JP5463895B2 - Particle manufacturing method, particle manufacturing apparatus, toner, and manufacturing method thereof - Google Patents

Description

  The present invention relates to a method for producing particles, an apparatus for producing particles, a toner, and a method for producing the same.

The developer used for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc. is, for example, an electrostatic latent image carrier on which an electrostatic charge image is formed in the development process. Once attached to the image carrier. Next, after being transferred from the electrostatic latent image carrier to a recording medium such as transfer paper in the transfer step, it is fixed on the recording medium in the fixing step.
In this case, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier (magnetic toner, Non-magnetic toners 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 toner production method using a suspension polymerization method or an emulsion polymerization aggregation method, so-called polymerization type toner, has been studied.
In addition to these methods, a method called volumetric shrinkage called a polymer dissolution suspension method has been studied (see Patent Document 1). In this method, the toner material is dispersed and dissolved in a volatile solvent such as a low boiling point organic solvent, and this is emulsified in an aqueous medium in the presence of a dispersing agent to form droplets, and then the volatile solvent is removed. .
Unlike suspension polymerization and emulsion polymerization aggregation methods, this method has a wide range of versatile resins that can be used, and is particularly useful for full-color processes that require transparency and smoothness of the image area after fixing. It is excellent in that it can be used.

  However, since the polymerization toner is premised on the use of a dispersant in an aqueous medium, the dispersant that impairs the chargeability of the toner remains on the toner surface and the environmental stability is impaired. It is known that a very large amount of washing water is required to remove this, and it is not always satisfactory as a production method.

On the other hand, a spray drying method has been known for a long time as a toner production method that does not use an aqueous medium (see Patent Document 2).
In this spray drying method, a molten liquid or a liquid in which a toner composition liquid is dissolved is formed into fine particles using various atomizers and discharged to obtain particles. Does not occur.
However, the particles obtained by the conventional spray granulation method are relatively coarse and large, and the particle size distribution is wide, which causes the characteristics of the toner itself to deteriorate.
Therefore, as an alternative toner manufacturing method, there has been proposed a method and apparatus for forming fine droplets using piezoelectric pulses and drying and solidifying them to form toner (see Patent Document 3).
In addition, a method has also been proposed in which fine droplets are formed by using thermal expansion in the nozzle, which is further dried and solidified to form a toner (see Patent Document 4).

Further, Patent Documents 3 and 4 have a gas flow supply means, and the gas supplied from the gas flow supply means is substantially discharged from each gas injection port provided between the head portions via a duct. It is described that the material is ejected at a uniform pressure, whereby the raw material is conveyed and solidified while maintaining the interval between the granular raw materials intermittently discharged from the discharge unit.
In the toner manufacturing method and apparatus described in Patent Documents 3 and 4, droplets can be discharged only from one nozzle using one piezoelectric body, and can be discharged per unit time. There is a problem that the number is small and productivity is poor.

Therefore, the applicant of the present application first ejects droplets of the toner composition liquid at a constant frequency from the nozzles by vibrating the nozzles by expansion and contraction of the piezoelectric body as the vibration generating means, and solidifies the droplets to solidify the toner. Has been proposed (see Patent Document 5).
In addition, the applicant of the present application includes a discharge member having a discharge hole and a vibration applying unit that vibrates the discharge member at a predetermined frequency, and the droplet is discharged from the discharge hole by vibrating the discharge member. A method of manufacturing toner by discharging, drying and solidifying the droplets has been proposed (see Patent Document 6).

However, as in Patent Documents 5 and 6, the configuration in which the gas flow is supplied to each discharge unit has to be a complicated apparatus configuration. Further, as shown in FIG. 31, the ejected droplets rapidly decrease in speed as the droplets become smaller. For example, 0.2 pl droplets are ejected from the nozzle at 10 m / sec after 1.5 mm. Becomes a speed of 1 m / sec or less. At this time, in the region where the frequency exceeds 100 kHz, the distance between the droplets is only 10 μm, and there is a problem that unification (merging) between the preceding and following droplets is unavoidable.
Further, as described in Patent Document 5, in the configuration in which the piezoelectric body is exposed to the peripheral portion of the nozzle and the nozzle is vibrated by expansion and contraction of the piezoelectric body, the region corresponding to the opening of the piezoelectric body Since a large amount of nozzle displacement cannot be obtained because only vibration is generated in the nozzle area, a toner composition liquid having a high viscosity (for example, 10 mPa · s) and a large amount of solid content is discharged. It is known that clogging is likely to occur when the toner is used, and the structure is still insufficient for stable and efficient toner production.
Further, although Patent Document 6 describes that the discharge member is vibrated with a piezoelectric body, the specific configuration thereof is not described, and does not exceed the range described in Patent Document 5. .

In addition, the applicant of the present application has been able to produce toner efficiently and stably over a long period of time, and has been found in conventional toner production methods in many characteristic values required for toner such as fluidity and chargeability. A method for producing a toner having a small variation due to particles is proposed (see Patent Document 7).
However, although it was confirmed that an air flow exceeding the speed of the liquid droplets was given to the ejected liquid droplets to reduce the coalescence of the ejected liquid droplets and the adhesion to the head, it was confirmed that the air flow was very close to the nozzle. In order to provide it, a complicated nozzle head structure is required, and in the absence of this, the coalescence of the liquid droplets may proceed before being put on the air stream.

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention provides a particle production method and particle production apparatus capable of efficiently and stably producing particles having a monodispersibility that has never been obtained, and fluidity and chargeability. An object of the present invention is to provide a toner that can form a high-quality image with a small fluctuation range and a method for producing the toner.

Means for solving the problems are as follows. That is,
<1> A periodic droplet forming step of applying vibration to any of the liquid chamber and nozzle plate to which at least a resin-containing particle composition solution is supplied, and periodically forming and discharging droplets from a plurality of nozzles;
A particle forming step of solidifying droplets of the discharged particle composition liquid,
In the periodic droplet forming step, at least a displacement other than vibration during droplet formation is applied to at least the nozzle plate.
<2> The method for producing particles according to <1>, wherein a horizontal displacement is applied to an ejection surface in a vertical direction with respect to a droplet ejection direction.
<3> The method for producing particles according to <1>, wherein a displacement is applied to the ejection surface in the vertical direction with an inclination in the horizontal direction with respect to the droplet ejection direction.
<4> The method for producing particles according to <1>, wherein a rotational motion is applied to the ejection surface in the vertical direction with an inclination in the horizontal direction with respect to the droplet ejection direction.
<5> The method for producing particles according to any one of <1> to <4>, wherein an airflow that flows in a droplet ejecting direction is formed through a constricted portion corresponding to a nozzle forming region disposed downstream of the droplet ejecting direction. It is.
<6> Periodic droplet forming means that vibrates at least one of the reservoir and the nozzle plate to which the particle composition liquid containing the resin is supplied, and periodically droplets are discharged from a plurality of nozzles;
In a particle production apparatus having at least particle formation means for solidifying the droplets of the discharged particle composition liquid,
In the particle manufacturing apparatus, the periodic droplet forming unit includes a displacement applying unit that further applies a displacement other than vibration at the time of droplet formation to at least the nozzle plate.
<7> The particle manufacturing apparatus according to <6>, wherein the displacement applying unit is a vibrator.
<8> The particle production apparatus according to any one of <6> to <7>, further including a throttle portion corresponding to a nozzle formation region arranged on the downstream side in the droplet ejection direction.
<9> A toner production method using the particle production method according to any one of <1> to <5>,
A toner manufacturing method, wherein the particle composition liquid is a toner composition liquid containing at least a resin and a colorant.
<10> A toner manufactured by the method for manufacturing a toner according to <9>.
<11> The toner according to <10>, wherein the toner has a weight average particle diameter of 1 μm to 20 μm and a toner particle size distribution (weight average particle diameter / number average particle diameter) of 1.00 to 1.15. is there.

According to the toner manufacturing method and toner manufacturing apparatus of the present invention, a toner composition liquid containing at least a resin and a colorant is ejected by vibration of a nozzle plate or vibration of a liquid. The toner composition liquid droplets ejected at this time are ejected in a direction substantially perpendicular to the nozzle formation surface. In the present invention, the nozzle plate is subjected to a displacement other than the vibration at the time of droplet formation, so that the nozzle Since the surface rotates in the vertical direction with respect to the ejection direction with vibration or inclination, the ejection direction is different for each droplet, and the front and rear droplet intervals can be ensured. Furthermore, an airflow that flows in the droplet discharge direction is formed through a constricted portion corresponding to the nozzle formation region disposed on the downstream side of the droplet discharge direction after 2 mm from the nozzle surface where the droplet velocity decreases, so that the droplets discharged The unification can be reliably prevented, the toner can be efficiently and stably produced over a long period of time, and a toner having a monodispersibility with an unprecedented particle size can be obtained.
Since the toner of the present invention is produced by the toner production method of the present invention, it has unprecedented monodispersibility, and has many characteristic values required for toner such as fluidity and chargeability. It is a high-quality product with little variation due to particles found in the manufacturing method.

  According to the present invention, it is possible to solve the conventional problems, and it is possible to efficiently and stably produce particles having monodispersibility over a long period of time, and the production of particles. It is possible to provide an apparatus, a toner that can form a high-quality image with little fluctuation range of fluidity and chargeability, and a method for producing the toner.

