JP2009258355A - Method for manufacturing toner, and toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a toner, by which a toner having a small particle diameter can be efficiently produced, the toner having excellent offset resistance and low temperature fixability and unprecedented monodispersibility of granularity without inducing degradation in storage property of the toner such as so-called blocking or filming on a photoreceptor caused by wax. <P>SOLUTION: The method for manufacturing a toner includes: a droplet forming step of injecting a toner composition liquid, which is prepared by dissolving or dispersing a toner composition containing at least a binder resin, a colorant and a release agent in a solvent, through a nozzle to produce droplets; and a particle forming step of converting the droplets of the toner composition liquid into solid particles. The method is characterized in that the binder resin is composed of two or more kinds of resins incompatible with each other, the melting point of the release agent is 30 to 70°C, and the melt viscosity of the release agent at 120°C is 1 to 30 mPa s. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

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

Developers used in electrophotography, electrostatic recording, electrostatic printing, and the like are once attached to an image carrier such as an electrostatic latent image carrier on which an electrostatic image is formed in the development process. Then, after being transferred from the electrostatic latent image carrier to a transfer medium such as transfer paper in the transfer step, it is fixed on the paper surface in the fixing step. At that time, as a developer for developing an electrostatic charge image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer not requiring a carrier (magnetic toner, Non-magnetic toners are known.
Conventional dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like are those obtained by melt-kneading a toner binder such as a styrene resin or a polyester resin together with a colorant and then finely pulverizing, so-called pulverized toner. Is widely used.

    Recently, a toner production method using a suspension polymerization method or an emulsion polymerization aggregation method, so-called polymerization type toner, has been studied. In addition to this, a method called volumetric shrinkage called a polymer dissolution suspension method has been studied (see Patent Document 1). In this method, a toner material is dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified and formed into droplets in an aqueous medium containing a dispersant, and then the volatile solvent is removed. Unlike the suspension polymerization method and emulsion polymerization aggregation method, this method is a versatile resin that can be used, and in particular, a polyester resin useful for a full color process that requires transparency and smoothness of the image area after fixing. It is excellent in that it can be used.

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

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

    Using a toner material containing a thermosetting resin or UV curable resin as a dispersoid, a dispersion finely dispersed in a dispersion medium is intermittently ejected as droplets from a nozzle, and then the droplets are aggregated and thermally cured. There has also been proposed a method of stabilizing the particle formation by curing a resin or a UV curable resin (see Patent Documents 5 and 6). However, these methods also have low productivity and are insufficient in terms of monodispersibility as in Patent Documents 1 to 4. Moreover, although resin is hardened after particle | grain formation, the subject regarding the fixing characteristic as mentioned above was not solved.

    In the case of the above-mentioned granulation method (Patent Document 5, Patent Document 6), it is characterized in that the vibrating part directly touches the fluid, but in such a configuration, the number of pores and vibrating parts match. Can achieve a sharp particle size distribution, but in the case of a large number of pores and a single excitation unit, the droplets discharged from the pores can be arranged according to the distance between the pores and the positional relationship of the excitation unit. It has been found that because the size changes, the toner particles produce different particle sizes between different orifices.

    In addition, these dry toners are generally used because of their high thermal efficiency, after being developed and transferred onto paper or the like, they are fixed by heating and melting using a heated roll or belt. At this time, if the temperature of the heat roll or belt is too high, a problem (hot offset) occurs in which the toner is excessively melted and fused to the heat roll or belt. On the other hand, if the heat roll or belt temperature is too low, there is a problem that the toner is not sufficiently melted and the fixing becomes insufficient. From the viewpoint of energy saving and downsizing of devices such as copying machines, toners are required that have higher hot offset generation temperatures (good hot offset resistance) and low fixing temperatures (good low temperature fixability). In addition, the toner must have heat-resistant storage stability that does not block the toner during storage and at ambient temperature in the apparatus. In particular, in full-color copying machines and full-color printers, the gloss and color mixing of the image are required, so the toner needs to have a lower melt viscosity, and a sharp-melt polyester toner binder is used. ing.

    However, since such toner tends to cause hot offset, conventionally, in a full-color device, silicone oil or the like is applied to a heat roll. However, the method of applying silicone oil to the hot roll requires an oil tank and an oil application device, and the device is complicated and large. In addition, it is inevitable that oil adheres to copy paper, OHP (overhead projector) film, etc., and there are problems such as writing properties with water-based ink and deterioration of color tone due to attached oil in OHP.

Therefore, in order to prevent toner fusion without applying oil to the heat roll, a method of adding a release agent such as wax to the toner is generally used. The arrangement state at is greatly affected. If the release effect is to be sufficiently exerted, it is most effective to make the wax exist on the toner surface rather than in the binder. As an attempt for this, in Patent Document 7, spherical wax is fixed on the toner surface, but the wax existing on the toner surface lowers the fluidity of the toner, so that developability and transferability are deteriorated and storage stability is deteriorated, so-called blocking. Such problems arise. In addition, there is a problem that the wax is prevented from obtaining a good image quality by causing filming due to transfer to a carrier or a photoreceptor during long-term use.
With respect to these problems, Patent Document 8 embeds wax in a graft polymer composed of a polyolefin resin and a vinyl resin, and disposes the wax while improving the above-mentioned problem by disposing the wax in the vicinity of the toner surface. Attempts to achieve the mold effect are still inadequate.

JP-A-7-152202 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977 JP 2006-28432 A JP 2006-28433 A JP 2001-305782 A Japanese Patent No. 3926640

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, the present invention can efficiently produce a toner having a small particle diameter, does not cause deterioration in toner storage stability caused by wax, so-called blocking or filming on a photoreceptor, and is resistant to offset and low temperature. Due to the excellent fixability and unprecedented particle size and monodispersibility, many of the characteristic values required for toners such as fluidity and charging characteristics have been found in previous production methods. To provide a method for producing a toner that forms a high-resolution, high-definition, high-quality image with no or very little variation due to particles, and that does not deteriorate over a long period of time, and a toner produced thereby. With the goal.

As a result of intensive studies to solve the above problems, the present inventor has released a toner composition solution in which a toner composition containing at least a binder resin, a colorant, and a release agent is dissolved or dispersed in a solvent from a nozzle. When the toner is produced by droplet formation, the binder resin is composed of two or more kinds of resins that are incompatible with each other, have a melting point of 30 to 70 ° C., and a melt viscosity at 120 ° C. of 1 to 1. The present invention was completed by finding that the above-mentioned problems can be solved by using a release agent having a viscosity of 30 mPa · s.
That is, the present invention relates to a toner manufacturing method having a configuration as described below.

(1) A droplet forming step of discharging a toner composition liquid in which a toner composition containing at least a binder resin, a colorant, and a release agent is dissolved or dispersed in a solvent into droplets by discharging from a nozzle; In the toner manufacturing method including a particle forming step of solidifying the dropletized toner composition liquid, the binder resin is composed of two or more kinds of resins that are incompatible with each other, and the melting point of the release agent is 30. A method for producing a toner, wherein the melt viscosity at 120 ° C. is from 1 to 30 mPa · s.
(2) The method for producing a toner according to (1), wherein the binder resin is a polyester resin and a styrene-acrylic resin, and (1) is a hydrocarbon wax.
(3) The method for producing a toner according to (1) or (2), wherein the release agent is a hydrocarbon wax.
(4) Any one of (1) to (3), wherein the release agent is a hydrocarbon wax modified with carboxylic acid or carboxylic anhydride and has an acid value of 1 to 90 mgKOH / g 2. A method for producing the toner according to 1.
(5) The droplet forming step periodically oscillates the toner composition liquid from the nozzles of the thin film by vibrating a thin film having a plurality of nozzles provided in a storage section for storing the toner composition liquid by mechanical vibration means. The method for producing a toner according to any one of (1) to (4), which is a periodic droplet forming step of discharging and forming droplets.
(6) The method for producing a toner according to (5), wherein the mechanical vibration means is vibration generation means formed in an annular shape around a region where the thin film nozzle is provided.
(7) The toner according to (5), wherein the mechanical vibration means is a vibration means having a vibration surface parallel to the thin film, and the vibration surface vibrates longitudinally in a vertical direction. Production method.
(8) The toner production method as described in (7), wherein the mechanical vibration means is a horn-type vibrator.
(9) The method for producing a toner according to any one of (5) to (8), wherein a vibration frequency of the mechanical vibration means is 20 kHz or more and less than 2.0 MHz.
(10) The particle size distribution (weight average particle size / number average particle size) produced by the production method according to any one of (1) to (9) is in the range of 1.00 to 1.15. Toner.

