JP4803811B2 - Toner manufacturing method, toner, and toner manufacturing apparatus - Google Patents

Description

  The present invention relates to a method for producing a toner used as a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc., a toner produced thereby, and the toner production method. The present invention relates to the toner manufacturing apparatus used.

  Developers used in electrophotography, electrostatic recording, electrostatic printing, and the like are temporarily attached to an image carrier such as an electrostatic latent image carrier on which an electrostatic charge image is formed in the development process. Then, after being transferred from the electrostatic latent image carrier to a transfer medium such as transfer paper in the transfer step, it is fixed on the paper surface in the fixing step. At that time, 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.

Conventional dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like are those obtained by melt-kneading a toner binder such as a styrene resin and a polyester resin together with a colorant and finely pulverizing them, so-called pulverized toner. 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 this, a method called volumetric shrinkage called a polymer dissolution suspension method has been studied (see Patent Document 1). In this method, a toner material is dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified and formed into droplets in an aqueous medium containing a dispersant, and then the volatile solvent is removed. Unlike the suspension polymerization method and emulsion polymerization aggregation method, this method is a versatile resin that can be used, and in particular, a polyester resin useful for a full color process that requires transparency and smoothness of the image area after fixing. It is excellent in that it can be used.

  However, since the above-described polymerization type toner is premised on the use of a dispersant in an aqueous medium, a dispersant that impairs the charging characteristics of the toner remains on the toner surface and the environmental stability is impaired. It is known that a defect occurs or a very large amount of washing water is required to remove this, and it is not always satisfactory as a manufacturing method.

  As an alternative method for producing toner, a method has been proposed in which fine droplets are formed using a piezoelectric pulse and then dried and solidified to form a toner (see Patent Document 2). Furthermore, a method has also been proposed in which fine droplets are formed by utilizing thermal expansion in the nozzle, and this is dried and solidified to form a toner (see Patent Document 3). Furthermore, a method for performing the same processing using an acoustic lens has been proposed (see Patent Document 4). However, in these methods, the number of droplets that can be ejected from one nozzle per unit time is small, and there is a problem that productivity is low, and at the same time, the spread of particle size distribution due to coalescence of droplets is unavoidable, Also in terms of monodispersity, it was not satisfactory.

In addition, a toner raw material containing a thermosetting resin or a UV curable resin is used as a dispersoid, finely dispersed in a dispersion medium, and the dispersion liquid is intermittently discharged as droplets from a nozzle. A method of stabilizing the particle formation by curing a thermosetting resin or a UV curable resin has also been proposed (see Patent Documents 5 to 9). However, these methods also have low productivity and are insufficient in terms of monodispersibility as in Patent Documents 1 to 4. Moreover, although resin is hardened after particle | grain formation, the subject regarding the fixing characteristic as mentioned above was not solved.
In the case of the granulation method described above (Patent Documents 5 to 9), it is characterized in that the vibration part directly touches the fluid. In the case of a large number of pores and one excitation part, the size of the liquid droplets ejected from the pores depends on the distance between the positions of the pores and the excitation part. It has been found that the toner particles produce different particle sizes between multiple orifices with different toner particles.

In general, toner is developed and transferred onto paper or the like, and then fixed by heating and melting using a heat roll. At that time, if the hot roll temperature is too high, there will be a problem that the toner is excessively melted and fused to the hot roll (hot offset). If the hot roll temperature is too low, the toner will not melt sufficiently and fixing will be insufficient Problem arises.
On the other hand, from the viewpoints of energy saving and device miniaturization, recent toners are required to have a higher hot offset generation temperature (hot offset resistance) and a lower fixing temperature (low temperature fixability) than conventional toners. Yes. In addition, heat storage stability is required so that the toner is not blocked during storage and at ambient temperature in the apparatus. In particular, full-color copying machines and full-color printers require glossiness and color mixing of their images, so the toner must have a lower melt viscosity and a sharp-melt polyester toner binder is used. However, since such toner tends to cause hot offset, conventionally, in a full-color device, silicone oil or the like is applied to a heat roll. However, the method of applying oil to the hot roll requires an oil tank and an oil application device, which makes the device complicated and large. In addition, it is inevitable that oil adheres to copy paper, OHP (overhead projector) film, etc., and there are problems such as writing properties with water-based ink and deterioration of color tone due to attached oil in OHP.

JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977 JP 2006-28432 A JP 2006-28433 A JP 2006-0775708 A JP 2006-077252 A JP 2006-167593 A

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention can efficiently produce a toner, and further has a single particle dispersibility with a particle size that has never been obtained so that many characteristic values required for the toner such as fluidity and charging characteristics are obtained. In developing agents for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc., which have no or very little variation due to particles as seen in conventional manufacturing methods. It is an object of the present invention to provide a toner production method to be used, a toner produced thereby, and a toner production apparatus using the toner production method.

The present inventors supply a toner composition liquid obtained by liquefying a toner composition containing at least a resin and a colorant to a storage part, and at least a part of the storage part is contacted by a vibrating unit through the storage part. While exciting the toner composition liquid, the toner composition liquid is discharged into a granulation space from a plurality of through holes provided in the storage portion, and the toner composition liquid is changed from a columnar state to a constricted state to form droplets, and the droplets In a toner obtained by a toner manufacturing method in which the toner is changed into solid particles in the granulation space, it has been found that the above problem can be solved by adding a reactive substance that increases the viscoelasticity of the resin of the toner composition to the toner. The present invention has been completed.
In the manufacturing method according to the present invention, the whole storage part having the through hole is excited by one vibration means, so that the raw material fluid discharged from the through hole provided in the storage part is vibrated equally. It is possible to generate a pressure density wave by adding 1 and more, and it is possible to simultaneously generate 100 or more droplet formation phenomena by one vibration means, thereby blocking the through-hole portion, productivity, and stability. Thus, it is possible to solve various problems in the prior art, to efficiently produce toner particles having a monodispersibility with an unprecedented particle size, and because the toner particles are excellent in monodispersibility, In many of the characteristic values required for toner, such as fluidity and charging characteristics, there is no or very little variation due to particles in the conventional production methods. It can be used as a toner for a developer for developing at an electrostatic image on the electrostatic printing and the like.