FIG. 1 is a schematic configuration diagram showing an embodiment of a toner manufacturing apparatus of the present invention to which the toner manufacturing method of the present invention is applied. FIG. 2 is an enlarged explanatory diagram for explaining an example of a droplet ejecting unit of the toner manufacturing apparatus. FIG. 3 is an explanatory bottom view of FIG. 2 as viewed from below. FIG. 4 is an enlarged cross-sectional explanatory view of the droplet discharge means of the droplet ejection unit. FIG. 5A is a schematic explanatory diagram of a thin film used for explaining an operation principle of droplet formation by a droplet discharge unit of the droplet ejection unit. FIG. 5B is a schematic explanatory diagram of a thin film used for explaining an operation principle of droplet formation by a droplet discharge unit of the droplet ejection unit. FIG. 6 is an explanatory diagram for explaining the fundamental vibration mode. FIG. 7 is an explanatory diagram for explaining the secondary vibration mode. FIG. 8 is an explanatory diagram for explaining the third vibration mode. FIG. 9 is an explanatory diagram when a convex portion is formed at the center of the thin film. FIG. 10A is a schematic explanatory diagram for explaining the operation principle of droplet formation by the droplet forming means. FIG. 10B is a schematic explanatory diagram used for an operation principle of droplet formation by the droplet forming means. FIG. 11 is an explanatory front sectional view for explaining another example of the droplet ejecting unit of the toner manufacturing apparatus. 12 is a left side cross-sectional explanatory view of FIG. FIG. 13 is a schematic diagram illustrating another example of the droplet ejecting unit. FIG. 14 is a schematic explanatory diagram for explaining another example of the airflow forming means. FIG. 15 is a schematic perspective explanatory view for explaining still another example of the airflow forming means. FIG. 16 is a cross-sectional explanatory diagram for specific description of the airflow forming means. FIG. 17 is a cross-sectional explanatory view taken along the line AA of FIG. 18 is a cross-sectional explanatory view taken along the line BB in FIG. FIG. 19 is a cross-sectional explanatory view for explaining the airflow forming means. FIG. 20 is a schematic explanatory diagram illustrating an example in which a nozzle plate includes a vibrator. FIG. 21 is a schematic explanatory diagram illustrating another example in which a nozzle plate includes a vibrator. FIG. 22 is a schematic explanatory diagram illustrating another example in which a vibrator is provided on a nozzle plate. FIG. 23 is a schematic explanatory diagram illustrating another example in which a vibrator is provided on a nozzle plate. FIG. 24 is a schematic explanatory diagram illustrating another example in which a nozzle plate includes a vibrator. FIG. 25 is a schematic explanatory diagram illustrating another example in which a vibrator is provided on a nozzle plate. FIG. 26 is a schematic explanatory diagram illustrating another example in which a vibrator is provided on a nozzle plate. FIG. 27 is a schematic explanatory view showing another example in which a nozzle plate is provided with a vibrator. FIG. 28 is a schematic explanatory view showing the discharge of particles when the nozzle plate is provided with a vibrator and a rotational motion is given to the nozzle plate. FIG. 29 is a graph showing the distribution state of the diameter of droplets ejected from the ejection head of Example 1 in degrees. FIG. 30 is a graph showing the distribution state of droplet diameters ejected from the ejection head of Comparative Example 1 in degrees. FIG. 31 is a velocity decay curve when droplets are ejected into the air at a velocity of 10 m / s.

(Particle production method and particle production apparatus)
The method for producing particles of the present invention includes at least a periodic droplet forming step and a particle forming step, and further includes other steps as necessary.
The particle production apparatus of the present invention includes at least a periodic droplet forming unit and a particle forming unit, and further includes other units as necessary.
The particle production method and particle production apparatus of the present invention will be described in detail below.

<Periodic droplet forming step and periodic droplet forming means>
The periodic droplet forming step is a step in which at least one of a liquid chamber and a nozzle plate to which a particle composition liquid containing a resin is supplied is displaced, and droplets are periodically discharged from a plurality of nozzles to be discharged. Can be carried out by periodic droplet forming means.

In the present invention, in the periodic droplet forming step, a displacement other than vibration at the time of droplet formation is further applied to at least the nozzle plate, and can be implemented by a displacement applying unit.
The displacement applying unit is preferably a vibrator in terms of simplicity and low cost.
Examples of the vibrator include piezoelectric ceramics mainly composed of lead zirconate titanate and barium titanate.

For example, (1) A mode in which a horizontal displacement is applied to the ejection surface in the vertical direction with respect to the droplet ejection direction, (2) A mode in which a horizontal displacement is applied to the ejection surface in the vertical direction with respect to the droplet ejection direction, and (3) a rotational motion is applied to the ejection surface in the vertical direction with a tilt in the horizontal direction relative to the droplet ejection direction. (4) A mode in which an airflow that flows in the liquid droplet ejecting direction is formed through a constricted portion corresponding to a nozzle forming region disposed on the downstream side in the liquid droplet ejecting direction.
As a means for realizing the aspect (1), for example, a bulk type piezoelectric ceramic is bonded and arranged at the center of the side surface of the head, the other is held by an elastic body such as a rubber material, and the piezoelectric element is excited. .
As a means for realizing the mode (2), for example, there is a method in which a bulk type piezoelectric ceramic is bonded and arranged at the end of the back surface of the head, and the piezoelectric element is excited.
As a means for realizing the aspect (3), for example, there is a method in which bulk piezoelectric ceramics are bonded and arranged at the four corners of the back surface of the head, and the respective elements are synchronized to excite the piezoelectric elements.
As means for realizing the aspect (4), for example, as shown in FIG. 16, a cover provided with a diaphragm toward the nozzle array portion is formed of a SUS thin plate (thickness (t) = 0.5 mm), and the surface For example, a layer with a Teflon coat applied.

<Particulation step and particle formation means>
The particle forming step is a step of solidifying the discharged droplets of the particle composition liquid, and can be performed by a particle forming means.
The particle forming means is not particularly limited as long as the droplets can be solidified into particles, and can be appropriately selected according to the purpose. For example, (1) the organic solvent contained in the droplets is evaporated into a dry gas, Examples thereof include a method of performing shrinkage solidification by drying, and (2) a method of blowing dry nitrogen and taking away the solvent in the liquid in the process of transporting droplets.

Here, the particles are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include toners, gap materials, powdery cosmetics, powdered drugs, and detergents. Among these, toner is particularly preferable.
When the particles are toner, the particle manufacturing apparatus of the present invention functions as a “toner manufacturing apparatus”.
When the toner is manufactured using the “particle manufacturing apparatus”, the “toner manufacturing method” of the present invention is carried out.

Hereinafter, an embodiment of a toner production apparatus for carrying out the toner production method of the present invention will be described with reference to the schematic configuration diagram of FIG.
The toner manufacturing apparatus 1 has a liquid droplet ejecting unit 2 as liquid droplet forming means, and the liquid droplet ejecting unit 2 disposed above, and solidifies the liquid droplets of the toner composition liquid discharged from the liquid droplet ejecting unit 2. The particle forming unit 3 as the particle forming means for forming the toner T, the toner collecting unit 4 for collecting the toner T formed by the particle forming unit 3, and the toner T collected by the toner collecting unit 4 Is transferred through the tube 5, a toner storage unit 6 as a toner storage unit that stores the transferred toner T, a raw material storage unit (storage tank) 7 that stores the toner composition liquid 10, and the raw material storage unit 7. A pipe (liquid feeding pipe) 8 for feeding the toner composition liquid 10 from the inside to the droplet jetting unit 2 and a pump 9 for feeding and supplying the toner composition liquid 10 during operation and the like are provided.

The toner composition liquid 10 from the raw material container 7 is supplied to the droplet ejection unit 2 by itself due to the droplet formation phenomenon by the droplet ejection unit 2, but is supplemented as described above when the apparatus is operating. In particular, the pump 9 is used to supply the liquid.
As the toner composition liquid 10, here, a solution or dispersion liquid in which a toner composition containing at least a resin and a colorant is dissolved or dispersed in a solvent is used.

In addition, here, an example in which one droplet ejecting unit 2 is arranged is illustrated, but preferably, as will be described later, a plurality of, for example, 100 to 1,000 liquids from the viewpoint of controllability. The droplet ejecting units 2 are arranged side by side on the top surface portion of the particle forming unit 3, and the toner composition liquid 10 is supplied to each droplet ejecting unit 2 by connecting a pipe 8 to the raw material containing unit 7.
As a result, more droplets can be discharged at a time, and the production efficiency can be improved.

Next, an example of the droplet ejecting unit will be described with reference to FIGS.
2 is a cross-sectional explanatory view of the liquid droplet ejecting unit 2, FIG. 3 is a main surface bottom explanatory view of FIG. 2 viewed from the lower side, and FIG. 4 is a schematic cross-sectional explanatory view of the droplet forming means.
The droplet ejecting unit 2 includes a droplet discharge unit 11 that discharges the toner composition liquid 10 containing at least a resin and a colorant into droplets, and a storage unit (liquid that supplies the toner composition liquid 10 to the droplet discharge unit 11. And a flow path member 13 in which a flow path) 12 is formed.

The droplet discharge means 11 includes a thin film 16 in which a plurality of nozzles (discharge ports) 15 are formed, and an electromechanical conversion means (element) 17 that is an annular vibration generating means that vibrates the thin film 16. .
Here, the thin film 16 is bonded and fixed to the flow path member 13 with a resin binding material that does not dissolve in solder or a toner composition liquid at the outermost peripheral portion (region shown by hatching in FIG. 3).
The electromechanical conversion means 17 is disposed around the deformable area 16 </ b> A of the thin film 16 (area not fixed to the flow path member 13).
A drive voltage (drive signal) having a required frequency is applied to the electromechanical conversion means 17 from a drive circuit (drive signal generation source) 23 through lead wires 21 and 22 to generate, for example, flexural vibration.

The material of the thin film 16 and the shape of the nozzle 15 are not particularly limited and may be appropriately selected. For example, the thin film 16 is formed of a metal plate having a thickness of 5 μm to 500 μm and the nozzle 15 is opened. A diameter of 3 μm to 35 μm is preferable from the viewpoint of generating fine liquid droplets having a very uniform particle diameter when the liquid droplets of the toner composition liquid are ejected from the nozzle 15.
The opening diameter of the nozzle 15 means a diameter if it is a perfect circle, and means a short diameter if it is an ellipse.
The number of the plurality of nozzles 15 is preferably 2 to 4,000, and more preferably 200 to 2,000.

