurality of concentric nodes in the discharge structure (circular film) and are substantially axisymmetric deformation shapes.
The vibration displacement can be measured by, for example, a laser Doppler vibrometer.

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

The product of the sound pressure Pac (r, t) and the sectional area Sn on the toner composition liquid supply side of the discharge hole is applied to the toner composition liquid in each discharge hole as a force Fn by vibration. The force Fn is represented by the following formula (2).
Fn = Pac (r, t) · Sn Equation (2)
The sound pressure Pac is not constant over the entire cross section of the ejection hole on the toner composition liquid supply side, but is regarded as having a sufficiently small cross-sectional area and approximated by a function of the radius (r) coordinate. A local loss and a pipe loss are caused with respect to the force Fn, and a discharge speed of the toner composition liquid is generated by the subtracted resultant force.

The discharge speed of the toner composition liquid is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 8 m / second to 20 m / second, and more preferably 12 m / second to 16 m / second. When the discharge speed is less than 8 m / second, droplets discharged from the plurality of discharge holes may be united, and when it exceeds 20 m / second, satellites may be generated. The satellite is a discharge droplet having a diameter approximately one-half of a droplet formed mainly.
The discharge speed is preferably uniform in all the discharge holes. Therefore, the ratio of the discharge speed at the discharge hole where the vibration displacement ΔL is maximum (ΔLmax) and the discharge speed at the discharge hole where the vibration displacement ΔL of the discharge structure is minimum (ΔLmin) (discharge speed of the discharge hole where ΔLmin is / As the discharge speed of the discharge hole which is ΔLmax, 0.5 to 1.0 is preferable, and 0.8 to 1.0 is more preferable.

  The method for measuring the ejection speed is not particularly limited and may be appropriately selected depending on the purpose. For example, the LED light is applied to the toner composition dispersion that has been formed into droplets, and the droplets are sandwiched between the LEDs. Observed by photographing with a CCD camera installed oppositely, the driving frequency of this LED is synchronized with the frequency of the droplet forming means (timing of vibration generation by the vibration generator and timing of light emission by applying voltage to the LED) ), The ejection of the toner composition liquid from the ejection holes can be confirmed. At this time, the liquid column discharged from the discharge hole due to the constant vibration causes the constriction of the liquid column at a constant interval (hereinafter, sometimes referred to as “liquid column constriction”). By splitting into a predetermined amount of droplets at the tip of the liquid column, toner particles having a constant particle diameter are continuously generated. From the discharged liquid column constriction and the vibration frequency, it can be estimated by calculation of discharge speed = constriction wavelength / frequency.

The toner composition liquid periodically discharged from the end portion on the discharge side of the plurality of discharge holes to the gas phase is disposed inside the discharge hole (liquid phase) at the end portion on the discharge side of the plurality of discharge holes. Since the sphere is formed by the surface tension difference from the outside (gas phase) of the discharge hole, liquid droplets are periodically discharged.
The vibration frequency of the discharge structure that enables droplet formation is not particularly limited and can be appropriately selected according to the area of the discharge structure, but generally a region of 20 kHz to 2.0 MHz is used. It is done. Among these, the range of 20 kHz to 500 kHz is preferable. If the vibration period is 20 kHz or more, the dispersion of fine particles such as pigment and wax in the toner composition liquid is promoted by the excitation of the liquid.
The amount of displacement of the sound pressure is not particularly limited and may be appropriately selected depending on the intended purpose. However, 10 kPa or more is preferable in that a fine particle dispersion promoting action is more suitably generated. Further, as the conditions of the toner composition liquid, in the region where the viscosity is 20 mPa · s or less and the interfacial tension is 20 mN / m to 75 mN / m, the satellite generation start region is the same, and the displacement of the sound pressure is 500 kPa. It is necessary that: Among these, 100 kPa or less is preferable.

<< Toner Composition Liquid >>
The toner composition liquid contains at least a resin and a colorant, and further contains a magnetic material, a wax, and other components as necessary.

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

-Resin-
There is no restriction | limiting in particular as said resin, According to the objective, it can select suitably, For example, vinyl resin and polyester resin which consist of a styrene monomer, an acrylic monomer, a methacryl monomer, a styrene monomer acrylic resin Polyol resin, phenol resin, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, terpene resin, coumarone indene resin, polycarbonate resin, petroleum resin and the like. These may be used alone or in combination of two or more.

--Vinyl resin--
There is no restriction | limiting in particular as said styrene monomer, According to the objective, it can select suitably, For example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p- Ethyl styrene, 2,4-dimethyl styrene, pn-amyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn- Styrene such as decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or derivatives thereof. Can be mentioned.

  There is no restriction | limiting in particular as said acrylic monomer, According to the objective, it can select suitably, For example, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate N-octyl acrylate, n-dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate and the like, or esters thereof.

  There is no restriction | limiting in particular as said methacryl monomer, According to the objective, it can select suitably, For example, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Methacrylic acid or esters thereof such as n-octyl methacrylate, n-dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. It is done.

  There is no restriction | limiting in particular as another monomer which forms the said vinyl resin, According to the objective, it can select suitably, For example, the following (1)-(18) etc. are mentioned. (1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8), vinyl naphthalenes; (9) acrylonitrile, Such as methacrylonitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic anhydride and alkenyl succinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; 16) Monomers having a carboxyl group such as anhydrides of the α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof; ) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1 -Hydroxy-1-methylhexyl) monomers having a hydroxy group such as styrene.

  The vinyl 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, Diacrylate compounds linked by alkyl chains such as 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, or acrylates of these compounds Replaced with methacrylate; diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 60 Diacrylate compounds linked by alkyl chains containing ether bonds such as diacrylate, dipropylene glycol diacrylate, etc., or those obtained by replacing acrylates of these compounds with methacrylates; others linked by chains containing aromatic groups and ether bonds Examples of the diacrylate compounds and dimethacrylate compounds; polyester-type diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.). These may be used individually by 1 type and may use 2 or more types together.

The polyfunctional crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, Examples include oligoester acrylates or those obtained by replacing acrylates of these compounds with methacrylate, triallyl cyanurate, triallyl trimellitate, and the like.
There is no restriction | limiting in particular as content of these crosslinking agents, Although it can select suitably according to the objective, 0.01 mass%-10 mass% with respect to the other monomer component which forms the said vinyl resin. Is preferable, and 0.03 mass%-5 mass% are more preferable.
Among these, an aromatic divinyl compound (particularly divinylbenzene), a diacrylate compound bonded with a bond chain containing one aromatic group and an ether bond is preferable in terms of fixability and offset resistance to the toner resin. . Moreover, among these, the combination of the monomer used as a styrene copolymer and a styrene-acryl copolymer is more preferable.

