JP2007199463A - Method for manufacturing particle, particularly toner particle, apparatus for manufacturing toner particle, and toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To efficiently provide toner which has entirely no or extremely reduced width of fluctuation due to particles and is used in a developer for developing an electrostatic latent image in, for example, electrophotography, electrostatic recording, electrostatic printing, etc. <P>SOLUTION: The particles are manufactured by supplying a raw material fluid to a storage section, emitting the raw material liquid from a plurality of through-holes while applying vibration to the storage section by a vibrating means being in contact with part of the storage section, so as to form the liquid droplets of the raw material fluid and solidifying the liquid droplets. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing toner particles used in a developer for developing electrostatic images in particles, particularly electrophotography, electrostatic recording, electrostatic printing, and the like, and a toner produced thereby.

  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 toner manufacturing method, a method has been proposed in which a pressure pulse is applied to a liquid to discharge a raw material from a through hole to form a fine droplet, which is then dried and solidified to form a toner (Patent Document). 2). Further, a method has been proposed in which microbubbles are formed by using the bubble pressure generated by applying thermal energy to the liquid chamber, 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, since a pressure pulse is applied (by a piezoelectric body), the volume of the storage section is changed, so that the discharge from the storage section to the discharge section and the supply to the storage section are performed. During ejection, liquid is pushed out from the ejection part in the pressurization direction / volume reduction direction inside the storage part and discharged in the form of droplets at the time of discharge, and for supplying a new toner composition liquid to the storage part In addition, the toner composition liquid is filled into the storage portion at a pressure in the pressure reducing direction / volume expansion direction. At this time, since the liquid (toner composition liquid) that has been in contact with the outside air at the discharge section is sucked into the storage section again, the toner composition liquid is dried (changes in solid content concentration), and the discharge section is a pore. As a result, sufficient productivity and toner particle quality (variation among particles) could not be achieved.

  In addition, since the pressure pulses of the vibrator are concentrated locally in the liquid chamber, it is difficult to form droplets at once from a plurality of ten or more through holes. In order to increase productivity, it is necessary to increase the number of vibrators equivalent to the increase in the number of through-holes, which makes control difficult and the configuration very complicated. Furthermore, it is difficult to increase the vibration frequency to 50 kHz or higher in consideration of the inertia of the liquid in the through hole. In addition, since the piezoelectric element that is usually used has a small mechanical displacement, it is necessary to cope with this by increasing or stacking the piezoelectric element, and thus it is difficult to integrate the through holes. In the liquid discharge method using the generation pressure of bubbles due to thermal energy as disclosed in Patent Document 3, the temperature in the heat source instantaneously becomes about 300 ° C., and organic matter alteration (kogation) occurs. Changes in droplet size over time during continuous operation were observed. In addition, it is difficult to control the size of the droplet.

Separately, there is an invention related to a granulating apparatus / method for forming droplets extruded from pores into particles in another industry, although it is not a method for producing a toner (composite material composition). (See Patent Document 5)
These are different from the toner production method and granulate a single composition such as metal and glass. In these methods, a discharge unit / orifice, a liquid storage unit, and a vibration unit are provided, and vibration is transmitted by direct contact with the liquid in the storage unit, and the vibration is discharged from the orifice. The fluid can break into droplets and form particles.

On the other hand, in order to use fine particles such as toner particles as a toner, it is necessary to produce a large number of particles, and the productivity becomes a big issue. From the viewpoint of productivity, it is possible to improve productivity by forming a large number of pores / orifices, but the number of vibration means directly affects the cost. Therefore, in order for the toner industry to ensure the productivity in producing toner particles, a configuration in which uniform particles can be produced with a single vibration means for a plurality of pores is essential.
Further, it is known that toner particles need to have a sharp particle size distribution (for reasons such as image fineness and uniformity of charging performance). Compared to conventional methods, granulation using an orifice may achieve a sharp particle size distribution that cannot be compared with conventional methods.

In the case of the above-described granulation method (see Patent Document 5 and Patent Document 6: Hitachi Metals), the vibration unit is characterized by being in direct contact with the fluid. In the case of such a configuration, a sharp particle size distribution can be achieved when the number of pores and the number of vibrating parts match, but in the case of a large number of pores and one vibrating part, the position of the pores and the vibrating part It has been found that the size of the droplets ejected from the pores changes according to the distance depending on the positional relationship, so that the toner particles produce different particle sizes between different orifices.
JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977 JP 2001-226706 A JP 2003-104744 A Rayleigh, Lord "On the Instability of Jets" Proc. London Math. Soc. 110: 4 [1878] Schneider JM, CD Hendricks, Rev. Instrum. 35 (10), 1349-50 [1964] Lindblad NR and JM Schneider, J. Sci. Instrum. 42, 635 [1965]

  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 provides a toner manufacturing apparatus that can efficiently produce toner with a simple configuration, good controllability and maintainability, and that can operate stably without blocking the through hole. Since the particles have unprecedented monodispersibility, many of the characteristic values required for the toner, such as fluidity and charging characteristics, are completely different from the fluctuations caused by the particles in the conventional production methods. There is provided a method for producing a toner used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, etc., which is not or very little, and a toner produced thereby For the purpose.