    The toner production method of the present invention has a melting point of 30 ° C. to 70 ° C., preferably 50 ° C. to 70 ° C. as a release agent, in addition to using two or more resins that are incompatible with each other as a binder resin. Since a release agent having a melt viscosity at 120 ° C. of 1 to 30 mPa · s is used, toner particles having unprecedented particle dispersibility and excellent offset resistance can be efficiently produced.

    The toner obtained by the production method of the present invention has no fluctuation range due to the variation in the particle size seen in the production methods of conventional pulverized toners and chemical toners, or extremely varies to the extent that it can be almost ignored. Therefore, even if development is repeated, the image is stable.

    In addition, the toner obtained by the method for producing a toner of the present invention uses a hydrocarbon wax having a very low melting point and a low viscosity, which has been difficult to use in conventional pulverized toners and chemical toners, as a release agent. Excellent anti-offset property due to inclusion. The very low melting point hydrocarbon wax can be used because it contains two or more kinds of resins that are incompatible with each other as the binder resin. Although the reason is not clear yet, it has been found that the wax is arranged at the interface between the resins, and the resin interface including the wax is always present inside the toner without protruding to the toner surface. As a result, a wax having a very low melting point can be used in the toner production method.

<Toner production device>
As described above, the toner composition liquid can be formed into droplets in the gas phase by using a one-fluid nozzle (pressurizing nozzle) that pressurizes the liquid and sprays it from the nozzle, or a mixture of the liquid and compressed gas for spraying. A rotary disk type spraying machine that uses a fluid spray nozzle and a rotating disk to form liquid droplets by centrifugal force is known. In order to obtain a small particle size toner, a multi-fluid spray nozzle and a rotating disk type are used. A sprayer is preferred. As a multi-fluid spray nozzle, an external mixing two-fluid nozzle is generally used, but various improvements such as an internal mixing two-fluid nozzle and a four-fluid nozzle are being studied in order to obtain further atomization and uniformity in particle size. . With the same aim for the rotating disk type sprayer, improvements such as a dish type, a bowl type, and a multi-blade type are being studied.
However, the toner obtained by these production methods may have a wide particle size distribution and require classification.

As a manufacturing method for obtaining a toner having a uniform particle size, the present inventors have improved this drawback, and periodically ejects a toner composition liquid from a thin film having a plurality of uniform diameter nozzles by mechanical vibration means to form droplets. A periodic droplet formation method was found.
That is, an apparatus used in the toner manufacturing method of the present invention (hereinafter also referred to as “toner manufacturing apparatus”) is a toner composition liquid that is a solution or dispersion of a toner material containing at least a resin and a colorant. A droplet forming means in which mechanical vibration means is formed in an annular shape around a thin film having a plurality of nozzles, or a machine that vertically vibrates a vibration surface parallel to the thin film having a plurality of nozzles. A droplet having a uniform particle diameter can be generated by discharging from each nozzle using a droplet forming unit provided with a mechanical vibration unit.

In the production method of the present invention, the droplets of the toner composition liquid are formed by mechanically vibrating a thin film having a plurality of nozzles to discharge the toner composition liquid from the nozzles. The mechanical vibration means may be arranged in any way as long as it vibrates in the direction perpendicular to the film having the nozzle. In the present invention, the following two methods are used.
One is a method using mechanical means (mechanical longitudinal vibration means) that has a vibration surface parallel to the thin film having a plurality of nozzles and longitudinally vibrates in the vertical direction (hereinafter also simply referred to as “horn type”). The other is a method of providing mechanical vibration means (annular mechanical vibration means) formed in an annular shape around a thin film having a plurality of nozzles (hereinafter also simply referred to as “ring type”). It is.
Hereinafter, each method will be described.

(Mechanical longitudinal vibration means)
First, an example of a toner manufacturing apparatus provided with mechanical longitudinal vibration means will be described with reference to the schematic configuration diagram of FIG.
The toner manufacturing apparatus 1 includes a droplet ejecting unit 2 as droplet forming means for discharging a toner composition liquid containing at least a resin and a colorant into droplets, and the droplet ejecting unit 2 is disposed above. A particle forming unit 3 as a particle forming unit that solidifies the droplets of the toner composition liquid formed into droplets discharged from the droplet ejecting unit 2 to form toner particles T, and a toner formed by the particle forming unit 3 Toner collecting unit 4 that collects particles T, and toner particles T collected by toner collecting unit 4 are transferred through tube 5 and toner serving as toner storing means for storing transferred toner particles T is stored. A storage unit 6, a raw material storage unit 7 for storing the toner composition liquid 10, a pipe (liquid supply pipe) 8 for supplying the toner composition liquid 10 from the raw material storage unit 7 to the droplet ejection unit 2, Toner composition liquid 10 during operation And a pump 9 for feeding supply.

    In addition, the toner composition liquid 10 from the raw material container 7 is supplied to the droplet ejection unit 2 in a self-sufficient manner due to the droplet formation phenomenon by the droplet ejection unit 2. In particular, the pump 9 is used to supply the liquid. Here, as the toner composition liquid 10, a solution or dispersion obtained by dissolving or dispersing a toner composition containing at least a resin and a colorant in a solvent is used.

Next, the droplet ejecting unit 2 will be described with reference to FIGS. FIG. 2 is a schematic cross-sectional explanatory view of the liquid droplet ejecting unit 2, and FIG. 3 is an explanatory bottom view of the main part when FIG.
The droplet ejection unit 2 includes a thin film 12 in which a plurality of nozzles (discharge ports) 11 are formed, mechanical vibration means (hereinafter referred to as “vibration means”) 13 that vibrates the thin film 12, and the thin film 12 and vibration means 13. And a flow path member 15 that forms a reservoir (liquid flow path) 14 for supplying a toner composition liquid 10 containing at least a resin and a colorant.

    The thin film 12 having the plurality of nozzles 11 is disposed in parallel to the vibration surface 13a of the vibration means 13, and a flow path is formed by a resin binder material in which a part of the thin film 12 does not dissolve in the solder or the toner composition liquid. It is bonded and fixed to the member 15 and has a substantially vertical positional relationship with the vibration direction of the vibration means 13. A communication means 24 is provided so that a voltage signal is applied to the upper and lower surfaces of the vibration generating means 21 of the vibration means 13, and the signal from the drive signal generating source 23 can be converted into mechanical vibration. As a communication means for providing an electrical signal, a lead wire whose surface is insulated is suitable. In addition, it is suitable for efficient and stable toner production that the vibration means 13 uses elements having a large vibration amplitude such as various horn type vibrators and bolted Langevin type vibrators described later.

