JP5343633B2 - Nozzle plate for toner production, toner production method and toner production apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nozzle plate that improves production efficiency of toner and can stably give the toner having a greatly reduced width of variation in fluidity or charging characteristics by forming uniform droplets, and to provide a method for manufacturing the toner and an apparatus for manufacturing the toner using the nozzle plate. <P>SOLUTION: The nozzle plate has nozzles formed therein and is disposed in a liquid reservoir section to store a toner material liquid prepared by dispersing or dissolving a toner composition containing a resin and a colorant. The nozzle plate is characterized in that the liquid reservoir sections where the nozzles are disposed, and flow passages to feed the toner material liquid to the liquid reservoir sections or to remove gas from the toner material liquid are integrally molded by using a composite material having a layer of silicon or silicon and silicon oxide. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a toner manufacturing nozzle plate, a toner manufacturing method, and a toner manufacturing apparatus, and more particularly to a toner manufacturing nozzle plate, a toner manufacturing method, and a toner manufacturing apparatus for manufacturing toner by a jet granulation method.

  As a toner used as a developer for developing an electrostatic image such as electrophotography, electrostatic recording, electrostatic printing, and the like, a polymerization type toner such as a so-called pulverized toner, a suspension polymerization method, an emulsion polymerization aggregation method or the like is used. Are known. In addition, a polymer dissolution suspension method is also known as a polymerization type toner (see Patent Document 1). In this polymer dissolution suspension method, the 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. Toner is produced. Unlike the suspension polymerization method and emulsion polymerization aggregation method, the toner produced by this method has a wide range of versatility in the resins that can be used, and is particularly useful for full color processes that require transparency and smoothness of the image area after fixing. It is excellent in that a polyester resin can be used.

  However, since the above-described polymerization toner is premised on the use of a dispersant in an aqueous medium, there is a problem that a dispersant that impairs the charging characteristics of the toner remains on the toner surface. In addition, there are problems such as the occurrence of problems such as the environmental stability being impaired by this dispersant, and the need for a large amount of washing water to remove the dispersant.

  On the other hand, a spray granulation method is known as a toner production method that does not use an aqueous medium (see Patent Document 2). This is a method in which a toner melt or solution is atomized and discharged using an atomizer and dried to obtain toner particles. For this reason, this manufacturing method does not cause problems due to the use of an aqueous medium.

  However, the toner particles obtained by the conventional spray granulation method are relatively coarse and large, and the particle size distribution is wide, which causes the characteristics of the toner itself to deteriorate.

  Therefore, as an alternative toner manufacturing method, there is known a method of forming fine droplets by using piezoelectric pulses, and further drying and solidifying the droplets, and a manufacturing apparatus for the method is also proposed (patent). Reference 3). Furthermore, a method has been proposed in which fine droplets are formed using thermal expansion in a nozzle, and this is dried and solidified in a granulation space to form a toner (see Patent Document 4).

  However, in the invention of the toner manufacturing method and apparatus described in Patent Documents 3 and 4 described above, droplets are ejected from one nozzle using one piezoelectric body, so the number of droplets that can be ejected per unit time is small. There is a problem that toner productivity is low.

  As another toner manufacturing method, a liquid storage part for storing a toner melt or solution is pressurized to generate a liquid column from the nozzle part, and the liquid column is divided by weak ultrasonic vibration to form droplets. There has been proposed a method and apparatus for producing a toner by drying and solidifying this (see Patent Document 5).

  However, in the toner manufacturing method and apparatus described in Patent Document 5 described above, the toner melt or solution is always unilaterally pressed in the nozzle discharge direction, and ultrafine particles such as a colorant (pigment) and a release material are generated. There is a problem peculiar to toner production that clogs the nozzle.

In order to increase the productivity of toner, it is desirable to set a large number of nozzles. To that end, the dimensions of the liquid reservoir and the thin film nozzle plate are set to the toner manufacturing apparatus described in the prior art 3 or 4. Needs to be much larger. In addition to these, in order to efficiently generate the liquid resonance phenomenon in the liquid reservoir, it is necessary to keep the rigidity of the constituent members constituting the liquid reservoir, particularly the thin film having the plurality of nozzles described above.
Furthermore, when the nozzle and the liquid reservoir are configured separately, a positioning process is required to join them, resulting in a decrease in yield and increased instability factors such as leakage from the joint and elution of the adhesive. I am letting.

  Further, the inventions described in Patent Documents 3 to 4 have a problem that the productivity of the toner does not increase because the liquid oozes out or bubbles are trapped and the stable droplet discharge is hindered.

  The present invention has been made in view of the above-described problems of the prior art, and improves the production efficiency of the toner. Further, in many characteristic values required for the toner, such as fluidity and charging characteristics, the present invention is not limited to the conventional manufacturing method. An object of the present invention is to stably obtain a toner having a very small fluctuation range compared to the obtained particles.

The present inventors diligently studied a nozzle configuration capable of realizing uniform droplet formation even when the number of nozzles arranged in the liquid reservoir is increased, and completed the present invention.
The above-described problems of the present invention are solved by the following solution means.

(1) A nozzle plate for manufacturing a toner, which is provided in a liquid storage section for storing a toner material liquid that is a dispersion or solution of a toner composition containing a resin and a colorant, and in which a nozzle is formed,
In the nozzle plate, a flow path for feeding the toner material liquid or degassing the toner material liquid in the liquid storage portion provided with the nozzle has a layer of silicon or silicon and its oxide. It is formed integrally with the nozzle by using a composite.
(2) In the nozzle plate for toner production according to (1), the composite is an SOI (Silicon on insulator) wafer, and the nozzle is formed on a first surface of the silicon or the SOI wafer. The flow path is formed on the second surface.
(3) The toner manufacturing nozzle plate according to (2), wherein a silicon oxide film is formed on the first surface, and a fluorine-based material film is further formed on the silicon oxide film. To do.
(4) In the nozzle plate for toner production described in (2) or (3), a silicon oxide film is formed on the second surface.
(5) The toner production nozzle plate according to any one of (1) to (4), wherein the diameter is reduced from a liquid reservoir for storing the toner material liquid to a nozzle.
(6) The toner manufacturing nozzle plate according to any one of (1) to (5), wherein the liquid storage section is provided with a flow path adjacent to a liquid chamber section having a nozzle. To do.
(7) In the toner manufacturing nozzle plate according to any one of (1) to (6), a liquid chamber portion in which the nozzle is provided is connected to a liquid supply flow path of the flow path, and the liquid chamber And the liquid supply flow paths are alternately arranged.
(8) The toner manufacturing nozzle plate according to any one of (1) to (7) is used, the size of the nozzle provided on the nozzle plate is 4 to 15 μm, and the nozzle plate is subjected to vibration generating means. Applying a vibration frequency of 20 kHz or more and less than 2.0 MHz to form droplets of the toner material liquid in which the toner material containing at least resin and colorant is dispersed or dissolved from each nozzle of the nozzle plate. A method for producing a toner, comprising: producing a toner particle by drying the toner material liquid thus formed.
(9) In the toner manufacturing method according to (8), the number of nozzles provided for each liquid storage unit that stores the toner material liquid is 100 to 40,000.
(10) The toner manufacturing nozzle plate according to any one of (1) to (7), a vibration applying unit that applies a vibration to the nozzle plate to form a droplet, and the droplet is discharged. A toner manufacturing apparatus having a solidifying unit that dries and solidifies liquid droplets in a space.