The electromechanical conversion means 17 is not particularly limited as long as it can apply a certain vibration to the thin film 16 at a constant frequency. As described above, a piezoelectric body that is excited by a bimorph type flexural vibration is preferable. .
Examples of the piezoelectric body include piezoelectric ceramics such as lead zirconate titanate (PZT). However, since the amount of displacement is generally small, the piezoelectric body is often used by being laminated.
In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO ₃ , and the like can be given.

A liquid supply tube 18 and a liquid circulation tube (or a bubble discharge tube) 19 connected to the liquid supply pipe 8 for supplying the toner composition liquid to the storage section 12 are connected to the flow path member 13 at least at one location. Yes.
The support member 20 attached to the flow path member 13 is installed and held on the top surface portion of the particle forming unit 3.
In addition, although the example which has arrange | positioned the droplet injection unit 2 in the top | upper surface part of the particle formation part 3 is demonstrated here, the droplet injection unit 2 is provided in the drying part side wall used as the particle formation part 3, or a bottom part. It can also be set as the structure to install.

  In this way, the droplet discharge means 11 constituting the droplet forming means has the annular electromechanical conversion means 17 around the deformable region 16A of the thin film 16 having the plurality of nozzles 15 facing the storage portion 12. As a result, the amount of displacement of the thin film 16 is relatively large compared to a configuration in which the electromechanical conversion means 17 holds the periphery of the thin film 16, for example. A plurality of nozzles 15 can be arranged in a region having an area (diameter of 1 mm or more), and more droplets can be stably formed and discharged at a time than the plurality of nozzles 15.

  The operation principle of the droplet discharge means 11 will be described with reference to FIG. 5. The peripheral portion 16B of the simple circular thin film 16 as shown in FIGS. 5A and 5B is fixed (more specifically, the deformable region 16A When the circular thin film 16 is vibrated in the case where the outer periphery is fixed), the basic vibration becomes a node at the periphery, and the displacement amount ΔL is maximum (ΔLmax at the center O of the thin film 16 as shown in FIG. ) And periodically vibrates in the vibration direction.

As shown in FIG. 6, it is preferable to vibrate the thin film 16 in a vibration mode in which the periphery is a node and does not have a node in the diameter direction (radial direction).
It is known that higher order vibration modes exist as shown in FIGS.
These modes have one or more concentric nodes in the circular thin film 16 and have a deformed shape that is substantially symmetrical in the radial direction.
Moreover, as shown in FIG. 9, by making the center part of the circular thin film 16 into the convex shape 16C, it becomes possible to control the traveling direction of the droplet and adjust the vibration amplitude.

Here, due to the vibration of the circular thin film 16, a pressure Pac proportional to the vibration speed Vm of the thin film 16 is applied to the liquid (toner composition liquid) in the vicinity of the plurality of nozzles 15 provided in the circular thin film 16.
The pressure is known to be generated as a reaction of the radiation impedance Zr of the medium (toner composition liquid), and can be expressed by the product of the radiation impedance and the membrane vibration velocity Vm using the equation shown in the following Equation 1.

<Formula 1>
Pa (r, t) = Zr * Vm (r, t)

The vibration velocity Vm of the thin film 16 is a function of time because it fluctuates periodically with time. For example, various periodic fluctuations such as a sine waveform and a rectangular waveform can be formed.
As described above, the vibration displacement in the vibration direction is different in each part of the thin film 16, and the vibration speed Vm is also a function of position coordinates on the thin film 16.
Since the preferable vibration mode of the thin film is a deformation shape symmetrical in the radial direction as described above, it is substantially a function of the radial coordinate.

As described above, a pressure proportional to the vibration displacement speed of the thin film 16 having a distribution is generated, and the toner composition liquid 10 in the storage unit 12 moves to the gas phase in response to a periodic change in pressure. Discharged.
The toner composition liquid 10 periodically discharged to the gas phase forms spheres due to the difference in surface tension between the liquid phase and the gas phase, and thus droplet formation occurs periodically. The liquid droplets are ejected from the nozzle 15.

This is schematically shown in FIGS. 10A and 10B.
By applying flexural vibration to the electromechanical conversion means 17 arranged around the deformable region of the thin film 16, the thin film 16 is bent in the direction opposite to the storage portion 12 as shown in FIG. 10A. And, as shown in FIG. 10B, it vibrates between the state bent to the storage part 12 side.
As a result, the toner composition liquid 10 is formed into droplets by the vibration of the thin film 16 and the droplets 31 are ejected (discharged).

Here, the vibration frequency of the thin film 16 that enables droplet formation is preferably in the range of 20 kHz to 2.0 MHz, and more preferably in the range of 50 kHz to 500 kHz.
If the vibration frequency is a vibration period of 20 kHz or more, the dispersion of fine particles such as pigment and wax in the toner composition liquid 10 is promoted by the excitation of the liquid.
Further, when the pressure is 10 kPa or more, the above-described fine particle dispersion promoting action is more preferably generated.

In this case, the diameter of the formed droplet 31 tends to increase as the vibration displacement increases in the region where the plurality of nozzles 15 of the thin film 16 are formed. If the vibration displacement is small, is a droplet formed? Or do not drop.
In order to reduce the variation in droplet size in the region where the plurality of nozzles 15 are formed, it is necessary to define the arrangement of the plurality of nozzles 15 at the optimum position of vibration displacement of the thin film 16. .

  According to the experiment, the maximum value ΔLmax of the vibration direction displacement (displacement amount) ΔL of the thin film 16 in the region where the plurality of nozzles 15 of the thin film 16 generated by the electromechanical conversion means 17 shown in FIGS. By arranging a plurality of nozzles 15 in a region where the ratio R (= ΔLmax / ΔLmin) of the minimum value ΔLmin is within 2.0, that is, the ratio R is within 2.0, variation in droplet size is caused. Can be kept in a necessary region as a toner capable of providing a high-quality image.

Furthermore, generation of satellite particles (particles having a diameter approximately one-tenth of that of the formed droplets) is a major factor causing variations in droplet size (diameter).
When the experiment was performed by changing the conditions of the toner composition liquid, since the satellite generation start region was the same in the region of the viscosity of 20 mPa · s or less and the surface tension of 20 mN / m to 75 mN / m, the pressure was It is preferably in the range of 10 Pa to 500 kPa, more preferably 10 Pa to 100 kPa.
The generation of satellites can be suppressed by setting the pressure within this range, that is, by arranging the plurality of nozzles 15 in the region of the thin film 16 where the pressure falls within this range.

Next, another example of the droplet ejecting unit will be described with reference to FIGS.
FIG. 11 is a schematic front explanatory view of the droplet ejecting unit, and FIG. 12 is a left side explanatory view of FIG.
The droplet ejecting unit 102 includes a thin film 116 in which a plurality of nozzles (discharge ports) 115 are formed, a vibration unit 111 that vibrates the thin film 113, and at least a resin and a colorant between the thin film 116 and the vibration unit 111. And a flow path member 113 that forms a reservoir (liquid flow path) 111 that supplies the toner composition liquid 10 containing the toner composition liquid 10. The toner composition liquid 10 is supplied to the reservoir 114 through the liquid supply pipe 118. A liquid circulation pipe 119 is provided as necessary.

Here, the vibration unit 111 includes a vibration generation unit 121 that generates vibration in which two piezoelectric bodies are stacked, and a horn-shaped vibration amplification unit 122 that amplifies the vibration generated by the vibration generation unit 121, and includes a vibration surface 111a. Is arranged in parallel with the thin film 116 with the toner composition liquid 10 in the storage portion 112 interposed therebetween.
In this case, the area of the vibration surface 111a that is the surface opposite to the coupling surface 111b of the vibration amplifying means 122 is formed wider than the area of the coupling surface 111b that couples the vibration generating means 121 and the vibration amplifying means 122.

The vibrating surface 111a is rectangular (here, “rectangular”).
In this case, the vibration area increases as the ratio of the long side (long side / short side) is larger than the short side of the vibration surface 111a.
Therefore, from the viewpoint of productivity, it is preferable to form a relationship of (long side / short side)> 2.0.
Since other configurations (material, shape, nozzle arrangement, etc.) are the same as those of the droplet ejecting unit 2 described above, the description thereof is omitted.

  Also in the droplet ejecting unit 102, the vibration surface 111a is vibrated by driving the vibration generating means 121 of the vibration means 111, and the vibration of the vibration surface 111a is propagated to the thin film 116 so that the thin film 116 is driven at the required vibration frequency. The droplets of the toner composition liquid 10 can be periodically discharged from the nozzle 115 of the thin film 116.

In this way, the vibration generating means and the vibration amplifying means constitute the vibration means to vibrate the thin film, whereby the thin film can be vibrated with a larger amount of displacement, and monodisperse toner can be efficiently produced. Can do.
In particular, since the vibration surface is formed wider than the coupling surface that couples with the vibration generating means, the thin film can be vibrated with a larger displacement with a small vibration generating means.
Furthermore, another example of the droplet ejecting unit will be described with reference to FIG. FIG. 13 is a cross-sectional perspective view of the ejection head 201. By the operation of the PZT vibrator 202 as the vibration means arranged on the upper surface of the ejection head 201, the liquid in the individual liquid chamber 203 is vibrated, and from the nozzle 204. Then, a droplet is discharged. At this time, a plurality of nozzles 204 may be arranged for each individual liquid chamber 203.

Returning to FIG. 1, airflow forming means 50 for generating an airflow that flows in the discharge direction of the droplets 31 discharged from the nozzles 15 of the droplet ejection unit 2 is provided.
The air flow forming means 50 is composed of a gas pressurizing means 51, an air flow introducing pipe 52, and an air flow distribution forming means 53.