  There is no restriction | limiting in particular as a polymerization initiator used for manufacture of the said vinyl resin, According to the objective, it can select suitably, For example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2 '-Azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethyl) Pentane), 2-phenylazo-2 ′, 4′-dimethyl-4′-methoxyvaleronitrile, 2,2′-azobis (2-methylpropane), methyl ethyl ketone peroxide, Ketone peroxides such as cetyl acetone peroxide and cyclohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3 -Tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, Decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropyl peroxydicarbonate Di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3 -Methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaur Rate, tert-butyl-oxybenzoate, tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy To-2-ethyl hexanoate, di -tert- butyl peroxy the hexa hydro terephthalate, and the like tert- butylperoxy azelate. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as said styrene-acrylic resin, Although it can select suitably according to the objective, Gel permeation chromatography (GPC) of the component (THF soluble part) soluble in tetrahydrofuran (THF) of the resin component is used. A resin in which at least one peak is present in a region having a molecular weight of 3,000 to 50,000 (in terms of number average molecular weight) and at least one peak is present in a region having a molecular weight of 100,000 or more in the molecular weight distribution by measurement used. From the viewpoints of fixing property, offset property and storage property. Moreover, it is preferable that components having a molecular weight distribution of 100,000 or less become 50% to 90%. Moreover, it is preferable to have a main peak in the area | region of molecular weight 5,000-30,000, and it is more preferable to have a main peak in the area | region of 5,000-20,000.
There is no restriction | limiting in particular as an acid value of the said vinyl resin, Although it can select suitably according to the objective, 0.1 mgKOH / g-100 mgKOH / g is preferable, 0.1 mgKOH / g-70 mgKOH / g is more preferable. 0.1 mg KOH / g to 50 mg KOH / g is particularly preferable.

--- Polyester resin--
The polyester resin can be synthesized by condensing a divalent or higher alcohol and a divalent or higher acid. In order to crosslink the polyester resin, it is preferable to use at least one of a trihydric or higher polyhydric alcohol and a trivalent or higher polyvalent carboxylic acid.

  The divalent alcohol component is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3 -To butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or bisphenol A Examples thereof include diols obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide. These may be used alone or in combination of two or more.

  The trihydric or higher polyhydric alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, penta Erythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, tri Examples include methylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene and the like. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as said acid component, According to the objective, it can select suitably, For example, benzene dicarboxylic acid, such as phthalic acid, isophthalic acid, terephthalic acid, or its anhydride; Succinic acid, adipic acid, sebacine Alkyl dicarboxylic acids such as acid and azelaic acid or anhydrides thereof; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic acid anhydride, Examples thereof include unsaturated dibasic acid anhydrides such as itaconic acid anhydride and alkenyl succinic acid anhydride.
The trivalent or higher polyvalent carboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trimetic acid, pyrometic acid, 1,2,4-benzenetricarboxylic acid, 1,2, 5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3- Dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empole trimer acid, or anhydrides thereof, partial lower alkyl esters, etc. Is mentioned. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as said polyester resin, Although it can select suitably according to the objective, By molecular weight distribution by the measurement using GPC of the THF soluble part of a resin component, it is molecular weight 3,000-50,000. A resin having at least one peak in the region is preferable from the viewpoint of toner fixing property and offset resistance, and a binder resin having at least one peak in the region having a molecular weight of 5,000 to 20,000 is more preferable. . Moreover, it is preferable that a component with a molecular weight of 100,000 or less is 60% to 100%.
There is no restriction | limiting in particular as an acid value of the said polyester resin, Although it can select suitably according to the objective, 0.1 mgKOH / g-100 mgKOH / g is preferable, 0.1 mgKOH / g-70 mgKOH / g is more preferable, 1 mgKOH / g to 50 mgKOH / g is particularly preferable.

As said resin, the monomer component which can react with both these resin may be contained in at least any one of the said vinyl resin and the said polyester resin.
The monomer capable of reacting with the vinyl resin among the monomers forming the polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, maleic acid, citraconic acid, and itaconic acid. Examples thereof include unsaturated dicarboxylic acids or anhydrides thereof.
Among the monomers that form the vinyl resin, those that can react with the polyester resin include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
Moreover, when using together polyester resin, vinyl resin, and other resin, what contains 60 mass% or more of resin whose acid value is 0.1 mgKOH / g-50 mgKOH / g is preferable.

The acid value is determined by the following methods (I) to (IV), and the basic operation is in accordance with JIS K-0070.
(I) The sample is used by removing additives other than the resin (polymer component) in advance, or the acid value and content of components other than the resin and the crosslinked resin are obtained in advance. 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 the acid value of a resin is measured from toner, the acid value and content of a colorant or a magnetic material are separately measured, and the acid value of the resin is obtained by calculation.
(II) 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.
(III) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / L KOH.
(IV) The amount of KOH solution used at this time is set to SmL, a blank is measured at the same time, the amount of KOH solution used at this time is measured as BmL, and the following equation (3) is calculated. f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W Formula (3)

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said resin, Although it can select suitably according to the objective, 35 to 80 degreeC is preferable from a viewpoint of toner preservability, and 40 to 75 degreeC is preferable. More preferred. When the glass transition temperature (Tg) is lower than 35 ° C., the toner is likely to be deteriorated in a high temperature atmosphere, and offset is likely to occur during fixing. The glass transition temperature (Tg) is 80 ° C. When it exceeds, fixing property may fall.
The glass transition temperature can be measured, for example, in accordance with JIS K7121, using a differential scanning calorimeter (for example, DSC210 (manufactured by Seiko Denshi Kogyo Co., Ltd.)) at a heating rate of 10 ° C./min.

-Colorant-
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, Yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phisa red, para Lortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pogment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Lazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Grits Enlake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon, and mixtures thereof. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.
There is no restriction | limiting in particular as content with respect to the toner of the said coloring agent, Although it can select suitably according to the objective, 1 mass%-15 mass% are preferable, and 3 mass%-10 mass% are more preferable.

  When a pigment is used as the colorant, it is preferable to include a pigment dispersant having high compatibility with the resin in terms of pigment dispersibility. Examples of commercial products of the pigment dispersant include trade names such as Azisper PB821, Azisper PB822 (above, manufactured by Ajinomoto Fine Techno Co.), Disperbyk-2001 (manufactured by Big Chemie), EFKA-4010 (manufactured by EFKA), and the like. Can be mentioned.

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

  The weight average molecular weight of the dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. However, the molecular weight of the maximum value of the main peak in terms of styrene conversion weight in measurement using GPC is 500 to 100,000 is preferable, 3,000 to 100,000 is more preferable, 5,000 to 50,000 is further preferable, and 5,000 to 30,000 is particularly preferable. When the 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 dispersion of the colorant may occur. May decrease.

  The colorant can also be used in the form of a masterbatch combined with the resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified polyester resin or the unmodified polyester resin, for example, polystyrene, poly p-chlorostyrene, polyvinyltoluene or other styrene or a substituted product thereof. Resin: Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Polymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene- α-Chloromethacryl Methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer Styrene resins such as coalesced styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral , Polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, 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.

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

  The amine value of the masterbatch resin is preferably 1 to 100, more preferably 10 to 50. When the amine value is less than 1 and the amine value exceeds 100, pigment dispersibility may be insufficient. The amine value can be measured by the method described in JIS K7237.