Means for solving the problems are as follows.
(1) A toner composition containing at least a polyester resin or a styrene acrylic copolymer resin and a colorant and 3,5-di-t-butyl- which is a reactive substance that increases the viscoelasticity of the resin of the toner composition The toner composition liquid obtained by liquefying iron salicylate is supplied to the storage part, and is provided in the storage part while exciting the toner composition liquid through the storage part by vibration means that contacts at least a part of the storage part. The toner composition liquid is discharged from a plurality of through-holes into a granulation space, the toner composition liquid is converted into droplets from a columnar state through a constricted state, and the droplets are changed into solid particles in the granulation space. Toner manufacturing method.
(2) Supplying a toner composition liquid obtained by liquefying a toner composition containing at least a polyester resin or a styrene acrylic copolymer resin and a colorant to the reservoir, and at least by the vibrating means in contact with a part of the reservoir While exciting the toner composition liquid through the storage section, the toner composition liquid is discharged from a plurality of through holes provided in the storage section into the granulation space, and the toner composition liquid is dropped from a columnar state through a constricted state to a droplet 3,5-di-t-butyl-salicylate iron that is a reactive substance that increases the viscoelasticity of the resin of the toner composition to solid particles obtained by converting the droplets into solid particles in the granulation space A toner manufacturing method comprising adding
(3) The toner production method as described in (1) or (2) above, wherein the toner composition liquid contains an organic solvent, and the change from droplets to solid particles is performed by solvent removal.
(4) The toner production according to any one of (1) to (3) above, wherein the through hole is a hole having an opening diameter of 1 to 40 μm perforated in a metal plate having a thickness of 5 to 50 μm. Method.
(5) An air stream is generated by flowing a dry gas in the same direction as the droplet discharge direction, and the droplets are transported in the solvent removal facility by the air stream, and the solvent in the droplets is removed during the transport. The toner manufacturing method according to any one of the above (1) to (4), wherein toner particles are formed.
(6) The method for producing a toner as described in (5) above, wherein the dry gas is either air or nitrogen gas.
(7) The method for producing a toner according to (5) or (6) above, wherein the temperature of the dry gas is 40 to 200 ° C.
(8) The solvent removal equipment has a transport path whose periphery is covered with an electrostatic curtain charged to a polarity opposite to the charge of the droplet, and allows the droplet to pass through the transport path. The method for producing a toner according to any one of (5) to (7), which is characterized in that
(9) A toner composition containing at least a polyester resin or a styrene acrylic copolymer resin and a colorant and 3,5-di-t-butyl which is a reactive substance that increases the viscoelasticity of the resin of the toner composition -A storage part having a plurality of through holes for storing a toner composition liquid in which iron salicylate is liquefied, and at least a part of the storage part, and exciting the toner composition liquid through the storage part And a vibrating means for converting the toner composition liquid into droplets from the columnar state through the constricted state through the through holes, and discharging the droplets into the granulation space; and toner particle formation for changing the droplets into solid particles in the granulation space The toner production method according to claim 1, wherein the toner is produced using a toner production apparatus having a means and a toner collection unit that collects toner particles.
(10) The toner production method as described in (9) above, wherein the vibration means has a vibration frequency of 50 kHz to 50 MHz.
(11) The toner manufacturing method as described in (9) or (10) above, wherein the vibration means has a vibration frequency of 100 kHz to 10 MHz.
(12) A transport path whose periphery is covered with an electric field curtain is formed in the granulation space, and the charge of toner particles formed by allowing droplets to pass through the transport path is temporarily neutralized by a static eliminator. The toner production method according to any one of (9) to (11) above, wherein the toner particles are accommodated in a toner collecting unit after the toner particles are collected.
(13) The toner production method as described in (12) above, wherein the charge removal by the charge remover is performed by soft X-ray irradiation.
(14) The toner production method as described in (12) above, wherein the charge removal by the charge remover is performed by plasma irradiation.
(15) The toner collecting portion has a tapered surface whose opening diameter is gradually reduced, and toner particles are used as dry particles from the outlet portion where the opening diameter is reduced from the inlet portion. And the toner particles are transferred to the toner storage container by the flow of the dry gas. The method for producing a toner according to any one of the above (9) to (14),
(16) The toner production method as described in (15) above, wherein the flow of the dry gas is a vortex.
(17) The toner according to any one of (9) to (16) above, wherein the toner collecting portion and the toner storage container are formed of a conductive material and are grounded. Production method.
(18) The method for producing a toner according to any one of the above (9) to (17), wherein the toner has an exposure specification.

  According to the present invention, the conventional problems can be solved, the toner can be produced efficiently, and the particles having a monodispersibility with an unprecedented particle size can be used. In many of the characteristic values required for the above, there is no or very little variation in the particle size observed in conventional manufacturing methods, and electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. It is possible to provide a method for producing a toner used as a developer for developing, a toner produced thereby, and a toner production apparatus using the toner production method.

  Specifically, there are no fluctuations due to particle variations seen in the conventional production methods for pulverized toners and chemical toners, or even extremely small fluctuations that can be almost ignored. 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 in particle size distribution, uniformity in shape, and uniformity in surface condition, the mechanical stress required to reach the toner charge amount set in the electrophotographic process is extremely small and wasteful. This is presumably due to a dramatic increase in toner life. This makes it possible to obtain an image with excellent image quality over a long period of time.

  Furthermore, in the present invention, a toner having a wide fixing temperature range can be obtained by containing a reactive substance that increases the viscoelasticity of the resin of the toner composition. In other words, the resin of the toner composition can be further fixed at a low temperature by using a low molecular weight material, and the hot offset resistance is excellent by using a reactive substance that increases the viscoelasticity of the low molecular weight resin. Toner can be provided. By achieving uniformity in toner particle size distribution, uniformity in shape, and uniformity in surface condition, a uniform toner layer is formed on a transfer medium such as paper by an electrophotographic process, and heat is evenly applied from the fixing device. By supplying the toner, the toner particles are rapidly melted sharply and fixed with a small fixing energy.

[Toner production method]
According to the toner manufacturing method of the present invention, a solution or dispersion of a toner material containing at least a resin and a colorant is discharged from a nozzle oscillated at a constant frequency to form droplets, and the droplets are dried. It is characterized by making it.
In the toner manufacturing method of the present invention, a toner composition liquid (dissolved or dispersed liquid) containing a toner composition containing at least a resin, a colorant, and a release agent is vibrated at a constant frequency and penetrated from the reservoir. It is characterized by being discharged through holes to form droplets and drying the droplets.

(Dropping phenomenon)
FIG. 3 is a schematic diagram showing the phenomenon of droplet formation in the liquid. The phenomenon of liquid column droplet formation in the present invention will be described with reference to FIG.
As explained in Non-Patent Document 1 below, the wavelength condition λ at which the liquid column is most unstable is expressed by the following equation (1) using the liquid column diameter d (jet). It is represented by
λ = 4.5d (jet) (1)
Here, the frequency f of the disturbance phenomenon that occurs can be expressed by the following equation (2), where v is the velocity of the liquid column.
f = v / λ (2)
Further, as described in Non-Patent Document 2 below, as a result of deriving conditions for forming uniform particles stably experimentally, it is possible to stably form uniform particles under the condition of the following formula (3). It is said that.
3.5 <λ / d (jet) <7.0 (3)
Furthermore, as explained in Non-Patent Document 3 below, based on the energy conservation law, the minimum jet velocity v (min) at which the liquid discharged from the through hole forms a liquid column is expressed by the following equation (4): It is expressed as
v (min) = (8σ / ρd (jet)) ^1/2 (4)
In Equation (4), σ represents the surface tension of the liquid, ρ represents the liquid density, and d (jet) represents the diameter of the liquid column. The conditional expressions (1) to (4) are useful for estimating the conditions for reproducing such a phenomenon. However, we consider that these relational expressions are the types of liquid substances, mixtures, and dispersions. However, the phenomenon that the liquid column is formed into droplets by the above disturbance by attaching the vibrator to the liquid chamber and vibrating the vibrator at the frequency f has been confirmed. Was established.

[Non-Patent Document 1] Rayleigh, Lord “On the Instability of Jets” Proc. London Math. Soc. 110: 4 [1878]
[Non-Patent Document 2] Schneider J. et al. M.M. , C.I. D. Hendricks, Rev. Instrum. 35 (10), 1349-50 [1964]
[Non-Patent Document 3] Lindblad N. et al. R. and J. et al. M.M. Schneider, J.A. Sci. Instrum. 42, 635 [1965]

[Toner production equipment]
An apparatus used in the toner manufacturing method of the present invention (hereinafter also referred to as “toner manufacturing apparatus”) is not particularly limited as long as it is an apparatus capable of manufacturing toner by the manufacturing method, and is appropriately selected. A storage part for storing a toner composition liquid (dissolved or dispersed) in which a toner composition containing at least a resin and a colorant is liquefied, and a plurality of penetrations provided in the storage part can be used. The toner composition liquid is excited through the storage part by contacting and vibrating with the hole and a part of the storage part, and the toner composition liquid is continuously discharged from the through hole to the granulation space to be constricted from the columnar state. It is preferable to use a toner manufacturing apparatus that has a vibration means for forming droplets through the toner and a toner particle forming means for drying the droplets by removing the solvent contained in the droplets to form toner particles.
As a preferable toner manufacturing apparatus, for example, as shown in FIG. 1, at least a storage unit 1 that stores at least the toner composition liquid as the droplet forming unit, a vibrating unit 2, and the vibrating unit are held. Support means 3 A liquid supply means 5 having the plurality of through-holes 4 for supplying the toner composition liquid discharged from the through-holes to the reservoir and releasing the liquid from the through-holes, and the toner particle forming means An apparatus having a solvent removal facility 6 and a toner collecting unit 7 is preferably used.