Means for solving the problems are as follows. That is,
<1> In a particle manufacturing method in which a raw material fluid discharged from a through-hole is formed into droplets to produce particles, the raw material fluid is supplied to the storage unit, and the storage unit is vibrated by vibration means that contacts a part of the storage unit. In addition, the particle manufacturing method is characterized in that the raw material liquid is discharged from a plurality of through-holes provided in the storage portion, the raw material fluid is formed into droplets, and the droplets are solidified in the granulation space.

In the particle production method according to <1>, the vibration unit is provided in one storage unit by contacting a part of the storage unit and applying vibration to the raw material fluid through the storage unit. In addition, since it is possible to generate a pressure density wave by equally vibrating the raw material fluids discharged from the plurality of through holes at the same time, more than 100 droplet formation phenomena are generated simultaneously by one vibration means. It becomes possible.
<2> In a toner particle manufacturing method in which toner composition raw material fluid discharged from a through hole is made into droplets to produce particles, vibration means for supplying the toner composition raw material fluid to the storage part and contacting a part of the storage part The toner composition raw material liquid is discharged from a plurality of through-holes provided in the storage portion while applying vibration to the storage portion, and the toner composition raw material fluid is formed into droplets, and the droplets are solidified in the granulation space. This is a method for producing toner particles.

In the toner particle manufacturing method according to <2>, the vibration unit is in contact with a part of the storage unit, and the raw material fluid is vibrated through the storage unit, so that it is provided in one storage unit. It is possible to generate a pressure density wave by applying equal vibration to the raw material fluid discharged from the formed through-holes simultaneously, so that ten or more droplet forming phenomena can be generated simultaneously by one vibration means. Therefore, it is possible to provide a toner particle manufacturing apparatus with extremely excellent productivity.
<3> The method for producing toner particles according to <1> or <2>, wherein the raw material fluid is formed into droplets from a columnar shape through a constricted state.
<3> indicates a state from a droplet of the raw material fluid to solidification.
<4> The number X of the vibrating means and the number Y of the through holes are
10 x X ≤ Y ≤ 10000 x X,
The method for producing toner particles according to any one of <1> to <3>, wherein the vibration unit is in contact with a part of the storage unit and excites the raw material fluid through the storage unit. .
In the toner particle manufacturing method according to <4>, since the vibration unit is supported by the support unit, the vibration component generated by the vibration unit can be efficiently transmitted to the storage unit. To provide a toner particle manufacturing method capable of uniformly giving vibrations to the raw material fluid discharged from a plurality of through-hole portions and forming particles having a very uniform particle diameter from the plurality of through-holes. Can do.

<5> The toner particle manufacturing method according to any one of <1> to <4>, wherein the volume fluctuation of the reservoir generated by the vibration of the vibration unit is smaller than the volume of one droplet. is there.
In the toner particle manufacturing method according to <5>, since the volume fluctuation in the reservoir caused by the vibration wave generated by the vibrating means is smaller than the volume of the droplet generated in one vibration cycle, Is not pulled back to the reservoir, so that bubbles can be prevented from entering the reservoir, and drying of the through-holes and poor liquid discharge do not occur.

<6> The toner particle manufacturing method according to any one of <1> to <5>, wherein the diameter of the through hole is 1.0 to 40.0 μm.
In the method for producing toner particles according to <6>, by being 1.0 to 40.0 μm, fine particle components of 1 μm or less contained in the toner particles can pass through without clogging in the vicinity of the through hole. Therefore, it becomes possible to manufacture toner particles stably.
<7> Any one of <1> to <6>, wherein the shape of the through hole is a shape in which the liquid inlet hole area is the largest, the sectional area is gradually reduced, and the liquid outlet is the smallest. The toner particle production method described in 1.
According to the particle manufacturing method of <7>, the shape of the through hole is tapered, and the cross-sectional area is gradually reduced, so that the fluid can flow out without causing turbulence in the liquid flow in the vicinity of the through hole. Therefore, toner particles can be stably produced without depositing fine particle components of 1 μm or less contained in the fluid.

