JP2010079021A - Toner and developing agent - Google Patents

Abstract

Many characteristic values such as fluidity and charging characteristics required for a toner composed of a group of particles having a small particle size and unprecedented monodispersibility have a range of fluctuations observed between toner particles. To provide no or very little toner. In addition, it has excellent offset resistance, low-temperature fixability, fixing releasability, heat-resistant storage, and filming resistance, and forms high-resolution, high-definition, high-quality images with no image deterioration over a long period of time. Providing toner.
A toner composition solution in which a toner composition having at least a binder resin, a colorant, and a release agent is dissolved or dispersed in an organic solvent is formed into droplets in a gas phase and then solidified. The toner, wherein the binder resin includes at least a cyclized rubber having a cyclization rate of 50 to 75% and a polyester resin, and the releasing agent has a melting point of 50 to 85 ° C.
[Selection] Figure 1

Description

  The present invention relates to a toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, and the like, and a developer containing the toner.

  Developers used for electrophotography, electrostatic recording, electrostatic printing, etc. 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, and then transferred. After being transferred from the electrostatic latent image carrier to a transfer medium such as transfer paper in the process, it is fixed on the paper surface in the fixing process. As the developer used in such an electrophotographic system, dry toners such as a two-component developer composed of a carrier and a toner and a one-component developer (magnetic toner, non-magnetic toner) that does not require a carrier are used. ing.

Conventionally, such dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like are so-called pulverizing types in which a toner binder such as a styrene resin or a polyester resin is melt-kneaded and pulverized with a colorant or the like. Toner is widely used. Recently, so-called polymerization type toners by suspension polymerization method or emulsion polymerization aggregation method are also used. In addition, a toner by a method called volumetric shrinkage called a polymer dissolution suspension method is also known (see Patent Document 1). The toner by this method is obtained by emulsifying and dispersing a dispersion or solution in which a toner material is dispersed or dissolved in a volatile solvent such as a low-boiling organic solvent in an aqueous medium in which a dispersant is present, and then removing the volatile solvent. It is obtained by removing. Unlike the above-described suspension polymerization method and emulsion polymerization aggregation method, the toner produced by this method has a wide range of versatile resins that can be used. For this reason, it is excellent in that a polyester resin useful for a full color process requiring transparency and smoothness of an image area after fixing can be used.
However, in the above-described polymerization type toner, since the dispersant is used in the aqueous medium, the dispersant remains on the toner surface and the environmental stability is impaired, or the charging characteristics of the toner are impaired. A malfunction occurs. Further, since a large amount of washing water is required to remove the dispersant, it is not always satisfactory, and it can be said that there is a problem from the viewpoint of earth resources.

As an alternative toner, there has been proposed a toner by a so-called droplet granulation method 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 toner obtained by using the thermal expansion in the nozzle to form the fine droplets as described above and then drying and solidifying the same is also known (see Patent Document 3). Furthermore, a toner obtained by a similar process using an acoustic lens has been proposed (see Patent Document 4).
However, these conventional droplet granulation toners have a problem that the number of droplets that can be ejected from a single nozzle per unit time is small and productivity is poor. At the same time, the generation of droplet particles caused by the coalescence of the droplets mixes the toner particles by the droplet particles resulting from the coalescence other than the monodisperse particles, thereby widening the particle size distribution of the toner particles. There is also a problem that it cannot be suppressed. As a result, conventional droplet method toners were not fully satisfactory.

Further, as these droplet granulation methods, a dispersion liquid in which a toner raw material containing a thermosetting resin or a UV curable resin is dispersed finely in a dispersion medium as a dispersoid is intermittently discharged as droplets from a nozzle. In addition, there is also known an invention in which droplet formation is aggregated and thermosetting resin or UV curable resin is cured to stabilize particle formation (see Patent Documents 5 and 6).
However, these inventions also have low productivity as in Patent Documents 1 to 4, and are insufficient in terms of monodispersibility. Further, although the resin is cured after the particles are formed, the above-described problems relating to fixing characteristics such as transparency and smoothness of an image after fixing have not been solved.
In the case of the droplet granulation method shown in Patent Documents 5 to 6 described above, the vibration unit directly touches the fluid (FIGS. 2, 4, and 5-8 of Patent Documents 5 to 6 and the description thereof). In the case of such a configuration, a sharp particle size distribution can be achieved when the number of pores and the number of vibrating parts match. However, for the purpose of increasing production, for example, when manufacturing by means of droplet forming means consisting of a large number of pores and one vibration part is adopted, depending on the distance between the pore position and the vibration part, It has been found that the size of the ejected droplets changes, producing toner with different particle sizes between different orifices.