Hereinafter, the toner manufacturing apparatus will be described in detail for each member.
(Reservoir)
Since the storage part needs to be held at least in a state where the toner composition raw material fluid is pressurized, it is made of a member such as a metal such as SUS or aluminum and preferably has a pressure resistance of about 10 MPa. However, it is not limited to this. In addition, for example, as shown in FIG. 2, a structure provided with a mechanism 9 that holds a plate having a through-hole connected by a pipe 8 that supplies a liquid to the reservoir is desirable. Moreover, the vibration means 2 which vibrates the whole storage part is in contact with the said storage part. The vibration means is connected to the vibration generator 10 and the conductive wire 11 and is preferably controlled. In order to stably form the liquid column, it is preferable to adjust the pressure in the reservoir or to provide the release valve 12 for removing the bubbles inside.

(Vibration means)
It is preferable that the vibration means 2 excites the whole storage part having the through hole by one vibration means.
The vibrating means is in contact with a part of the reservoir and applies vibrations to the raw material fluid via the reservoir, so that the raw material fluid discharged from the through hole provided in one reservoir is collectively equivalent. Since it is possible to generate a pressure density wave by applying vibration, it is possible to simultaneously generate 100 or more droplet forming phenomena by one vibration means.
The vibrating means 2 for applying vibration to the storage unit 1 is not particularly limited as long as it can provide reliable vibration at a constant frequency, and can be appropriately selected and used. For example, it is preferable that the through hole is vibrated at a constant frequency by expansion and contraction of the piezoelectric body.
The piezoelectric body has a function of converting electrical energy into mechanical energy. Specifically, it is expanded and contracted by applying a voltage, and the through hole can be vibrated by the expansion and contraction.

Examples of the piezoelectric body include piezoelectric ceramics such as lead zirconate titanate (PZT). Generally, since the amount of displacement is 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.
The fixed frequency is not particularly limited and may be appropriately selected according to the purpose. However, 100 kHz to 10 MHz is preferable, and 200 kHz to 2 MHz is preferable from the viewpoint of generating micro droplets having a very uniform particle diameter. More preferred.
The vibration means 2 is in contact with the storage portion, and the storage portion holds a plate having a through hole, and the vibration means and the plate having the through hole uniformly vibrate the liquid column generated from the through hole. From the viewpoint of giving, it is most preferable that they are arranged in parallel, and even if deformation occurs in the vibration process, it is desirable that the relationship be maintained within an inclination of 10 °.
Even if only one through hole 3 is provided, particle production is possible. However, from the viewpoint of efficiently generating micro droplets having a very uniform particle diameter, a plurality of through holes 3 are provided and liquid discharged from each through hole is provided. The droplets are preferably dried with one solvent removal facility, in the example shown, the solvent removal facility 5.

  From the viewpoint of further improving productivity, it is more preferable to provide a plurality of reservoirs having the vibration means. At this time, the productivity of the toner particles is determined by the product of the number of droplets (frequency) generated per unit time, the number of vibration means, and the number of through-holes acting by one vibration means. From the viewpoint of operability, it is sufficient that the number of through-holes acted by one vibration means as much as possible, that is, the number of through-holes possessed by one reservoir is as large as possible. Not. Therefore, the number of through-holes associated with one reservoir that is vibrated by the one vibrating means is preferably 10 to 10,000 from the viewpoint of productivity and controllability. In order to more surely generate fine droplets having a very uniform particle size, it is more preferably 10 to 1,000.

(Supporting means)
The support means 3 for fixing and supporting a part of the vibration means 2 is provided for fixing the storage section and the vibration means to the apparatus. The material is not particularly limited, but may be a rigid body such as metal. That's fine. If necessary, a rubber material, a resin material, or the like as a vibration reducing material may be provided in part so as not to disturb the vibration of the reservoir due to excessive resonance.

(Through hole)
As described above, the through hole (nozzle) 4 is a member that discharges the toner composition raw material fluid as a liquid column. There is no restriction | limiting in particular as a material and shape of the said through-hole, Although it can be set as the shape selected suitably, For example, a discharge hole is formed with a metal plate with a thickness of 5-50 micrometers, and the opening diameter is 1. The fine liquid droplets having an extremely uniform particle size can be generated at a vibration frequency of 100 kHz or more without clogging the fine particle dispersion of 1 μm or less contained in the toner composition raw material fluid. From the viewpoint of achieving both. This is because the frequency region in which droplets can be stably obtained by the droplet formation phenomenon decreases substantially as the diameter of the through-hole increases, so that the vibration frequency of 100 kHz or more is considered in consideration of productivity. Is assumed. The aperture diameter means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse.

(Liquid feeding / pressurizing means)
The means 5 for supplying the liquid to the common liquid chamber is preferably a metering pump such as a tube pump, a gear pump, a rotary pump, or a syringe pump. Moreover, the pump of the type pressurized and sent with compressed air etc. may be used. With these liquid supply means, the common liquid chamber is filled with the toner composition raw material fluid, and the pressure can be increased to a pressure at which droplets can be formed. The liquid pressure can be measured with a pressure gauge attached to the pump or a dedicated pressure sensor.

(Solvent removal equipment)
The solvent removal equipment 6 is not particularly limited as long as the solvent of the droplets 13 can be removed, but an air flow is generated by flowing a dry gas in the same direction as the droplet 13 discharge direction. The toner particles 15 are preferably formed by transporting the droplets 13 in the solvent removal equipment 6 and removing the solvent in the droplets 13 during the transportation. Here, “dry gas” means a gas having a dew point temperature of −10 ° C. or lower under atmospheric pressure.
The dry gas is not particularly limited as long as it is a gas that can dry the droplets 13, and examples thereof include air and nitrogen gas.
Although there is no restriction | limiting in particular as a method of flowing the said dry gas to the solvent removal installation 6, For example, the method of connecting a dry gas supply tube to a solvent removal installation and flowing a dry gas in a solvent removal installation is mentioned.

The temperature of the drying gas is preferably higher in terms of drying efficiency, and even if a drying gas having a boiling point higher than the solvent used is used due to the characteristics of spray drying, the constant rate drying region during drying is used. Thus, the droplet temperature does not rise above the boiling point of the solvent, and the resulting toner is not thermally damaged. However, since the main constituent material of the toner is a thermoplastic resin, when it is exposed to a dry gas that is higher than the boiling point of the resin to be used after drying, that is, in the rate-decreasing drying region, the toner is liable to be thermally fused. There is a risk that the monodispersibility may be impaired. Therefore, specifically, the temperature of the dry gas is preferably, for example, 40 to 200 ° C, more preferably 60 to 150 ° C, and particularly preferably 75 to 85 ° C.
In addition, an electric field curtain charged with a polarity opposite to the electric charge of the droplets is provided on the inner wall surface of the solvent removal facility 6 from the viewpoint of preventing the droplets 13 from adhering to the wall surface of the solvent removal facility 6. It is preferable to form a transport path whose periphery is covered with the electric field curtain, and allow droplets to pass through the transport path.

(Staticizer)
After neutralizing the electric charge of the toner particles 15 formed by passing the droplets 13 through the conveyance path, a static eliminator is provided as a member for accommodating the toner particles 15 in the toner storage container. I can do it.
There is no particular limitation on the method of static elimination by the static eliminator, and a conventionally known method can be appropriately selected and used. However, since neutralization can be efficiently performed, for example, soft X-ray irradiation , Plasma irradiation, etc. are preferable.