    The vibration unit 13 includes a vibration generation unit 21 that generates vibrations and a vibration amplification unit 22 that amplifies the vibrations generated by the vibration generation unit 21. The drive unit (drive signal generation source) 23 drives a required frequency. When a voltage (drive signal) is applied between the electrodes 21 a and 21 b 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 arranged in parallel with the thin film 12. The vibrating surface 13a is periodically vibrated, and the thin film 12 is vibrated at a required frequency by the periodic pressure caused by the vibration of the vibrating surface 13a.

    The vibrating means 13 is not particularly limited as long as it can give a certain longitudinal vibration to the thin film 12 at a constant frequency, and can be appropriately selected and used, but the thin film 12 is vibrated. Therefore, the vibration generating means 21 is preferably a piezoelectric body 21A that is excited by a bimorph type flexural vibration. The piezoelectric body 21A has a function of converting electrical energy into mechanical energy. Specifically, by applying a voltage, flexural vibration is excited and the thin film 12 can be vibrated.

Examples of the piezoelectric body 21A constituting the vibration generating means 21 include piezoelectric ceramics such as lead zirconate titanate (PZT). However, since the amount of displacement is generally small, they are often used by being laminated. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO ₃ , and the like can be given.
The vibration means 13 may be arranged in any way as long as it gives vibration in the vertical direction to the thin film 12 having the nozzle 11, but the vibration surface 13 a and the thin film 12 are arranged in parallel.
In the illustrated example, a horn type vibrator is used as the vibration means 13 composed of the vibration generation means 21 and the vibration amplification means 22, and this horn type vibration amplifies the amplitude of the vibration generation means 21 such as a piezoelectric element. Since it can be amplified by the horn 22A as the means 22, the vibration generating means 21 itself for generating mechanical vibration may be a small vibration, and the mechanical load is reduced, leading to a long life as a production apparatus.

As the horn type vibrator, a known typical horn shape may be used, and examples thereof include a step type as shown in FIG. 4, an exponential type as shown in FIG. 5, a conical type as shown in FIG. Can do. In these horn-type vibrators, a piezoelectric body 21A is arranged 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. Lead wires 24 are arranged above and below the piezoelectric body 21, and an AC voltage signal is given from the drive circuit 23. The maximum vibration surface of these horn vibrators is designed to have a shape of 13a.
Further, as the vibration means 13, a particularly high-strength bolted Langevin type vibrator can be used. This bolted Langevin type vibrator is mechanically coupled with piezoelectric ceramics and will not be damaged during high amplitude excitation.

    The configuration of the reservoir, the mechanical vibration means, and the thin film will be described in detail with reference to the schematic diagram of FIG. The storage unit 14 is provided with at least one liquid supply tube 18, and as shown in a partial cross-sectional view, the liquid is introduced into the liquid storage unit through the flow path. Moreover, it is also possible to provide the bubble discharge tube 19 as needed. The droplet ejection 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 15. In addition, although the example which has arrange | positioned the droplet injection unit 2 in the top | upper surface part of the particle formation part 3 is demonstrated here, the droplet injection unit 2 is provided in the drying part side wall used as the particle formation part 3, or a bottom part. It can also be set as the structure to install.

    The size of the vibration means 13 that generates mechanical vibration is generally increased as the oscillation frequency decreases, and according to the necessary frequency, the vibration means is directly drilled to provide a reservoir. be able to. It is also possible to vibrate the entire storage part efficiently. In this case, the vibration surface is defined as a surface on which the thin films having the plurality of nozzles are bonded.

    Different examples of the droplet jetting unit 2 having such a configuration will be described with reference to FIGS. The example shown in FIG. 7 uses a horn-type vibrator 80 composed of a piezoelectric body 81 as a vibration generating unit and a horn 82 as a vibration amplifying unit as the vibration unit 80 (13). A reservoir (flow path) 14 is formed. The droplet jetting unit 2 is preferably fixed to the wall surface of the particle forming unit 3 (drying means) by a fixing unit (flange unit) 83 integrally formed with the horn 82 of the horn-type vibrator 80. Loss of vibration From the viewpoint of preventing this, it may be fixed using an elastic body (not shown).

    The example shown in FIG. 8 is a bolt-clamped Langevin type vibrator configured by mechanically firmly fixing piezoelectric bodies 91A and 91B and horns 92A and 92B as vibration generating parts as bolts as vibration means 90 (13). 90 is used to form a reservoir (flow path 14) in the horn 92A. Depending on the frequency condition, the element may be large, and as shown in the drawing, the fluid introduction / discharge path and the reservoir can be processed in a part of the vibrator, and a metal thin film having a plurality of thin films can be attached.

    FIG. 1 shows an example in which only one droplet ejecting unit 2 is attached to the particle forming unit 3, but a plurality of droplet ejecting units 2 are arranged above the particle forming unit 3 (drying tower). Paralleling is preferable from the viewpoint of improving productivity, and the number thereof is preferably in the range of 100 to 1000 from the viewpoint of controllability. In this case, the toner composition liquid 10 is supplied to each storage section 14 of the droplet ejection unit 2 through the pipe 8 to the raw material storage section (common liquid reservoir) 7. The toner composition liquid 10 may be configured to be supplied in a self-contained manner as droplets are formed, or may be configured to supply the liquid supplementarily using the pump 9 during operation of the apparatus. it can.

Another example of the droplet ejecting unit will be described with reference to FIG. FIG. 9 is a schematic cross-sectional explanatory view of the liquid droplet ejecting unit.
In the droplet ejecting unit 2, similarly to the above-described example, a horn-shaped vibrator is used with the vibrating means 13, and the flow path member 15 that surrounds the vibration generating means 13 and supplies the toner composition liquid 10 is disposed. The reservoir 14 is formed on the horn 22 of the vibration generating means 13 at the portion facing the thin film 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 the nozzles 11 of the thin film 12 is one, but a plurality of nozzles 11 are provided as described above. As shown in FIG. 10, from the viewpoint of controllability, a plurality of, for example, 100 to 1,000 droplet ejection units 2 are arranged side by side on the top of the drying tower constituting the particle forming unit 3. Thereby, productivity can be further improved.

(Annular mechanical vibration means)
FIG. 11 shows the apparatus shown in FIG. 1 in which the droplet ejection unit is replaced with a ring type.
The ring type droplet ejecting unit 2 will be described with reference to FIGS. 12 is a cross-sectional explanatory view of the liquid droplet ejecting unit 2, FIG. 13 is a main surface bottom explanatory view of FIG. 12 viewed from the lower side, and FIG. 14 is a schematic cross-sectional explanatory view of droplet forming means.
The liquid droplet ejecting unit 2 includes a liquid droplet forming unit 11 that discharges the toner composition liquid 10 containing at least a resin and a colorant into liquid droplets, and a storage unit that supplies the liquid droplet forming unit 11 with the toner composition liquid 10. (Liquid flow path) 14 having a flow path member 15 formed thereon.

    The droplet forming means 16 includes a thin film 12 in which a plurality of nozzles (discharge ports) 11 are formed, and an annular vibration generating means (electromechanical conversion means) 17 that vibrates the thin film 12. Here, the thin film 12 is bonded and fixed to the flow path member 15 with a resin binding material that does not dissolve in the solder or the toner composition liquid at the outermost peripheral portion (region shown by hatching in FIG. 14). The vibration generating means 17 is arranged around the deformable area 16A (area not fixed to the flow path member 15) of the thin film 12. A drive voltage (drive signal) having a required frequency is applied to the vibration generating means 17 from a drive circuit (drive signal generation source) 23 through lead wires 21 and 22 to generate, for example, flexural vibration.