  On the other hand, in electrophotographic toners, toners with excellent low-temperature fixability are required as the speed and energy saving of image forming apparatuses are increased. On the other hand, low-temperature fixing such as offset resistance and storage stability (blocking resistance) is required. There is a need for toners that have properties that are contrary to their properties. For this reason, a toner using an aromatic polyester resin has been proposed. However, since this is poorly compatible with the release agent to be used, it is necessary to separate the release agent from the toner and use it in a carrier or a developing device in use over time. Has problems such as contamination.

In view of the binder resin in the toner, Patent Document 7 discloses a toner using a resin containing a diene monomer such as butadiene, isoprene and chloroprene as a constituent component. Although it has been shown that these contain a diene compound part, good results in chargeability can be obtained, but homopolymers composed of these diene monomers are liquids at room temperature having a glass transition point Tg of 0 ° C. or less. Therefore, it is difficult to use them alone, and it is necessary to use a copolymer with another monomer. Patent Document 8 shows that a toner containing a wax is obtained by a suspension polymerization method of a styrene-diene compound copolymer. This invention uses a diene compound and a vinyl polymerized resin, and suppresses problems caused by separation of wax.
On the other hand, Patent Document 9 discloses a thermoplastic elastomer having entropy elasticity, and Patent Documents 10 and 11 disclose a self-condensation product of polyisoprene homopolymer, that is, cyclized rubber, cis. It is shown that a cyclized product of 1,4-polyisoprene and a wax are used in combination. As described above, the polyisoprene resin itself is a resin having a Tg of about −70 ° C. By cyclizing the resin, entropy elasticity is obtained, and it can be used as a thermoplastic room temperature solid resin.
These resins are those whose molecular weight and wax to be used are appropriately selected, and by forming a resin in which the wax is melted, excellent low temperature storage and hot offset resistance are achieved while achieving low temperature softening of the toner. Can be obtained. However, although excellent fixability is exhibited, since the resin has elasticity, in order to obtain a toner by a pulverization method, there is a problem that the pulverization property is inferior and the productivity is extremely poor.

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 Japanese Patent No. 3780159 Japanese Patent No. 3131759 Japanese Patent Laid-Open No. 2007-079348 JP 2003-345064 A Japanese Patent No. 4049547

This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in a prior art, and to achieve the following objectives.
In other words, the present invention is a variation in which many characteristic values such as fluidity and charging characteristics required for a toner composed of a particle group having a small particle size and monodispersibility never seen before are observed between the toner particles. The object of the present invention is to provide a toner having no or very little width. In addition, the present invention is excellent in all of offset resistance, low temperature fixability, fixing releasability, heat resistant storage stability, and filming resistance, and forms a high resolution, high definition and high quality image. An object is to provide a toner that does not deteriorate. Still another object of the present invention is to provide a developer using the toner.

  In order to solve the above problems, the toner of the present invention has the following constitutions (1) to (9), and the developer of the present invention has the following constitution (10).

(1) A toner obtained by solidifying a toner composition liquid, in which a toner composition having at least a binder resin, a colorant, and a release agent is dissolved or dispersed in an organic solvent, and then forming liquid droplets in a gas phase. Because
The toner according to claim 1, wherein the binder resin includes at least a polyester resin and a cyclized rubber having a cyclization rate of 50 to 75%, and a melting point of the release agent is 50 to 85 ° C.
(2) The toner according to (1), wherein the droplet formation is performed by vibrating a nozzle plate having discharge holes and continuously discharging the toner composition liquid from the discharge holes.
(3) In the toner according to (1) or (2), the droplet formation is performed by vibrating a thin film formed with a plurality of nozzles provided in a storage portion for storing the toner composition liquid by a vibrating means. The toner composition liquid is periodically discharged from each of the toners.
(4) The toner according to (3), wherein the vibration unit is a vibration generation unit formed in an annular shape around a region where the thin film nozzle is provided.
(5) The toner according to (3), wherein the vibration means is a vibration means having a vibration surface parallel to the thin film, and the vibration surface vibrates vertically in the vertical direction.
(6) The toner according to any one of (3) to (5), wherein the vibration frequency of the vibration unit is 20 kHz or more and less than 2.0 MHz.
(7) The toner according to any one of (1) to (6), wherein the vibrating means is a horn type vibrator.
(8) The toner according to any one of (2) to (7), wherein the nozzle has an opening diameter of 1 to 40 μm.
(9) The toner according to any one of (1) to (8), wherein the solidification after the droplet formation is performed by removing a solvent from the toner composition liquid formed into the droplets. Toner.