<8> The toner particle manufacturing method according to any one of <1> to <7>, wherein the circularity of the outlet shape of the through hole is 90% or more.
According to the method for producing toner particles according to <8>, since the circularity of the outlet shape of the through-hole is 90% or more, the liquids flowing out adjacent to each other can be combined without disturbing the flow direction of the liquid. Toner particles can be stably produced without being clogged with fine particles of 1 μm or less contained in the fluid.
<9> The toner particle manufacturing method according to any one of <1> to <8>, wherein an interval between the adjacent through holes is at least three times an average value of the diameters of the through hole outlets. .
According to the particle manufacturing method according to <9>, when the interval between the adjacent through holes is three times or more the average value of the diameters of the through hole outlets, the adjacent liquid flowing out is brought into contact with each other. Therefore, the liquid can be discharged stably and toner particles can be manufactured stably.

<10> The method for producing toner particles according to any one of <1> to <9>, wherein a frequency of vibration applied by the vibration unit is 100 kHz to 10 MHz.
According to the method for producing toner particles according to <10>, it is possible to form 100,000 to 10,000,000 monodispersed droplets per second from one through hole. A toner particle production method having excellent productivity can be provided.
<11> The toner particle production method according to any one of <1> to <10>, wherein the toner composition raw material fluid is a fluid in a non-uniform state in which insoluble matters are dispersed. .

<12> The toner particle production method according to <11>, wherein the toner composition raw material fluid contains a volatile organic solvent.
According to the method for producing toner particles according to <12>, the insoluble matter is dispersed in the organic solvent, so that the fluid can flow out from the through hole.
<13> Any one of <1> to <12>, wherein the raw material fluid or the toner composition raw material fluid includes a pressurizing unit that generates a pressure difference between the storage unit and the droplet forming unit. The toner particle production method described in 1.
In the method for producing toner particles according to <13>, a liquid column is stably formed from the plurality of through holes by generating a pressure difference between the storage portion and the droplet forming portion by the pressurizing unit. It becomes possible.

<14> The method for producing toner particles according to <13>, wherein the continuously released raw material fluid or the toner composition raw material fluid has a continuous columnar shape immediately after being discharged from the through hole. It is.
<15> The toner particle manufacturing method according to <13> or <14>, wherein the vibration unit generates a pressure fluctuation of 50% or less in the fluid and forms a constriction in the liquid column.
In the method for producing toner particles according to <15>, by suppressing the pressure fluctuation applied to the toner composition raw material fluid to 50% or less, drying of the liquid component in the vicinity of the through hole is prevented, and the liquid is stably discharged. The toner particles can be stably produced.

<16> The constriction period λ and the diameter Dj of the fluid column are 3.0 × Dj <λ <8.0 × Dj
The method for producing toner particles according to any one of <12> to <15>, wherein the fluid column tip is changed into a droplet.
In the toner particle manufacturing method according to <16>, it is possible to give a weak pressure density variation to the liquid column generated from the plurality of through holes by a vibrating unit.
When the constriction period λ and the diameter Dj of the fluid column are 3.0 × Dj <λ <8.0 × Dj, it becomes possible to form droplets having a very uniform diameter due to Rayleigh instability.

<17> From <1> to <1>, wherein a drying unit and / or a solidifying unit are provided in a downstream portion of the through hole to release the raw material fluid or the toner composition raw material fluid, and the droplets are solidified. 16>. The toner particle manufacturing method according to any one of 16).
<18> The toner particle production method according to <17>, wherein the solidification is a solvent removal.
In the method for producing toner particles according to <18>, since the fluid containing the toner raw material formed into droplets can be dried by the drying means and / or the solidifying means, respectively, the diameter is larger than that of the toner particles. Dry particles can be obtained using the through-holes, and blockage of the through-holes can be prevented.