As the gas pressurizing means 51, a compressor or blower generally used in industry can be suitably used.
One air flow distribution forming means 53 is preferably provided for one droplet ejecting unit 2.
Therefore, as shown in FIG. 14, when a plurality of droplet ejection units 2 are arranged with respect to the particle forming unit 3, each droplet ejection is performed from one gas pressurizing means 51 through the air flow introduction pipe 52. It is preferable that the air flow is branched and introduced into the air flow distribution forming means 53 provided for the unit 2.
However, when a plurality of droplet ejection units 2 are arranged with respect to the particle forming unit 3, as shown in FIG. 15, one air flow distribution forming means 53 is provided for the plurality of droplet ejection units 2. You can also.

  The air flow distribution forming means 53 introduces the gas pumped from the gas pressurizing means 51 and discharges the droplets through the constricted portion 54 corresponding to the nozzle forming region disposed on the downstream side in the droplet discharge direction of the thin film 16 of the droplet ejection unit 2. An air flow path 56 that forms an air flow 55 flowing in the direction is formed.

Here, an example of airflow forming means when the droplet ejecting unit 102 described with reference to FIGS. 11 and 12 is used as the droplet ejecting unit will be described with reference to FIGS. 16 to 18.
16 is a front cross-sectional explanatory view for explaining the air flow distribution forming means of the air flow forming means, FIG. 17 is a cross-sectional explanatory view taken along the line AA in FIG. 16, and FIG. 18 is a cross-sectional view along BB in FIG. It is a section explanatory view which meets a line.
An air flow path forming member 53 is disposed as an air flow distribution forming means on the outer peripheral portion of the liquid droplet ejecting unit 102, and a gas introduction path 57 is disposed between the air flow path forming member 53 and the liquid droplet ejecting unit 102 from above in FIG. Through which pressurized gas is introduced.

The air flow path forming member 53 has a throttle portion 54 for restricting the air flow path 56 on the downstream side in the droplet discharge direction (the direction of arrow C) corresponding to the nozzle formation region of the thin film 116 of the droplet ejecting unit 102. The velocity of the gas flow (airflow 55) is increased at the throttle 54.
Note that “squeezing the air flow path” means that the cross-sectional area of the air flow path 56 (shaded area) in FIG. 17 showing the cross section along the line AA in FIG. The cross-sectional area of the air flow path 56 (the area | region which has shaded) in FIG. 18 which shows the cross section along a line is narrow.

  As shown in FIG. 19, the shape of the air flow path 56 can be various as long as the above conditions are satisfied, and the introduction angle θ of the airflow 55 and the opening width D of the restricting portion 54 are droplets. The optimum form to prevent coalescence (merging) is adopted.

Accordingly, as shown in FIG. 19, when the droplets 31 of the toner composition liquid 10 are discharged from the plurality of nozzles 115 of the droplet ejection unit 102, the discharged liquid droplets 31 are throttled by the throttle portion 54. As a result, the air flow 55B flows at a relatively higher speed than the initial velocity of the droplets 31 and the intervals between the sequentially ejected droplets 31 are widened so that the ejected droplets 31 are united (combined). Thus, the toner can be manufactured stably.
In this case, the velocity of the air flow 55 generated from the air flow path 56 is higher than the initial velocity of the droplet 31 discharged from the throttle portion 54, so that the droplet interval is extended even at a high frequency, and the collision of the droplets is prevented. It becomes possible to prevent.

Next, FIGS. 20 to 27 show an example in which a vibrator 211 as a displacement applying unit is attached to the nozzle plate 210. 20 to 27, a laminated body 211 represents a vibrator, and a laminated body 212 represents an elastic body.
As the vibrator 211, for example, a piezoelectric ceramic element mainly composed of bulk type lead zirconate titanate and barium titanate is used.
As the elastic body 212, for example, a silicone rubber material 5 mm square and a thickness (t) = 2 mm are used.
20 to 23, the vibrator 211 is attached to the side surface of the nozzle plate 210 so as to vibrate in the horizontal direction.
24 to 27 show examples in which the nozzle plate 210 is arranged on the back surface portion and has an angle with respect to the ejection direction. As a result, the droplets whose ejection direction has been changed from the nozzles are spread three-dimensionally in the space in front of the nozzle plate (see FIG. 28), and a sufficient droplet interval can be secured. Thereafter, the discharged droplets are placed in an air stream and dried and solidified.

Next, returning to FIG. 1, the particle forming unit 3 that solidifies the droplets 31 of the toner composition liquid 10 to form the toner T will be described.
Here, as described above, since the toner composition liquid 10 is a solution or dispersion liquid in which a toner composition containing at least a resin and a colorant is dissolved or dispersed in a solvent, the droplets 31 are dried and solidified. As a result, the toner T is formed.
That is, in this embodiment, the particle forming unit 3 is a solvent removing unit that forms the toner T by drying and removing the solvent of the droplets 31 (hereinafter, the particle forming unit 3 is referred to as “solvent removing unit” or Also called “drying section”).

Specifically, the particle forming unit 3 causes the droplet 31 emitted from the nozzle 15 of the droplet ejecting unit 2 to be dried by a dry gas (dry gas) 35 that flows in the same direction as the flying direction of the droplet 31. By transporting, the solvent of the droplets 31 is removed, and the toner T is formed.
The dry gas 35 means a gas having a dew point temperature of −10 ° C. or lower under atmospheric pressure.
The dry gas 35 may be any gas that can dry the droplets 31. For example, air, nitrogen, or the like can be used.

Next, the toner collecting unit 4 as a toner collecting unit that collects the toner T formed by the particle forming unit 3 will be described.
The toner collecting unit 4 is provided continuously to the particle forming unit 3 on the downstream side in the particle flight direction of the particle forming unit 3, and the opening diameter is gradually reduced from the inlet side (liquid ejecting unit 2 side) to the outlet side. It has the taper surface 41 which does.
Then, for example, an air flow 42 that is a vortex flow toward the downstream side is generated in the toner collection unit 4 by suction from the toner collection unit 4 using a suction pump (not shown), and the toner T is collected by the air flow 42. I try to gather.
In this way, the centrifugal force is generated by the eddy current (air flow 42) to collect the toner T, so that the toner T can be reliably collected and transferred to the toner storage unit 6 on the downstream side.

In addition, the inlet portion of the toner collecting unit 4 is provided with a discharging unit 43 that temporarily neutralizes (discharges) the charge of the toner T formed by the particle forming unit 3.
The neutralization unit 43 uses a soft X-ray irradiation device 43A that irradiates the toner T with soft X-rays. However, as the neutralization unit 43, a plasma irradiation unit that performs plasma irradiation on the toner T can also be used. .

The toner T collected by the toner collecting unit 4 is transferred and stored in the toner storage unit 6 through the tube 5 as it is by a vortex (air flow 42).
In this case, when the toner collecting portion 4, the tube 5, and the toner storage portion 6 are formed of a conductive material, it is preferable that these are grounded (connected to ground). In addition, it is preferable that this manufacturing apparatus is an explosion-proof specification as a whole.
Further, the toner T may be pumped from the toner collection unit 4 toward the toner storage unit 6, or the toner T may be sucked from the toner storage unit 6 side.

Next, the toner manufacturing method of the present invention by the toner manufacturing apparatus 1 configured as described above will be described.
The droplet ejecting unit will be described with reference to an example of the droplet ejecting unit 2 using the annular vibrating means 17 in FIGS.
As described above, the electromechanical conversion of the droplet discharge means 11 is performed in the state where the toner composition liquid 10 in which the toner composition containing at least a resin and a colorant is dispersed or dissolved is supplied to the storage portion 12 of the droplet ejection unit 2. By applying a drive signal of a required drive frequency to the means 17, bending vibration is generated in the electromechanical conversion means 17, and the thin film 16 is periodically vibrated by the bending vibration of the electromechanical conversion means 17, and this thin film 16, the toner composition liquid 10 in the storage unit 12 is periodically formed into droplets from a plurality of nozzles 15 and discharged as droplets 31 into the particle forming unit 3 (see FIG. 1) as a solvent removal unit.

Then, the droplet 31 discharged into the particle forming unit 3 is transported by the dry gas 35 flowing in the same direction as the flying direction of the droplet 31 in the particle forming unit 3, whereby the solvent is removed and the toner T Is formed.
The toner T formed in the particle forming unit 3 is collected by the air flow 42 in the toner collecting unit 4 on the downstream side, sent to the toner storing unit 6 via the tube 5 and stored.

As described above, since the plurality of nozzles 15 are provided in the droplet discharge means 11 of the droplet ejection unit 2, a large number of droplets 31 of the toner composition liquid that have been formed into a plurality of droplets are simultaneously released. Therefore, the toner production efficiency is dramatically improved. Further, in the present invention, by applying a displacement other than the vibration at the time of droplet formation to the nozzle plate, the nozzle surface rotates in the vertical direction in the ejection direction with vibration or inclination. Unlikely, it is possible to ensure the interval between the front and rear droplets.
In addition, as described above, the droplet forming unit 11 has a configuration in which the annular electromechanical conversion unit 17 is arranged around the deformable region 16A of the thin film 16 having the plurality of nozzles 15 facing the storage unit 12. Therefore, a large displacement of the thin film 16 can be obtained, and by disposing a plurality of nozzles 15 in a region where this large displacement can be obtained, many droplets 31 can be stabilized at a time without causing clogging of the nozzles 15. Therefore, stable and efficient toner production becomes possible.
Furthermore, it has been confirmed that a toner having a monodispersibility with an unprecedented particle size can be obtained.

  In this embodiment, the toner composition liquid 10 is a solution obtained by dissolving or dispersing a toner composition containing at least a resin and a colorant in a solvent. The organic solvent contained is evaporated to a dry gas in a solvent removing unit (particle forming means) and contracted and solidified by drying to form a toner. However, the present invention is not limited to this.