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

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

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

-Magnetic material-
There is no restriction | limiting in particular as said magnetic body, According to the objective, it can select suitably, For example, (1) Iron oxide containing magnetic iron oxides, such as a magnetite, a maghemite, a ferrite, or another metal oxide, 2) Metals such as iron, cobalt and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, etc. And alloys with these metals, and (3) mixtures thereof.

Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , _{PbFe 12 O, NiFe 2 O 4} , NdFe 2 O, BaFe 12 O 19, MgFe 2 O 4, MnFe 2 O 4, LaFeO 3, iron powder, cobalt powder, and nickel powder. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of iron trioxide and γ-iron trioxide are preferable.

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

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

-Wax-
The wax is not particularly limited and may be appropriately selected depending on the intended purpose. For example, aliphatic hydrocarbons such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, and sazol wax. Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax; beeswax, lanolin, whale wax, etc. Animal waxes; mineral waxes such as ozokerite, ceresin and petrolatum; waxes based on fatty acid esters such as montanic acid ester wax and castor wax; partially or all fatty acid esters such as deoxidized carnauba wax Deoxidation Such as the ones and the like. These may be used alone or in combination of two or more.

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

  In addition, the wax is made by narrowing the 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, and a low molecular weight solid fatty acid or a low molecular weight solid. Also preferred are alcohols, low molecular weight solid compounds and other impurities removed.

  There is no restriction | limiting in particular as melting | fusing point of the said wax, Although it can select suitably according to the objective, 70 to 140 degreeC is preferable at the point which balances fixing property and offset resistance, 70 to 120 degreeC. Is more preferable. 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 use of the wax include a combination of two or more different waxes having a melting point difference of 10 ° C. to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.
The wax having a plasticizing action is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a wax having a low melting point, a branch having a molecular structure or a structure having a polar group Etc. The wax having a releasing action is not particularly limited and may be appropriately selected depending on the purpose. For example, a wax having a high melting point, a molecular structure having a linear structure, or having no functional group Nonpolar ones can be mentioned.

  When the waxes are of two types and each have a similar 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. The difference between the melting points of the two types of waxes is preferably 10 ° C. to 100 ° C. from the viewpoint of effectively expressing functional separation. When the difference between the melting points is less than 10 ° C., the function separation effect may be difficult to appear, and when it exceeds 100 ° C., the function may not be emphasized by interaction. As melting | fusing point of one wax of said 2 types of wax, 70 to 120 degreeC is preferable and 70 to 100 degreeC is more preferable.

  As for the wax, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exert a plastic action, and those having a more linear structure or functional group Nonpolar or non-denatured straight materials that do not have a mold exhibit a releasing action.

  The combination of the waxes is not particularly limited and may be appropriately selected depending on the purpose. For example, a polyethylene homopolymer or copolymer having ethylene as a main component and a polyolefin homopolymer having an olefin other than ethylene as a main component or Copolymer combination, polyolefin and graft modified polyolefin combination, alcohol wax, fatty acid wax or ester wax and hydrocarbon wax combination, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax, Fischer-Tropsch wax and polyolefin wax Combination of paraffin wax and microcrystal wax, carnauba wax, cande Rawakkusu, a combination of a hydrocarbon wax and rice wax or montan wax.

  In the endothermic peak observed in the DSC measurement of the toner, it is preferable that the peak top temperature of the maximum peak is in the range of 70 ° C. to 110 ° C. in terms of facilitating the balance between toner storage and fixing properties. More preferably, it has a maximum peak in the region of 110 ° C.

The temperature of the peak top of the endothermic peak of the wax observed in DSC measurement is defined as the melting point of the wax.
The wax or toner DSC measuring device is preferably measured with a high-precision internal heat input compensation type differential scanning calorimeter. As a measuring method, it carries out according to ASTM D3418-82. The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 ° C./min after once raising and lowering the temperature and taking a previous history.

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

-Other ingredients-
The other components are not particularly limited, and can protect the electrostatic latent image carrier or carrier, improve cleaning properties, adjust thermal characteristics, electrical characteristics or physical characteristics, adjust resistance, adjust softening points, improve fixing rate, etc. For example, fluidity improvers; cleaning properties improvers; surfactants such as various metal soaps and fluorine surfactants; dioctyl phthalate, tin oxide, zinc oxide, carbon Conductivity imparting agents such as black and antimony oxide; external additives; lubricants such as polytetrafluoroethylene, zinc stearate and polyvinylidene fluoride; abrasives such as cesium oxide, silicon carbide and strontium titanate; anti-caking agent; development And a property improver.
The other components include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having a functional group, and other organosilicons for the purpose of controlling the charge amount. You may process with various processing agents, such as a compound. The inorganic fine powder may be hydrophobized as necessary.

--- Fluidity improver ---
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. Examples thereof include carbon black; fluorine resin powder such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; wet process Fine powder silica such as silica and dry process silica; fine powder unoxidized titanium, fine powder unalumina, or treated silica, treated titanium oxide, treated alumina which are surface-treated with a silane coupling agent, a titanium coupling agent or silicone oil Etc. 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 not particularly limited and may be appropriately selected depending on the intended purpose. The average primary particle size is preferably 0.001 μm to 2 μm, preferably 0.002 μm to 0.2 μm. More preferred.

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.
Specific examples of commercially available silica fine powders produced by vapor phase oxidation of the silicon halogen compound include trade names such as AEROSIL-130, -300, -380, -TT600, -MOX170, -MOX80, -COK84 (and above). Ca-O-SiL-M-5, -MS-7, -MS-75, -HS-5, -EH-5 (above, manufactured by CABOT); Wacker HDK-N20 V15, manufactured by Nippon Aerosil Co., Ltd. -N20E, -T30, -T40 (manufactured by ACKER-CHEMIE); D-CFineSi1ica (manufactured by Dow Corning); Franco1 (manufactured by Franci1).
Further, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of the silicon halogen compound is more preferable. The treated silica fine powder is preferably obtained by treating the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is 30% to 80%. Hydrophobization is imparted by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. A method of treating fine silica powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferred.

  There is no restriction | limiting in particular as said organosilicon compound, According to the objective, it can select suitably, For example, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane , Vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, dimethylvinylchlorosilane, divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, Allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane , Β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltri Methoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule Silyl such as dimethylpolysiloxane, dimethylsilicone oil or the like containing 0 to 1 hydroxyl group bonded to Si in the unit located at the end. N'oiru and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

There is no restriction | limiting in particular as a number average particle diameter of the said fluid improvement agent, Although it can select suitably according to the objective, 5 nm-100 nm are preferable, and 5 nm-50 nm are more preferable. The number average diameter can be determined by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.
As the specific surface area of the flowability improving agent according to the measured nitrogen adsorption by the BET method is not particularly limited, suitably it can be selected, preferably at least ^{30 m} 2 / g according to the ^purpose, 60m 2 / ^{g~400m 2} / g is more preferable.
The specific surface area of the surface-treated fine powder is not particularly limited and may be appropriately selected depending on the intended purpose, is preferably at least ^{20m 2 / g, 40m 2 /} g~300m 2 / g and more preferably . The specific surface area of the fine powder can be determined by a BET specific surface area measuring device.