According to the nozzle plate, the toner manufacturing method and the toner manufacturing apparatus having the nozzle plate according to the present invention, a plurality of liquid storage portions having nozzles made of a hard member and the liquid storage portions are connected to each other, or a toner material Since the toner material liquid is formed into droplets from a nozzle plate with an integrated flow path for liquid delivery, the degassed droplets can be stably formed in a uniform size. Can be produced in a large area, whereby the toner can be produced efficiently, and furthermore, a toner having a monodispersibility with an unprecedented particle size can be obtained.
Further, according to the toner production method and apparatus of the present invention, the produced toner has a very small range of fluctuation between particles in the characteristic values required for the toner such as fluidity and charging characteristics. A toner having almost uniform characteristics can be obtained.

FIG. 2 is a schematic diagram illustrating an example of a toner manufacturing apparatus according to the present invention. FIG. 2 is a diagram illustrating a droplet discharge unit used in the toner manufacturing apparatus illustrated in FIG. 1. It is a figure for demonstrating the manufacturing process which manufactures the nozzle plate of this invention. It is a figure which shows four structural examples of the liquid chamber which has the nozzle in the nozzle plate of this invention. It is a figure which shows the structural example which formed the liquid chamber which has the nozzle in the nozzle plate of this invention in the taper shape. It is a figure which shows the structural example which formed the flow path 214 or 215 in the liquid chamber which has the nozzle in the nozzle plate of this invention. It is a figure which shows the example which comprised the liquid chamber which has the nozzle in the nozzle plate of this invention by the flow path 214 and the flow path 215, and was comprised. It is a figure which shows the structural example which provided the nozzle row which connected the liquid chamber which has the nozzle in the nozzle plate of this invention by the flow path 214 and the flow path 215, and the flow path row | line | column 216, (A) is the top view, (B) is the perspective view. It is a perspective view which shows the vibration application member 13 of FIG. It is sectional drawing which shows the shape of three examples of an ultrasonic horn. It is sectional drawing which shows the structure by which the droplet discharge unit which consists of a plurality of droplet discharge units of FIG. 1 is hold | maintained at the drying tower. It is sectional drawing which shows the mechanism in which a droplet is formed in a droplet discharge unit. FIG. 5 is a cross-sectional view showing another droplet discharge unit used in the toner manufacturing apparatus shown in FIG. 1. FIG. 14 is a cross-sectional view showing a configuration in which a plurality of droplet discharge units shown in FIG. 13 are held in a drying tower.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments for carrying out the present invention will be described with reference to the accompanying drawings. First, a toner manufacturing apparatus according to the present invention will be described with reference to an example shown in FIG.

  A toner manufacturing apparatus 1 shown in FIG. 1 includes a droplet discharge unit 2, a particle forming unit 3, a toner collecting unit 4, a tube (toner storage piping tube) 5, and a toner storage unit 6. Is done. The droplet discharge unit 2 has a function as droplet forming means for discharging the toner material liquid 10 having at least a resin and a colorant into droplets. The droplet discharge unit 2 is disposed above the toner manufacturing apparatus 1. The droplets of the toner material liquid discharged from the droplet discharge unit 2 are solidified by the particle forming unit 3 as the particle forming means to form toner particles T. The formed toner particles T are collected by the toner collecting unit 4, and the toner particles T are transferred through the tube 5. The transferred toner particles T are stored in a toner storage unit 6 as toner storage means. The toner manufacturing apparatus 1 also feeds the toner composition liquid 10 from the raw material container 7 (toner material liquid container tank) 7 that contains the toner material liquid 10 to the droplet discharge unit 2 from the raw material container 7. An excessive toner composition liquid from the droplet discharge unit 2, a pipe (liquid supply pipe) 8-1 for performing the operation, a pump (toner material liquid supply means) 9 for supplying the toner material liquid 10 by pressure during operation, and the like. A pipe (recovery pipe) 8-2 for recovery in the raw material container 7 is provided.

The above-described toner material liquid 10 is supplied from the raw material container 7 to the droplet discharge unit 2 in a self-sufficient manner by droplet formation by the droplet discharge unit 2. The toner material liquid 10 is configured such that liquid supply is performed to the droplet discharge unit 2 by using the pump 9 supplementarily as described above when the apparatus is operating. The toner material liquid 10 is a solution or dispersion in which a toner composition containing at least a resin and a colorant is dissolved or dispersed in a solvent. The toner material liquid 10 will be described later. As shown in the figure, such a toner material liquid 10 is sent from the raw material container 7 to the droplet discharge unit 2 through the pipe 8-1 by the pump 9, and the surplus toner material liquid 10 is supplied to the pipe 8. It is most preferable to construct a circulation system that passes through -2 to reach the raw material container 7.
Hereinafter, each configuration including the droplet discharge unit of the toner manufacturing apparatus will be described individually.

<Droplet discharge unit>
1. Overall Configuration First, the droplet discharge unit 2 will be described with reference to FIG. 2 and FIGS. FIG. 2A is a schematic cross-sectional view of the droplet discharge unit 2, and FIG. 2B is an assembly diagram using each part of the droplet discharge unit 2 shown in FIG.

  As shown in FIG. 2, the droplet discharge unit 2 includes a thin film nozzle plate 12 in which a plurality of nozzles (discharge ports) 11 are formed, a storage member 111 that stores the toner material liquid 10, and a storage member 111, a vibration unit 13 that applies ultrasonic vibration of a predetermined frequency to the nozzle plate 12, and a storage unit 14 that supplies the toner material liquid 10 between the nozzle plate 12 and the vibration unit 13.

  As shown in FIG. 7 and the like, it is desirable that the position is fixed between the vibration means 13 and the reservoir wall by a vibration separating member 116b so as not to transmit vibration. Moreover, as shown in FIG. 2, you may employ | adopt the form fixed directly to a wall through the part 17 of the node with small vibration amplitude of a vibration means. The toner material liquid 10 is supplied to and discharged from the liquid storage section 14 through pipes 18 (18-1, 18-2) used for liquid supply and liquid circulation. The liquid storage area 19 is divided by a plurality of liquid storage walls 14.