(10) A developer comprising the toner according to any one of (1) to (9) and a carrier.

According to the present invention, it is possible to provide a toner that solves the above problems.
That is, according to the present invention, the toner is composed of a single particle group having a small particle size and a particle size, and has any of low temperature fixability, offset resistance, fixing release property, heat resistant storage stability, and filming resistance. It is possible to provide a toner that is excellent and has no image deterioration over a long period of time both in the initial stage and over time.

The binder resin used in the toner of the present invention is a mixture of cyclized rubber and polyester resin.
The cyclized rubber is obtained by cyclizing an unsaturated olefin resin typified by isoprene, and the glass transition point (Tg) of the resin can be adjusted by appropriately selecting the cyclization rate. The toner of the present invention preferably has a high Tg in order to prevent performance deterioration in the usage environment, particularly in a high temperature and high humidity environment. However, conventional thermoplastic resins such as styrene acrylic and polyester are consumed by the fixing device. In order to lower the electric power, when a resin that melts to an appropriate melt viscosity at a low temperature is produced, Tg tends to be low. In conventional toners, it can be said that attention is generally paid to how to lower the Tg.

The cyclized rubber represented by the cyclized isoprene resin exhibits extremely high compatibility with waxes. By using a mixture of the cyclized rubber and the wax, the wax can easily be finely dispersed and / or compatible with the cyclized rubber, whereby the cyclized rubber is plasticized. In other words, by selecting a resin (cyclized rubber) having a suitable cyclization rate and a wax, using a partially plasticized cyclized rubber so as to quickly soften at the target fixing temperature. As a result, the power consumption of the fixing device can be reduced.
At that time, since a cyclized rubber having a higher Tg can be used as compared with styrene acrylic or polyester resin, it is possible to obtain a toner having good storage stability at high temperature and high humidity while obtaining low temperature fixability. . As described above, the toner of the present invention is excellent in low-temperature fixability and storage stability at high temperature and high humidity. On the other hand, the cyclized rubber absorbs wax well, so that the wax does not easily act as a release agent. Therefore, cyclized rubber is generally used as a dispersed form in a polyester resin so as to have a domain diameter of 0.1 to 1 μm, and the polyester resin part contains a wax dispersed independently of the cyclized rubber, so that the releasability is improved. Can solve the problem. Since the cyclized rubber has poor compatibility with the polyester resin, it can be dispersed in an island shape in the polyester resin, and the wax dispersed independently of the cyclized rubber in the polyester resin is absorbed by the cyclized rubber. Without releasing the mold release.

  The cyclized rubber used in the toner of the present invention is composed of a cyclized part and a non-cyclized part. The ratio of the cyclized portion in the cyclized rubber is indicated by the cyclization rate, and this cyclization rate is an important factor that determines the degree of plasticization and the elastic modulus in the rubbery temperature region. It has also been found that there is an optimum wax melting point to plasticize the cyclized rubber to the desired degree, depending on the cyclization rate of the cyclized rubber. That is, as a result of intensive studies, the present inventors have found that a configuration that achieves the above object can be obtained by optimally designing the cyclization rate of the cyclized rubber and the melting point of the wax. That is, preferably, the cyclized rubber is a polyisoprene resin having a cyclization rate of 50 to 75%, and the wax (release agent) preferably has a melting point of 50 to 85 ° C.

The suitable wax (release agent) used in the toner of the present invention more preferably contains at least one of carnauba wax and paraffin wax.
As a result, it is found that cyclized rubber has an appropriate plastic effect with wax, does not cause the wax to be released from the toner, and is less likely to cause contamination of the carrier and each member during use. It was done. In order to produce the toner of the present invention, it is possible to use a conventional kneading and pulverizing method, but the cyclized rubber is extremely poor in pulverization properties, and the resin in which the cyclized rubber is internally added is also very low in productivity.
Therefore, in the present invention, it is preferable to use a method in which a toner composition liquid in which at least a part of the binder resin is dissolved is formed into droplets and solidified.