    The droplet forming means 16 is provided with an annular vibration generating means 17 around the deformable region 16A of the thin film 12 having the plurality of nozzles 11 facing the storage portion 14, for example, the comparison shown in FIG. Compared to the configuration in which the vibration generating means 17A holds the periphery of the thin film 12 as in the example configuration, the displacement amount of the thin film 12 is relatively large, and a relatively large area (φ1 mm or more) from which this large displacement amount can be obtained. ), A plurality of nozzles 11 can be arranged, and more droplets can be stably formed and discharged at a time than the plurality of nozzles 15.

    In FIG. 11, an example in which one droplet ejecting unit 2 is arranged is illustrated, but preferably, as shown in FIG. 16, a plurality of, for example, 100 to 1,000 (for example, from the viewpoint of controllability) In FIG. 16, only four droplet ejecting units 2 are arranged side by side on the top surface portion 3A of the particle forming unit 3, and each droplet ejecting unit 2 has a pipe 8A in the raw material storage unit 7 (common liquid reservoir). Then, the toner composition liquid 10 is supplied. As a result, more droplets can be discharged at a time, and the production efficiency can be improved.

(Droplet formation mechanism)
Next, the mechanism of droplet formation by the droplet ejecting unit 2 as the droplet forming means will be described.
As described above, the droplet ejecting unit 2 causes the thin film 12 having the plurality of nozzles 11 facing the storage unit 14 to propagate the vibration generated by the vibration means 13 that is a mechanical vibration means, thereby periodically causing the thin film 12 to move. By vibrating, a plurality of nozzles 11 are arranged in a relatively large area (φ1 mm or more), and droplets can be stably formed and discharged from the plurality of nozzles 11.

When the peripheral portion 12A of the simple circular film 12 as shown in FIG. 17 is fixed, the basic vibration has a node around the periphery, and as shown in FIG. 18, the cross section where the displacement ΔL is maximum (ΔLmax) at the center O of the thin film. It becomes a shape and vibrates up and down periodically in the vibration direction.
Further, it is known that higher order modes as shown in FIGS. 19 and 20 exist. These modes have one or a plurality of concentric nodes in a circular film and are substantially axisymmetric deformation shapes. In addition, as shown in FIG. 21, the central portion has a convex shape 12c, so that the traveling direction of the droplet can be controlled and the vibration amplitude can be adjusted.

By the vibration of the circular thin film, the liquid near the nozzle provided in the circular films each place, the sound pressure P _ac proportional to the vibration speed Vm of the film occurs. It is known that the sound pressure is generated as a reaction of the radiation impedance Zr of the medium (toner composition liquid). The sound pressure is a product of the radiation impedance and the membrane vibration velocity Vm, and is expressed using the following equation (1). Is done.
P _ac (r, t) = Z _r · V _m (r, t) (1)
Since the vibration velocity Vm of the film varies periodically with time, it is a function of time (t), and various periodic variations such as a sine waveform and a rectangular waveform can be formed. Further, as described above, the vibration displacement in the vibration direction is different in each part of the film, and Vm is also a function of the position coordinates on the film. The vibration mode of the film used in the present invention is an axial object as described above. Therefore, it is substantially a function of the radius (r) coordinate.

As described above, a sound pressure proportional to the vibration displacement speed of the distributed film is generated, and the toner composition liquid is discharged into the gas phase in response to the periodic change of the sound pressure.
Since the toner composition liquid periodically discharged to the gas phase forms a sphere due to a difference in surface tension between the liquid phase and the gas phase, droplet formation occurs periodically.

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

    Here, the diameter of the formed droplet tends to increase as the vibration displacement in the vicinity of the nozzle of the film increases. When the vibration displacement is small, a droplet is formed or does not become a droplet. In order to reduce such a variation in droplet size at each nozzle site, it is necessary to define the nozzle arrangement at an optimum position of the membrane vibration displacement.

In the present invention, as illustrated in FIGS. 18 to 20, the ratio R (= ΔL _max) of the maximum value ΔL _max and the minimum value ΔL _mim of the vibration direction displacement ΔL of the film near the nozzle generated by the mechanical vibration means. / ΔL _min ) is found to be able to keep the variation of the droplet size in a necessary region as toner fine particles capable of providing a high-quality image by disposing the nozzle at a site where 2.0 / _{min or} less. It was.
By changing the conditions of the toner composition liquid, the viscosity is 20 mPa · s or less, the surface tension is 20 to 75 mN /
Since the satellite generation start region is the same in the region m, the displacement amount of the sound pressure needs to be 500 kPa or less, more preferably 100 kPa or less.

(Thin film with multiple nozzles)
As described above, the thin film having the nozzle is a member that discharges a solution or dispersion of the toner material into droplets.
The material of the thin film 12 and the shape of the nozzle 11 are not particularly limited and may be appropriately selected. For example, the thin film 12 is formed of a metal plate having a thickness of 5 to 500 μm and An opening diameter of 3 to 35 μm is preferable from the viewpoint of generating fine liquid droplets having a very uniform particle diameter when the liquid droplets of the toner composition liquid 10 are ejected from the nozzle 11. The opening diameter of the nozzle 11 means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse. The number of the plurality of nozzles 11 is preferably 2 to 3000.

(Dry)
The drying process for removing the solvent from the droplets is performed by discharging the droplets into a gas such as heated dry nitrogen. If necessary, secondary drying such as fluidized bed drying or vacuum drying is further performed.

<Toner>
The toner of the present invention is a toner manufactured by the toner manufacturing method of the present invention described above. As the toner, a toner having a monodispersed particle size distribution can be obtained by the toner manufacturing method. Specifically, the particle size distribution (weight average particle size / number average particle size) of the toner is preferably in the range of 1.00 to 1.15.

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

    The toner of the present invention contains two or more resins that are incompatible with each other as a binder resin, and contains a very low melting point, low viscosity acid-modified hydrocarbon wax as a release agent. However, as the other toner materials, the same toner materials as conventional electrophotographic toners can be used.

(Toner composition)
The toner composition contains at least two kinds of resins and colorants that are incompatible with each other, a very low melting point, low viscosity acid-modified hydrocarbon wax as a release agent, and if necessary, It contains other components such as a charge control agent, a magnetic material, a fluidity improver, a lubricant, a cleaning aid, and a resistance adjuster.

(solvent)
The solvent is preferably an organic solvent, and the organic solvent is not particularly limited. However, since it is easy to remove, the boiling point is preferably less than 150 ° C. For example, toluene, xylene, benzene, carbon tetrachloride, chloride Examples include methylene, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. . Among them, since the solubility of the polyester resin is excellent, the organic solvent preferably has a solubility parameter of 8 to 9.8 (cal / cm ³ ) ^1/2 , and 8.5 to 9.5 (cal / cm). ³ ) ^1/2 is more preferred. Furthermore, since the interaction with the modifying group of the release agent is large and the crystal growth of the release agent can be effectively suppressed, ester solvents and ketone solvents are preferable, and removal is easy. Therefore, ethyl acetate and methyl ethyl ketone are particularly preferable.

(resin)
Incompatible with each other means that a dried product obtained by drying a resin mixed solution dissolved in a solvent is opaque. If the dried product is transparent, an ultrathin section is prepared with a microtome, stained with RuO4, etc., then observed with a transmission electron microscope (TEM), and judged to be incompatible if phase separated. .
Conventionally known binder resins for toner are used as the binder resin, but those having no cross-linked structure are preferred because they are required to be soluble in a solvent. For example, vinyl polymers such as styrene monomers, acrylic monomers, methacrylic monomers, copolymers of these monomers or two or more types, polyester resins, polyol resins, phenol resins, Examples include polyurethane resins, polyamide resins, epoxy resins, xylene resins, terpene resins, coumarone indene resins, polycarbonate resins, petroleum resins, and the like. Among these, it is preferable to use a copolymer resin and a polyester resin of a styrene monomer and a (meth) acrylic monomer. It is sufficient that at least two types of resins are incompatible, and three or more types may be mixed.