2-1: Thin Film Having Nozzle The nozzle plate 12, which is a thin film having a plurality of nozzles, is bonded and fixed to the storage member 111 with a resin that does not dissolve in the toner material liquid 10. Examples of the material of the nozzle plate 12 include Ni or silicon, and a composite (including SOI) containing silicon and silicon oxide. By using a Si-based material, it is possible to form a nozzle having high shape accuracy and a large aspect ratio using an existing semiconductor process. Specifically, the nozzle plate 12 has a thickness of 10 to 600 μm and an opening diameter of the discharge port of 4 to 15 μm. Thereby, the uniform droplet L can be generated from the discharge port.

  If the thickness is less than 10 μm, the rigidity may be reduced and the resonance frequency of the nozzle plate 12 may be reduced. If the thickness exceeds 600 μm, a silicon process for manufacturing a nozzle for discharging the droplets L or the like may be performed. However, it may take time to manufacture. In addition, if the nozzle opening diameter is less than 4 μm, the colorant contained in the toner material liquid may be deposited on the discharge port, and it may be difficult to stably discharge the droplets L. When it exceeds, powder particle formation efficiency falls. The diameter of the nozzle opening means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse.

Such a silicon process can be formed by adopting a forming method in which the cross-sectional shape of the nozzle as described below is a two-stage type. It is most desirable to use a silicon substrate, particularly an SOI (Silicon on Insulator) substrate, as a material used for carrying out such a method. This method will be described with reference to FIG.
A resist 220 is coated on both surfaces of the substrate 210 (preferably an SOI substrate) (FIG. 3A). As the SOI substrate 210, for example, a substrate having a dielectric layer (SiO ₂ ) 212 and an active layer 213 on a silicon layer (support layer) 211 and a resist layer 220 coated on both surfaces of this substrate is prepared. Next, it is covered with a photomask in which a nozzle pattern is formed on the Si support layer surface 211 coated with the resist layer 220, and is exposed to ultraviolet rays to form the resist layer 220 as a nozzle pattern (FIG. 3B). Anisotropic dry etching using ICP (Induced Coupled Plasma) discharge is performed from the surface side of the support layer 112, which is the surface side of the resist layer 220 on which the nozzle pattern is formed, to form the first nozzle hole 211a, Using the same method, the surface side of the active layer 213 provided with the resist layer 220 is subjected to similar anisotropic dry etching to form the second nozzle 213a in the active layer 213 (FIG. 3C). . Finally, the exposed portion of the dielectric layer 212 (the portion excluding the portion where the support layer 211 and the active layer 213 are joined via the dielectric layer 113) is removed by etching with, for example, a hydrofluoric acid-based etchant, A two-stage through-hole (a nozzle having a two-stage structure of 211a and 213a) is obtained (FIG. 3D). By adopting such a method, the deep nozzle shape can be formed uniformly, which is most preferable. The 211 side formed by etching is referred to as the liquid chamber side, and the active layer 213 side is referred to as the outside of the nozzle.

In addition, even if a silicon substrate is used instead of the SOI substrate, the nozzle plate 12 that is a thin film in which a plurality of nozzles are formed can be manufactured in the same manner. In this case, the depth t _L of the opening can be adjusted by adjusting the etching time. Since the silicon thin film obtained in this way is also highly rigid, the resonance frequency of the nozzle plate 12 is increased. In general, in order to increase the rigidity of the thin film, it is preferable to increase the thickness of the nozzle plate 12 and reduce the surface area.

  The storage partition wall 111b is joined to the nozzle plate 12 with a solvent or the like having resistance to the solvent used in the toner material liquid 10. The material of the storage partition wall 111b is not particularly limited as long as it has solvent resistance with respect to the solvent used in the toner material liquid 10, and examples thereof include metals, ceramics, and plastics.

The structure of each liquid chamber will be described with reference to FIG.
FIG. 4A shows a basic shape, and φ _L is the diameter of the structure serving as the liquid chamber (nozzle liquid chamber) 211a and 1/2 of the depth t _L of the liquid chamber (liquid storage portion) 211a. 1/15, φ _S (nozzle diameter) is 4 to 15 μm, and t _S (the thickness of the nozzle portion) at this time is preferably 10 to 30 μm. FIG. 4B shows an example in which a liquid repellent (liquid repellent for discharge liquid) 300 is formed on the nozzle surface by coating or vapor deposition. In FIG. 4C, the active layer 213 is removed by dry etching, the oxide film 212 of the SiO ₂ layer, which is the dielectric layer on the nozzle surface side, is left, and a liquid repellent 300 is applied or deposited on the nozzle surface. An example is shown. Reference numeral 212 denotes a nozzle formed in the oxide film 212 of the SiO ₂ layer. FIG. 4D shows a configuration in which a silicon oxide film (SiO ₂ film) 400 is deposited on the back surface (on the silicon 211).

FIG. 5 is an example in which the φ _L portion of the liquid chamber 211a is provided in a tapered shape by adjusting the etching conditions, and more specifically, an example in which the diameter is narrowed toward the nozzle 213a. Indicates. The adjustment of the etching conditions is controlled, for example, by changing the etching rate by gradually increasing (or gradually decreasing) the temperature of the etching solution, or by changing the time ratio between etching and deposition. It can be formed by using a method of performing half etching. Thus, in the present invention, the liquid chamber 211a can be provided by forming the side wall of the liquid chamber 211a formed in the truncated cone into a tapered shape like the truncated cone.

In addition, after depositing and forming a silicon oxide film (SiO ₂ film) or when leaving the SiO ₂ layer 212 as a dielectric layer, a fluorine film is provided on the SiO ₂ layer or the SiO ₂ film by CVD. The layer can also be easily formed from a fluorine-based material using a fluororesin. By forming such a material using fluorine, the surface free energy of the nozzle surface can be reduced, so that the nozzle surface is unlikely to squeeze out and bubbles can be suppressed. For this reason, the toner production apparatus using such a nozzle plate can stably discharge the toner material liquid, and the yield of toner production can be improved.

2-2: Integrated formation of nozzle, flow path, and liquid chamber FIG. 6 shows an example in which the flow path 214 (215) is formed by half-etching the wall surface of the liquid chamber. FIG. 7 is a view of an example in which a flow path formed by such half-etching is arranged as viewed from the flow path side, and the toner material liquid is supplied from the left side of the paper (see the arrow flowing into the liquid chamber 211a in FIG. 7). By forming the central flow path 215, the bubble discharge efficiency is increased. 8A is a plan view of the entire image of the nozzle plate 12 as seen from the liquid chamber surface, and FIG. 8B is a perspective view thereof. The liquid flow paths 214 and 215 and the nozzle 211a row are alternately arranged. . FIG. 8 shows an example in which the rows of nozzle structures (nozzle structures composed of the liquid chamber 211a and the nozzle 213a) formed in two stages and the rows of flow paths 216 are alternately arranged. In such a nozzle plate 12, the flow path is also integrally formed, and unnecessary joints can be omitted, so that the yield in toner production can be improved.