  The cyclized rubber, wax, and polyester resin, which are the constituent elements of the toner of the present invention, are dispersed by dispersing cyclized rubber in an island shape in the polyester resin (resin dispersion) by selecting appropriate conditions by a conventional kneading method. Body). In the process, the wax is easily absorbed by the cyclized rubber. This resin dispersion can be obtained as a polyester resin solution (toner composition liquid) in which a cyclized rubber encapsulating wax is dispersed by dissolving or dispersing in a solvent that dissolves polyester. In addition, since cyclized rubber is well compatible with wax, if all waxes are present in the same phase as cyclized rubber, low temperature fixability is excellent, but leaching of the wax at the time of fixing is reduced. Therefore, releasability is difficult to express.

In order to develop releasability, it is only necessary to disperse the wax in a phase different from that of the cyclized rubber. For example, a resin in which the waxes are dispersed in a resin not containing the cyclized rubber is prepared in advance and cyclized with this. It is preferable to mix with rubber.
For example, a dispersion liquid 1 containing a resin and a wax is prepared, and a toner composition liquid is prepared by mixing the previously prepared cyclized rubber and a dispersion liquid 2 containing a plasticizing wax and resin. To do. A toner composition liquid can be prepared by further dispersing or dissolving a colorant such as pigment or carbon, and a charge control agent, if necessary, in the resin dispersion.
The toner composition liquid is periodically discharged from each of the plurality of nozzles by the vibration applied by the vibration means from the plurality of nozzles provided in the storage portion for storing the toner composition liquid which is the mixed solution or dispersion liquid. Then, droplets are formed, and toner particles are obtained by drying the toner composition of the droplets.

  In the toner of the present invention, since the release agent moves into the droplets during drying, the release agent is hardly exposed on the surface of the finally obtained toner. Further, the release agent is finely dispersed in the droplet while maintaining an appropriate dispersion diameter. This phenomenon is presumably caused by the difference in partitioning ability between the binder resin and the release agent for the liquid phase and the gas phase and the high compatibility between the binder resin and the release agent. For this reason, the homogeneity of the obtained toner particles is increased, and the number of defective toners is extremely reduced. In addition, since there is no release agent on the toner surface, a toner having excellent filming resistance can be obtained. Furthermore, since the release agent is dispersed with an appropriate dispersion diameter inside the toner, the release agent quickly migrates to the toner surface at the time of heat fixing, and excellent fixing release properties can be exhibited. Further, since the release agent does not aggregate in the toner composition liquid, clogging of the nozzle in the droplet forming process does not occur.

  Furthermore, in the present invention, toner particles having an unprecedented particle size having a small particle size and monodispersibility can be produced. For this reason, in many characteristic values required for toner such as fluidity and charging characteristics, there is no or very little variation in the particle-to-particle variation observed in the conventional production methods. . That is, with the toner of the present invention, a monodisperse toner can be obtained, which is substantially the same in shape and size among the toner particles constituting the toner of the present invention, and is also required for the toner described above. This means that many of the characteristic values obtained are substantially the same between toner particles.

Further, in the toner of the present invention, the toner composition liquid described above is discharged from the storage portion in which the vibration generating means is provided in an annular shape around the area where the nozzle is provided, and is formed into droplets. By setting the vibration frequency of the vibration generating means to 20 kHz or more and less than 2.0 MHz, the above-described monodisperse toner can be obtained, and thus the above-described effects can be obtained more reliably.
Hereinafter, a suitable manufacturing apparatus for obtaining the toner of the present invention will be described.

<Toner production device>
As a manufacturing method for obtaining the toner of the present invention, it is preferable to use a periodic droplet forming apparatus that periodically discharges a toner composition liquid from a thin film having a plurality of uniform diameter nozzles by mechanical vibration means to form droplets. Is preferred.
That is, as a toner manufacturing apparatus used for manufacturing the toner of the present invention, a toner composition liquid that is a solution or dispersion of a toner material containing at least a resin and a colorant is used as a thin film having a plurality of nozzles. Droplet forming means formed by forming vibration generating means in an annular shape around the periphery or provided with vibration generating means for vertically vibrating a vibration surface parallel to a thin film having a plurality of nozzles. Use. With such a toner manufacturing apparatus, droplets having a uniform particle diameter (single dispersion diameter) can be generated by discharging the toner composition liquid from the nozzles described above.