<19> The solid content concentration ((raw material amount−organic solvent amount) / (raw material amount)) in the raw material fluid is 3 to 20 wt%, <17> or <18> A toner particle manufacturing method.
<20> A toner obtained by the production method according to any one of <1> to <19>.
<21> The toner obtained in <20> is a toner having a particle size distribution in the range of 1.00 to 1.05 and a weight average particle size of 1 to 20 μm.
<22> A continuous particle manufacturing apparatus including a particle raw material fluid storage unit, vibration means attached to the storage unit, and a discharge unit having a plurality of through holes for discharging the particle raw material fluid. A plurality of through holes corresponding to the means are arranged, and the correspondence relationship between the number X of the vibrating means and the number Y of the through holes is 10 × X ≦ Y ≦ 10000 × X.
And the vibrating means applies vibrations to the raw material fluid through the storage section.
In the particle manufacturing apparatus according to <22>, the vibrating unit is in contact with a part of the storage unit, and vibrates the raw material fluid through the storage unit, whereby the through hole provided in one storage unit Since it is possible to generate vibrations by applying equal vibrations to the released raw material fluids at the same time, it is possible to simultaneously generate 100 or more droplet forming phenomena by one vibration means.
<23> A continuous toner particle manufacturing apparatus comprising a toner composition raw material fluid storage section, vibration means attached to the storage section, and a discharge section having a plurality of through holes for discharging the toner composition raw material fluid. A plurality of through holes corresponding to one vibration means are arranged, and the correspondence between the number X of vibration means and the number Y of through holes is 10 × X ≦ Y ≦ 10000 × X.
And the vibration means imparts vibration to the toner composition raw material fluid through the storage section.
By the <23>, uniform toner particles can be obtained.
<24> The manufacturing apparatus includes a drying unit and / or a solidifying unit, and solidifies the droplets.
With the <24>, solid particles can be continuously produced.
<25> The toner particle manufacturing apparatus according to any one of <22> to <24>, wherein the diameter of the through hole is 1.0 to 40.0 μm.
By <25>, particles having excellent characteristics, such as toner particles, can be obtained.
<26> The toner particle manufacturing apparatus according to any one of <22> to <25>, wherein a vibration frequency of the vibration unit is 100 kHz to 10 MHz.
By limiting the vibration frequency, uniform particles, particularly toner particles, can be obtained.

  According to the present invention, conventional problems such as blockage of the through-hole portion, productivity, and stability can be solved, particles, particularly toner can be efficiently produced, and single dispersibility with an unprecedented particle size can be achieved. In many of the characteristic values required for toners such as fluidity and charging characteristics, there is no or very little variation due to particles as seen in conventional production methods. In addition, it is possible to provide a method for producing a toner used as a developer for developing an electrostatic charge image in electrostatic recording, electrostatic printing, and the like, and a toner produced thereby.

  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.

(Toner production method)
The toner composition has a reservoir for storing a toner composition raw material fluid containing at least a binder resin and a colorant, vibration means, and the through hole.
The toner composition raw material liquid discharged from the through hole is quantitatively supplied to the storage part, and is quantitatively discharged from the through hole to be converted into a liquid column,
The number X of vibration means and the number Y of the through holes in the toner particle manufacturing apparatus are 10 x X ≤ Y ≤ 10000 x X,
The vibration means is in contact with a part of the storage part and excites the toner composition raw material fluid through the storage part. The toner composition raw material fluid may be formed into droplets by this excitation, and the droplets may be dried to form solid toner particles.
The liquid column droplet formation phenomenon will be described with reference to FIG.

-Droplet phenomenon-
As explained in Non-Patent Document 1, the uniform liquid droplet formation phenomenon of the liquid column is 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). expressed.
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, as a result of deriving the conditions for forming stable uniform particles experimentally, uniform particles can be stably formed under the condition of the following formula (3). There is.
3.5 <λ / d (jet) <7.0 (3)
Furthermore, as explained in Non-Patent Document 3, based on the energy conservation law, the minimum jet V (min) speed at which the liquid discharged from the through hole forms a liquid column is expressed by the following equation (4). It is expressed as follows.
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. It is confirmed that the liquid column can be changed into droplets by the above disturbance by attaching the vibrator to the liquid chamber and vibrating it at the frequency f. Was established.

-Device-
The apparatus used in the particle production method or toner particle production method of the present invention (hereinafter also referred to as “toner particle production apparatus”) is not particularly limited as long as it is an apparatus capable of producing toner by this production method. Can be selected and used as appropriate,
The toner particle manufacturing apparatus includes at least a storage unit that stores the toner composition raw material fluid, a vibration unit, a support unit that holds the vibration unit, and the plurality of through holes, and is discharged from the through holes. The toner composition raw material liquid is quantitatively supplied to the reservoir, and is quantitatively released from the through hole.
A plurality of the through-holes are arranged for one of the vibrating means, and the vibrating means is in contact with a part of the reservoir and excites the toner composition raw material fluid via the reservoir. And a toner particle forming unit configured to form toner particles by drying the droplets by removing the solvent contained in the droplets and forming toner particles. preferable.

  As the preferable toner manufacturing apparatus, for example, as shown in FIG. 2, at least a storage unit 1 for storing at least the toner composition raw material fluid as the droplet forming unit, a vibrating unit 2, and the vibrating unit Support means 3 for holding the plurality of through-holes 4 for quantitatively supplying the toner composition raw material liquid discharged from the through-holes to the storage section and discharging quantitatively from the through-holes A device having a liquid supply means 5, a solvent removal facility 6 as the toner particle forming means, and a toner collecting portion 7 is preferably mentioned.