  By setting the number of nozzles 213a arranged in one liquid storage unit 14 to 1,000 to 40,000, the production amount can be sufficiently secured with a compact configuration. The toner particle size distribution (weight average particle diameter / number average particle diameter) obtained by the toner manufacturing apparatus using the nozzle plate of the present invention is preferably in the range of 1.00 to 1.15. The weight average particle diameter is preferably in the range of 1 to 20 μm.

[Vibration means]
The vibration means 13 uses mechanical ultrasonic vibration at a high amplitude as a liquid, for example, a laminated PZT (Lead Zirconium Titanate) or a combination of an ultrasonic vibrator and an ultrasonic horn described later. Anything can be given as long as it can be given.

  As shown in FIG. 2, for example, a vibration generating unit 21 that generates vibration and a vibration amplifying unit 22 that amplifies the vibration generated by the vibration generating unit 21, and a drive circuit (drive signal generation source) 23. When a drive voltage (drive signal) having a required frequency is applied between the electrodes 21a and 21b of the vibration generating means 21, vibration is excited in the vibration generating means 21, and this vibration is amplified by the vibration amplifying means 22, and the nozzle plate. The vibration surface 13a arranged in parallel with the plate 12 vibrates periodically, and the pressure of the reservoir liquid is periodically vibrated by the vibration of the vibration surface 13a.

  Here, as shown in FIG. 9, the vibration means 13 is a surface opposite to the coupling surface 13 b of the vibration amplification means 22 with respect to the area of the coupling surface 13 b for coupling the vibration generation means 21 and the vibration amplification means 22. The area of the vibration surface 13a is formed wide. The vibrating surface 13a is rectangular (here, “rectangular”). In this case, the vibration area increases as the ratio of the short side a to the long side b (long side b / short side a) of the vibration surface 113a increases. Therefore, from the viewpoint of productivity, it is preferable to form a relationship of (long side b / short side a)> 2.0.

[Vibration generating means]
As shown in FIG. 10, as the piezoelectric body 21A constituting the vibration generating means 21, for example, piezoelectric ceramics such as lead zirconate titanate (PZT) can be cited. Often done. In addition, examples of the piezoelectric body 21A include piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , and KNbO ₃ .

The vibration generating means 21 is not particularly limited as long as it can provide a certain longitudinal vibration to the toner material liquid in the liquid storage section 14 at a constant frequency, and can be appropriately selected and used. However, since the vibration surface 13a having a large area is excited with a low voltage, the vibration generating means 21 is preferably a piezoelectric body 21A.
The piezoelectric body 21A has a function of converting electrical energy into mechanical energy.

  Further, as the vibration generating means 21, it is more preferable to use a particularly high-strength bolted Langevin type vibrator. This bolted Langevin type vibrator is mechanically coupled with a piezoelectric material and is not damaged during high amplitude excitation. The vibration frequency generated by the vibration generating means 21 is preferably 20 kHz or more and less than 2.0 MHz, so that dispersed fine particles (for example, pigment fine particles) inside the toner material liquid are not deposited on the nozzle portion 213a. .

[Vibration amplification means]
As the vibration amplification means 22 coupled to the vibration generation means 21 as described above, for example, a horn type vibration amplifier can be used. Since the horn-type vibrator can amplify the amplitude generated by the vibration generating means 21 such as a piezoelectric element by the horn 22A as the vibration amplifying means 22, the vibration by the vibration generating means 21 itself that generates mechanical vibration is not generated. Small vibration is sufficient and the mechanical load can be reduced, leading to longer life.

  Here, as the horn type vibrator, a known typical horn shape may be used. For example, a step type as shown in FIG. 10A, an exponential type as shown in FIG. The conical type as shown in c) can be mentioned. In these horn-type vibrators, the piezoelectric body 21A is disposed on the surface of the horn 22A having a large area. The piezoelectric body 21A uses longitudinal vibration to induce efficient vibration of the horn 22A, and the horn 22A has a small area. The surface is a vibration surface 13a, and the vibration surface 13a is designed to be the maximum vibration surface.

[Liquid reservoir and liquid reservoir area]
The members constituting the partition wall of the liquid reservoir are made of a common material such as metal, ceramics, and plastic that does not dissolve in the spray liquid (toner composition liquid) and does not cause modification of the spray liquid. Moreover, the liquid storage part 14 is divided | segmented into the some liquid storage area | region 14 by the some partition 111b.

[Flow path part]
A liquid supply tube 18-1 for supplying a toner material liquid to the liquid storage section 14 and a bubble discharge tube (or a liquid circulation tube) 18-2 for discharging bubbles are respectively connected to the flow path section 15 at least at one place. Yes. The droplet discharge unit 2 is installed and held on the top surface portion of the particle forming unit 3 by a support member (not shown) attached to the flow path member 13. Here, as shown in FIG. 1, an example in which the droplet discharge unit 2 is disposed on the top surface portion of the particle forming unit 3 will be described. It can also be set as the structure which installs the droplet ejection unit 2. FIG.

[Overall unit configuration (consolidated)]
In the above description, an example in which only one droplet discharge unit 2 is attached to the particle forming unit 3 is shown in FIG. Further, as shown in FIGS. 11 and 14, a plurality (four, but the number is only an example), the droplet discharge unit 2 is placed above the particle forming unit 3 (drying tower). It is preferable to provide them in parallel from the viewpoint of improving productivity, and the number thereof is preferably in the range of 100 to 1,000 from the viewpoint of controllability. In this case, each liquid storage section 14 of the droplet discharge unit 2 is connected to the raw material storage section (common liquid reservoir) 7 via the pipe 8 and supplied with the toner material liquid 10 (see FIG. 1). The toner material liquid 10 may be configured to be supplied in a self-contained manner as the liquid droplets are formed, or may be configured to circulate liquid using the pump 9 as an auxiliary device when the apparatus is operating. it can.

(Operating mechanism)
Next, the mechanism of droplet formation by the droplet discharge unit 2 as the droplet forming means will be described with reference to FIG. The vibration generated on the vibration surface 13a by the vibration means is transmitted to the liquid in the reservoir, and the liquid in the reservoir causes a liquid resonance phenomenon. In the plurality of nozzles provided in the nozzle plate 12, the liquid is discharged to the gas side (particle forming unit 3 (drying tower)) in a state of being uniformly pressurized. By the action of the resonance of the entire liquid, the liquid is uniformly ejected from all the nozzles 11 within a predetermined size range, and furthermore, dispersed fine particles contained in the toner material liquid in a large amount on the storage portion surface of the thin film. Since the reservoir is floated without being deposited, the liquid can be stably sprayed.

[Particle forming part]
Next, returning to FIG. 1, the particle forming unit 3 that solidifies the droplets 31 of the toner material liquid 10 to form toner particles T will be described. Here, as described above, as the toner material liquid 10, the droplet 31 is obtained using a solution or dispersion obtained by dissolving or dispersing a toner composition containing at least a resin and a colorant in a solvent. The toner particles T are formed by drying and solidifying the droplets 31. That is, in this embodiment, the particle forming unit 3 is a solvent removing unit that removes the solvent of the droplet 31 to diverge the solvent from the droplet and solidify it to form the toner particles T (hereinafter, particle formation). Part 3 is also referred to as “solvent removing part” or “drying part”.)