The mixing ratio of the resin is preferably 5/95 to 95/5, more preferably 15/85 to 85/15. If it is smaller than 5/95 or larger than 95/5, the wax in the toner particles tends to be present on the toner surface, and filming occurs over time. In addition, storage stability is lost due to bleed-out of the wax.
The weight average molecular weight of the resin is preferably 3,000 to 9,0000, more preferably 5,000 to 7,0000. If it is less than 3,000, the cold offset property and the storage stability are poor. When it is larger than 9,0000, the hot offset property and the ejection stability from the nozzle are inferior.

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

  Examples of the acrylic monomer include acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate, and acrylic. Examples include 2-ethylhexyl acid, stearyl acrylate, 2-chloroethyl acrylate, acrylic acid such as phenyl acrylate, or esters thereof.

  Examples of the methacrylic monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, n-dodecyl methacrylate, and methacrylic acid. And methacrylic acid or esters thereof such as 2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

  Examples of the polymerization initiator used for producing the vinyl polymer or copolymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, , 1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2 ' , 4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexane Ketone peroxides such as Sanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroper Oxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl Peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydi -Bonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexyl Sulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexarate, tert-butyl peroxylaurate, tert-butyl-oxybenzoate, tert- Butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-ter Examples thereof include t-butyl peroxyhexahydroterephthalate and tert-butyl peroxyazelate.

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

  Examples of the acid component that forms the polyester polymer include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or Unsaturated dibasic acids such as anhydride, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride And unsaturated dibasic acid anhydrides. Examples of the trivalent or higher polyvalent carboxylic acid component include trimet acid, pyromet acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene Carboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, or anhydrides thereof, partial lower alkyl esters, and the like. These binder resins preferably have a glass transition temperature (Tg) of 35 to 80 ° C., more preferably 40 to 75 ° C., from the viewpoint of toner storage stability. When Tg is lower than 35 ° C., the toner is likely to deteriorate in a high temperature atmosphere, and when Tg exceeds 80 ° C., the fixability may be lowered.

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

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

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

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

The dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific examples of commercially available products include “Ajisper PB821” and “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co., Ltd.). , “Disperbyk-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like.
The dispersant is preferably blended in the toner at a ratio of 0.1 to 10% by mass with respect to the colorant. When the blending ratio is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it is more than 10% by mass, the chargeability under high humidity may be deteriorated.

The weight average molecular weight of the dispersant is the maximum molecular weight of the main peak in terms of styrene mass in gel permeation chromatography, preferably 500 to 100,000, and from the viewpoint of pigment dispersibility, 3,000 to 100 1,000 is more preferred. In particular, 5,000 to 50,000 are preferable, and 5,000 to 30,000 are most preferable. When the molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant decreases. There are things to do.
The addition amount of the dispersant is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 1 part by mass, the dispersibility may be lowered, and if it exceeds 50 parts by mass, the chargeability may be lowered.

(Release agent)
In the present invention, the melting point is 30 ° C. to 70 ° C. (preferably 50 ° C. to 70 ° C.) as a release agent, and the melt viscosity at 120 ° C. is 1 to 30 mPa · s. A release agent which is s is used. When the melt viscosity is less than 30 ° C., storage stability is impaired due to bleeding out of the wax in the toner particles. On the other hand, if it is higher than 70 ° C., the hot offset property is impaired.
In particular, it is preferable to use an acid-modified hydrocarbon wax as the mold release agent, and the use of the acid-modified hydrocarbon wax produces an effect of preventing nozzle clogging.
Examples of the hydrocarbon wax include polyolefin waxes such as paraffin wax, sasol wax, polyethylene wax, and polypropylene wax, and two or more kinds may be used in combination. Among these, paraffin wax having a low melting point is preferable in terms of low-temperature fixability and offset resistance.

  The method for acid-modifying the hydrocarbon wax is not particularly limited. For example, JP-A 54-30287, JP-A 54-81306, JP-A 60-16442, JP-A 3- The methods disclosed in 1992267, JP 2000-10338 A, and the like can be used. Examples of the acid for modifying the hydrocarbon wax include unsaturated polyvalent carboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride. Maleic anhydride is preferred because of its excellent reactivity and improved dispersibility of the release agent.

  In the present invention, in addition to using two or more kinds of resins that are incompatible with each other as the binder resin as described above, the melting point is 30 ° C. to 70 ° C., preferably 50 ° C. to 70 ° C. as a release agent. By using a release agent having a melt viscosity at 120 ° C. of 1 to 30 mPa · s, low-temperature fixability and offset resistance can be achieved as a toner. Further, by using an acid-modified hydrocarbon wax as a releasing agent, the wax is stably finely dispersed in the dispersion liquid, so that the toner composition liquid is periodically discharged by mechanical vibration means to form droplets. There is an effect that the clogging of the nozzle can be prevented in the manufacturing method.

  In the present invention, the release agent preferably has an acid value of 1 to 90 mgKOH / g, and more preferably 5 to 50 mgKOH / g from the viewpoint of dispersibility of the release agent and offset resistance. When the acid value is less than 1 mg KOH / g, the dispersibility of the release agent becomes insufficient, and nozzle clogging occurs. Even if the toner can be formed, various properties such as fluidity, chargeability, and fixability of the toner may be deteriorated. On the other hand, when the acid value exceeds 90 mgKOH / g, it may be detached from the liquid in the step of spraying from a nozzle to form droplets, which may reduce offset resistance. In addition, the separability from the polyester resin is lowered, and the offset resistance may be insufficient.

  The acid value was measured using a potentiometric automatic titrator DL-53 Titrator (manufactured by METTLER TOLEDO), electrode DG113-SC (manufactured by METTLER TOLEDO) and analysis software LabX Light Version 1.000.000. The At this time, the apparatus is calibrated using a mixed solvent of 120 ml of toluene and 30 ml of ethanol, the measurement temperature is 23 ° C., and the measurement conditions are as follows.

Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

Specifically, the measurement is performed as follows based on the measurement method described in JIS K0070-1992. First, 0.5 g of a sample is added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.), and then 30 ml of ethanol is added to obtain a sample solution. Next, titration with a pre-standardized 0.1N potassium hydroxide alcohol solution gives the titration amount X [ml], and the formula acid value = X × N × 56.1 / sample weight [mg KOH / g ]
Therefore, the acid value is determined. However, N is a factor of the alcohol solution of 0.1N potassium hydroxide.

  In the present invention, the release agent preferably has a melt viscosity at 120 ° C. of 1 to 30 mPa · s, and more preferably 1 to 20 mPa · s, from the viewpoints of fixability and offset resistance. When the melt viscosity is less than 1.0 mPa · s, the fluidity of the toner may be inferior, and when it exceeds 30 mPa · s, the offset resistance may be deteriorated. The melt viscosity is measured using a Brookfield rotary viscometer.

In the present invention, the release agent has a melting point of 30 to 70 ° C. More preferably, it is 50-70 degreeC. Here, the melting point is the temperature of an endothermic peak at which the endothermic amount is maximized in a differential thermal curve obtained by differential scanning calorimetry (DSC). As a DSC measuring instrument, it is preferable to measure with a high-precision internal heat type input compensation type differential scanning calorimeter. As a measuring method, it carries out according to ASTM D3418-82. The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 ° C./min after once raising and lowering the temperature and taking a previous history. If the melting point is less than 30 ° C., it will melt during the production of the toner. On the other hand, when the melting point exceeds 70 ° C., since the release agent is included in the toner, it is difficult for the toner surface to ooze out during fixing and the low-temperature fixability and offset resistance may be lowered.
In this invention, it is preferable that the addition amount of a mold release agent is 0.1-20 weight part with respect to 100 weight part of resin, and 0.5-10 weight part is further more preferable. If this addition amount is less than 0.1 parts by weight, the effect of the release agent may not be sufficiently obtained, and offset resistance may decrease. If it exceeds 20 parts by weight, the fluidity of the toner may decrease. , It may stick to the developing device.