(Toner collecting part)
The toner collecting unit 7 is a member provided at the bottom of the toner particle manufacturing apparatus from the viewpoint of efficiently collecting and transporting toner.
The structure of the toner collecting portion 7 is not particularly limited as long as the toner can be collected and can be appropriately selected. From the above viewpoint, a tapered surface whose opening diameter is gradually reduced is provided as in the illustrated example. The toner particles 15 are formed from the outlet portion whose opening diameter is smaller than that of the inlet portion, the dry gas 14 is used to form the flow of the dry gas, and the toner particles are stored in the toner by the flow of the dry gas. It is preferably transferred to a container.
As the transfer method, as shown in the illustrated example, the toner particles 15 may be pumped to the toner storage container by the dry gas 14, or the toner particles 15 may be sucked from the toner storage container side.
Although there is no restriction | limiting in particular as a flow of the said dry gas, From a viewpoint which can generate the centrifugal force and can convey the toner particle 15 reliably, it is preferable that it is a vortex | eddy_current.
Furthermore, from the viewpoint of more efficiently transporting the toner particles 15, the toner collection unit 7 and the toner collection container are formed of a conductive material and are connected to the ground. More preferred. The toner manufacturing apparatus preferably has an exposure specification.

(Droplet)
As described above, the liquid droplets 13 are discharged from the through-holes 4 provided in the reservoir 1 that is vibrated at a constant frequency with a solution or dispersion of a toner material containing a specific substance. Is generated. The toner material will be described in a separate “toner” section.
The method for dissolving or dispersing the toner composition is not particularly limited, and a commonly used method can be appropriately selected. Specifically, a toner binder such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin may be melt-kneaded with a colorant or the like and finely pulverized, or obtained during the production. The kneaded product may be once dissolved in an organic solvent in which the resin component is soluble and then processed as fine droplets.

(Function)
According to the toner production method of the present invention described in detail above, the number of droplets generated from the through hole 4 is very large, tens of thousands to several million per second, and more discharge holes are provided. It is also easy to do. In addition, it can be said to be the most suitable method for producing toner from the viewpoint of obtaining a very uniform droplet diameter and sufficient productivity. Further, in this production method, the particle diameter of the toner finally obtained can be accurately determined by the following calculation formula (1), and there is almost no change in the particle diameter depending on the material used.

〔a formula〕
Dp = (6QC / πf) ^(1/3) (1)
Where Dp: solid particle diameter, Q: liquid flow rate (determined by pump flow rate and through-hole diameter), f: vibration frequency, C: volume concentration of solid content.
The toner particle diameter can be accurately calculated only by the above formula (1), but more simply can be obtained by the following formula (2).
〔a formula〕
Solid content volume concentration (volume%) = (solid particle diameter / droplet diameter) ³ (2)

  That is, the diameter of the toner particles obtained by the present invention is twice the opening diameter of the through hole regardless of the vibration frequency at which the droplet is ejected. Therefore, the target solid particle diameter can be obtained by obtaining and adjusting the solid content concentration in advance from the relationship of the above formula (2). For example, when the through-hole diameter is 7.5 μm, the droplet diameter is 15 μm. Therefore, if the solid content volume concentration is 6.40% by volume, 6.0 μm solid particles can be obtained. In this case, the vibration frequency is preferably higher from the viewpoint of productivity, but Q (liquid flow rate) is determined from the calculation formula (1) according to the vibration frequency determined here.

In the conventional manufacturing method, the particle size often varies greatly depending on the material used. In this manufacturing method, the particle size as set is controlled by managing the droplet diameter and solid content concentration at the time of discharge. It becomes possible to continuously obtain particles having a diameter.
Further, since the toner obtained by the present invention has a very uniform particle size, the fluidity in the toner base is very high. Therefore, even when an external additive is added for the purpose of reducing the adhesive force to a manufacturing apparatus or the like, the effect can be exhibited in an extremely small amount. Considering the deterioration of external additives due to stress and the safety of fine particles to the human body, it is preferable not to use such external additives as much as possible, which is also an advantage of the present invention.

[toner]
The toner of the present invention is a toner manufactured by the toner manufacturing method of the present invention described above.
As the toner, a toner having a monodispersed particle size distribution can be obtained by the toner manufacturing method.
Specifically, the particle size distribution (mass average particle diameter / number average particle diameter) of the toner is preferably in the range of 1.00 to 1.05. Moreover, as a mass mean particle diameter, it is preferable that it is 1-20 micrometers.
The toner obtained by the toner manufacturing method can be easily redispersed, that is, floated in an air current by electrostatic repulsion effect. For this reason, the toner can be easily transported to the developing region without using a transporting unit 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.

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

[Toner material]
The toner material contains at least a resin, a colorant, and a reactive substance that increases the viscoelasticity of the resin, and if necessary, other components such as a wax, a charge control agent, and a fluidity improver. To do.
Hereinafter, the toner material will be described.

(resin)
Examples of the resin include at least a binder resin.
As the binder resin, it is preferable to increase the viscoelasticity of the binder resin by acting with a reactive substance. Regarding its action, a covalent bond, an ionic bond, a hydrogen bond, etc. can be considered.
Among the commonly used resins, it can be used appropriately considering the reactivity. For example, vinyl polymers such as acrylic monomers and methacrylic monomers, these monomers or two kinds Copolymers, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins, coumarone indene resins, polycarbonate resins, petroleum resins , Etc.
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. Examples include 2-ethylhexyl acid, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid such as phenyl acrylate, or esters thereof.
Examples of the methacrylic monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid. And methacrylic acid or esters thereof such as 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

  The following (1)-(16) is mentioned as an example of the other monomer which forms the said vinyl polymer or a copolymer. (1) Vinyl halides such as vinyl chloride, vinyl chloride, vinyl bromide and vinyl fluoride; (2) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (3) Vinyl methyl ether and vinyl Vinyl ethers such as ethyl ether and vinyl isobutyl ether; (4) vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; (5) N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N -N-vinyl compounds such as vinylpyrrolidone; (6), vinylnaphthalenes; (7) acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc .; (8) maleic acid, citraconic acid, itaconic acid, Alkenyl succinic acid, fumaric acid, Unsaturated dibasic acids such as conic acid; (9) unsaturated dibasic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride; (10) maleic acid monomethyl ester , Maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester, citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester (11) Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid; (12) α, β-unsaturated acids such as crotonic acid and cinnamic acid; ) Crotonic acid anhydride, cinnamic acid anhydride, etc. α, β-unsaturated acid anhydrides; (14) anhydrides of the α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, their acid anhydrides and their monohydric acids Monomers having a carboxyl group such as esters; (15) acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (16) 4- (1-hydroxy A monomer having a hydroxy group such as -1-methylbutyl) styrene and 4- (1-hydroxy-1-methylhexyl) styrene.

Among resins that are usually used, there are resins having low reactivity, but they may be used in combination with the above-mentioned resins.
For example, styrene monomers include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-amyl styrene. , P-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene such as chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or a derivative thereof.
Examples of other monomers forming the vinyl polymer or copolymer include monoolefins such as ethylene, propylene, butylene and isobutylene; polyenes such as butadiene and isoprene.

In the toner of the present invention, the vinyl polymer or copolymer of the binder resin may be used in combination with a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic vinyl vinyl 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. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.
Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

  Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds in place of methacrylate, triallyl cyanide. Examples include nurate and triallyl trimellitate.

  These cross-linking agents are preferably used in an amount of 0.01 to 10 parts by mass, and 0.03 to 5 parts by mass, with respect to 100 parts by mass of the other monomers forming the vinyl polymer or copolymer. More preferred. 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, Ketone peroxides such as rohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide , Lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylpero Xidicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclo Hexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexarate, tert-butyl peroxylaurate, tert-butyl-oxybenzoate, tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisophthalate, tert-butylperoxyallyl carbonate, isoamylperoxy-2-ethylhexanoate, di- tert- butylperoxy to hexa hydro terephthalate, tert- butylperoxy azelate, and the like.

In the case where the binder resin is a styrene-acrylic resin, the molecular weight distribution by GPC soluble in the resin component tetrahydrofuran (THF) is at least one in the region of molecular weight 3,000 to 50,000 (in terms of number average molecular weight). A resin having a peak and 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, and 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 most preferably 0.1 mgKOH / g to 50 mgKOH / g.