  Specifically, the particle forming unit 3 is configured to cause the droplet 31 discharged from the plurality of nozzles 11 of the droplet discharge unit 2 to flow in the same direction as the flying direction of the droplet 31 (dry gas). The toner particles T are formed by removing the solvent of the droplets 31 by being conveyed by 35. The dry gas 35 means a gas having a dew point temperature of −10 ° C. or lower under atmospheric pressure. Such a dry gas 35 may be any gas that can dry the droplets 31. For example, air, nitrogen, or the like can be used.

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

  The toner particles T collected by the toner collection unit 4 are transferred to the toner storage unit 6 via the tube 5 and stored by vortex (air flow 42) as they are. In this case, it is preferable that the toner collection unit 4, the tube 5, and the toner storage unit 6 are formed of a conductive material and are grounded (connected to ground). The entire toner manufacturing apparatus 1 is preferably explosion-proof. In addition, the toner particles T may be pumped from the toner collection unit 4 toward the toner storage unit 6, or the toner particles T may be sucked from the toner storage unit 6 side.

(Toner production method)
Next, a toner manufacturing method according to the present invention will be described using the toner manufacturing apparatus 1 configured as described above. As described above, the vibration generating means is supplied with the toner material liquid 10 in which the toner composition containing at least the resin and the colorant is dispersed or dissolved in the liquid storage section 14 of the droplet discharge unit 2 being supplied to the liquid storage section 14. By applying a drive signal having a required drive frequency to 21, vibration is generated in the vibration generating means 21, and this vibration is amplified by the vibration amplifying means 22 so that the toner material liquid in the liquid storage unit 14 resonates.
The vibration of the vibration surface 13a of the vibration means 13 is propagated to the toner material liquid 10 in the liquid storage section 14 to generate periodic pressure fluctuations, whereby the toner material liquid is periodically discharged from the plurality of nozzles 11 when pressurized. The droplets are formed and discharged as droplets 31 into the particle forming unit 3 (see FIG. 1) as a solvent removing unit.

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

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

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

  Furthermore, with reference to FIG. 13, an example in which an air flow path for supplying an air flow for dispersing a droplet is provided in the droplet discharge unit will be described. FIG. 13 is a schematic cross-sectional explanatory view of the droplet discharge unit. As in the above-described example, this droplet discharge unit uses a horn-type vibrator as the vibration generating means 13 and arranges a flow path member 15 that surrounds the vibration generating means 13 and supplies the toner material liquid 10. The liquid reservoir 14 is formed on the horn 22 of the vibration generating means 13 at a portion facing the nozzle plate 12. Further, an air flow path forming member 36 that forms an air flow path 37 through which the air flow 35 flows is disposed around the flow path member 15 at a required interval. In order to simplify the illustration, the number of nozzles 11 of the nozzle plate 12 is one, but a plurality of nozzles 11 are provided as described above.

  Moreover, as shown in FIG. 14, it is desirable from the viewpoint of productivity to arrange a plurality of units in an air channel. And preferably, for example, from the viewpoint of controllability, 1,000 to 10,000 droplet discharge units 2 are arranged side by side in the drying tower storage section constituting the particle forming section 3. Thereby, productivity can be further improved.

  As described above, since the plurality of nozzles 11 are provided in the droplet discharge unit 2, a large number of droplets 31 of the toner material liquid formed into a plurality of droplets at the same time are continuously discharged. Production efficiency is dramatically improved. By disposing a plurality of nozzles 11 in a region in the nozzle plate 12, a large number of droplets 31 can be discharged at one time, and the liquid in the liquid storage unit is prevented from depositing dispersed fine particles present in the toner material liquid due to vibration. The toner 11 can be stably and efficiently manufactured without clogging of the nozzle 11. Further, it has been confirmed that a toner having a monodispersibility with an unprecedented particle size can be obtained.

Next, a toner composition that is a toner material that can be used in the present invention will be described.
As the toner composition, the same toner as the conventional electrophotographic toner can be used. That is, a toner composition that has at least a resin (toner binder) such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin, and a colorant, and is a toner material such as a release agent. An object is dissolved or dispersed in an organic solvent to form a toner material liquid, and fine droplets are discharged from the nozzle 11 to the particle forming unit 3 by the above-described toner manufacturing method, and dried and solidified to produce the desired toner particles. It is possible. Further, the toner material is melted and kneaded, and the obtained kneaded material is once dissolved or dispersed in various solvents to form a toner material liquid. The toner material liquid is dried and solidified as fine droplets by the toner manufacturing method. Thus, it is possible to obtain the target toner.

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

(resin)
Examples of the resin used for the toner material 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. Polymerized vinyl polymer, copolymer obtained by polymerizing two or more of these monomers, polyester polymer, polyol resin, phenol resin, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin Terpene resin, coumarone indene resin, polycarbonate resin, petroleum resin, 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, and pn-amyl styrene. , P-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene such as chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or a derivative 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.

  Examples of other monomers used to form the vinyl polymer or copolymer include the following (1) to (18). (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 acid anhydride and alkenyl succinic acid anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid, etc. Unsaturated dibasic acid ester; (14) α, β-unsaturated acid such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydride 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 according to the present invention, the vinyl polymer or copolymer used for the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. The following are mentioned as a crosslinking agent used in this case. Aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 hexanediol Diacrylate, neopentyl glycol diacrylate, diacrylate compounds linked by alkyl chain such as those obtained by replacing acrylate of these compounds with methacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene Glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, acrylics of these compounds Diacrylate compounds connected with an alkyl chain containing an ether bond, such as those substituted for over preparative to methacrylate.

  In addition, a diacrylate compound or a dimethacrylate compound linked by a chain containing an aromatic group and an ether bond is also included. Furthermore, polyester-type diacrylates, such as a brand name MANDA (made by Nippon Kayaku Co., Ltd.), are also mentioned.

  Examples of the polyfunctional cross-linking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and triacrylates of the above compounds. The thing replaced with triallyl trimellitate is mentioned.

  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 cross-linking agents, from the viewpoint of improving the fixing property and offset resistance to the resin for toner, diacrylate bonded by an aromatic divinyl compound (particularly divinylbenzene), a bond chain containing one aromatic group and an ether bond. 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 for producing the vinyl polymer or copolymer in the binder resin used in the toner of the present invention include 2,2′-azobisisobutyronitrile and 2,2′-azobis. (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2 '-Azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethyl) Pentane), 2-phenylazo-2 ′, 4′-dimethyl-4′-methoxyvaleronitrile, 2,2′-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetate Ketone peroxides such as peroxide and cyclohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3- Tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, deca Noyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropyl peroxydicarbonate, di-2- Tylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxy Carbonate, acetylcyclohexylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxy-2-ethylhexarate, tert-butylperoxylaurate, tert-butyloxy Benzoate, tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethyl Hexanoate, di -tert- butyl peroxy the hexa hydro terephthalate, tert- butylperoxy azelate, and the like.