For example, the toner composition may be melted and liquefied in a heated storage portion to form a toner composition liquid, which is discharged and discharged as droplets, and then the droplets are cooled and solidified to form toner.
Alternatively, a toner composition liquid containing a thermosetting substance may be used and discharged as droplets, and then heated to be cured and solidified to form a toner.

<Toner>
The toner of the present invention is a toner manufactured by a toner manufacturing method using the above-described toner manufacturing apparatus, and thus a toner having a monodispersed particle size distribution can be obtained.

The toner has a weight average particle diameter of preferably 1 μm to 20 μm, and more preferably 2 μm to 6 μm.
The particle size distribution (weight average particle diameter / number average particle diameter) of the toner is preferably 1.00 to 1.15, and more preferably 1.00 to 1.05.
Here, the weight average particle size and particle size distribution (weight average particle size / number average particle size) of the toner can be measured by, for example, a laser diffraction type particle size distribution measuring apparatus (SIMAZU-SALD-2200, manufactured by Shimadzu Corporation). it can.

The toner manufactured by the toner manufacturing method of the present invention can be easily re-dispersed, that is, floated in an air stream by electrostatic repulsion effect.
For this reason, the toner can be prepared and transported to the development area without using the transport means used in the conventional electrophotographic system.
That is, even a weak air current has sufficient transportability, and the toner can be transported to the development area with a simple air pump and developed as it is.
Development is so-called power cloud development, and since there is no disturbance in image formation due to airflow, extremely good electrostatic latent image development can be performed.
Further, the toner of the present invention can be applied without any problem even if it is a conventional development system.
At this time, members such as a carrier and a developing sleeve are simply used as a toner conveying unit, and there is no need to consider a frictional charging mechanism that has been conventionally shared in function.
Accordingly, since the degree of freedom of the material is greatly increased, the durability can be greatly improved, an inexpensive material can be used, and the cost can be reduced.

Next, the toner material (toner composition liquid) that can be used in the present invention will be described.
First, a toner composition liquid in which the toner composition is dispersed and dissolved in a solvent will be described.

As the toner material, the same material as the conventional electrophotographic toner can be used. That is, a toner binder such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin is dissolved in various organic solvents, a colorant is dispersed, and a release agent is dispersed or dissolved. The target toner can be produced by drying and solidifying into fine droplets by the toner production method.
It is also possible to obtain the desired toner by drying and solidifying the liquid obtained by dissolving or dispersing the kneaded material obtained by hot-melt kneading the toner material into various solvents once into fine droplets by the toner production method. It is.

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

〔resin〕
Examples of the resin include at least a binder resin.
The binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include vinyl polymers such as styrene monomers, acrylic monomers, methacrylic monomers, and the like. Copolymer or polyester polymer, 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, etc. are mentioned.

  Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and pn-amyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, Examples thereof include styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof.

  Examples of the acrylic monomer include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic acid 2 -Ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, and the like.

  Examples of the methacrylic monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid 2 -Ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

The following (1) to (18) may be mentioned as other monomers that form the vinyl polymer or copolymer.
(1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; (8) vinyl naphthalenes; (9) acrylonitrile, methacrylate. Ronitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic acid anhydride and alkenyl succinic acid anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid, etc. Unsaturated (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 α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, these acid anhydrides or monoesters thereof; (17) 2- Acrylic acid or methacrylic acid hydroxyalkyl esters such as hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy- Monomers having a hydroxy group such as 1-methylhexyl) styrene.

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

Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond.
Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, or those obtained by replacing the acrylate of these compounds with methacrylate, Examples include allyl cyanurate and triallyl trimellitate.

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

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

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

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

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

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

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

  When the binder resin is a polyester resin, the toner has fixability and offset resistance because at least one peak exists in the molecular weight range of 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component. In addition, as a THF soluble component, a binder resin in which a component having a molecular weight of 100,000 or less is 60% to 100% is preferable, and at least one peak is present in a region having a molecular weight of 5,000 to 20,000. The binder resin present is more preferred.

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

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

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

  Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin has 0.1-50 mgKOH / g is preferable.

In the present invention, the acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation conforms to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 ml beaker, and 150 ml of a mixed solution of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The amount of KOH solution used at this time is Sml, and a blank is measured at the same time. The amount of KOH solution used at this time is Bml, and the following formula is used.
However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W
The toner binder resin and the composition containing the binder resin preferably have a glass transition temperature (Tg) of 35 ° C. to 80 ° C., more preferably 40 ° C. to 75 ° C., from the viewpoint of toner storage stability. preferable.
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.
On the other hand, when the glass transition temperature (Tg) exceeds 80 ° C., fixability may be lowered.

  There is no restriction | limiting in particular as a magnetic body which can be used by this invention, According to the objective, it can select suitably, For example, (1) Magnetic iron oxides, such as a magnetite, a maghemite, and a ferrite, oxidation containing other metal oxides Iron, (2) metals such as iron, cobalt, nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, An alloy with a metal such as tungsten or vanadium, (3) or a mixture thereof is used.

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 , and PbFe _12. Examples thereof include 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 triiron tetroxide and γ-iron sesquioxide are preferable.

Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used.
Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, And gallium.
Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium.
The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may be present on the surface as an oxide or hydroxide. Is preferably contained as an oxide.

The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH.
Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grain production | generation, or adding salt of each element and adjusting pH.
As the usage-amount of the said magnetic body, 10 mass parts-200 mass parts of magnetic bodies are preferable with respect to 100 mass parts of binder resin, and 20 mass parts-150 mass parts are more preferable.
The number average particle diameter of these magnetic materials is preferably 0.1 μm to 2 μm, and more preferably 0.1 μm to 0.5 μm.
The number average particle diameter can be obtained, for example, by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.

In addition, as magnetic characteristics of the magnetic material, those having a coercive force of 20 oersted to 150 oersted, saturation magnetization of 50 emu / g to 200 emu / g, and residual magnetization of 2 emu / g to 20 emu / g are applied. preferable.
The magnetic material can also be used as a colorant.

[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, Pigment Scarlet 3B, Bordeaux 5B, Tolujing 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 or a mixture thereof.

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

The colorant can also be used as a master batch combined with a resin.
As the binder resin to be kneaded together with the production of the master batch or the master batch, in addition to the modified polyester resin and unmodified polyester resin mentioned above, for example, styrene such as polystyrene, poly p-chlorostyrene, polyvinyl toluene, or the like Substitute polymer: styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer Coalescence, styrene-α-chlorme Methyl crylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid Styrene copolymers such as copolymers and styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane , Polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

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

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

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

  The dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific examples of commercially available products include “Ajisper PB821” and “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.). ), “Disperbyk-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like.

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

The mass average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene in gel permeation chromatography, and is preferably 500 to 100,000, and from the viewpoint of pigment dispersibility, 3,000 to 100 5,000 is more preferable, 5,000 to 50,000 is still more preferable, and 5,000 to 30,000 is particularly preferable.
When the mass average molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the mass average molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant increases. May decrease.

  The addition amount of the dispersant is preferably 1 part by mass to 200 parts by mass, and more preferably 5 parts by mass to 80 parts by mass with respect to 100 parts by mass of the colorant. When the addition amount is less than 1 part by mass, the dispersibility may be lowered, and when it exceeds 200 parts by mass, the chargeability may be lowered.

[Other ingredients]
<Career>
The toner of the present invention may be mixed with a carrier and used as a two-component developer.
As the carrier, ordinary carriers such as ferrite and magnetite and resin-coated carriers can be used.

  The resin-coated carrier comprises a carrier core particle and a coating material that is a resin that coats (coats) the surface of the carrier core particle.

Examples of the resin used for the covering material include styrene-acrylic resins such as styrene-acrylic acid ester copolymers and styrene-methacrylic acid ester copolymers, acrylic resins such as acrylic acid ester copolymers and methacrylic acid ester copolymers. Preferable examples include fluorine-containing resins such as resin, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, polyamide resin, polyvinyl butyral, and aminoacrylate resin.
In addition to these, resins that can be used as a coating material for a carrier such as an ionomer resin and a polyphenylene sulfide resin can be used.
These resins may be used alone or in combination of two or more.
A binder type carrier core in which magnetic powder is dispersed in a resin can also be used.

  In the resin-coated carrier, as a method for coating the surface of the carrier core with at least a resin coating agent, a method in which the resin is dissolved or suspended in a solvent and adhered to the applied carrier core, or a method in which the resin core is simply mixed in a powder state Is applicable.

  The ratio of the resin coating material to the resin-coated carrier may be appropriately determined, but is preferably 0.01% by mass to 5% by mass, and more preferably 0.1% by mass to 1% by mass with respect to the resin-coated carrier.

  Examples of use in which a magnetic material is coated with a coating agent of two or more kinds of mixtures include (1) dimethyldichlorosilane and dimethyl silicon oil (mass ratio 1: 5) with respect to 100 parts by mass of fine titanium oxide powder. Those treated with 12 parts by mass of the mixture, and (2) those treated with 20 parts by mass of a mixture of dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) with respect to 100 parts by mass of the silica fine powder.

  Among the resins, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, and a silicone resin are preferably used, and a silicone resin is particularly preferable. Examples of the mixture of the fluorine-containing resin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, a mixture of polytetrafluoroethylene and a styrene-methyl methacrylate copolymer, Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10), styrene-2-ethylhexyl acrylate copolymer (copolymer mass ratio 10:90 to 90:10) and styrene Examples thereof include a mixture with 2-ethylhexyl acrylate-methyl methacrylate copolymer (copolymer mass ratio 20 to 60: 5 to 30:10:50).

Examples of the silicone resin include modified silicone resins produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with a silicone resin.
As the magnetic material for the carrier core, for example, oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof can be used.