Hereinafter, the toner manufacturing apparatus will be described in detail for each member.
--- Storage part--
Since the storage portion 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. Further, for example, as shown in FIG. 3, 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 and to provide the release valve 12 for removing 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 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 constant 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 to arrange them 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 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 opening diameter means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse.

-Supplying and 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 droplet 6 can be removed, but an air flow is generated by flowing a dry gas 14 in the same direction as the droplet 13 flight 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 transport. 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 capable of drying the droplets 6, and examples thereof include air and nitrogen gas.

-Toner collection part-
The toner collecting unit 5 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 5 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 in the illustrated example, the toner particles 15 may be pumped to the toner storage container by a dry gas, 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.
Further, from the viewpoint of more efficiently transporting the toner particles 15, it is more preferable that the toner collecting portion and the toner collecting container are formed of a conductive material and are connected to the ground. preferable. The toner manufacturing apparatus preferably has an exposure specification.

-Action-
According to the toner particle manufacturing method of the present invention described in detail above, the number of droplets generated from one through hole is very large, tens of thousands to several million per second. It is hard to happen. For this reason, it can be said that it is the most suitable method for producing toner from the viewpoint of obtaining a very uniform droplet diameter and having sufficient productivity.
Since the toner particle manufacturing apparatus of the present invention can control the droplet formation phenomenon in a large number of through-holes of 10 to 10,000 very uniformly with one vibration means, in addition to the above-mentioned productivity, It can be said that this is a high toner production apparatus.

In the conventional manufacturing method, the particle size often varies greatly depending on the material used, but in this manufacturing method, the particle size as set is managed by managing the droplet diameter when discharging and the solid content concentration. It is possible to continuously obtain particles having
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 above-described toner manufacturing method of the present invention.
As the toner, a toner having a monodispersed particle size distribution can be obtained by the toner manufacturing method.
Specifically, the particle size distribution (weight average particle diameter / number average particle diameter) of the toner is preferably in the range of 1.00 to 1.05. Moreover, as a weight average particle diameter, it is preferable that it is 1-20 micrometers.

The toner material that can be used in the present invention can be the same as the 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 and a colorant and, if necessary, other components such as a carrier and a wax.

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

Examples of the styrene monomer 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, Examples thereof include styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof.
Examples of acrylic monomers include acrylic acid, or methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic acid. Examples include 2-ethylhexyl, 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 2 -Ethylhexyl, stearyl methacrylate, phenyl methacrylate, methacrylic acid such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate or esters thereof, and the like.

  The following (1)-(18) is mentioned as an example of the other monomer which forms the said vinyl polymer or a copolymer. (1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8), vinyl naphthalenes; (9) acrylonitrile, Such as methacrylonitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic anhydride and alkenyl succinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid, etc. (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; 16) Monomers having a carboxyl group such as anhydrides of the α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof; ) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1 -Hydroxy-1-methylhexyl) monomers having a hydroxy group such as styrene.

  In the toner of the present invention, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent 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 crosslinking agents are preferably used in an amount of 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, with respect to 100 parts by mass of other monomer components.

  Among these crosslinkable monomers, diacrylates bonded to a toner resin by a bond chain containing one aromatic divinyl compound (especially divinylbenzene), one aromatic group and an ether bond from the viewpoint of fixability and offset resistance. Preferred examples include compounds. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

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

When the binder resin is a styrene-acrylic resin, the molecular weight distribution by GPC soluble in the resin component tetrahydrofuran (THF) has at least one peak in the region of molecular weight 3,000 to 50,000 (in terms of number average molecular weight). A resin which is present and has 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 molecular weight region of 5,000 to 30,000 is more preferable. A binder resin having a main peak in the region of 5,000 to 20,000 is most preferable.
The acid value when the binder resin is a vinyl polymer such as styrene-acrylic resin is preferably 0.1 mgKOH / g to 100 mgKOH / g, and preferably 0.1 mgKOH / g to 70 mgKOH / g. More preferably, it is 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, and the amount of KOH solution used at this time is B (ml), which is calculated by the following equation (1). However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (1)

  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 mixtures thereof are used.
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 determined by measuring an enlarged photograph taken with a transmission electron microscope with a digitizer or the like.
Further, the magnetic properties of the magnetic material are preferably 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 when applied with 10K oersted.
The magnetic material can also be used as a colorant.