  When the binder resin is a styrene-acrylic resin, the molecular weight distribution by GPC (Gel Permeation Chromatography) soluble in tetrahydrofuran (THF), the resin component, has a molecular weight of 3,000 to 50,000 (in terms of number average molecular weight). A resin in which at least one peak is present and at least one peak is present 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% by weight is preferable, and a binder resin having a main peak in a region having a molecular weight of 5,000 to 30,000 is more preferable. A binder resin having a main peak in the region of 5,000 to 20,000 is most preferable.

  The binder resin used in the toner of the present invention and the composition containing the binder resin preferably have a glass transition temperature (Tg) of 35 to 80 ° C., and 40 to 75 ° C. from the viewpoint of toner storage stability. Is more preferable. 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.

The toner of the present invention is a magnetic toner or a non-magnetic toner, and in the case of a magnetic toner, a magnetic material is contained.
Examples of magnetic materials that can be used 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, nickel, and the like. Alloys of metals and 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 | grains production | generation, or adding salt of each element and adjusting pH.

  As the usage-amount of the said magnetic body, 10-200 mass parts of magnetic bodies are preferable with respect to 100 mass parts of binder resin, and 20-150 mass parts is more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 μm, and more preferably 0.1 to 0.5 μm. The number average diameter can be obtained by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.

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

(Coloring agent)
The colorant used as the toner material 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, Lead Red, Lead Zhu, Cadmium Red, Cadmium Mercury Red, antimony vermilion, permanentre 4R, Parared, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol 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 Rake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Rune, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc Green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green go , Acid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.

  The content of the colorant is preferably 1 to 15% by mass and more preferably 3 to 10% by mass with respect to the toner material (in terms of solid content).

  The colorant used in the toner according to the present invention can also be used in the form of 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, and the like. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant with a high shear force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Also, a master made by a so-called flushing method, an aqueous paste containing water of a colorant, which is mixed and kneaded together with a resin and an organic solvent, transferred to the resin side, and a moisture and organic solvent component is removed. Since the wet cake of the colorant can be used as it is, the batch 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 mgKOH / g, and a colorant dispersed therein. The acid value is 20 mgKOH / g or less, the amine value Is more preferably 10 to 50 mg KOH / g, and the colorant is dispersed and used. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered, and the pigment dispersibility may be insufficient. Further, when the amine value is less than 1 mgKOH / g and when the amine value exceeds 100 mgKOH / g, 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.

(Dispersant)
In addition, a dispersant can be used for the toner material, and such a dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. “Ajisper PB821”, “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.), “Disperbyk-2001” (manufactured by BYK 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 main peak molecular weight in terms of styrene conversion molecular weight in GPC, 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 becomes high and the dispersibility of the colorant may be lowered. When the molecular weight exceeds 100,000, the affinity with the solvent is increased and the dispersibility of the colorant is lowered. There is.

[Other ingredients]
<Career>
The toner according to 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 silicone 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 dimethyl silicone 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. Among these, copper-zinc-iron-based ferrites mainly composed of copper, zinc, and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium, and iron components are preferable.

The resistance value of the carrier is preferably 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the unevenness of the surface of the carrier and the amount of resin to be coated.

  The carrier having a particle size of 4 to 200 μm can be used, preferably 10 to 150 μm, more preferably 20 to 100 μm. In particular, the resin-coated carrier preferably has a 50% particle size of 20 to 70 μm.

  In the two-component developer, it is preferable to use 1 to 200 parts by mass of the toner of the present invention with respect to 100 parts by mass of the carrier, and 2 to 50 parts by mass of toner with respect to 100 parts by mass of the carrier. More preferred.

<Wax>
In the present invention, a wax may be contained as a release agent together with the binder resin and the colorant.
The wax is not particularly limited and can be appropriately selected from those usually used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sazol wax, etc. Oxidized aliphatic hydrocarbon waxes such as polyethylene oxide wax, block oxides thereof, candelilla wax, carnauba wax, wood wax, jojoba wax, etc. Waxes based on fatty acid esters such as animal waxes such as lanolin and whale wax, mineral waxes such as ozokerite, ceresin and petrolatum, montanic acid ester wax and castor wax. Deoxidized carnauba wax or the like is obtained by deoxidizing a part or all of a fatty acid ester.

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

  Examples of more suitable release agents 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 catalysts such as Ziegler catalysts and metallocene catalysts under low pressure. Polyolefin polymerized using, polyolefin polymerized using radiation, electromagnetic wave or light, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, Jintole method, hydrocol method Synthetic hydrocarbon waxes synthesized by the Age method, etc., synthetic waxes using a compound having 1 carbon atom as a monomer, hydrocarbon waxes having a functional group such as a hydroxyl group or a carboxyl group, hydrocarbon waxes and functional groups You Mixture of hydrocarbon 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 (a narrow molecular weight distribution) using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a liquid crystal deposition method, Also, low molecular weight solid fatty acids, low molecular weight solid alcohols, low molecular weight solid compounds, and other impurities are preferably used.

  The melting point of the wax (release agent) 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 exert a plastic action, and those having a more linear structure or a functional group. Non-polar and non-denatured straight ones that do not have 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, candelilla wax, Rice wax or montan wax and hydrocarbon wax The combination of the scan and the like.

  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 temperature of the peak top of the endothermic peak of the wax measured by DSC (Differential Scanning Calorimetry) is defined as the melting point of the wax.

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

<Fluidity improver>
A fluidity improver may be added to the toner according to the present invention. The fluidity improver improves the fluidity of the toner (is easy to flow) by being 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. Further, a treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.

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

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

  Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include, for example, AEROSIL (trade name of Nippon Aerosil Co., Ltd., hereinafter the same) -130, -300, -380, -TT600, -MOX170, -MOX80, -COK84: Ca-O-SiL (trade name of CABOT, hereinafter the same)-M-5, -MS-7, -MS-75, -HS-5, -EH-5, Wacker HDK (WACKER-CHEMIE product) -N20 V15, -N20E, -T30, -T40: D-CFineSi1ica (Dow Corning brand name): Franco1 (Fransi1 brand name), and the like.

  Further, 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. Among the treated silica fine powders, those obtained by treating the silica fine powder having a degree of hydrophobicity measured by a methanol titration test of preferably 30 to 80% are particularly preferred. Hydrophobization is imparted by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, a method of treating a silica fine powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferable.