  There is no restriction | limiting in particular as the addition amount with respect to the toner particle of the said fluid improvement agent, Although it can select suitably according to the objective, 0.03 mass%-8 mass% are preferable.

--- Cleanability improver--
The cleaning property improver is not particularly limited and can be appropriately selected as long as it removes the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium. For example, zinc stearate, Examples thereof include fatty acid metal salts such as calcium stearate and stearic acid; polymer particles produced by soap-free emulsion polymerization such as polymethyl methacrylate particles and polystyrene particles.
There is no restriction | limiting in particular as a volume average particle diameter of the said polymer particle, Although it can select suitably according to the objective, 0.01 micrometer-1 micrometer are preferable.

--External additive--
There is no restriction | limiting in particular as said external additive, According to the objective which assists fluidity | liquidity, developability, and electrification property, it can select suitably, For example, an inorganic fine particle, polymeric fine particle, etc. are mentioned. Among these, the external additive is preferably inorganic fine particles.

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

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

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

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

--Developability improver--
The developer improver is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include white fine particles and black fine particles having a polarity opposite to that of toner particles. A small amount of the developer is preferable. When preparing the developer, inorganic fine particles such as hydrophobic silica fine powder may be added and mixed in order to improve the fluidity, storage stability, developability and transferability of the developer.

-Preparation method of toner composition liquid-
The method for preparing the toner composition liquid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the resin is dissolved in an organic solvent, the colorant is dispersed, and if necessary, the Examples include a method of dispersing or dissolving other components, a method of melting and kneading the resin and the colorant and, if necessary, the other components as necessary, and dissolving or dispersing the obtained kneaded material in an organic solvent. .

<Particle forming step, particle forming means>
The particle forming step is a step of solidifying the droplet (toner composition liquid) formed in the droplet forming step to form particles, and is preferably performed by particle forming means.
There is no restriction | limiting in particular as said particle | grain formation means, According to the objective, it can select suitably, For example, the means which has a collection part, a drying part, etc. are mentioned.

<< Particle Forming Means >>
-Collector-
The collecting unit is a member that dries and solidifies the liquid droplets (toner composition liquid) discharged in the liquid droplet forming process and conveyed by the conveying airflow while being conveyed by the conveying airflow.
Here, the carrier airflow is preferably a carrier airflow generated from the inside of the annular vibration generator, but the carrier airflow may be generated outside the droplet forming unit.

-Drying section-
The drying unit is a member that performs secondary drying in order to further dry the droplets dried and solidified by the collection unit. If the organic solvent remains in the toner, not only the toner characteristics such as heat-resistant storage stability, fixability, and charging characteristics fluctuate with time, but the organic solvent volatilizes at the time of fixing by heating. Sufficient drying is necessary because the possibility of adverse effects on the skin increases. For this reason, secondary drying by the drying unit is advantageous in that the organic solvent in the toner composition liquid can be sufficiently dried.
There is no restriction | limiting in particular as said drying part, According to the objective, it can select suitably, For example, a fluid bed dryer, a vacuum dryer, etc. are mentioned.

<< Particle formation >>
Next, the particle forming step will be described with reference to the drawings, but the present invention is not limited to this.
In FIG. 1, a droplet 23 of toner composition liquid discharged from a droplet discharge unit 2 is dried and solidified when being transported downward by gravity in a particle forming unit 3 as particle forming means. Particles T are formed. At this time, not only by gravity, but also by a transport air flow (not shown) generated from the inside of an annular vibration generator, it prevents coalescence between ejected droplets, and more uniform dispersion This is preferable in that a highly functional toner can be obtained. Alternatively, the outer transport airflow 53 may be generated from the upper side to the lower side of the particle forming unit 3 outside the droplet discharge unit 2, and the droplets 23 may be transported by the outer transport airflow 53. By generating these transport airflows, it is possible to prevent the discharged droplets 23 from being decelerated due to air resistance. When the droplets 23 are continuously discharged, before the droplets 23 are dried before By decelerating by the air resistance, the droplets 23 ejected later catch up with the droplets 23 ejected before, so that the droplets 23 coalesce and become one, and the particle size of the droplets 23 increases. Can be suppressed. The toner particles T that have been dried and solidified are neutralized by the neutralization device 43, collected by the toner collecting unit 4, and transferred through the air flow path 42 and the tube 7 in the air flow path forming member 41, and the toner storage section. 5 is stored.

<< Toner >>
According to the toner manufacturing apparatus and the toner manufacturing method of the present invention, a toner having a monodispersed particle size distribution can be obtained.
The particle size distribution (weight average particle size / number average particle size) of the toner particles is not particularly limited and may be appropriately selected depending on the intended purpose. -1.07 is more preferable. When the particle size distribution exceeds 1.15, there is a large variation in the particle system, the chargeability between the particles becomes non-uniform, and abnormal images such as background stains are generated, and image quality such as granularity is deteriorated. There is.

The weight average particle diameter of the toner particles is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 μm to 20 μm, and more preferably 3 μm to 10 μm. If the weight average particle is less than 1 μm, the number of finely charged particles increases, and adheres firmly to the carrier, thereby depriving the charged sites of the carrier and reducing developability, that is, generating an abnormal image. In addition to causing it, inhalation may affect the human body.
The method for measuring the particle size distribution of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method of measuring with a flow particle image analyzer (Flow Particle Image Analyzer).

The toner manufacturing method and apparatus of the present invention can eject droplets simultaneously from a plurality of ejection holes, have a wide area capable of ejecting highly monodisperse droplets, and have a large number of droplets that can be ejected per unit time. A highly versatile toner can be produced efficiently. Therefore, the toner manufactured by the toner manufacturing method and manufacturing apparatus of the present invention can be suitably used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like.
As the developer, any electrostatic latent image carrier used in conventional electrophotography can be used. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image carrier, An electrostatic latent image carrier, a zinc oxide electrostatic latent image carrier and the like can be suitably used.

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

Example 1
<Preparation of colorant dispersion>
Using a mixer having a stirring blade, 17 parts by mass of carbon black (Regal 400, manufactured by Cabot) 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. It was. The obtained primary dispersion is secondarily dispersed using a bead mill (LMZ manufactured by Ashizawa Finetech Co., Ltd., zirconia beads 0.3 mmφ) to completely remove aggregates having a particle size of 5 μm or more, and a colorant dispersion Was prepared.

<Preparation of wax dispersion>
Next, using a mixer having a stirring blade, 18 parts by mass of carnauba wax and 2 parts by mass of a wax dispersant were primarily dispersed in 80 parts by mass of ethyl acetate. The wax dispersant used was a polyethylene wax grafted with a styrene-butyl acrylate copolymer. The obtained primary dispersion was heated to 80 ° C. with stirring to dissolve the carnauba wax, and then cooled to room temperature to precipitate the carnauba wax so that the maximum diameter was 3 μm or less. Further, a wax dispersion was prepared by secondary dispersion using a bead mill (LMZ manufactured by Ashizawa Finetech Co., Ltd., zirconia beads 0.3 mmφ) so that the maximum diameter was 1 μm or less.