--Colorant--
The colorant is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, 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 together with the production of the master batch or the master batch, in addition to the above-mentioned modified and unmodified polyester resins, for example, polystyrene, poly p-chlorostyrene, polyvinyltoluene and other styrene and its substitutes Polymer: Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate Copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene -Α-Chloromethyl methacrylate Polymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, Styrene copolymers such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl Examples include butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, there is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high 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 weight average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene conversion weight in gel permeation chromatography, preferably 500 to 100,000, and more preferably 3000 to 100,000 from the viewpoint of pigment dispersibility. In particular, 5000 to 50000 is preferable, and 5000 to 30000 is 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 100000, the affinity with the solvent increases and the dispersibility of the colorant decreases. There is.
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.

-Other ingredients-
<Career>
The toner of the present invention may be mixed with a carrier and used as a two-component developer. As the carrier, ordinary carriers such as ferrite and magnetite and resin-coated carriers can be used.
The resin-coated carrier comprises a carrier core particle and a coating material that is a resin that coats (coats) the surface of the carrier core particle.

  Examples of the resin used 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.

Examples of elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done. Of 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 set to 106 to 1010 Ω · cm by adjusting the degree of unevenness on the surface of the carrier and the amount of resin to be coated.

The carrier having a particle diameter 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.

<Wax>
In the present invention, a wax may 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 based on fatty acid esters such as animal waxes such as beeswax, lanolin and whale wax, mineral waxes such as ozokerite, ceresin and petrolatum, and montanic ester waxes and castor waxes. 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 fatty acids such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnapyl 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 sepasic acid amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Grafted with aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate, and aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid. Examples include waxes, partial ester compounds of fatty acids such as behenic acid monoglyceride and polyhydric alcohols, and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  More preferred examples include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, and polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure. Polyolefins, polyolefins polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefins obtained by thermal decomposition of high molecular weight polyolefins, 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 highly accurate 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.

<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, Fine powder non-alumina, treated silica obtained by subjecting them to surface treatment with a silane coupling agent, titanium coupling agent or silicone oil, treated titanium oxide, treated alumina, and the like can be mentioned. Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.
The particle size of the fluidity improver is preferably 0.001 to 2 μm, and 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 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 preferred method, a method of treating silica fine powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferable.

  Examples of organosilicon compounds include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, 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 μm to 2 μm, and more preferably 5 μm to 500 μm.

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 silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, Etc. are preferable.

The primary particle diameter of the inorganic fine particles is preferably 5 μm to 2 μm, and more preferably 5 μm to 500 μm. 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 weight of the toner, and more preferably 0.01 to 2.0% by weight.

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

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 rainbow dispersion in 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 polyester resin as a binder resin, 30 parts by mass of the carbon black dispersion, and 5 parts by mass of carnauba wax are mixed with 1000 parts by mass of ethyl acetate, and a mixer having stirring blades is used as in the preparation of the colorant dispersion. Then, the mixture was stirred for 10 minutes and dispersed. 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 with through-holes used was 10 concentric circles with a 20 μm-thick nickel plate with a circular exit hole with a diameter of 8.0 μm removed by laser ablation using a mask reduction projection method with a femtosecond laser. Produced. 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. FIG. 4 shows a state in which the liquid droplet droplet formation phenomenon is photographed.

[Toner preparation conditions]
Dispersion solid content: 6.0%
Liquid flow rate: 40 ml / hr
Dry air flow rate: Sheath 2.0 L / min, In-apparatus air 3.0 L / min In-apparatus temperature: 27-28 ° C
Dew point temperature: -20 ° C
Common liquid chamber vibration frequency: 601.0 kHz
The dried and solidified toner particles were collected by a cyclone. Particle size of collected particles The particle size distribution of the collected particles was measured with a flow particle image analyzer (FPIA-2000). The ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn was 1.0. 2. 2.6 g of toner base particles having a number average particle diameter of 6.0 μm were obtained in 1 hour of production.

-Toner evaluation-
The obtained toner was evaluated as follows. The results are shown in Table 1.
<Particle size distribution>
Examples of the measuring device for the particle size distribution of toner particles by the Coulter counter method include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measuring device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter of the toner can be obtained.
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 .35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

<Thin wire reproducibility>
The developer was put into a modified machine in which a developing unit 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 with an average particle size of 50 μm Coating material constituent 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)
A plate having through-holes of Example 1 having 100 pieces in a staggered lattice shape as shown in FIG. 5 produced by the same processing method in a square range with a side of 0.5 mm was used. All were the same except that the liquid flow rate was 407 ml / hr.
The dried and solidified toner particles were collected by a cyclone. 25.0 g of toner base particles having a Dv / Dn of 1.02 and a number average particle diameter of 6.0 μm were obtained in 1 hour. The obtained toner was evaluated as described above, and the results are shown in Table 1.