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

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary.
Any known charge control agent can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified) Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Industries), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Manufactured by Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents and mold release agents can be melt-kneaded together with the masterbatch and resin, and of course, they may be added when dissolved and dispersed in an organic solvent.

(Fluidity improver)
A fluidity improver may be added to the toner of the present invention. The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface.
Examples of the fluidity improver include, for example, vinylidene fluoride fine powder, fluorine resin powder such as polytetrafluoroethylene fine powder, wet-process silica, fine-process silica such as dry-process silica, fine powder unoxidized titanium, fine powder non-alumina. , Treated silica obtained by surface treatment with a silane coupling agent, titanium coupling agent or silicone oil, treated titanium oxide, treated alumina, and the like. Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.
The particle size of the fluidity improver is preferably 0.001 to 2 μm, more preferably 0.002 to 0.2 μm, as an average primary particle size.

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

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

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

The number average particle diameter of the fluidity improver is preferably 5 to 100 nm, more preferably 5 to 50 nm.
The specific surface area by measuring nitrogen adsorption by the BET method, preferably at least ^{30m 2 / g, 60~400m 2 /} g is more preferable.
The surface-treated fine powder, preferably at least ^{20m 2 / g, 40~300m 2 /} g is more preferable.
The application amount of these fine powders is preferably 0.03 to 8 parts by mass with respect to 100 parts by mass of the toner particles.

(Cleaning improver)
Examples of the cleaning improver for improving the removal of toner remaining on the electrostatic latent image carrier or the primary transfer medium after transferring the toner to a recording paper or the like include, for example, zinc stearate, calcium stearate, stearic acid. And polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate 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.
Since these fluidity improvers and cleaning property improvers are used by being attached to or fixed on the surface of the toner, they are also called external additives. A machine or the like is used. For example, a V-type mixer, a rocking mixer, a Laedige mixer, a Nauter mixer, a Henschel mixer, and the like can be mentioned. When immobilization is also performed, a hybridizer, a mechanofusion, a Q mixer, and the like can be given.

(Career)
The toner of the present invention may be mixed with a carrier and used as a two-component developer. As the carrier, ordinary carriers such as ferrite and magnetite and resin-coated carriers can be used.
The resin-coated carrier comprises a carrier core particle and a coating material that is a resin that coats (coats) the surface of the carrier core particle.
Examples of the resin used in the coating material include styrene-acrylic ester copolymers, styrene-acrylic resins such as styrene-methacrylic ester copolymers, acrylic ester copolymers, methacrylic ester copolymers, and the like. Preferable examples include fluorine-containing resins such as acrylic resins, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride, silicone resins, polyester resins, polyamide resins, polyvinyl butyral, and aminoacrylate resins. In addition to these, resins that can be used as a coating (coating) material for carriers such as an ionomer resin and a polyphenylene sulfide resin can be used. These resins may be used alone or in combination of two or more.
A binder type carrier core in which magnetic powder is dispersed in a resin can also be used.

In the resin-coated carrier, as a method for coating the surface of the carrier core with at least a resin coating agent, a method in which the resin is dissolved or suspended in a solvent and adhered to the applied carrier core, or a method in which the resin core is simply mixed in a powder state Is applicable.
The ratio of the resin coating material to the resin-coated carrier may be appropriately determined, but is preferably 0.01 to 5% by mass and more preferably 0.1 to 1% by mass with respect to the resin-coated carrier.

Examples of use in which a magnetic substance is coated with a coating agent of two or more kinds of mixtures include (1) dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) with respect to 100 parts by mass of fine titanium oxide powder. Those treated with 12 parts by mass of the mixture, and (2) those treated with 20 parts by mass of a mixture of dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) with respect to 100 parts by mass of the silica fine powder.
Among the resins, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, and a silicone resin are preferably used, and a silicone resin is particularly preferable.
Examples of the mixture of the fluorine-containing resin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, a mixture of polytetrafluoroethylene and a styrene-methyl methacrylate copolymer, Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10), styrene-acrylic acid 2-ethylhexyl copolymer (copolymer mass ratio 10:90 to 90:10) and styrene- A mixture with 2-ethylhexyl acrylate-methyl methacrylate copolymer (copolymer mass ratio 20 to 60: 5 to 30:10:50) is mentioned.

Examples of the silicone resin include modified silicone resins produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with a silicone resin.
Examples of the magnetic material for the carrier core include oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof.
The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done. Among these, copper-zinc-iron-based ferrites mainly composed of copper, zinc, and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium, and iron components are preferable.

The resistance value of the carrier is preferably 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the degree of unevenness on 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.

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

    EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to the following Example at all. In addition, unless otherwise indicated, a part and% represent a mass part and mass%.

<Production Example 1 of Acid-Modified Hydrocarbon Wax>
100 parts of paraffin wax Paraffin-115 (manufactured by Nippon Seiwa Co., Ltd., melting point: 47 ° C.) was placed in a reaction vessel in which a stir bar and a thermometer were set, and heated to 150 ° C. with a heater to melt the wax. Next, a solution of maleic anhydride and organic peroxide di-t-butyl peroxide dissolved in toluene was added dropwise and reacted for 5 hours with stirring. After completion of the reaction, toluene was removed under a nitrogen purge to synthesize modified paraffin wax A. The modified paraffin wax A had a melting point of 52 ° C., an acid value of 10 mgKOH / g, and a melt viscosity at 120 ° C. of 15 mPa · s.
At this time, modified hydrocarbon waxes (modified paraffin waxes B to D) having an acid value of 20 to 100 mgKOH / g as shown in Table 1 were synthesized by adjusting the dropping amount of the solution and the reaction time.

[Example 1]
-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
20 parts of carbon black (Regal 400; manufactured by Cabot) and 2 parts of a pigment dispersant were primarily dispersed in 78 parts of ethyl acetate using a mixer having stirring blades. As the pigment dispersant, Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a secondary dispersion from which aggregates were completely removed. Furthermore, a liquid having a pore size of 0.45 μm (manufactured by PTFE) and passing through a submicron region was prepared.

-Preparation of dispersion with added resin and wax-
A container equipped with a stirring blade and a thermometer is charged with 186 parts of a polyester resin (weight average molecular weight 20,000), 10 parts of modified paraffin wax A and 2,000 parts of ethyl acetate as a binder resin, heated to 85 ° C. for 20 minutes. The mixture was stirred to dissolve the polyester resin and the modified paraffin wax, and then rapidly cooled to precipitate fine particles of the modified paraffin wax. This dispersion was further finely dispersed by a strong shearing force using a dyno mill.

-Preparation of toner composition dispersion-
Next, the resin as the binder resin shown below, the colorant dispersion and the wax dispersion are added, and the mixture is stirred for 10 minutes using a mixer having stirring blades, and uniformly dispersed to obtain a solid content. A 10% toner composition dispersion was obtained.
-Polyester resin solid content 20% ethyl acetate solution: 325 parts-Styrene-n-butyl acrylate copolymer solid content 20% ethyl acetate solution: 108 parts-Colorant dispersion: 42 parts-Wax dispersion: 25 parts Ethyl acetate: 167 parts However, weight average molecular weight of polyester resin: 61,000, glass transition point: 60 ° C., weight average molecular weight of styrene-n-butyl acrylate copolymer resin: 55,000, glass transition point: 61 ° C.