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

<Production of toner>
In the toner production apparatus shown in FIGS. 1 to 3, a toner production apparatus provided with a disk-shaped vibration generator in place of the annular vibration generator 17 was used for toner production. 500 mL of the obtained toner composition dispersion was supplied to a plurality of ejection holes (nozzles) 15 of the droplet forming means 11 of the toner manufacturing apparatus.
The used discharge structure (thin film, nozzle plate) 16 is a nickel plate having an outer diameter of 25 mm and a thickness of 100 μm. ) A 10 μm discharge hole 15 was produced by electroforming. The discharge hole was provided around the disc-shaped vibration generator 17 as will be described later.
In addition, the opening diameter of the discharge hole was made constant in the thickness direction of the discharge structure. That is, as shown in FIG. 11A, the angle from the liquid contact surface to the discharge port in the section of the discharge hole in the thickness direction of the discharge structure (hereinafter, referred to as “discharge hole angle”). ) 200 was 90 °.

Further, a SiO ₂ film was formed on the entire exposed surface of the discharge structure by RF sputtering, and a fluorine-based compound (OPTOOL, manufactured by Daikin Industries, Ltd.) was deposited on the SiO ₂ film to form a liquid repellent film. The film thickness of the liquid repellent film was 50 nm as measured using a non-contact type film thickness measuring device (ellipsometer, manufactured by Mizoji Optical Co., Ltd.). The contact angle of the liquid repellent film was measured using a contact angle meter (DM500, manufactured by Kyowa Interface Science Co., Ltd.), and the contact angle of the toner composition dispersion was 58 °.

The disc-shaped vibration generator was lead zirconate titanate (PZT) having an outer diameter of 10 mm and a thickness of 1.0 mm. The fixing portion has a cylindrical portion diameter (outer diameter) of 6 mm that fixes the central portion of the discharge structure 16 as 6 mm, and an inner diameter of the frame 14 that fixes the outermost peripheral portion of the discharge structure 16 (the outermost diameter of the discharge structure 16). The length between the point at which the frame 14 for fixing the outer peripheral part and the tube 20 during liquid supply are in contact, and the point at which the frame 14 for fixing the outermost peripheral part of the discharge structure 16 and the bubble discharge tube 21 are in contact) is 15 mm. The outer diameter (the inner length of the two support members 19) was 26 mm stainless steel (SUS304). That is, the width of the frame 14 that fixes the outermost peripheral portion of the discharge structure 16 is 5.5 mm. The joint surface 13b between the vibration generator 17 and the discharge structure 16 and the joint surface 13a between the frame and the discharge structure 16 are both made of epoxy resin (elastic modulus 1.3 × 10 ⁸ Pa), and the heating condition is 170 ° C. × Joined in 5 minutes.
Therefore, in FIG. 3, the inner diameter of the vibration region of the discharge structure is 10 mm, the outer diameter is 15 mm, and the width of the vibration region (the length of 16B in FIG. 3) is a 2.5 mm ring. The discharge holes of the discharge structure have an annular area between 0.8 mm and 1.7 mm from the vibration generator side of this vibration area, and the pitch of the adjacent discharge holes (the shortest distance between the center parts of the discharge holes) is about It was provided in an annular shape so as to have a staggered arrangement of 140 μm.

After preparing the toner composition dispersion, the droplets were discharged under the toner production conditions shown below, and then the droplets were dried and solidified to produce toner base particles of Example 1.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 ° C to 28 ° C
Discharge hole frequency: 43.32 kHz
Applied voltage to PZT Sin wave pp value: 131V
The “ejection hole frequency” is an input vibration frequency to the vibration generator 17 by the drive signal generation source 51 shown in FIG.

The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. The discharge rate was 21.85 g / min based on the toner composition dispersion. The toner standard after drying was about 1.97 g / min.
When the particle size distribution of the particles collected after 1 hour from the operation was measured by a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) by the measurement method shown below, the weight average particle size (D4) Was 6.38 μm, the number average particle diameter (Dn) was 5.19 μm, and D4 / Dn was 1.23.

-Measuring method of toner particle size distribution-
A measurement method using a flow particle image analyzer (Flow Particle Image Analyzer) will be described below.
The particle size distribution of the toner, toner particles, and external additives was measured using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation).
The measurement is performed by removing fine dust through a filter, and as a result, in ^10-3 water of 10 ⁻³ cm ³ of water having a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) of 20 or less particles. Add a few drops of a nonionic surfactant (trade name: Contaminone N, manufactured by Wako Pure Chemical Industries, Ltd.), add 5 mg of a measurement sample, and an ultrasonic disperser (trade name: UH-50, manufactured by STM). At 20 kHz and 50 W / 10 cm ³ for 1 minute, and further dispersed for a total of 5 minutes, so that the particle concentration of the measurement sample is 4,000 particles / 10 ⁻³ cm ^{3 to} 8,000 particles / 10. ^The particle size distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm was measured using a sample dispersion liquid of ⁻³ cm ³ (for particles in the measurement equivalent circle diameter range).
The sample dispersion was allowed to pass through a flow path (spread along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, the strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Taken as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area was calculated as the equivalent circle diameter.
In about 1 minute, the equivalent circle diameter of 1,200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 μm to 400 μm into 226 channels (divided into 30 channels for one octave). In actual measurement, particles were measured in a range where the equivalent circle diameter was 0.60 μm or more and less than 159.21 μm.

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

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

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

(Example 2)
Example 2 uses a toner manufacturing apparatus provided with an annular vibration generator 17 shown in FIGS. 1 to 3 in place of the toner manufacturing apparatus provided with a disk-like vibration generator in Example 1. The toner base particles of Example 2 were produced in the same manner as in Example 1 except that the toner production conditions were changed to the conditions shown below. As the annular vibration generator 17, lead zirconate titanate (PZT) having an inner diameter of 4 mm, an outer diameter of 10 mm, and a thickness of 1.0 mm was used.
The vibration region of the discharge structure is a ring with an inner diameter of 10 mm, an outer diameter of 15 mm, and a vibration region width of 2.5 mm.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 ° C to 28 ° C
Discharge hole frequency: 44.1 kHz
Applied voltage to PZT Sin wave pp value: 135V

The dried toner base particles were neutralized by soft X-ray irradiation and collected by suction with a filter having 1 μm pores. The discharge rate was 22.26 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 2.00 g / min.
When the particle size distribution of the particles collected after 1 hour from the operation was measured by a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation) by the measurement method shown below, the weight average particle size (D4) Was 6.25 μm, the number average particle diameter (Dn) was 5.12 μm, and D4 / Dn was 1.22.

(Example 3)
Example 3 is the same as Example 2 except that the thickness of the vibration generator 17 is changed to 3.0 mm and the toner production conditions are changed to the conditions shown below. 3 toner base particles were prepared.
The vibration region of the discharge structure is a ring with an inner diameter of 10 mm, an outer diameter of 15 mm, and a vibration region width of 2.5 mm.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 ° C to 28 ° C
Discharge hole frequency: 52.9 kHz
Applied voltage to PZT Sin wave pp value: 122V

The dried toner base particles were neutralized by soft X-ray irradiation in the same manner as in Example 1 and collected by suction with a filter having 1 μm pores. The discharge rate was 26.67 g / min based on the toner composition dispersion. The toner standard after drying was about 2.40 g / min.
The particle size distribution of the particles collected after 1 hour has elapsed after operation The particle size distribution of the collected particles was measured in the same manner as in Example 1 using a flow type particle image analyzer (trade name: FPIA-2000, manufactured by Sysmex Corporation). As a result, the weight average particle diameter (D4) was 6.53 μm, the number average particle diameter (Dn) was 5.31 μm, and D4 / Dn was 1.23.