(Example 3)
The plate having through-holes of Example 1 was used in which 1024 pieces in a staggered pattern produced by the same processing method exist in a square range of 4.0 mm on a side. All were the same except that the liquid flow rate was 4016 ml / hr.
The dried and solidified toner particles were collected by a cyclone. 272 g of toner base particles having a ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn of 1.03 and a number average particle diameter of 6.0 μm were produced in one hour. The obtained toner was evaluated as described above, and the results are shown in Table 1.

Example 4
Example 3 was the same as Example 3 except that the frequency of Example 3 was 400 kHz and the liquid flow rate was 2780 ml / hr.
The dried and solidified toner particles were collected by a cyclone. 183 g of toner base particles having a ratio Dv / Dn of 1.03 and a number average particle diameter of 6.0 μm between the volume average particle diameter Dv and the number average particle diameter Dn of the obtained particles was produced in 1 hour. The obtained toner was evaluated as described above, and the results are shown in Table 1.

(Example 5)
The plate having through-holes of Example 1 in which 1024 pieces in a staggered pattern produced by the same processing method exist in a square range of 4.0 mm on a side was used. All were the same except that ten reservoirs having one vibration means were arranged and the flow rate of liquid fed to one reservoir was 4016 ml / hr.
The dried and solidified toner particles were collected by a cyclone. 2720 g of toner base particles having a ratio Dv / Dn of 1.05 and a number average particle diameter of 6.0 μm between the volume average particle diameter Dv and the number average particle diameter Dn of the obtained particles was produced in 1 hour. 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 a dispersion liquid, and a pressure pulse is applied to the storage unit by expansion and contraction of a piezoelectric body, whereby a liquid substance can be discharged as a droplet from a nozzle. Instead of a device provided with a head part, after a droplet was discharged under the following toner production conditions, the droplet was dried and solidified to produce a toner. In addition, the apparatus of Example 1 is a structure which pressurizes the inside of a storage part, discharges an internal liquid from a through-hole, forms a liquid column, induces disturbance to the said liquid column by vibration, and is made into a droplet. On the other hand, the apparatus of Comparative Example 1 is greatly different in that a pressure pulse is applied to the dispersion liquid storage portion by a piezoelectric element, and droplets are discharged by the energy of the pressure pulse. Further, the number of droplet discharge portions used in this comparative example was one.

[Toner preparation conditions]
Dispersion specific gravity: ρ = 1.888 g / cm ³
Dry air flow rate: In-apparatus air 3.0L / min 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). The weight average particle size was 7.8 μm, and the number average particle size was 5.2 μm. Toner base particles having a wide particle size distribution were obtained. The production amount per hour was 0.86 g.
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 the first embodiment, a storage unit for storing the dispersion liquid, and a pressure pulse obtained by converging the pressure pulse generated by the expansion and contraction of the piezoelectric body in the storage unit with an acoustic lens, 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. In addition, the apparatus of Example 1 is a structure which pressurizes the inside of a storage part, discharges an internal liquid from a through-hole, forms a liquid column, induces disturbance to the said liquid column by vibration, and is made into a droplet. On the other hand, the apparatus of Comparative Example 2 is greatly different in that a pressure pulse is applied to the dispersion liquid storage portion by a piezoelectric element and droplets are ejected by the energy of the pressure pulse. Further, the number of droplet discharge portions used in this comparative example was one.
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 particle image analyzer (FPIA-2000). The weight 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. The production amount per hour was 0.86 g. 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. Further, the number of droplet discharge portions used in this comparative example was one.
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 weight 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. The production amount per hour was 0.86 g.
The obtained toner was evaluated as described above, and the results are shown in Table 1.

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

It is explanatory drawing of the droplet formation phenomenon of a liquid column. It is explanatory drawing of an example of a toner particle manufacturing apparatus. It is explanatory drawing of an example of a storage part. It is a photograph of the droplet formation phenomenon of the liquid column. It is a figure which shows the example of arrangement | positioning of a zigzag-like through-hole.