  Examples of elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, vanadium, etc. Is mentioned. Among these, copper-zinc-iron ferrites mainly composed of copper, zinc and iron components, and manganese-magnesium-iron ferrites mainly composed of manganese, magnesium and iron components are particularly preferable.

The resistance value of the carrier is preferably 10 ⁶ Ω · cm to 10 ¹⁰ Ω · cm by adjusting the degree of unevenness on the surface of the carrier and the amount of resin to be coated.
The particle size of the carrier is preferably 4 μm to 200 μm, more preferably 10 μm to 150 μm, and still more preferably 20 μm to 100 μm.
In particular, the resin-coated carrier preferably has a 50% particle size of 20 μm to 70 μm.

  In the two-component developer, the toner of the present invention is preferably used in an amount of 1 part by mass to 200 parts by mass with respect to 100 parts by mass of the carrier, and 2 parts by mass to 50 parts by mass of the toner with respect to 100 parts by mass of the carrier. More preferably it is used.

<Wax>
In the toner of the present invention, a wax may be contained together with the binder resin and the colorant.
The wax is not particularly limited and can be appropriately selected from commonly used ones such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, and sazol wax. Oxides of aliphatic hydrocarbon waxes such as aliphatic hydrocarbon waxes, polyethylene oxide waxes or block copolymers thereof, plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax, beeswax, lanolin Animal waxes such as whale wax, mineral waxes such as ozokerite, ceresin and petrolatum, waxes mainly composed of fatty acid esters such as montanic ester wax and castor wax, and fatty acid esters such as deoxidized carnauba wax. Part Those deoxygenated all are and the like.

  Examples of the wax include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, and linear alkyl carboxylic acids having a linear alkyl group, and unsaturated acids such as prandidic acid, eleostearic acid, and valinalic acid. Fatty acids, stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnaupyl alcohol, seryl alcohol, mesyl alcohol, saturated alcohols such as long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acid amides, lauric acid Fatty acid amide such as amide, methylene biscapric acid amide, ethylene bislauric acid amide, saturated fatty acid bisamide such as hexamethylene bis stearic acid amide, ethylene bis oleic acid amide, hexamethylene bis oleic acid Amides, unsaturated fatty acid amides such as N, N′-dioleyl adipate amide, N, N′-dioleyl sepasin amide, m-xylene bis stearamide, N, N-distearyl isophthalamide, etc. Aromatic bisamides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate, waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid, Examples thereof include partial ester compounds of fatty acids such as behenic acid monoglyceride and polyhydric alcohols, and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  More preferred examples include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, and polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure. Polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method, age method, etc. Hydrocarbon wax synthesized by the above, a synthetic wax having a compound having one carbon atom as a monomer, a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group, a hydrocarbon wax and a hydrocarbon group having a functional group A mixture of box, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with vinyl monomers such as maleic anhydride.

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

The melting point of the wax is preferably 70 ° C. to 140 ° C., and more preferably 70 ° C. to 120 ° C., in order to balance the fixability and the offset resistance.
When the melting point is less than 70 ° C., the blocking resistance may be lowered, and when it exceeds 140 ° C., the anti-offset effect may be hardly exhibited.
Further, by using two or more different types of waxes in combination, the plasticizing action and the releasing action which are the actions of the wax can be expressed simultaneously.

Examples of the types of wax having a plasticizing action include waxes having a low melting point, those having a branch on the molecular structure, and those having a polar group.
Examples of the wax having a releasing action include a wax having a high melting point, and the molecular structure includes a linear structure and a non-polar one having no functional group.
Examples of use include a combination of two or more different waxes having a melting point difference of 10 ° C. to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.

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

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

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

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

  In the present invention, the peak top temperature of the endothermic peak of the wax measured by DSC is defined as the melting point of the wax.

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

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

Examples of the fluidity improver include, for example, carbon black, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder unoxidized titanium, Fine powder non-alumina, treated silica obtained by subjecting them to surface treatment with a silane coupling agent, titanium coupling agent or silicone oil, treated titanium oxide, treated alumina, and the like can be mentioned.
Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.

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

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

  Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include AEROSIL (manufactured by Nippon Aerosil Co., Ltd., trade names, the same shall apply hereinafter) -130, -300, -380, -TT600, -MOX170,- MOX80, -COK84: Ca-O-SiL (trade name, manufactured by CABOT) -M-5, -MS-7, -MS-75, -HS-5, -EH-5, Wacker HDK (WACKER-CHEMIE -N20, -V15, -N20E, -T30, -T40: D-CFine Si1ica (manufactured by Dow Corning, trade name): Franco1 (manufactured by Franci1, trade name), and the like.

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

Examples of organosilicon compounds include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, and dimethylvinylchlorosilane. , Divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethyl chloride Losilane, triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, Examples include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to Si.
Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

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

The specific surface area by measuring nitrogen adsorption by the BET method, preferably at least ^{30m 2 / g, 60m 2 /} g~400m 2 / g is more preferable.
The surface-treated fine powder, preferably at least ^{20m 2 / g, 40~300m 2 /} g is more preferable.

  The application amount of these fine powders is preferably 0.03 to 8 parts by mass with respect to 100 parts by mass of the toner.

In the toner according to the present invention, as other additives, protection of the electrostatic latent image carrier / carrier, improvement of cleaning properties, adjustment of thermal characteristics / electrical characteristics / physical characteristics, resistance adjustment, softening point adjustment, fixing rate For the purpose of improvement, various metal soaps, fluorosurfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, and inorganic such as titanium oxide, aluminum oxide, alumina A fine powder or the like can be added as necessary.
These inorganic fine powders may be hydrophobized as necessary.
Also, lubricants such as polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, strontium titanate, anti-caking agents, and white and black fine particles having a polarity opposite to that of the toner. A small amount can also be used as a developability improver.
These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control and the like. It is also preferable to treat with a treating agent or various treating agents.

In preparing the developer, inorganic fine particles such as the hydrophobic silica fine powder mentioned above may be added and mixed in order to improve the fluidity, storage stability, developability and transferability of the developer.
For mixing external additives, a general powder mixer can be appropriately selected and used. However, it is preferable to equip a jacket or the like to adjust the internal temperature.
In order to change the history of the load applied to the external additive, the external additive may be added in the middle or gradually, or the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. The load may then be given a relatively weak load and vice versa.

  Examples of the mixer that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like.

  The method for further adjusting the shape of the obtained toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner material composed of a binder resin and a colorant is melt-kneaded and then finely pulverized. The material is mechanically adjusted using a hybridizer, mechano-fusion, etc., or the so-called spray drying method is used to dissolve and disperse the toner material in a solvent in which the toner binder is soluble, and then removed using a spray drying device. Examples thereof include a method of obtaining a spherical toner by forming a solvent, and a method of forming a spherical toner by heating in an aqueous medium.

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

The specific surface area by the BET method ^is preferably 20m ² / g~500m 2 / g.

  The proportion of the inorganic fine particles used is preferably 0.01% by mass to 5% by mass of the toner, and more preferably 0.01% by mass to 2.0% by mass.

  In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation systems such as silicone, benzoguanamine, and nylon, thermosetting resins And polymer particles.

  Such an external additive can be made hydrophobic by the surface treatment agent and prevent deterioration of the external additive itself even under high humidity.

  Examples of the surface treatment agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, a modified silicone oil, Etc. are preferable.

The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm.
As the specific surface area by BET method is ^preferably 20m ² / g~500m 2 / g. The use ratio of the inorganic fine particles is preferably 0.01% by mass to 5% by mass of the toner, and more preferably 0.01% by mass to 2.0% by mass.

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

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

Next, the toner composition liquid used when cooling and solidifying by the particle forming means (particle forming step) will be described.
As a toner composition obtained by heating and melting and cooling and solidifying, it is preferable to use as a main component a material from which a low-viscosity melt can be obtained as follows.

  Specifically, monoamide, bisamide, tetraamide, polyamide, ester amide, polyester, polyvinyl acetate, acrylic acid and methacrylic acid polymers, styrene polymers, ethylene vinyl acetate copolymer, polyketone, silicone, coumarone, It can be composed of one to many components selected from fatty acid esters, triglycerides, natural resins, natural waxes, synthetic waxes and the like.

  Examples of the polyamide resin include, for example, Versamide 711, Versamide 725, Versamide 930, Versamide 940, Versalon 1117, Versalon 1138, Versalon 1300 (manufactured by Henkel), Tormide 391, Tormide 393, Tormide 394, Tormide 395, Tomide 397, tomide 509, tomide 535, tomide 558, tomide 560, tomide 1310, tomide 1396, tomide 90, tomide 92 (above, manufactured by Fuji Kasei Co., Ltd.), polyester as KTR2150 (above, manufactured by Kao Corporation), polyacetic acid As vinyl, AC401, AC540, AC580 (above, manufactured by Allied Chemical Co.), as silicone, silicone SH6018 (manufactured by Toray Silicone Co., Ltd.), silico Down KR215, silicone KR216, silicone KR220 (manufactured by Shin-Etsu Silicone Co., Ltd.), as coumarone, Esukuron G-90 (manufactured by Nippon Steel Chemical Co., Ltd.), and the like.

  Examples of fatty acids include acids selected from stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, and melissic acid, or esters thereof. These may be used individually by 1 type and may use 2 or more types together.