Example 4
In Example 4, the inner diameter of the vibration generator 17 is changed to 9 mm and the outer diameter is changed to 15 mm, the cylindrical portion diameter of the frame 14 is changed to 11 mm, and the inner diameter is changed to 20 mm. The toner base particles of Example 4 were produced in the same manner as in Example 2 except that the conditions were changed as shown. That is, the width of the frame 14 that fixes the outermost peripheral portion of the discharge structure 16 is 3 mm.
The vibration region of the discharge structure is a ring with an inner diameter of 15 mm, an outer diameter of 20 mm, and a vibration region width of 2.5 mm.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 ° C to 28 ° C
Discharge hole frequency: 43.7 kHz
Applied voltage to PZT Sin wave pp value: 140V

The dried toner base particles were neutralized by soft X-ray irradiation in the same manner as in Example 1 and collected by suction with a filter having 1 μm pores. The discharge rate was 30.87 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 2.78 g / min.
The particle size distribution of the particles collected after 1 hour has elapsed after operation The particle size distribution of the collected particles was measured in the same manner as in Example 1 using a flow type particle image analyzer (trade name: FPIA-2000, manufactured by Sysmex Corporation). As a result, the weight average particle diameter (D4) was 6.66 μm, the number average particle diameter (Dn) was 5.46 μm, and D4 / Dn was 1.22.

(Example 5)
In Example 5, the inner diameter of the frame 14 is changed to 20 mm in Example 2, and the discharge hole of the discharge structure is provided in the annular region between 1.6 mm and 3.4 mm from the vibration generator side of the vibration region. The toner base particles of Example 5 were produced in the same manner as in Example 2 except that the toner production conditions were changed to the conditions shown below. That is, the width of the frame 14 that fixes the outermost peripheral portion of the discharge structure 16 is 3 mm.
The vibration region of the discharge structure is a ring with an inner diameter of 10 mm, an outer diameter of 20 mm, and a vibration region width of 5.0 mm.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 ° C to 28 ° C
Discharge hole frequency: 25.7 kHz
Applied voltage to PZT Sin wave pp value: 151V

The dried toner base particles were neutralized by soft X-ray irradiation in the same manner as in Example 1 and collected by suction with a filter having 1 μm pores. The discharge rate was 31.13 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 2.80 g / min.
Measurement of particle size distribution of particles collected after 1 hour has elapsed after operation using a flow particle image analyzer (trade name: FPIA-2000, manufactured by Sysmex Corporation) in the same manner as in Example 1. As a result, the weight average particle diameter (D4) was 6.38 μm, the number average particle diameter (Dn) was 5.32 μm, and D4 / Dn was 1.20.

(Example 6)
In Example 6, the toner base particles of Example 6 were produced in the same manner as in Example 2 except that the toner was produced by the following method in Example 2.
500 mL of the toner composition dispersion prepared by the method described in Example 2 was supplied to a plurality of ejection holes (nozzles) 15 of the droplet forming unit 11 of the toner manufacturing apparatus shown in FIGS. 1 and 6A.
The used discharge structure (thin film, nozzle plate) 16 has an air flow path 40 having a diameter of 3 mm (hereinafter sometimes referred to as “inner diameter of the discharge structure”) at the center, an outer diameter of 25 mm, and a thickness of 100 μm. In the nickel plate, a discharge hole 15 having a perfect circular discharge opening diameter (diameter) of 10 μm at the end of the discharge hole on the discharge side (gas phase side) was produced by electroforming. The discharge holes were provided around the vibration generator 17 as will be described later. That is, the width of the discharge structure 16 is 11 mm.
In addition, the opening diameter of the discharge hole was made constant in the thickness direction of the discharge structure. That is, as shown in FIG. 11A, the discharge hole angle 200 was 90 °.

Further, a SiO ₂ film and a liquid repellent film were formed on the entire exposed surface of the discharge structure by the same method as in Example 1. The film thickness of the liquid repellent film measured by the same method as in Example 1 was 50 nm, and the contact angle of the toner composition dispersion of the liquid repellent film was 58 °.

In FIG. 6A, the annular vibration generator 17 was made of lead zirconate titanate (PZT) having an inner diameter of 4 mm, an outer diameter of 10 mm, and a thickness of 1.0 mm. That is, the width of the vibration generator 17 is 3 mm. The fixing part has an inner diameter (diameter of the air flow path 40 (opening diameter of the outlet)) of 3 mm and a cylindrical part diameter (outer diameter) of 6 mm, which fixes the central part of the discharge structure 16. And stainless steel (SUS304) having an inner diameter of 15 mm and an outer diameter of 26 mm for fixing the outermost peripheral portion of the discharge structure 16 was used. That is, the width of the frame 14 that fixes the central portion of the discharge structure 16 is 1.5 mm, and the width of the frame 14 that fixes the outermost peripheral portion is 5.5 mm. The joint surface 13b between the vibration generator 17 and the discharge structure 16 and the joint surface 13a between the frame and the discharge structure 16 are both made of epoxy resin (elastic modulus 1.3 × 10 ⁸ Pa), and the heating condition is 170 ° C. × Joined in 5 minutes.
Therefore, in FIG. 6A, the inner diameter of the vibration region of the ejection structure is 10 mm, the outer diameter is 15 mm, and the width of the vibration region is 2.5 mm. The discharge holes of the discharge structure have an annular area between 0.8 mm and 1.7 mm from the vibration generator side of this vibration area, and the pitch of the adjacent discharge holes (the shortest distance between the center parts of the discharge holes) is about It was provided in an annular shape so as to have a staggered arrangement of 140 μm.
A carrier air flow having an outlet flow velocity of 10 m / sec was generated in the air flow path 40 inside the annular portion of the frame 14 and the discharge structure 16.

Regarding toner preparation conditions, toner base particles of Example 6 were prepared in the same manner as in Example 2 except that the conditions shown below were changed in Example 2.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 ° C to 28 ° C
Discharge hole frequency: 43.1 kHz
Applied voltage to PZT Sin wave pp value: 132V

The dried toner base particles were neutralized by soft X-ray irradiation in the same manner as in Example 1 and collected by suction with a filter having 1 μm pores. The discharge rate was 21.74 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 1.96 g / min.
Measurement of particle size distribution of particles collected after 1 hour has elapsed after operation using a flow particle image analyzer (trade name: FPIA-2000, manufactured by Sysmex Corporation) in the same manner as in Example 1. As a result, the weight average particle diameter (D4) was 5.84 μm, the number average particle diameter (Dn) was 5.08 μm, and D4 / Dn was 1.15.