Explanation of symbols

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

Claims (26)

  In the particle manufacturing method for producing particles by dropletizing the raw material fluid discharged from the through-hole, supplying the raw material fluid to the storage part, while applying vibration to the storage part by vibration means in contact with a part of the storage part, A method for producing particles, characterized in that the raw material liquid is discharged from a plurality of through-holes provided in a reservoir, the raw material fluid is made into droplets, and the droplets are solidified in a granulation space.   In a toner particle manufacturing method in which toner composition raw material fluid discharged from a through-hole is formed into droplets to produce particles, the toner composition raw material fluid is supplied to a storage part, and the storage is performed by vibration means in contact with a part of the storage part. The toner composition raw material liquid is discharged from a plurality of through-holes provided in the storage portion while vibration is applied to the storage portion, the toner composition raw material fluid is formed into droplets, and the droplets are solidified in the granulation space. A method for producing toner particles. 3. The method for producing toner particles according to claim 1, wherein the raw material fluid is formed into droplets from a columnar shape through a constricted state. The number X of the vibration means and the number Y of the through holes are
10 x X ≤ Y ≤ 10000 x X,
4. The toner particle manufacturing method according to claim 1, wherein the vibration unit is in contact with a part of the storage unit and excites the raw material fluid through the storage unit. 5.   5. The toner particle manufacturing method according to claim 1, wherein a volume fluctuation of the storage portion generated by vibration of the vibration unit is smaller than a volume of one droplet.   6. The toner particle manufacturing method according to claim 1, wherein the maximum diameter of the through hole is 1.0 to 40.0 [mu] m.   7. The toner particle according to claim 1, wherein the shape of the through hole is such that the liquid inlet hole area is the largest, the sectional area is gradually reduced, and the liquid outlet is the smallest. Production method.   8. The toner particle manufacturing method according to claim 1, wherein the circularity of the outlet shape of the through hole is 90% or more.   9. The toner particle manufacturing method according to claim 1, wherein an interval between the adjacent through holes is at least three times the average value of the diameters of the through hole outlets.   10. The toner particle manufacturing method according to claim 1, wherein a frequency of vibration applied by the vibration unit is 100 kHz to 10 MHz.   11. The toner particle manufacturing method according to claim 1, wherein the toner composition raw material fluid is a fluid in a non-uniform state in which insoluble substances are dispersed.   12. The method for producing toner particles according to claim 11, wherein the toner composition raw material fluid contains a volatile organic solvent.   13. The toner particle manufacturing method according to claim 1, further comprising a pressurizing unit that generates a pressure difference between the raw material fluid or the toner composition raw material fluid and the droplet forming unit. .   The toner particle manufacturing method according to claim 13, wherein the continuously released raw material fluid or the toner composition raw material fluid has a continuous columnar shape immediately after being discharged from the through hole.   The toner particle manufacturing method according to claim 14, wherein the vibration unit generates a pressure fluctuation of 50% or less in the columnar fluid to form a constriction in the liquid column. The constriction period λ and the diameter Dj of the fluid column are 3.0 × Dj <λ <8.0 × Dj.
Because
15. The toner particle manufacturing method according to claim 14, wherein the fluid column tip is changed into a droplet.   17. The apparatus according to claim 1, further comprising a drying unit and / or a solidifying unit at a downstream portion of the through-hole through which the raw material fluid or the toner composition raw material fluid is discharged, and the droplets are solidified. 2. The toner particle manufacturing method according to 1.   The toner particle manufacturing method according to claim 17, wherein the solidification is a solvent removal.   19. The toner particle manufacturing method according to claim 17, wherein a solid content concentration in the raw material fluid ((raw material amount−organic solvent amount) / (raw material amount)) is 3 to 15 wt%.   A toner produced by the production method according to claim 1.   The toner obtained in claim 20 has a particle size distribution in the range of 1.00 to 1.05 and a weight average particle size of 1 to 20 μm. A continuous particle manufacturing apparatus comprising a particle raw material fluid storage section, vibration means attached to the storage section, and a discharge section having a plurality of through holes for discharging the particle raw material fluid, corresponding to one vibration means A plurality of through-holes are arranged, and the correspondence relationship between the number X of vibration means and the number Y of through-holes is 10 × X ≦ Y ≦ 10000 × X
And the vibration means applies vibrations to the raw material fluid through the storage section. A continuous toner particle manufacturing apparatus comprising: a toner composition raw material fluid storage section; vibration means attached to the storage section; and a discharge plate having a plurality of through holes for discharging the toner composition raw material fluid. A plurality of through holes corresponding to one vibration means are arranged, and the correspondence between the number X of vibration means and the number Y of through holes is 10 × X ≦ Y ≦ 10000 × X.
And the vibration means imparts vibration to the toner composition raw material fluid via the reservoir. 24. The toner particle manufacturing apparatus according to claim 23, wherein the manufacturing apparatus includes a drying unit and / or a solidifying unit to solidify the droplets. The toner particle manufacturing apparatus according to claim 23 or 24, wherein the diameter of the through hole is 1.0 to 40.0 µm. 26. The toner particle manufacturing apparatus according to claim 23, wherein the vibration means has a vibration frequency of 100 kHz to 10 MHz.

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