  Examples of fatty acid amides include lauric acid amide, stearic acid amide, oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid ester amide, palmitic acid amide, behenic acid amide, and brassicic acid amide. Examples of the N-substituted fatty acid amide include N, N′-2-hydroxystearic acid amide, N, N′-ethylenebisoleic acid amide, N, N′-xylene bisstearic acid amide, stearic acid monomethylolamide, N -Oleyl stearic acid amide, N-stearyl stearic acid amide, N-oleyl palmitic acid amide, N-stearyl erucic acid amide, N, N'-dioleyl adipic acid amide, N, N'-dioleyl sebacic acid amide, N , N′-distearylisophthalic acid amide, 2-stearamide ethyl stearate and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the N-substituted fatty acid amide include N, N′-2-hydroxystearic acid amide, N, N′-ethylenebisoleic acid amide, N, N′-xylene bisstearic acid amide, stearic acid monomethylolamide, N -Oleyl stearamide, N-stearyl stearamide, N-oleyl palmitate, N-stearyl erucamide, N, N'-dioleyl adipate, N, N'-dioleyl sebacamide, N , N′-distearylisophthalic acid amide and the like. These may be used individually by 1 type and may use 2 or more types together.

  As fatty acid ester, monohydric or polyhydric alcohol fatty acid ester is preferable. Examples include sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, polyethylene glycol monostearate, polyethylene glycol distearate, propylene glycol monostearate, ethylene glycol distearate, and the like.

  Specifically, rheodol SP-S10, rheodol SP-S30, rheodol SA10, emazole P-10, emazole S-10, emazole S-20, emazole B, rheodol super SP-S10, emmanon 3299, emmanon 3299, exepar PE-MS (both manufactured by Kao Corporation)

More preferred are fatty acid esters of glycerin such as stearic acid monoglyceride, palmitic acid monoglyceride, oleic acid monoglyceride, behenic acid monoglyceride and the like.
Specifically, rheodol MS-50, rheodol MS-60, rheodol MS-165, rheodol MO-60, Exepal G-MB (above, manufactured by Kao Corporation), deodorized and refined carnauba wax no. 1. Refined candelilla wax No. 1 1 (manufactured by Noda Wax Co., Ltd.), synchro wax ERL-C, synchro wax HR-C (manufactured by Croda), KF2 (manufactured by Kawaken Fine Chemical Co., Ltd.) can be used.
Further, as the special ester wax, for example, EXCEPARL DS-C2 (manufactured by Kao Corporation), Kawaslip-L, Kawaslip-R (above, Kawaken Fine Chemical Co., Ltd.) and the like are selected.
Further, higher alcohol esters of higher fatty acids such as myricyl serotate, ceryl serotate, ceryl montanate, myricyl palmitate, myricyl stearate, cetyl palmitate, cetyl stearate, and the like can be mentioned.

Here, alkyl groups are present in both fatty acids and alcohols.
At least one selected from these fatty acid esters, or a mixture of two or more can be used.
These fatty acid esters have a low melt viscosity and stable fluidity when the ink is melted. In addition, the fatty acid esters are more flexible and stronger in surface protection than carbon-carbon bonds. Also endure.
Preferred fatty acid esters have a penetration of more than 1 and are easy to pressurize. Furthermore, the viscosity when jetting is less than 20 mPa · s is suitable.

Polyamides are generally roughly classified into aromatic polyamides and dimer acid polyamides. In the present invention, dimer (dimer) acid-based polyamides are particularly preferable.
Furthermore, it is optimal that the base acid is oleic acid, linoleic acid, linolenic acid or eleostearic acid.
Specifically, Macromelt 6030, Macromelt 6065, Macromelt 6071, Macromelt 6212, Macromelt 6217, Macromelt 6224, Macromelt 6228, Macromelt 238, Macro6lt 6239, Macro6lt 6239, Macro6lt , DPX 335-11, DPX 830, DPX 850, DPX 025, DPX 927, DPX 1160, DPX 1163, DPX 1175, DPX 1196, DPX 1358 (above, made by Henkel Hakusui), SYLVAMIDE-5 (made by Arizona Chemical) , UNIREZ 2224, UNIREZ 970 (manufactured by Union Camp Corporation), and the like.

  Examples of the glyceride include at least one or two selected from rosin ester, lanolin ester, hydrogenated castor oil, partially hydrogenated castor oil, extremely hardened oil of soybean oil, extremely hardened oil of rapeseed oil, extremely hardened vegetable oil, and the like. The above can be mixed and used.

  Examples of waxes include petroleum waxes such as paraffin wax and microcrystalline wax, plant waxes represented by candelilla wax and carnauba wax, polyethylene wax, hardened castor oil, higher fatty acids such as stearic acid and behenic acid, and higher alcohols. , Ketones such as stearone and laurone, particularly fatty acid ester amides, saturated or unsaturated fatty acid amides, fatty acid esters and the like.

  Furthermore, as long as it is compatible with other ink components such as fatty acid, fatty acid amide, glyceride and wax, it can be used in any conceivable combination. The colorant and the like are the same as described above.

  Various known crushing or dispersing apparatuses can be used for mixing and dispersing the components without any particular limitation. These include categories such as high-speed rotary mills, roller mills, container drive media mills, media agitation mills, jet mills, etc., or rotary cylindrical mills, vibratory ball mills, centrifugal ball mills, media agitation mills, and colloid mills. For example, cutter mill, cage mill, hammer mill, centrifugal classification mill, stamp mill, fret mill, centrifugal mill, ball bearing mill, ring roll mill, table mill, rolling ball mill, tube mill, conical mill, tricon mill, pot mill, cascade mill, centrifugal Fluidization mill, annular mill, high speed disperser, impeller disperser, gate mixer, bead mill, sand mill, pearl mill, cobra mill, pin mill, morinex mill, stirring mill, universal mill, century mill, pressure mill, Jitter mill, 2-roll extruder, 2-roll mill, 3-roll mill, niche mill, kneader, mixer, stone mill, caddy mill, planetary mill, high swing mill, annular mill, stirring tank type stirring mill, vertical flow pipe stirring mill, ball mill , Paddle mixer, tower mill, attritor, sentry mill, sand grinder, glen mill, attrition mill, planetary mill, vibration mill, flow jet mixer, thrasher mill, peg mill, micro full dither, clear mix, rhino mill, homogenizer, pin bead mill, A horizontal bead mill, a pin mill, a majack mill, etc. are mentioned.

  The toner composition mixed, pulverized, and dispersed by the pulverization or dispersion apparatus is introduced into the storage unit 12 while maintaining the molten state, and discharged from the nozzle 15 of the droplet forming means 11 to form droplets. Alternatively, the toner composition liquid obtained by the pulverization or dispersion apparatus is once cooled, solidified, coarsely pulverized, and stored, and the coarsely pulverized product is introduced into the storage unit 12 and heated, melted, and then formed into droplets. A droplet may be formed by discharging from the nozzle 15 of the means 11.

Next, a description will be given of a toner composition liquid in the case where a toner composition liquid containing a radiation curable substance is made into particles and irradiated with light to undergo a curing reaction to form fine particles.
Here, as the radiation curable substance, generally known as a radiation sensitive resin or a radiation curable resin, a polyisoprene, a polybutadiene, a poly (meth) acrylate ester of polyether, a cinnamon bark of polyvinyl alcohol. And acid esters, novolak resins, polyglycidyl methacrylate, chlorinated polymethylstyrene, and the like.

These radiation curable substances are diluted with a solvent or a polymerizable monomer, and a radiation crosslinking agent or a radiation polymerization initiator is added thereto.
Examples of the polymerizable monomer include vinyl aromatic monomers such as styrene, α-methylstyrene, vinyltoluene, chlorostyrene, and divinylbenzene; (meth) acrylic acid, methyl (meth) acrylate, (meth) Acrylic monomers such as n-butyl acrylate, hydroxyethyl (meth) acrylate, ethylene glycol di (meth) acrylate and (meth) acrylonitrile; vinyl ester monomers such as vinyl formate and vinyl acetate; Examples thereof include vinyl halide monomers such as vinyl chloride and vinylidene chloride; diallyl phthalate, triallyl cyanurate, and the like.

  These polymerizable monomers may be used alone or in combination of two or more kinds, and contain 0.05 part by weight to 3 parts by weight of styrene, (meth) acrylic acid ester, and divinylbenzene. This is preferable because the offset phenomenon can be prevented while maintaining the property.

Examples of the radiation crosslinking agent or radiation polymerization initiator include azide compounds such as aromatic azide and trichloromethyltriazide, silver halide, bisimidazole derivatives, cyanine dyes, ketocoumarin dyes, and the like.
An azo radical polymerization initiator such as azobisisobutyronitrile and azobisvaleronitrile can also be used.

Further, the wavelength of light for curing the droplet 31 of the toner composition liquid containing the radiation curable substance while floating is preferably from ultraviolet to 480 nm, more preferably from 250 nm to 410 nm, and a high pressure or low pressure mercury lamp is used as the light source. Can do.
The energy required for the curing is preferably several mJ / cm ² to several J / cm ² .

  Examples of the present invention will be described below, but the present invention is not limited to these examples. This embodiment is an example in which the “particle production apparatus” of the present invention is used as a “toner production apparatus”, and toner production performed using the “toner production apparatus” Corresponds to “Toner Production Method”.

Example 1
-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
Carbon black (Regal 400, manufactured by Cabot) 17 parts by mass, pigment dispersant (Ajisper PB821, Ajinomoto Fine Techno Co., Ltd.) 3 parts by mass, 80 parts by mass of ethyl acetate, using a mixer having stirring blades, primary dispersion I let you.
The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion in which aggregates having a particle size of 5 μm or more were completely removed.

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

-Preparation of toner composition liquid-
Next, a toner composition liquid having the following composition was prepared.
[Composition of toner composition liquid]
100 parts by weight of polyester resin as a binder resin, 30 parts by weight of the colorant dispersion, 30 parts by weight of the wax dispersion, and 840 parts by weight of ethyl acetate are stirred for 10 minutes using a mixer having stirring blades. , Uniformly dispersed.
The pigment and wax particles did not aggregate due to shock due to solvent dilution.