The following are mentioned as a monomer which comprises a polyester-type polymer.
Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 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 trivalent or higher alcohol together.
Examples of the trihydric or higher polyhydric alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, such as dipentaerythritol, tripentaerythritol, 1,2,4- Butanetriol, 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene , Etc.

  Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And unsaturated dibasic acid anhydrides. Examples of the trivalent or higher polyvalent carboxylic acid component include 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 exists in a region having a molecular weight of 5,000 to 20,000. More preferable is a binder resin.
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. Most preferably, 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 a mixed solution 150 (ml) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The amount of KOH solution used at this time is S (ml), a blank is measured at the same time, the amount of KOH solution used at this time is B (ml), and the following calculation formula (3) is used. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (3)

  The toner binder resin and the composition containing the binder resin preferably have a glass transition temperature (Tg) of 35 to 80 ° C., more preferably 40 to 75 ° C., from the viewpoint of toner storage stability. If the Tg is lower than 35 ° C., the toner is likely to deteriorate in a high temperature atmosphere, and offset may easily occur during fixing. On the other hand, when Tg exceeds 80 ° C., fixability may be deteriorated.

Examples of the magnetic material that can be used in the present invention include (1) iron oxide containing magnetic iron oxide such as magnetite, maghemite, and ferrite, and other metal oxides, and (2) metals such as iron, cobalt, and nickel, or Alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, (3) and these A mixture of
Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , _{PbFe 12 O, NiFe 2 O 4} , NdFe 2 O, BaFe 12 O 19, MgFe 2 O 4, MnFe 2 O 4, LaFeO 3, iron powder, cobalt powder, nickel powder, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of triiron tetroxide and γ-iron trioxide are particularly 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, 10-200 mass parts of magnetic bodies are preferable with respect to 100 mass parts of binder resin, and 20-150 mass parts is more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 μm, and more preferably 0.1 to 0.5 μm. The number average diameter can be obtained by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.
Further, as the magnetic properties of the magnetic material, those having a coercive force of 20 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g are preferable, respectively.
The magnetic material can also be used as a colorant.

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

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

The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. There is also a method of removing water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.
As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.

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

The dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific examples of commercially available products include “Ajisper PB821” and “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.). , “Disperbyk-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like.
The dispersant is preferably blended in the toner at a ratio of 0.1 to 10% by mass with respect to the colorant. When the blending ratio is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it is more than 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 1,000 is more preferable. In particular, 5,000 to 50,000 are preferable, and 5,000 to 30,000 are most preferable. When the molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant decreases. There are things to do.
The addition amount of the dispersant is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 1 part by mass, the dispersibility may be lowered, and if it exceeds 50 parts by mass, the chargeability may be lowered.

(Reactive substance)
As reactive substances that increase viscoelasticity, there are substances that increase the molecular weight by crosslinking or elongation reaction with the binder resin, or substances that cause substantial intermolecular bonds by ionizing bonds or coordinate bonds. . As such a reactive substance, a substance which increases viscoelasticity by reacting with a functional group having polarity in the binder resin and crosslinking is preferable. Here, the substance to be cross-linked is different from amines and ketones used for cross-linking or elongation of monomers in a solvent. Examples of the substance that increases the viscoelasticity include metal compounds. Specifically, metal salts of naphthenic acid or higher fatty acids, azo metal complexes, salicylic acid metal salts, or metal complexes of zinc, chromium, iron, zirconium, etc. In addition, a chelate compound selected from silicon, zirconium, and aluminum, or a metal alcoholate thereof may be used. The amount of the reactive substance used is in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the toner composition. The range of 0.2 to 5 parts by weight is preferable.

  The reactive substance may be added by dissolving or dispersing the toner composition in a liquefied toner composition liquid, supplying the composition liquid to a storage section, and storing the composition liquid, and the toner provided from the nozzle provided in the storage section. A step of continuously releasing the composition liquid to form a columnar state, a vibration step of vibrating at least the nozzle or the reservoir by the vibration means, and the toner composition liquid discharged from the nozzle being made into droplets by the vibration means A droplet forming step, a method of forming particles for solidifying the toner composition liquid formed into droplets, and a method of externally adding a reactive substance after forming toner particles. A known method is used for the external addition method. The obtained toner particles are mixed with different kinds of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles and colorant fine particles, or fixed on the surface by applying mechanical impact force to the mixed powder. By fusing, it is possible to prevent detachment of foreign particles from the surface of the resulting composite particles.

  Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Henschel mixer, Q-type mixer (Mitsui Metal Mining Co., Ltd.), Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.), and the pulverization air pressure is lowered. Hybridization Examples include a system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

(Other ingredients)
<Wax>
In the present invention, a wax can be contained together with the binder resin and the colorant.
The wax of the present invention is not particularly limited, and those that are usually used can be appropriately selected and used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sax. Plant waxes such as aliphatic hydrocarbon waxes such as sol wax, oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof, candelilla wax, carnauba wax, wood wax, jojoba wax, etc. Waxes mainly composed of animal waxes such as beeswax, lanolin and spermaceti, mineral waxes such as ozokerite, ceresin and petrolatum, and fatty acid esters such as montanic ester wax and castor wax. Deoxidized carnauba wax and other fatty acid esters that have been partially or wholly deoxidized are included.

  Examples of the wax further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group, prandidic acid, eleostearic acid, and valinal acid. Unsaturated alcohols such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnupyl alcohol, seryl alcohol, mesyl alcohol, or long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acids Fatty acid amides such as amide and lauric acid amide, methylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide and other saturated fatty acid bisamides, ethylene bis oleic acid amide, hexamethylene bis Unsaturated fatty acid amides such as oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasinic acid amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Grafted onto aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate, and aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid. Examples thereof include waxes, partial ester compounds of polyhydric alcohols such as behenic acid monoglycerides, and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  More preferable 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, Fitzscher Tropsch wax, Jintole method, hydrocol method, age method Synthetic hydrocarbon waxes synthesized by the above, synthetic waxes having a compound having one carbon atom, hydrocarbon waxes having functional groups such as hydroxyl groups or carboxyl groups, hydrocarbon waxes and hydrocarbons having functional groups Mixture of system wax, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such vinyl monomers of maleic acid.

In addition, these waxes have a sharp molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.
The melting point of the wax is preferably 70 to 140 ° C., and more preferably 70 to 120 ° C., in order to balance the fixability and the offset resistance. If it is less than 70 degreeC, blocking resistance may fall, and if it exceeds 140 degreeC, an offset-proof effect may become difficult to express.

Further, by using two or more different types of waxes in combination, the plasticizing action and the releasing action which are the actions of the wax can be expressed simultaneously.
Examples of the types of wax having a plasticizing action include waxes having a low melting point, those having a branch on the molecular structure, and those having a polar group.
Examples of the wax having a releasing action include a wax having a high melting point, and the molecular structure includes a linear structure and a non-polar one having no functional group. Examples of use include a combination of two or more different waxes having a 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 to 100 ° C., functional separation is effectively expressed. If it is less than 10 ° C., the function separation effect may be difficult to appear, and if it exceeds 100 ° C., the function may not be emphasized by interaction. At this time, the melting point of at least one of the waxes is preferably 70 to 120 ° C, and more preferably 70 to 100 ° C, because the function separation effect tends to be easily exhibited.

As for the wax, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exhibit a plastic action, and those having a more linear structure or functional group Nonpolar or non-denatured straight materials that do not have a mold exhibit a releasing action. Preferred combinations include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene, polyolefins and graft modified polyolefins, alcohol waxes, fatty acid waxes or ester waxes. And hydrocarbon wax combinations, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax combination, Fischer-Tropsch wax and polyolefin wax combination, paraffin wax and microcrystal wax combination, Carnauba Wax, Can Delila wax, rice wax or montan wax and hydrocarbon-based wax Like a combination of.
In any case, since it becomes easy to balance the toner storage stability and the fixing property, the peak top temperature of the maximum peak is in the region of 70 to 110 ° C. in the endothermic peak observed in the DSC measurement of the toner. Preferably, it has a maximum peak in the region of 70 to 110 ° C.