-Preparation of toner-
The obtained toner composition liquid was supplied to the ring-type vibrator head of the toner manufacturing apparatus shown in FIG.
In addition, the used thin film produced the discharge hole (nozzle) of diameter 8micrometer in the shape of a perfect circle in the nickel plate of outer diameter 8.0mm and thickness 20micrometer by the process by an electroforming method. The discharge holes were provided only in a range of about 5 mmφ at the center of the thin film in a staggered pattern so that the distance between the discharge holes was 100 μm. As the piezoelectric body, lead zirconate titanate (PZT) was used by lamination, and the vibration frequency was set to 100 KHz.

After the dispersion was prepared, the droplets were discharged under the following toner production conditions, and then the droplets were dried and solidified to produce toner base particles.
[Toner preparation conditions]
Dry air flow rate: Nitrogen gas for dispersion 2.0 L / min, Dry nitrogen gas in apparatus 30.0 L / min In-apparatus temperature: 27-28 ° C
Dew point temperature: -20 ° C
Nozzle frequency: 98 kHz

The dried and solidified particles were collected by suction with a filter having 1 μm pores. Further, 1.0% by weight of hydrophobic silica (H2000, manufactured by Clariant Japan) was externally added to the particles using a Henschel mixer (manufactured by Mitsui Mining) to obtain a black toner a.
A cross-sectional photograph of this toner a is shown in FIG.
The results of measuring the particle size of this toner are shown in Table 2. The weight average particle size (D4) was 5.3 μm, Dv / Dn was 1.02, and the particle size distribution was very sharp.
The toner was continuously produced for 5 hours, but the nozzle was not clogged.

-Fabrication of carrier-
Silicone resin (organostyl silicone) 100 parts Toluene 100 parts γ- (2-aminoethyl) aminopropyltrimethoxysilane 5 parts
Carbon black 10 parts The above mixture was dispersed with a homomixer for 20 minutes to prepare a coating layer forming solution. This coating layer forming liquid was used for a spherical magnetite 100 having a particle diameter of 50 μm using a fluidized bed type coating apparatus.
The magnetic carrier A was obtained by coating on the surface of 0 part.

-Production of developer-
The toner carrier a4 parts and the magnetic carrier A96 parts are mixed with a ball mill to prepare a two-component developer 1, and evaluation of cold offset property, hot offset property, filming property and storage stability (blocking resistance) is performed. Went. The evaluation results are shown in Table 3. The cold offset property, hot offset property, filming property and storage stability (blocking resistance) were all good.

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

<Cold offset property>
As a fixing roller, using a device in which a fixing unit of a copying machine MF-200 (manufactured by Ricoh) using a Teflon (registered trademark) roller is modified, type 6000 paper manufactured by Ricoh is set, and the temperature of the fixing roller is 5 The copying test was performed while changing the temperature step by step. The minimum value of the fixing roller temperature at which the residual ratio of the image density after rubbing the fixed image with a pad becomes 70% or more was defined as the minimum fixing temperature (cold offset property). The lower limit fixing temperature is preferably low because power consumption can be suppressed. If it is 135 ° C. or lower, it is at a level causing no problem in practical use. The results are shown in Table 3 when the fixing lower limit temperature (cold offset generation temperature) is 135 ° C. or lower, and when it is 135 ° C. or higher, x.

<Hot offset property>
The developer was put in a commercially available copying machine (Imagiono 455; manufactured by Ricoh), and the image was output using a Ricoh type 6000 paper while changing the fixing temperature from a low temperature to a high temperature, and the glossiness of the image decreased. The offset occurrence temperature was defined as the temperature or when an offset image was seen in the image. The results are shown in Table 3 when the offset generation temperature is 200 ° C. or higher, and when the offset generation temperature is lower than 200 ° C.

<Filming properties>
The developer was put in a commercially available copying machine (Imagiono 455; manufactured by Ricoh Co., Ltd.), and running was performed using a type 6000 paper manufactured by Ricoh Co., Ltd. at a printing ratio of 7%. The film on the photoconductor after 20,000 sheets, 50,000 sheets and 100,000 sheets, and the presence or absence of abnormal images (half-tone density unevenness) due to filming were evaluated. The occurrence of filming is more disadvantageous as the number of running sheets increases, and the results are shown in Table 3 with the following evaluation criteria.
Good ○: Not generated even at 100,000 sheets, △: Generated at 50,000 sheets, ×: Generated at 20,000 sheets

<Storage stability (blocking resistance)>
Weigh 10 g of toner, put it in a 20 ml glass container, tap the glass bottle 100 times, leave it in a thermostatic chamber set at 55 ° C. and 80% humidity for 24 hours, and then check the penetration with a penetration meter. It was measured. The smaller the penetration value, the more stable the storage (the better the blocking resistance). The evaluation criteria are as follows, and the results are shown in Table 3.
Good ○: 15 mm or more, Δ: 10 mm to 15 mm, ×: less than 10 mm

[Example 2]
The toner composition liquid obtained in Example 1 was supplied to the head of the horn type vibrator shown in FIG.
The used nozzle plate was produced by electrocasting a perfect circular discharge hole having a diameter of 10 μm on a nickel plate having an outer diameter of 8.0 mm and a thickness of 20 μm. The discharge holes were provided in a staggered pattern so that the distance between the discharge holes was 100 μm, and only in the range of about 5 mmφ at the center of the nozzle plate. In this case, the number of effective ejection holes is about 1000.

After the dispersion was prepared, the droplets were discharged under the following toner production conditions, and then the droplets were dried and solidified to produce toner base particles.
[Toner preparation conditions]
Dry air flow rate: Nitrogen gas for dispersion 2.0L / min, Dry nitrogen gas in the apparatus 30.0L / min Drying inlet temperature: 60 ° C
Drying outlet temperature: 45 ° C
Dew point temperature: -20 ° C
Drive frequency: 180 kHz

The dried and solidified particles were collected by suction with a filter having 1 μm pores. Further, 1.0% by weight of hydrophobic silica (H2000, manufactured by Clariant Japan Co.) was externally added to the particles using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain black toner b.
The results of measuring the particle size of this toner are shown in Table 2. The weight average particle size (D4) was 5.3 μm, Dv / Dn was 1.02, and the particle size distribution was very sharp.
The toner was continuously produced for 5 hours, but the nozzle was not clogged.
A developer was prepared using the same carrier as in Example 1, and the results of the same evaluation as in Example 1 are shown in Table 3. Cold offset property, hot offset property, filming property, and storage stability are shown in Table 3. The property was good.

[Example 3]
A toner c and a developer were obtained in the same manner as in Example 2 except that the wax was changed to the modified paraffin wax B in Example 2. The results of the same evaluation as in Example 1 are shown in Table 3, but the nozzle clogging does not occur, the particle size distribution is very sharp, cold offset property, hot offset property, filming property and storage stability. The properties were all good.

[Example 4]
A toner d and a developer were obtained in the same manner as in Example 2 except that the ratio of the polyester resin and the styrene-n-butyl acrylate copolymer resin was changed from 75/25 to 50/50 in Example 2. The results of the same evaluation as in Example 1 are shown in Table 3, but the nozzle clogging does not occur, the particle size distribution is very sharp, cold offset property, hot offset property, filming property and storage stability. The properties were all good.

[Example 5]
A toner e and a developer were obtained in the same manner as in Example 2 except that the ratio of the polyester resin and the styrene-n-butyl acrylate copolymer resin was changed from 75/25 to 25/75 in Example 2. The results of the same evaluation as in Example 1 are shown in Table 3, but the nozzle clogging did not occur, the particle size distribution was very sharp, and the filming property and the storage stability were both good. . Cold offset property and hot offset property slightly decreased.