(Example 7)
Example 7 is the same as Example 6 except that the outlet flow velocity of the conveying airflow is changed to 30 m / second and the toner production conditions are changed to the conditions shown below. Toner base particles were prepared.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 ° C to 28 ° C
Discharge hole frequency: 46.2 kHz
Applied voltage to PZT Sin wave pp value: 132V

The dried toner base particles were neutralized by soft X-ray irradiation in the same manner as in Example 1 and collected by suction with a filter having 1 μm pores. The discharge rate was 23.30 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 2.10 g / min.
The particle size distribution of the particles collected after 1 hour has elapsed after operation The particle size distribution of the collected particles was measured in the same manner as in Example 1 using a flow type particle image analyzer (trade name: FPIA-2000, manufactured by Sysmex Corporation). As a result, the weight average particle diameter (D4) was 5.47 μm, the number average particle diameter (Dn) was 4.88 μm, and D4 / Dn was 1.12.

(Example 8)
Example 8 is the same as Example 7 except that the thickness of the vibration generator 17 was changed to 3.0 mm and the toner production conditions were changed to the conditions shown below. 8 toner base particles were prepared.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 ° C to 28 ° C
Discharge hole frequency: 54.4 kHz
Applied voltage to PZT Sin wave pp value: 128V

The dried toner base particles were neutralized by soft X-ray irradiation in the same manner as in Example 1 and collected by suction with a filter having 1 μm pores. The discharge rate was 27.44 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 2.47 g / min.
Measurement of particle size distribution of particles collected after 1 hour has elapsed after operation using a flow particle image analyzer (trade name: FPIA-2000, manufactured by Sysmex Corporation) in the same manner as in Example 1. As a result, the weight average particle diameter (D4) was 6.20 μm, the number average particle diameter (Dn) was 5.25 μm, and D4 / Dn was 1.18.

Example 9
In Example 9, the inner diameter of the discharge structure in Example 8 was changed to 7 mm. That is, the discharge structure 16 has a width of 9 mm. In the eighth embodiment, the inner diameter of the vibration generator 17 is changed to 9 mm and the outer diameter is changed to 15 mm. The toner base particles of Example 9 were produced in the same manner as in Example 8, except that the production conditions were changed to the conditions shown below.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 ° C to 28 ° C
Discharge hole frequency: 42.0 kHz
Applied voltage to PZT Sin wave pp value: 144V

The dried toner base particles were neutralized by soft X-ray irradiation in the same manner as in Example 1 and collected by suction with a filter having 1 μm pores. The discharge rate was 29.64 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 2.67 g / min.
The particle size distribution of the particles collected after 1 hour has elapsed after operation The particle size distribution of the collected particles was measured in the same manner as in Example 1 using a flow type particle image analyzer (trade name: FPIA-2000, manufactured by Sysmex Corporation). As a result, the weight average particle diameter (D4) was 5.53 μm, the number average particle diameter (Dn) was 4.89 μm, and D4 / Dn was 1.13.

(Comparative Example 1)
In Comparative Example 1, toner base particles of Comparative Example 1 were prepared in the same manner as in Example 2, except that the toner was prepared in the following manner in Example 2.
500 mL of the toner composition dispersion liquid was supplied to a plurality of ejection holes (nozzles) 15 of the droplet forming means 11 of the toner manufacturing apparatus shown in FIGS.
The used discharge structure (thin film, nozzle plate) 16 is a nickel plate having an outer diameter of 25 mm and a thickness of 100 μm. ) A 10 μm discharge hole 15 was produced by electroforming. The discharge hole was provided inside the annular vibration generator 17 as will be described later.
In addition, the opening diameter of the discharge hole was made constant in the thickness direction of the discharge structure. That is, as shown in FIG. 11A, the discharge hole angle 200 was 90 °.

Further, a SiO ₂ film and a liquid repellent film were formed on the entire exposed surface of the discharge structure by the same method as in Example 1. The film thickness of the liquid repellent film measured by the same method as in Example 1 was 50 nm, and the contact angle of the toner composition dispersion of the liquid repellent film was 58 °.

In FIG. 5, the annular vibration generator 17 was lead zirconate titanate (PZT) having an inner diameter of 4 mm, an outer diameter of 15 mm, and a thickness of 1.0 mm. It was. That is, the width of the discharge structure 16 is 5.5 mm. The frame 14 as the fixing portion was made of stainless steel (SUS304) having an inner diameter of 12 mm and an outer diameter of 26 mm. That is, the width of the frame 14 that fixes the outermost peripheral portion of the discharge structure 16 is 7 mm. The joint surface 13b between the vibration generator 17 and the discharge structure 16 and the joint surface 13a between the frame and the discharge structure 16 are both made of epoxy resin (elastic modulus 1.3 × 10 ⁸ Pa), and the heating condition is 170 ° C. × Joined in 5 minutes.
As shown in FIG. 5, the discharge hole is perpendicular to the center of the surface (the center of the discharge structure) perpendicular to the thickness direction of the discharge structure 16 (the center of the discharge structure) (opening axis). With the vertical line as the center, it is circular so that the pitch of adjacent discharge holes (the shortest distance between the center parts of the discharge holes) is about 140 μm in a range of 3 mm in diameter in the opening surface direction. Provided. Note that the vibration region of the discharge structure is circular with an outer diameter of 4 mm.

The toner base particles of Comparative Example 1 were produced in the same manner as in Example 2 except that the toner production conditions in Example 2 were changed to the conditions shown below.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 ° C to 28 ° C
Discharge hole frequency: 41.8 kHz
Applied voltage to PZT Sin wave pp value: 9V

The dried toner base particles were neutralized by soft X-ray irradiation in the same manner as in Example 1 and collected by suction with a filter having 1 μm pores. The discharge rate was 0.99 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 0.09 g / min.
The particle size distribution of the particles collected after 1 hour has elapsed after operation The particle size distribution of the collected particles was measured in the same manner as in Example 1 using a flow type particle image analyzer (trade name: FPIA-2000, manufactured by Sysmex Corporation). As a result, the weight average particle diameter (D4) was 6.78 μm, the number average particle diameter (Dn) was 5.51 μm, and D4 / Dn was 1.23.

(Comparative Example 2)
Comparative Example 2 is the same as Comparative Example 1 except that the thickness of vibration generator 17 is changed to 3.0 mm and the toner production conditions are changed to the conditions shown below. 2 toner base particles were prepared.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 ° C to 28 ° C
Discharge hole frequency: 75.7 kHz
Applied voltage to PZT Sin wave pp value: 8V

The dried toner base particles were neutralized by soft X-ray irradiation in the same manner as in Example 1 and collected by suction with a filter having 1 μm pores. The discharge rate was 2.15 g / min on the basis of the toner composition dispersion. The toner standard after drying was about 0.19 g / min.
The particle size distribution of the particles collected after 1 hour has elapsed after operation The particle size distribution of the collected particles was measured in the same manner as in Example 1 using a flow type particle image analyzer (trade name: FPIA-2000, manufactured by Sysmex Corporation). As a result, the weight average particle diameter (D4) was 6.44 μm, the number average particle diameter (Dn) was 5.37 μm, and D4 / Dn was 1.20.