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

<Charge control agent>
In the present invention, a charge control agent can be contained together with the binder resin and the colorant. In particular, a high charge amount can be imparted by fixing the charge control substance to the surface of the toner. That is, by fixing the toner on the surface of the toner, the amount and state of presence on the toner surface are stabilized, and the charge amount can be stabilized. In particular, the stability of the charge amount is increased in the toner having the configuration of the present invention. Examples of charge control agents include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), Examples thereof include alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts and metal salts of salicylic acid derivatives.
The amount of the charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, but is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents and release agents can be melt-kneaded together with the masterbatch and the resin, and of course, they may be added when dissolved and dispersed in an organic solvent.

<Fluidity improver>
A fluidity improver may be added to the toner of 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, Examples include finely powdered non-alumina, treated silica obtained by subjecting them to a surface treatment with a silane coupling agent, a titanium coupling agent, or silicone oil, treated titanium oxide, and treated alumina. Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.
The particle size of the fluidity improver is preferably 0.001 to 2 μm, more preferably 0.002 to 0.2 μm, as an average primary particle size.

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

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

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

The number average particle diameter of the fluidity improver is preferably 5 to 100 nm, more preferably 5 to 50 nm.
The specific surface area by measuring nitrogen adsorption by the BET method, preferably at least ^{30m 2 / g, 60~400m 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 particles.

In the toner of 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, adjustment of softening point, improvement of fixing rate For purposes such as various types of metal soaps, fluorosurfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, inorganic fine powders such as titanium oxide, aluminum oxide, alumina, etc. A body etc. can be added as needed. These inorganic fine powders may be hydrophobized as necessary. In addition, lubricants such as polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, strontium titanate, anti-caking agents, white particles and black particles having opposite polarity to the toner particles, Can also be used in small amounts as a developability improver.
These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control and the like. It is also preferable to treat with a treating agent or various treating agents.

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 load history applied to the external additive, the external additive may be added in the middle or gradually, and the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed. The load may then be given a relatively weak load and vice versa.
Examples of the mixer that can be used include a V-type mixer, a rocking mixer, a Roedige mixer, a Nauter mixer, a Henschel mixer, and the like.
A method for further adjusting the shape of the obtained toner is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner material composed of a binder resin and a colorant is melt-kneaded and then finely pulverized. Using a hybridizer, mechano-fusion, etc., the resulting material is mechanically adjusted, 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 using a spray-drying device. Examples thereof include a method of removing a solvent to obtain a spherical toner 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, and diatomaceous earth. , Chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like.

The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, more preferably 5 mμ to 500 mμ.
The specific surface area according to the BET method is preferably 20 to 500 m ² / g.
The proportion of the inorganic fine particles used is preferably 0.01 to 5% by mass of the toner, and more preferably 0.01 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 system such as silicone, benzoguanamine and nylon, thermosetting resin 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 mμ to 2 μm, and more preferably 5 mμ to 500 mμ. Moreover, as a specific surface area by BET method, it is preferable that it is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and more preferably 0.01 to 2.0% by mass.

  Examples of the cleaning property improver for removing the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymethyl methacrylate. 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 to 1 μm.

[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 in the coating material include styrene-acrylic ester copolymers, styrene-acrylic resins such as styrene-methacrylic ester copolymers, acrylic ester copolymers, methacrylic ester copolymers, and the like. Preferable examples include fluorine-containing resins such as acrylic resins, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride, silicone resins, polyester resins, polyamide resins, polyvinyl butyral, and aminoacrylate resins. In addition to these, resins that can be used as a coating (coating) material for carriers 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 to 5% by mass and more preferably 0.1 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 A mixture with 2-ethylhexyl acrylate-methyl methacrylate copolymer (copolymer mass ratio 20 to 60: 5 to 30:10:50) is mentioned.
Examples of the silicone resin include modified silicone resins produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with a silicone resin.
Examples of the magnetic material for the carrier core include oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof.

  The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done. Among these, copper-zinc-iron-based ferrites mainly composed of copper, zinc, and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium, and iron components are preferable.

The resistance value of the carrier is preferably 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the unevenness of the surface of the carrier and the amount of resin to be coated.
The carrier having a particle size of 4 to 200 μm can be used, preferably 10 to 150 μm, more preferably 20 to 100 μm. In particular, the resin-coated carrier preferably has a 50% particle size of 20 to 70 μm.
In the two-component developer, it is preferable to use 1 to 200 parts by mass of the toner of the present invention with respect to 100 parts by mass of the carrier, and 2 to 50 parts by mass of toner with respect to 100 parts by mass of the carrier. More preferred.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example at all.

[Example 1]
-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
Carbon black (Regal 400; manufactured by Cabot) 15 parts by mass and pigment dispersant 3 parts by mass were primarily dispersed in 82 parts by mass of ethyl acetate using a mixer having stirring blades. As the pigment dispersant, Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion from which aggregates were completely removed. Further, a liquid having a pore size of 0.45 μm (manufactured by PTFE) and passing through a submicron region was prepared.

-Preparation of dispersion with added resin and wax-
Next, a dispersion liquid having the following composition to which a resin as a binder resin and a wax were added was prepared.
100 parts by mass of a polyester resin as a binder resin, 30 parts by mass of the carbon black dispersion, 5 parts by mass of carnauba wax, iron salicylate (3,5-di-t-Bu-iron salicylate, manufactured by Oriental Chemical Industries: X-11 ) 0.85 parts by mass were dispersed in 1,000 parts by mass of ethyl acetate by stirring for 10 minutes using a mixer having stirring blades as in the preparation of the colorant dispersion. It was possible to completely prevent pigments from aggregating due to shock caused by solvent dilution. The dispersion liquid at this stage was filtered with a 0.45 μm filter (made by PTFE) in the same manner as in the preparation of the colorant dispersion liquid, but it was confirmed that no clogging occurred and all passed. The electrolytic conductivity of this dispersion was 3.5 × 10 ⁻⁷ S / m.

-Preparation of toner-
The obtained dispersion was further diluted with ethyl acetate so that the solid content was 6.0%, and the liquid was supplied to the storage unit 1 of the toner production apparatus shown in FIG. The plate having the through-hole used was a removal plate (laser ablation) by a mask reduction projection method using a femtosecond laser with a through-hole (nozzle hole) having a perfect circular exit diameter of 8.0 μm on a nickel plate having a thickness of 20 μm. 500 pieces were produced on concentric circles. The portion where the through-hole was present was a square area with a side of 0.5 mm.
After the dispersion was prepared, droplets were formed under the following toner production conditions, and then the droplets were dried and solidified to produce a toner.

[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.888 g / cm ³
Dry air flow rate: Orifice sheath 2.0 L / min, In-apparatus air 3.0 L / min Dry air temperature: 80-82 ° C.
In-apparatus temperature: 27-28 ° C
Dew point temperature: -20 ° C
Electrode applied voltage: 2.5 KV
Common liquid chamber vibration frequency: 220 kHz
The dried and solidified toner particles were collected by suction with a filter having 1 μm pores. Particle size of collected particles The particle size distribution of the collected particles was measured with a flow type particle image analyzer (FPIA-2000). The mass average particle size was 6.0 μm, and the number average particle size was 6.0 μm. Toner base particles that were completely monodispersed were obtained. A scanning electron micrograph of this toner base is shown in FIG.