[Example 6]
A toner f and a developer were obtained in the same manner as in Example 2 except that the wax in Example 2 was changed to an ester wax (manufactured by NOF Corporation; WEP-2). The results of the same evaluation as in Example 1 are shown in Table 3, but the nozzle clogging did not occur, the particle size distribution was very sharp, and the cold offset property and the hot offset property were good. Both filming property and storage stability were slightly decreased.

[Comparative Example 1]
In Example 1, toner g and developer were obtained in the same manner as in Example 1 except that the wax was changed to carnauba wax. The results of the same evaluation as in Example 1 are shown in Table 3, but the nozzle clogging does not occur, the particle size distribution is very sharp, and the cold offset property, filming property, and storage stability are good. However, the hot offset property was not good.

[Comparative Example 2]
A toner h and a developer were obtained in the same manner as in Example 2 except that the wax was changed to the modified paraffin wax C in Example 2. The results of the same evaluation as in Example 1 are shown in Table 3, but the nozzle clogging does not occur, the particle size distribution is very sharp, and the cold offset property, filming property, and storage stability are good. However, the hot offset property was not good.

[Comparative Example 3]
A toner i and a developer were obtained in the same manner as in Example 2 except that the wax was changed to the modified paraffin wax D in Example 2. The results of the same evaluation as in Example 1 are shown in Table 3, but the nozzle clogging does not occur, the particle size distribution is very sharp, and the cold offset property, filming property, and storage stability are good. However, the hot offset property was not good.

[Comparative Example 4]
In Example 2, a toner j and a developer were obtained in the same manner as in Example 2 except that the ratio of the polyester resin and the styrene-n-butyl acrylate copolymer resin was changed from 75/25 to 100/0. A cross-sectional photograph of this toner is shown in FIG.
The results of the same evaluation as in Example 1 are shown in Table 3, but the nozzle clogging did not occur, the particle size distribution was very sharp, and the cold offset property and the hot offset property were good. Filming property and storage stability were not good.

[Comparative Example 5]
In Example 2, a toner k and a developer were obtained in the same manner as in Example 2 except that the ratio of the polyester resin to the styrene-n-butyl acrylate copolymer resin was changed from 75/25 to 0/100. The results of the same evaluation as in Example 1 are shown in Table 3. The nozzle clogging did not occur and the particle size distribution was very sharp, but the cold offset property, hot offset property, filming property and None of the storage stability was good.

  The toner produced by the production method of the present invention has excellent monodispersibility, can form an image with high resolution, high definition, high quality, and no deterioration over a long period of time, and low temperature fixing. Therefore, it can be suitably used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like.

FIG. 3 is a schematic configuration diagram of an example of a toner manufacturing apparatus provided with a mechanical longitudinal vibration unit according to the present invention. It is a schematic sectional drawing of the droplet jetting unit in FIG. It is principal part bottom surface explanatory drawing of the droplet ejection unit of FIG. It is explanatory drawing which shows the example of a step type horn type | mold vibrator. It is explanatory drawing which shows the example of an exponential horn type | mold vibrator. It is explanatory drawing which shows the example of a conical type horn type | mold vibrator. It is typical sectional explanatory drawing of the other example of a droplet jetting unit. It is typical sectional explanatory drawing of the other example of a droplet jetting unit. It is typical sectional explanatory drawing of the other example of a droplet jetting unit. FIG. 10 is an explanatory diagram in a case where a plurality of droplet ejection units of FIG. 9 are provided. FIG. 3 is a schematic configuration diagram of an example of a toner manufacturing apparatus provided with an annular mechanical vibration unit of the present invention. It is a schematic sectional drawing of the droplet jetting unit in FIG. It is principal part bottom surface explanatory drawing of the droplet ejection unit of FIG. It is a schematic sectional explanatory drawing of the droplet formation means of this invention. It is a schematic sectional explanatory drawing of the comparative structural example of a droplet formation means. 13 is an example in which a plurality of droplet ejection units in FIG. 12 are arranged. It is a figure for demonstrating the vibration of a thin film. It is a graph which shows the relationship of displacement (DELTA) L and a nozzle arrangement | positioning area | region of the fundamental vibration of the thin film which generate | occur | produces with a mechanical vibration means. It is a graph which shows the relationship between displacement (DELTA) L and a nozzle arrangement | positioning area | region of the vibration of the high-order mode of the thin film which generate | occur | produces with a mechanical vibration means. It is a graph which shows the relationship between displacement (DELTA) L and a nozzle arrangement | positioning area | region of the vibration of the high-order mode of the thin film which generate | occur | produces with a mechanical vibration means. It is a schematic sectional explanatory drawing which shows the example of the thin film which center part has convex shape. 3 is a cross-sectional photograph of the toner of Example 1. FIG. 6 is a cross-sectional photograph of a toner of Comparative Example 4. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet jet unit 3 Particle formation part 4 Toner collection part 5 Tube 6 Toner storage part 7 Raw material storage part 8, 8A Piping 9 Pump 10 Toner composition liquid 11 Nozzle 12 Thin film 13, 80, 90 Vibrating means 13a Vibrating surface 14 Reservoir 15 Channel member 16 Droplet forming means 16A Deformable area 17 Vibration generating means 18 Liquid supply tube 19 Bubble discharge tube 21 Vibration generating means 21A, 81, 91A, 91B Piezoelectric bodies 21a, 21b Electrode 22 Vibration amplification Means 22A, 82, 92A, 92B Horn 23 Drive signal source 24 Communication means (lead wire)
35 Air flow 36 Air flow path forming member 37 Air flow path 83 Fixing portion

Claims (10)

  A droplet forming step of discharging a toner composition liquid, in which a toner composition containing at least a binder resin, a colorant, and a release agent is dissolved or dispersed in a solvent, into droplets from a nozzle, and droplet formation And a particle forming step for converting the toner composition liquid into solid particles, wherein the binder resin is composed of two or more kinds of incompatible resins, and the releasing agent has a melting point of 30 to 70 ° C. And a melt viscosity at 120 ° C. of the release agent of 1 to 30 mPa · s.   2. The toner manufacturing method according to claim 1, wherein the binder resin is a polyester resin and a styrene-acrylic resin.   3. The toner production method according to claim 1, wherein the release agent is a hydrocarbon wax.   The toner according to any one of claims 1 to 3, wherein the release agent is a hydrocarbon wax modified with a carboxylic acid or a carboxylic anhydride, and has an acid value of 1 to 90 mgKOH / g. Production method.   The droplet forming step periodically discharges the toner composition liquid from the nozzles of the thin film by vibrating a thin film having a plurality of nozzles provided in a storage part for storing the toner composition liquid by mechanical vibration means, The method for producing a toner according to claim 1, wherein the toner is a periodic droplet forming step for forming droplets.   6. The toner manufacturing method according to claim 5, wherein the mechanical vibration means is vibration generation means formed in an annular shape around a region where the thin film nozzle is provided.   6. The toner manufacturing method according to claim 5, wherein the mechanical vibration means is a vibration means having a vibration surface parallel to the thin film, and the vibration surface longitudinally vibrates in a vertical direction.   8. The toner manufacturing method according to claim 7, wherein the mechanical vibration means is a horn type vibrator.   The toner manufacturing method according to claim 5, wherein a vibration frequency of the mechanical vibration unit is 20 kHz or more and less than 2.0 MHz.   A toner produced by the production method according to claim 1, wherein the particle size distribution (weight average particle diameter / number average particle diameter) is in the range of 1.00 to 1.15. .