  Examples of the organosilicon compound include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, dimethylvinylchlorosilane, Divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α -Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane , Triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 siloxane units per molecule, each of which is located at the end Examples thereof include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to. 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 according to the present invention, as other additives, protection of the electrostatic latent image carrier / carrier, improvement of cleaning properties, adjustment of thermal characteristics / electrical characteristics / physical characteristics, resistance adjustment, softening point adjustment, fixing rate For the purpose of improvement, various metal soaps, fluorosurfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, and inorganic such as titanium oxide, aluminum oxide, alumina A fine powder or the like can be added as necessary. These inorganic fine powders may be hydrophobized as necessary. 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.

  When preparing the developer, in order to improve the flowability, storage stability, developability and transferability of the developer, inorganic fine particles such as the above-mentioned hydrophobic silica fine powder are added and mixed as external additives. May be. Such external additives can be mixed by appropriately selecting a general powder mixer, but it is preferable to use a jacket equipped with 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, or the rotational speed, rolling speed, time, temperature, etc. of the mixer may be changed. A strong load may be given first, then a relatively weak load, and vice versa.

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

  The method for further adjusting the shape of the toner to be used is not particularly limited and can be appropriately selected according to the purpose. For example, a method of mechanically sphering the shape of the toner using a hybridizer, mechanofusion, or the like can be used.

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, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, and the like.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm.

The specific surface area according to the BET method is preferably 20 to 500 m ² / g.

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

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

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

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

  The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. 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 development method using the toner in the present invention, all of the electrostatic latent image carriers used in the conventional electrophotography can be used. For example, an organic electrostatic latent image carrier, an amorphous silica electrostatic latent image carrier. Body, selenium electrostatic latent image carrier, zinc oxide electrostatic latent image carrier, and the like can be suitably used.

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

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

-Preparation of toner composition dispersion (toner material liquid)-
Next, a toner composition dispersion liquid having the following composition to which a resin as a binder resin, the colorant dispersion liquid, and the wax dispersion liquid were added was prepared.
100 parts by mass of a polyester resin as a binder resin, 30 parts by mass of the colorant dispersion, and 30 parts by mass of the wax dispersion were stirred for 10 minutes using a mixer having stirring blades in 840 parts by mass of ethyl acetate. And uniformly dispersed. Pigments and wax particles did not aggregate due to shock due to solvent dilution. The electric conductivity of the toner composition dispersion was 1.8 × 10 ⁻⁷ S / m.

-Preparation of toner-
The obtained toner composition dispersion (toner composition liquid) was supplied to the droplet discharge unit 2 of the above-described toner manufacturing apparatus. The above-described method is used to form a two-stage (convex) shape shown in FIG. 3D on an SOI substrate having a thickness of 500 μm, the diameter of the opening 213a is 8.5 μm, and the diameter of the opening 213a is 100 μm. The opening 213a was used as the liquid discharge side. The nozzles were provided in a staggered pattern so that the distance between the discharge holes was 100 μm. The liquid storage part used what was comprised by the liquid storage area | region divided | segmented equally. The excitation frequency used in this example and the configuration of the liquid reservoir are shown below. The voltage waveforms applied to the vibration means were all sine waves. The evaluation was performed using only one droplet discharge unit shown in FIG.
<Liquid reservoir configuration and drive frequency>
Excitation frequency: 32.7 kHz
Number of divided liquid reservoirs (number of liquid reservoir areas (number of liquid chambers)): 6
Liquid reservoir longitudinal direction dimension A: 8 mm
Liquid reservoir short side dimension B: 8mm
Number of nozzles per liquid storage area: 480
Flow rate of air flow supplied from the air flow path: Average linear velocity near the nozzle
20m / s

After preparing the toner composition dispersion, the droplets were discharged under the condition that the dry nitrogen gas in the apparatus was 30.0 L / min, and then the droplets were dried and solidified to produce toner base particles.
After drying and solidifying the toner base particles, cyclone is collected, and 1.0 mass% of hydrophobic silica (H2000, manufactured by Clariant Japan) is externally added using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Got.
The toner particles were collected, and the particle size distribution of the toner particles was measured with a flow particle image analyzer (FPIA-2000) under the following measurement conditions. As a result, the weight average particle diameter (D4) was 5.3 μm, and the number average particle diameter (Dn) was 5.1 μm. The amount of toner particles obtained after 1 hour of operation was 9.8 g.

-Toner evaluation-
The obtained toner was evaluated as follows. The results are shown in Table 1.
<Particle size distribution>
A measurement method using a flow particle image analyzer will be described below.
The measurement of toner, toner particles and external additives using a flow particle image analyzer can be performed using, for example, a flow particle image analyzer FPIA-2000 manufactured by Toa Medical Electronics.
The measurement is performed by removing fine dust through a filter, and as a result, in ^10-3 water of 10 ⁻³ cm ³ of water having a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) of 20 particles or less Add a few drops of nonionic surfactant (Wako Pure Chemical Industries, Contaminone N), add 5 mg of the measurement sample, and use an ultrasonic dispersing device (STM, UH-50) at 20 kHz, 50 W / 10 cm ³ . Dispersion treatment is performed for 1 minute under the conditions, and further, dispersion treatment is performed for a total of 5 minutes, and the sample dispersion is such that the particle concentration of the measurement sample is 4000 to 8000 pieces / 10 ⁻³ cm ³ (for particles in the equivalent diameter range of the measurement circle) Using the liquid, the particle size distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is measured.
The sample dispersion liquid is passed through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, the strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other so as to sandwich the flow cell. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals so that each particle flowing through the flow cell has a two-dimensional image having a certain range (area) parallel to the flow cell. Taken as. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter.
According to the above method, the equivalent circle diameter of 1200 or more particles can be measured in about 1 minute, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having the prescribed equivalent circle diameter are determined. It can be measured. As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the range of 0.06-400 μm into 226 channels (divided into 30 channels for one octave). In actual measurement, particles are measured in the range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.

<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, then magnify the image at 100x using an optical microscope, and compare the line omission state with the stage sample. (◎, ○, Δ and ×) were evaluated.
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 a negatively charged toner, an organic electrostatic latent image carrier was used, and in the case of a positively charged toner, an amorphous silicone electrostatic latent image carrier was used.

In the developing method, a two-component developer composed of toner and carrier was used as the developer. That is, a resin-coated carrier used in conventional electrophotography was used as a carrier as a developer conveying means. The following were used as carriers.
[Carrier]
Core material: Spherical ferrite particles having an average particle size of 50 μm Coating material constituent material: Silicone resin After preparing a dispersion in which silicone resin is dispersed in toluene, the core is spray-coated with the dispersion in a heated state, fired, After cooling, carrier particles having an average coated resin film thickness of 0.2 μm were prepared.

[Example 2]
In Example 1, the target toner was obtained under the same conditions as in Example 1 except that the nozzles were arranged in a lattice pattern at a pitch of 100 μm and the number of nozzles per liquid storage area was 6,400.

  When the particle size distribution of the toner particles was measured in the same manner as in Example 1, the weight average particle size (D4) was 5.4 μm, and the number average particle size (Dn) was 5.2 μm. The amount of toner produced per hour was 320 g.