-Toner evaluation-
The obtained toner was evaluated as follows. The results are shown in Table 1.
<Particle size distribution>
The weight average particle diameter (D4) and number average particle diameter (Dn) of the toner of the present invention were measured with an aperture diameter of 100 μm using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.), and analysis software ( Beckman Coulter Multisizer 3 Version 3.51). Specifically, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) was added to a glass 100 ml beaker, 0.5 g of each toner was added, and the mixture was stirred with a micropartel. Subsequently, 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size. As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Using particles of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, particles having a particle diameter of 2.00 μm to less than 40.30 μm were targeted. After measuring the volume and number of toner particles or toner, the volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained. As an index of the particle size distribution, D4 / Dn obtained by dividing the weight average diameter (D4) of the toner by the number average particle diameter (Dn) is used. If it is completely monodisperse, it becomes 1, and the larger the value, the wider the distribution.

<Charge amount>
It was measured with a suction type charge amount measuring device. Specifically, the toner was sucked in a range of 200 to 250 mg in a Faraday cage equipped with a filter capable of collecting the toner, and an electrometer was connected thereto, and the total charge amount of the sucked toner was measured. At this time, the mass increased from the previously measured filter mass is measured with a five-digit precision chemical balance as the toner mass on the filter, the total charge is divided by the collected toner mass, and the charge per unit mass (q / M). There is “Model 210HS-2A” manufactured by Trek Japan Co., Ltd. as a commercially available charge amount measuring device having the same measurement principle, but a self-made measuring device having the same configuration was used. As a filter for collecting the toner, glass microfiber (Whatman) having a diameter of 21 mm was used. Although there is almost no measurement difference depending on the suction time, the suction time is defined within 30 seconds here.

<Amount of charge at room temperature and high humidity (NH)>
Measurement was carried out by the above-described charge amount measurement method in an environmental test room at a temperature of 30 ° C. and a humidity of 90%. The measurement was performed after leaving the sample in this environment for 12 hours.

<Charge amount distribution>
The charge amount distribution of the toner was measured by a charge amount distribution measuring device (E-Spart Analyzer EST-2 type manufactured by Hosokawa Micron Corporation). Specifically, the toner was directly introduced into the toner inlet of the measuring machine so that 500 to 600 particles could be measured per minute with a feeder, and the charge amount distribution was measured. As an index indicating the distribution of the charge amount, the mode value (peak value) [q / d] and the width of the distribution (half width) at the half height of the most frequent frequency are used. As the characteristics of the toner, it is preferable that the charge amount is high and the charge amount distribution is sharper, but generally, the half value width indicating the charge amount distribution tends to increase as the charge amount increases. If the mode value is 0.25 fC / μm or more and the half value width of the charge amount distribution is 0.2 or less, it is determined that the charge amount distribution is excellent.

<Thin wire reproducibility>
The developer was put into a modified machine in which a developing unit portion of a commercially available copying machine (Imagiono 271; manufactured by Ricoh) was improved, and running was performed using 6000 paper manufactured by Ricoh with a printing ratio of 7%. Compare the original 10th image and the 30,000th image thin line with the original, and observe it with an optical microscope at a magnification of 100x, and evaluate it in 4 stages while comparing the line missing state with the stage sample. did. The image quality is higher in the order of ◎>○>△> ×. In particular, the evaluation of x is a level that cannot be adopted as a product. In the case of negatively charged toner, an organic electrostatic latent image carrier was used, and in the case of positively charged toner, an amorphous silicon electrostatic latent image carrier was used.
In development method 1, the toner was directly conveyed to the development site by an air stream and developed with a powder cloud. In development method 2, a resin-coated carrier used in conventional electrophotography was used as a conveying means. The following were used as carriers.

[Carrier]
Core material: Spherical ferrite particles having an average particle size of 50 μm Coat material: Silicone resin Disperse the silicone resin in toluene, adjust the dispersion, spray coat the core material in a heated state, fire and cool, Carrier particles having an average coated resin film thickness of 0.2 μm were prepared.

[Example 2]
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the diameter of the discharge hole was 5 μm and the solid content concentration was 8 times. Also in this case, the toner had a mass average particle diameter of 6.0 μm and a number average particle diameter of 6.0 μm, and completely monodispersed toner base particles were obtained.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

[Example 3]
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the diameter of the ejection hole was 20 μm and the solid content concentration was 0.125 times. Also in this case, the toner had a mass average particle diameter of 6.0 μm and a number average particle diameter of 6.0 μm, and completely monodispersed toner base particles were obtained.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

[Example 4]
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the frequency was 440 kHz and the liquid flow rate supplied from the syringe pump was doubled. Also in this case, the toner had a mass average particle diameter of 6.0 μm and a number average particle diameter of 6.0 μm, and completely monodispersed toner base particles were obtained.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

[Example 5]
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the frequency was 110 kHz and the liquid flow rate supplied from the syringe pump was 0.5 times. Also in this case, the toner had a mass average particle diameter of 6.0 μm and a number average particle diameter of 6.0 μm, and completely monodispersed toner base particles were obtained.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

[Example 6]
A target toner was obtained in the same manner as in Example 1 except that in Example 1, a styrene acrylic copolymer resin having a specific gravity of 1.05 was used instead of the polyester resin. Also in this case, the toner had a mass average particle diameter of 6.0 μm and a number average particle diameter of 6.0 μm, and a completely monodispersed toner base particle was obtained. To be different from the results of Example 1. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

[Example 7]
Instead of the nozzles used in Example 1, 10 nozzles with a perfect circle diameter of 10 μm were fabricated on a nickel plate with a thickness of 20 μm by processing with a femtosecond laser, and the center diameter of the plate was within a circle of 1.5 mm. A target toner was obtained in the same manner as in Example 1 except that 20 nozzles were provided concentrically, a total of 200 ejection holes. Also in this case, the toner had a mass average particle diameter of 6.0 μm and a number average particle diameter of 6.0 μm, and completely monodispersed toner base particles were obtained.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

[Example 8]
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the amount of ethyl acetate used in the dispersion added with resin and wax was changed to 5,350 parts by mass. Also in this case, the toner had a mass average particle diameter of 5.0 μm and a number average particle diameter of 5.0 μm, and completely monodispersed toner base particles were obtained. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

[Example 9]
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the amount of ethyl acetate used in the dispersion added with resin and wax was 10,449 parts by mass. Also in this case, the toner had a mass average particle diameter of 4.0 μm and a number average particle diameter of 4.0 μm, and completely monodispersed toner base particles were obtained. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

[Example 10]
In Example 1, the target toner was obtained in the same manner as in Example 1 except that the amount of ethyl acetate used in the dispersion added with resin and wax was 24,767 parts by mass. Also in this case, the toner had a mass average particle diameter of 3.0 μm and a number average particle diameter of 3.0 μm, and completely monodispersed toner base particles were obtained. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

[Comparative Example 1]
-Preparation of dispersion-
A colorant dispersion, a dispersion containing a resin and a wax were prepared under the same conditions as in Example 1.
-Preparation of toner-
In place of the apparatus used in the first embodiment, a storage unit for storing the dispersion liquid and a head unit capable of applying a piezoelectric pulse to the storage unit by expansion and contraction of a piezoelectric body and discharging droplets from the nozzles are provided. Then, after the droplets were discharged under the following toner production conditions, the toner was produced by drying and solidifying the droplets. The apparatus of Example 1 has a structure in which vibration is applied to the nozzle itself, whereas the apparatus of Comparative Example 1 is greatly different in that a piezoelectric pulse is applied to the dispersion liquid storage unit.