-Preparation of toner-
The obtained toner composition liquid was supplied to the droplet jetting unit 102 using the horn-type vibrator of FIG. 11 in the toner manufacturing apparatus of FIG.
A thin film 116 having a plurality of nozzles 115 having a diameter of 8.0 μm was produced by processing by electroforming.
The nozzles 115 were formed in a rectangular (rectangular) range with a length of 120 mm and a width of 5 mm of the thin film 116 so that the distance between the nozzles 115 was 100 μm.
In this embodiment, as shown in FIG. 20, four ultrasonic cleaning bulk vibrators 211 (resonance frequency 28 kHz) are attached to the side surface of the nozzle plate 210, the vibration frequency is 28 kHz, and the amplitude is about 10 μm.

  In the air flow forming means 50, the structure described in FIG. 16 is used, nitrogen is used as the gas, the pressure at the air flow inlet 57 to the air flow path forming member 53 as the air flow distribution forming means is 5 kPa, and the introduction angle θ of the air flow 55 is The aperture width D of the throttle part 54 was set to 10 mm at 135 degrees.

After preparing the toner composition liquid, the liquid droplets were discharged under the following toner production conditions, and the liquid droplets were dried and solidified to produce a toner.
[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.154 g / cm ³
・ Dry air flow rate: Dry nitrogen 30.0L / min in the apparatus ・ Dry inlet temperature: 60 ° C
・ Drying outlet temperature: 45 ℃
・ Dew point temperature: -20 ℃
・ Vibration signal waveform: 100 kHz
The vibration signal waveform is a waveform of a drive signal given to the vibration generating means 121.

  The dried and solidified toner was collected by suction with a filter having 1 μm pores to obtain a toner. Note that adhesion of the toner composition liquid to the thin film 116 was not observed even after continuous operation for 2 hours.

  Next, FIG. 29 shows the result of measuring the discharged droplets with a laser droplet observation system (LaVision, manufactured by LaVision GMBH). The observation position is sampled 100 times at a position of about 2 mm from the nozzle plate. From the results of FIG. 29, it was found that a monodisperse particle size distribution was exhibited.

(Example 2)
In Example 1, as shown in FIG. 21, two ultrasonic cleaning bulk vibrators 211 (resonance frequency 28 kHz) and two elastic bodies (bulk type silicone rubber 5 mm square, thickness (on the side surface of the nozzle plate 210) A toner was prepared in the same manner as in Example 1 except that t) = 2 mm) 212 was attached.

(Example 3)
In Example 1, as shown in FIG. 24, on the upper surface of the nozzle plate 210, one ultrasonic cleaning bulk vibrator 211 (resonance frequency 28 kHz) and one elastic body (bulk type silicone rubber 5 mm square, thickness ( t) = 2 mm) A toner was prepared in the same manner as in Example 1 except that 212 was attached.

Example 4
In Example 1, as shown in FIG. 25, toner was prepared in the same manner as in Example 1 except that two ultrasonic cleaning bulk vibrators 211 (resonance frequency 28 kHz) were attached to the upper surface of the nozzle plate 210. Produced.

(Example 5)
In Example 1, as shown in FIG. 26, the toner was prepared in the same manner as in Example 1 except that four ultrasonic cleaning bulk vibrators 211 (resonance frequency 28 kHz) were attached to the upper surface of the nozzle plate 210. Produced.

(Example 6)
In Example 1, as shown in FIG. 27, on the upper surface of the nozzle plate 210, two ultrasonic cleaning bulk vibrators 211 (resonance frequency 28 kHz) and two elastic bodies (bulk type silicone rubber 5 mm square, thickness ( A toner was prepared in the same manner as in Example 1 except that t) = 2 mm) 212 was attached.

(Comparative Example 1)
In Example 1, a toner was produced in the same manner as in Example 1 except that the ultrasonic cleaning bulk vibrator 211 was not attached to the nozzle plate 210.
Next, FIG. 30 shows the results of measuring the discharged droplets with a laser droplet observation system (LaVision, manufactured by LaVision GMBH). From the results of FIG. 30, it was found that the particles contained particles that were clearly seen to be united.

  Next, the produced toners of Examples 1 to 6 and Comparative Example 1 were evaluated for the weight average particle size (D4) and particle size distribution (D4 / Dn) of the toner as follows. The results are shown in Table 1.

<Toner Weight Average Particle Size (D4) and Particle Size Distribution (D4 / Dn)>
The weight average particle diameter (D4) and particle size distribution (D4 / Dn) of the toner were measured using a flow type particle image analyzer FPIA-2000 manufactured by Toa Medical Electronics Co., Ltd.
The measurement is performed by removing fine dust through a filter. As a result, in 10 ml of water having 10 or less particles having a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) in 10 ⁻³ cm ³ of water. Add a few drops of nonionic surfactant (Contaminone N, manufactured by Wako Pure Chemical Industries, Ltd.), add 5 mg of the sample to be measured, and condition of 20 kHz, 50 W / 10 cm ³ with UH-50 manufactured by STM in for 1 minute dispersion treatment, further, the sample dispersion particle concentration of the measurement sample subjected to distributed processing 4000-8000 pieces ^{/ 10} -3 cm ³ (as the target particles measuring circle equivalent diameter range) of the total of 5 minutes Is used to measure the particle size distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm.
The sample dispersion is passed through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: 200 μm). In order to form an optical path that passes across the thickness of the flow cell, the strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area was calculated as the equivalent circle diameter.
In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 μm to 400 μm into 226 channels (divided into 30 channels for one octave). In actual measurement, particles are measured in the range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.

From the results in Table 1, the toner production method of the present invention and the toner produced thereby can produce the toner efficiently. In addition, since the particles have unprecedented monodispersibility, many of the characteristic values required for toners, such as fluidity and chargeability, have a range of variation due to particles seen in previous production methods. It can be used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing or the like, which has no or very little.
Specifically, there is no fluctuation range due to particle dispersion seen in the conventional production methods for pulverized toners and chemical toners, or even extremely small fluctuations that are almost negligible. Has characteristics.
The realization of these characteristics can be said to be a characteristic that can be obtained only by the present invention. However, the realization of this characteristic makes it possible to form an image almost faithful to the latent image formed on the photosensitive member.
In addition, the same feature makes it possible to maintain the effect over a long period of time. In other words, by achieving uniformity of particle size distribution, uniformity of shape, and uniformity of surface condition, the mechanical stress required to reach the toner charge amount set in the electrophotographic process is very small and wasteful. This is presumably due to a dramatic increase in toner life. This makes it possible to form an image with excellent image quality over a long period of time.

  The particle production method and particle production apparatus of the present invention are capable of efficiently and stably producing particles having a monodispersibility that has never been obtained, and are particularly suitable for toner production. .

DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet jet unit 3 Particle formation part (solvent removal part)
DESCRIPTION OF SYMBOLS 4 Toner collection part 5 Tube 6 Toner collection part 7 Raw material accommodating part 8 Piping 10 Toner composition liquid 11 Drop discharge means 12 Storage part 13 Flow path member 15 Nozzle 16 Thin film 16A Deformable area 17 Electromechanical conversion means (vibration generation means )
31 droplet 35 dry gas 42 air flow (vortex)
43 Static elimination means 50 Airflow forming means 51 Gas pressurizing means 53 Airflow distribution forming means (air flow path forming means)
54 Constriction part 55 Air flow 56 Air flow path T Toner particle 102 Droplet ejection unit 111 Vibrating means 112 Reserving part 115 Nozzle 116 Thin film 121 Vibration generating means 122 Vibration amplifying means 201 Jetting head 202 Vibrator 203 Individual liquid chamber 204 Nozzle 210 Nozzle plate 211 Vibrator 212 Elastic body

JP-A-7-152202 Japanese Patent Publication No.57-201248 Japanese Patent No. 3786034 Japanese Patent No. 3786035 JP 2006-293320 A JP 2006-297325 A JP 2008-286947 A

Claims (11)

Periodic droplet forming step of vibrating at least one of a liquid chamber and a nozzle plate to which a particle composition liquid containing a resin is supplied, and periodically discharging droplets from a plurality of nozzles;
A particle forming step of solidifying droplets of the discharged particle composition liquid,
In the periodic droplet forming step, at least a displacement other than vibration during droplet formation is applied to at least the nozzle plate.   The method for producing particles according to claim 1, wherein a horizontal displacement is applied to an ejection surface in a vertical direction with respect to a droplet ejection direction.   The method for producing particles according to claim 1, wherein a displacement is applied to the ejection surface in the vertical direction with an inclination in the horizontal direction with respect to the droplet ejection direction.   The method for producing particles according to claim 1, wherein a rotational motion is applied with an inclination in a horizontal direction to an ejection surface in a vertical direction with respect to a droplet ejection direction.   The method for producing particles according to any one of claims 1 to 4, wherein an airflow that flows in a droplet ejecting direction is formed through a constricted portion corresponding to a nozzle forming region arranged downstream in the droplet ejecting direction. Periodic droplet forming means that vibrates at least one of a liquid chamber and a nozzle plate to which a particle composition liquid containing a resin is supplied, periodically drops droplets from a plurality of nozzles, and discharges them.
In a particle production apparatus having at least particle formation means for solidifying the droplets of the discharged particle composition liquid,
The apparatus for producing particles, wherein the periodic droplet forming means includes a displacement applying unit that further applies at least a displacement other than vibration during droplet formation to the nozzle plate.   The particle manufacturing apparatus according to claim 6, wherein the displacement applying unit is a vibrator.   The apparatus for producing particles according to any one of claims 6 to 7, further comprising a throttle portion corresponding to a nozzle formation region arranged on the downstream side in the droplet ejection direction. A toner production method using the particle production method according to claim 1,
A toner production method, wherein the particle composition liquid is a toner composition liquid containing at least a resin and a colorant.   A toner produced by the toner production method according to claim 9.   The toner according to claim 10, wherein the toner has a weight average particle diameter of 1 μm to 20 μm and a toner particle size distribution (weight average particle diameter / number average particle diameter) of 1.00 to 1.15.