Example 3
In Example 1, the target toner was obtained under the same conditions as in Example 1 except that the nozzles were staggered at a pitch of 100 μm and the number of nozzles per liquid storage area was 7,390.
<Liquid reservoir configuration and drive frequency>
Excitation frequency: 32.7 kHz
Number of liquid storage section divisions (number of liquid storage areas (number of liquid chambers?)): 6
Liquid reservoir longitudinal direction dimension A: 8 mm
Liquid reservoir short side dimension B: 8mm
Number of nozzles per liquid storage area: 7,390
Flow rate of air flow supplied from the air flow path: Average linear velocity near the nozzle
20m / s

  When the particle size distribution of the toner particles was measured in the same manner as in Example 1, the weight average particle size (D4) was 5.4 μm, and the number average particle size (Dn) was 5.2 μm. The amount of toner produced per hour was 382 g.

Example 4
In Example 3, the target toner was obtained under the same conditions as in Example 3 except that the excitation frequency was 40.2 kHz.

  When the particle size distribution of the toner particles was measured in the same manner as in Example 1, the weight average particle size (D4) was 5.2 μm, and the number average particle size (Dn) was 5.0 μm. The amount of toner produced per hour was 465 g.

Example 5
In Example 3, the target toner was obtained under the same conditions as in Example 3 except that the excitation frequency was changed to 57.3 kHz.

  When the particle size distribution of the toner particles was measured in the same manner as in Example 1, the weight average particle size (D4) was 5.2 μm, and the number average particle size (Dn) was 5.0 μm. The amount of toner produced per hour was 668 g.

[Comparative Example 1]
In Example 3, the target toner is the same as in Example 3 except that the nozzle plate is 50 μm thick nickel formed by electroforming so that the nozzle outlet diameter is Φ10 μm, and the excitation frequency is 60 kHz. Got.

  When the particle size distribution of the toner particles was measured in the same manner as in Example 1, the weight average particle size (D4) was 5.6 μm, and the number average particle size (Dn) was 5.0 μm. The amount of toner produced per hour was 227 g.

As shown in Table 1, it was found that the present invention can be efficiently converted into a toner, and the toner characteristics are extremely good.
In Comparative Example 1, the same number of nozzles as in Example 3 were formed on a very thin nickel nozzle, but the nickel thin film had a vibration mode and not only a sparse liquid discharge, but also a liquid Drop size also varied. As a result, it is considered that the particle size distribution deteriorated.

An image obtained by developing using the toner prepared in the present invention was extremely excellent in image quality faithful to the electrostatic latent image.
The toner production method of the present invention can produce toner efficiently, and the produced toner is a particle having a monodispersibility with an unprecedented particle size. Electrostatic charge images in electrophotography, electrostatic recording, electrostatic printing, etc., with no or very little variation due to particles seen in conventional manufacturing methods in many characteristic values required for toners, etc. It can be used as a developer for developing the toner.

DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet discharge unit 3 Particle formation part (drying tower)
4 Toner Collection Portion 5 Toner Storage Piping Tube 6 Toner Storage Portion 7 Toner Material Liquid Storage Tank 8 Piping 8-1 Piping (Input Side Piping)
8-2 Piping (Exhaust side piping)
9 Toner material liquid supply means (pump)
DESCRIPTION OF SYMBOLS 10 Toner material liquid 11 Nozzle 12 Nozzle plate 13 Vibrating means 13a Vibrating surface 13b Coupling surface 14 Liquid storage part 15 Flow path part 17 Section 18 Piping 18-1 Input side piping 18-2 Discharge side piping 19 Storage part 21 Vibration generating means ( Ultrasonic transducer)
DESCRIPTION OF SYMBOLS 22 Ultrasonic horn 23 Ultrasonic power supply part 31 Droplet 35 Dry gas 36 Fixing member 37 Air flow path 111 Storage member 111b Storage partition part 113 Vibration isolation member 114 Fixing member 210 SOI substrate 211 Support layer 211a Liquid chamber (nozzle liquid chamber)
212 Dielectric layer 213 Active layer 213a Opening (nozzle)
214, 215, 216 Flow path 300 Liquid repellent 400 Silicon oxide film T Toner base particle

JP-A-7-152202 Japanese Patent Laid-Open No. 54-80752 Japanese Patent No. 3786034 Japanese Patent No. 3786035 JP 2007-199463 A

Claims (10)

A nozzle plate for producing a toner, wherein a nozzle is formed in a liquid storage section for storing a toner material liquid which is a dispersion or solution of a toner composition containing a resin and a colorant;
In the nozzle plate, a flow path for feeding the toner material liquid or degassing the toner material liquid in the liquid storage portion provided with the nozzle has a layer of silicon or silicon and its oxide. A nozzle plate for toner production, wherein the nozzle plate is formed integrally with the nozzle using a composite.   2. The nozzle plate for manufacturing toner according to claim 1, wherein the composite is an SOI (Silicon on insulator) wafer, the nozzle is formed on a first surface of the silicon or the SOI wafer, and on a second surface. A nozzle plate for toner production, wherein the flow path is formed.   3. The toner manufacturing nozzle plate according to claim 2, wherein a silicon oxide film is formed on the first surface, and a fluorine-based material film is further formed on the silicon oxide film. Nozzle plate.   4. The toner production nozzle plate according to claim 2, wherein a silicon oxide film is formed on the second surface.   5. The nozzle plate for toner production according to claim 1, wherein the diameter of the nozzle plate is reduced from a liquid reservoir for storing the toner material liquid to a nozzle.   6. The nozzle plate for toner production according to claim 1, wherein the liquid storage portion is provided with a flow path adjacent to a liquid chamber portion having a nozzle. .   7. The nozzle plate for manufacturing toner according to claim 1, wherein a liquid chamber portion provided with the nozzle is connected to a liquid supply flow path of the flow path, and the liquid chamber and the liquid supply flow are provided. A nozzle plate for toner production, wherein the paths are alternately arranged.   The nozzle plate for toner production according to any one of claims 1 to 7, wherein the nozzle provided on the nozzle plate has a size of 4 to 15 µm, and vibration generation means is provided on the nozzle plate so as to have a frequency of 20 kHz or more and less than 2.0 MHz. The toner material liquid in which the toner material containing at least the resin and the colorant is dispersed or dissolved is formed into droplets from each nozzle of the nozzle plate by applying the vibration frequency of the nozzle plate, and the formed toner material liquid is dried. A method for producing toner, comprising producing toner particles by forming toner particles.   9. The toner manufacturing method according to claim 8, wherein the number of nozzles provided for each liquid storage portion storing the toner material liquid is 100 to 40,000.   8. The toner production nozzle plate according to claim 1, vibration applying means for applying a vibration to the nozzle plate to form a droplet, and drying the droplet in a space from which the droplet is discharged. And a solidifying part that solidifies by being made.