[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.888 g / cm ³
Dry air flow rate: Air in the apparatus 3.0 L / min Dry air temperature: 80 to 82 ° C
In-apparatus temperature: 27-28 ° C
Dry air (dew point temperature): -20 ° C
Piezoelectric pulse frequency: 20 kHz
The dried and solidified toner particles were collected by suction with a filter having 1 μm pores. Particle size of collected particles The particle size distribution of the collected particles was measured by a flow type particle image analyzer (FPIA-2000). Toner base particles having a wide particle size distribution were obtained. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

[Comparative Example 2]
-Preparation of dispersion-
A colorant dispersion, a dispersion containing a resin and a wax were prepared under the same conditions as in Example 1.
-Preparation of toner-
In place of the apparatus used in Example 1, a storage unit for storing a dispersion liquid, and a piezoelectric pulse generated by the expansion and contraction of a piezoelectric body in the storage unit, and a pressure pulse obtained by converging with an acoustic lens, a droplet The toner was produced under the same conditions as in Comparative Example 1 except that the apparatus was provided with a head unit capable of ejecting from the nozzle. The apparatus of Example 1 has a structure in which vibration is applied to the nozzle itself, whereas the apparatus of Comparative Example 2 is greatly different in that a piezoelectric pulse is applied to the dispersion liquid storage unit.
The dried and solidified toner particles were collected by suction with a filter having 1 μm pores. Particle size of the collected particles The particle size distribution of the collected particles was measured with a flow particle image analyzer (FPIA-2000). The mass average particle size was 7.2 μm, and the number average particle size was 5.6 μm. Toner base particles having a wide particle size distribution were obtained. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

[Comparative Example 3]
-Preparation of dispersion-
A colorant dispersion, a dispersion containing a resin and a wax were prepared under the same conditions as in Example 1.
Instead of the droplet discharge unit of the apparatus used in Example 1, thermal energy is given by a storage unit that stores the dispersion, and a heating element that generates heat by applying an alternating voltage to the dispersion stored in the storage unit, Toner was produced under the same conditions as in Comparative Example 1 instead of the apparatus provided with a head part capable of ejecting liquid droplets from the nozzle by volume expansion due to bubbles generated in the storage part.
The dried and solidified toner particles were collected by suction with a filter having 1 μm pores. Particle size of collected particles The particle size distribution of the collected particles was measured with a flow type particle image analyzer (FPIA-2000). The mass average particle size was 7.9 μm, and the number average particle size was 4.6 μm. Toner base particles having a large particle size distribution with many fine particles of 1 μm or less were obtained. A scanning electron micrograph of this toner base is shown in FIG.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

  As shown in Table 1, it was found that the toner can be efficiently converted into a toner according to the present invention, and the toner characteristics are extremely good. In addition, an image obtained by developing using the toner produced in the present invention was extremely excellent in image quality faithful to the electrostatic latent image.

  The toner production method and toner production apparatus of the present invention can produce toner efficiently and, furthermore, are particles having a monodispersibility with an unprecedented particle size. In many of the characteristic values required for toner, there is no or very little variation due to particles as seen in conventional manufacturing methods, so electrostatic charge in electrophotography, electrostatic recording, electrostatic printing, etc. It is suitably used as a developer for developing an image.

It is explanatory drawing of an example of the toner particle manufacturing apparatus for implementing this invention. It is explanatory drawing of an example of the storage part in this invention. It is a figure explaining the droplet formation phenomenon of a liquid column. 2 is a scanning electron micrograph of the toner base produced in Example 1. FIG. 6 is a scanning electron micrograph of the toner base produced in Example 6. 6 is a scanning electron micrograph of the toner base produced in Example 8. FIG. 10 is a scanning electron micrograph of the toner base produced in Example 9. 6 is a scanning electron micrograph of the toner base produced in Example 10. 4 is a scanning electron micrograph of the toner base produced in Comparative Example 1. 4 is a scanning electron micrograph of a toner base produced in Comparative Example 2. 6 is a scanning electron micrograph of a toner base produced in Comparative Example 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Storage part 2 Vibration means 3 Support means 4 Through-hole 5 Liquid supply means 6 Solvent removal equipment 7 Toner collection part 8 Piping 9 Through-hole holding mechanism 10 Vibration generator 11 Conductive wire 12 Release valve 13 Droplet 14 Drying means 15 Toner particle

Claims (18)

A toner composition containing at least a polyester resin or a styrene acrylic copolymer resin and a colorant, and a 3,5-di-tert-butyl-salicylate iron which is a reactive substance that increases the viscoelasticity of the resin of the toner composition ; The toner composition liquid obtained by liquefying the toner composition is supplied to the storage section, and a plurality of penetrating holes provided in the storage section are excited while the toner composition liquid is excited through the storage section by vibration means that contacts at least a part of the storage section. A toner manufacturing method comprising: discharging the toner composition liquid from a hole into a granulation space; forming the toner composition liquid from a columnar state through a constricted state into droplets; and transforming the droplets into solid particles in the granulation space. Method. A toner composition liquid obtained by liquefying a toner composition containing at least a polyester resin or a styrene acrylic copolymer resin and a colorant is supplied to the storage section, and the storage section is formed by vibration means in contact with at least a part of the storage section. The toner composition liquid is discharged into the granulation space through a plurality of through holes provided in the storage portion while exciting the toner composition liquid through the storage portion, and the toner composition liquid is formed into droplets from a columnar state through a constricted state. 3,5-di-t-butyl-salicylate iron , which is a reactive substance that increases the viscoelasticity of the resin of the toner composition, is externally added to the solid particles obtained by changing the droplets into solid particles in the granulation space. And a toner manufacturing method.   The toner manufacturing method according to claim 1, wherein the toner composition liquid contains an organic solvent, and the change from droplets to solid particles is performed by solvent removal.   The toner manufacturing method according to claim 1, wherein the through hole is a hole having an opening diameter of 1 to 40 μm formed in a metal plate having a thickness of 5 to 50 μm.   By causing a dry gas to flow in the same direction as the droplet discharge direction, an air flow is generated, and the air flow causes the droplets to be transported in the solvent removal equipment, and the solvent in the droplets is removed during the transport. The toner manufacturing method according to claim 1, wherein toner particles are formed.   6. The toner manufacturing method according to claim 5, wherein the dry gas is one of air and nitrogen gas.   The method for producing a toner according to claim 5 or 6, wherein the temperature of the dry gas is 40 to 200 ° C.   The solvent removal equipment has a transport path whose periphery is covered with an electrostatic curtain charged with a polarity opposite to the charge of the droplet, and allows the droplet to pass through the transport path. The method for producing a toner according to claim 5. Toner composition containing at least a polyester resin or styrene acrylic copolymer resin and a colorant, and a reactive substance that increases the viscoelasticity of the resin of the toner composition, 3,5-di-t-butyl-iron salicylate storing a toner composition liquid prepared by liquefying the door, and a reservoir having a plurality of through holes, it is in contact with at least part of the accumulating portion, and exciting the toner constituent liquid through the reservoir, Vibration means for converting the toner composition liquid into droplets from the columnar state through the constricted state through the through-holes and discharging the droplets into the granulation space; toner particle forming means for changing the droplets into solid particles in the granulation space; The toner production method according to claim 1, wherein the toner is produced using a toner production apparatus having a toner collection unit that collects toner particles.   The toner manufacturing method according to claim 9, wherein a vibration frequency of the vibration unit is 50 kHz to 50 MHz.   The method for producing toner according to claim 9 or 10, wherein the vibration frequency of the vibration means is 100 kHz to 10 MHz.   After forming a conveyance path whose periphery is covered with an electric field curtain in the granulation space, the charge of the toner particles formed by passing droplets through the conveyance path is temporarily neutralized by a static eliminator The toner production method according to claim 9, wherein the toner particles are contained in a toner collecting unit.   The method for producing a toner according to claim 12, wherein the static elimination by the static eliminator is performed by soft X-ray irradiation.   The method for producing toner according to claim 12, wherein the charge removal by the charge eliminator is performed by plasma irradiation.   The toner collecting portion has a tapered surface whose opening diameter is gradually reduced. From the outlet portion where the opening diameter is reduced from the inlet portion, toner particles are used as a dry gas to form a flow of the dry gas. The method for producing toner according to claim 9, wherein the toner particles are transferred to a toner storage container by the flow of the dry gas.   The toner manufacturing method according to claim 15, wherein the flow of the dry gas is a vortex.   The method for producing toner according to claim 9, wherein the toner collecting portion and the toner storage container are formed of a conductive material and are grounded.   The toner manufacturing method according to claim 9, wherein the toner has an exposure specification.