(Comparative Example 3)
Comparative Example 3 is the same as Comparative Example 1, except that the thickness of the ejection structure is changed to 40 μm, the thickness of the vibration generator 17 is changed to 3.0 mm, and the arrangement and shape of the ejection holes are as shown below. The toner base particles of Comparative Example 2 were produced in the same manner as in Comparative Example 1 except that the conditions were changed to the conditions shown below.
-Disposition and shape of discharge holes-
As for the arrangement of the plurality of discharge holes, a perpendicular (opening axis) to the opening surface is drawn at the center (center of the discharging structure) of the surface (opening surface of the discharging hole) perpendicular to the thickness direction of the discharging structure 16. Centered on this perpendicular line, in the range of a diameter of 3 mm in the direction of the opening surface, the pitch of adjacent discharge holes (the shortest distance between the center portions of the discharge holes) was provided in a circular pattern so as to be a staggered arrangement of about 140 μm. .
As shown in FIG. 11B, each discharge hole has a tapered shape in which the opening diameter decreases in the toner composition discharge direction, and the taper angle (discharge hole angle 200) is changed depending on the position of the discharge hole. . The taper angle is an angle formed by the side surface of the discharge hole with respect to the perpendicular (opening axis).
The taper angle at each position of the discharge holes was viewed in a two-row staggered arrangement with the discharge hole at the center of the discharge structure as the first one, like the discharge hole 15 indicated by the black circle in FIG. When the taper angle of the first discharge hole and the second taper angle outside the first discharge hole are θ ₁ = 13 °, the third and fourth taper angles are θ ₂ = 15 °, the fifth and sixth taper angles were θ ₃ = 17 °, and the seventh taper angle was θ ₄ = 19 °.
Further, like the discharge holes 15 indicated by gray circles in FIG. 12, the taper angles of the other discharge holes were similarly changed depending on the positions.
-Toner preparation conditions-
Toner composition dispersion specific gravity: ρ = 1.19 g / cm ³
Dry air flow rate: Dry nitrogen gas in the device 30.0 L / min Temperature in the device: 27 ° C to 28 ° C
Discharge hole frequency: 127.7 kHz
Applied voltage to PZT Sin wave pp value: 41.9V

The dried toner base particles were neutralized by soft X-ray irradiation in the same manner as in Example 1 and collected by suction with a filter having 1 μm pores. The discharge rate was 14.77 g / min based on the toner composition dispersion. The toner standard after drying was about 1.33 g / min.
The particle size distribution of the particles collected after 1 hour has elapsed after operation The particle size distribution of the collected particles was measured in the same manner as in Example 1 using a flow type particle image analyzer (trade name: FPIA-2000, manufactured by Sysmex Corporation). As a result, the weight average particle diameter (D4) was 5.72 μm, the number average particle diameter (Dn) was 5.41 μm, and D4 / Dn was 1.06.

  The production conditions of the toners of Examples 1 to 9 and Comparative Examples 1 to 3 are shown in Tables 1 and 2 below, and the results are shown in Table 3 below.

From Examples 1 to 9, the central portion and the outermost peripheral portion of the discharge structure are fixed, and the toner composition liquid is discharged from a plurality of discharge holes provided in the non-fixed portion. It was found that the area where the droplets can be ejected increases and the toner yield increases.
Further, according to Examples 6 to 9, the discharge structure is annular, and a structure that generates a transport airflow that transports the droplets inside the ring allows the discharged droplets to be united. It was found that a toner having higher monodispersibility can be obtained.
In addition, the particle size distribution D4 / Dn of Example 8 is larger than that of Example 7 because the thickness of the vibration generator of Example 8 is thicker than that of Example 7, and thus transported after droplets are ejected. This is thought to be because the distance to get on the airflow became longer.
On the other hand, according to Comparative Examples 1, 2, and 3, the discharge amount and the yield were low in the structure in which the plurality of discharge holes are provided inside the annular vibration generator.

  The toner manufacturing method and apparatus of the present invention can eject droplets simultaneously from a plurality of ejection holes, have a wide area capable of ejecting highly monodisperse droplets, and have a large number of droplets that can be ejected per unit time. A highly versatile toner can be produced efficiently. Therefore, the toner manufactured by the toner manufacturing method and manufacturing apparatus of the present invention can be suitably used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like.

DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet discharge unit 3 Particle formation part (solvent removal part)
3A Top surface part of particle forming part 4 Toner collecting part 5 Toner storing part 6 Raw material container 7 Tube 8, 8A Liquid feeding pipe (pipe)
DESCRIPTION OF SYMBOLS 9 Liquid return pipe 10 Toner composition liquid 11 Droplet formation means 12 Toner composition liquid flow path 12A Peripheral part of discharge structure 13a Discharge structure (thin film, nozzle plate, discharge plate) joint 13b Vibration generator joint 14 Frame ( Channel member)
15 Discharge hole (nozzle, through hole)
16 Discharge structure (thin film, nozzle plate, discharge plate)
16A Deformable region of discharge structure 17, 17A Vibration generator (electromechanical conversion means)
19 support member 20 liquid supply tube (liquid supply hole)
21 Bubble discharge tube (discharge hole)
23 Liquid droplet 40 Carrying air channel 41 Air channel forming member 42 Air channel 43 Static neutralizer 44 Carrying airflow 45 Carrying air channel inlet 46 Carrying air channel outlet 50 Lead wire 51 Drive circuit (drive signal generation source)
52 Liquid common supply 53 Outside transport airflow 100 Pump 200 Angle of discharge hole T Toner particle

JP-A-7-152202 JP-A-57-201248 Japanese Patent No. 3786034 Japanese Patent No. 3786035 JP 2008-276146 A JP 2008-281915 A JP 2008-292976 A

Claims (5)

Droplet forming means for forming a droplet by discharging a toner composition liquid containing at least a resin and a colorant from a plurality of discharge holes, and particle formation for solidifying the dropletized toner composition liquid to form particles A toner production apparatus comprising:
The droplet forming means includes a discharge structure in which a central portion and an outermost peripheral portion are fixed and the plurality of discharge holes are provided in a non-fixed portion, and a vibration generator having a disk shape or an annular shape. And a plurality of ejection holes of the ejection structure are provided around the vibration generator.   The toner manufacturing apparatus according to claim 1, wherein a plurality of discharge holes of the discharge structure are provided in an annular shape around the vibration generator.   3. The toner manufacturing apparatus according to claim 1, wherein the vibration generating body has an annular shape, and includes a transport air flow generation unit that generates a transport air flow for transporting the ejected droplets inside the ring.   The toner production apparatus according to claim 3, wherein an outlet flow velocity of the conveying air current is 10 m / second to 50 m / second. A method for producing toner using the toner production apparatus according to claim 1, comprising:
A toner composition liquid containing at least a resin and a colorant is ejected from the plurality of ejection holes of the ejection structure having a plurality of ejection holes fixed to the central portion and the outermost peripheral portion and provided to the non-fixed portion. A method for producing a toner, comprising: a droplet forming step for forming a toner; and a particle forming step for solidifying the droplet-formed toner composition liquid to form particles.