To produce the toner of the present invention, the toner composition liquid droplets are periodically discharged from each of the nozzles by mechanically vibrating the thin film having a plurality of nozzles. Drops are formed. The vibration generating means may be arranged in any direction 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.
(1) A method using vibration generating means (longitudinal vibration generating means) having a vibration surface parallel to the thin film having a plurality of nozzles and longitudinally vibrating in the vertical direction (hereinafter also simply referred to as “horn type”).
(2) A method of providing a vibration generating means (annular vibration generating means) formed in an annular shape around a thin film having a plurality of nozzles (hereinafter also simply referred to as “ring type”).
Hereinafter, each method will be described.

(Longitudinal vibration generating means)
First, an example of a toner manufacturing apparatus provided with longitudinal vibration generating means will be described with reference to the schematic configuration diagram of FIG.
The toner manufacturing apparatus 1 drops and discharges a toner composition liquid containing at least a binder resin (cyclized rubber or polyester resin having a cyclization rate of 50 to 75%), a release agent (wax), and a colorant. A droplet ejecting unit 2 as droplet forming means, and the droplet ejecting unit 2 are arranged above, and the droplets of the toner composition liquid formed into droplets discharged from the droplet ejecting unit 2 are solidified to form a toner. Particle forming unit 3 as particle forming means for forming particles T, toner collecting unit 4 for collecting toner particles T formed by particle forming unit 3, and toner particles collected by toner collecting unit 4 T is transferred through the tube 5, a toner storage unit 6 as a toner storage unit that stores the transferred toner particles T, a raw material storage unit 7 that stores the toner composition liquid 10, and from within the raw material storage unit 7 To the droplet ejection unit 2 A pipe (liquid feed pipe) 8 for feeding the over composition liquid 10, and a pump 9 for pumping supplying toner composition liquid 10, such as during operation.

  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. As the toner composition liquid 10, here, a toner composition containing at least a binder resin (cyclized rubber or polyester resin having a cyclization rate of 50 to 75%), a release agent (wax), and a colorant is used as a solvent. A dissolved or dispersed solution or dispersion 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 (nozzle plate) 12 in which a plurality of nozzles (ejection holes) 11 are formed, mechanical vibration means (hereinafter referred to as “vibration means” 13) that vibrates the thin film 12, and the thin film 12. A reservoir for supplying a toner composition liquid 10 containing at least a binder resin (cyclized rubber or polyester resin having a cyclization rate of 50 to 75%), a release agent (wax), and a colorant between the vibration means 13 and the vibration means 13. (Liquid flow path) 14 and a flow path member 15 are provided.

  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 the communication means 24 for giving an electric 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 vibration and a vibration amplification unit 22 that amplifies the vibration generated by the vibration generation unit 21, and drives the drive circuit (drive signal generation source) 23 at a required frequency. When a voltage (driving 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. 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, examples of the piezoelectric body 21A include piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , and KNbO ₃ .

  The vibration 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, the piezoelectric body 21A is disposed on the surface of the horn 22A having a large area. The piezoelectric body 21A uses longitudinal vibration to induce efficient vibration of the horn 22A, and the horn 22A has a small area. The surface is a vibration surface 13a, and the vibration surface 13a is designed to be the maximum vibration surface.

Lead wires (communication means) 24 are disposed above and below the piezoelectric body 21, and an AC voltage signal is applied 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 structure of the storage part (liquid flow path) 14, the mechanical vibration means 13, and the thin film 12 is demonstrated in detail using the schematic of FIG. The storage unit 14 is provided with at least one liquid supply tube 18, and the liquid is introduced into the storage unit 14 through a flow path as shown in a partial cross-sectional view. 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 shown in FIG. 1 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 (liquid 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) shown in FIG. 1 by a fixing unit (flange unit) 83 formed integrally with the horn 82 of the horn type vibrator 80. . From the viewpoint of preventing vibration loss, an elastic body (not shown) may be used for fixing.

  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 (liquid channel 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 example described above, 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 in the vibration amplifying means (horn) 22 of the vibration generating means 13 at a 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 vibration means)
FIG. 11 shows the apparatus shown in FIG. 1 in which the droplet ejecting 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 an explanatory bottom view of the main part when FIG. 12 is viewed from the lower side, and FIG.
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 has a configuration shown in FIG. 15, for example, by arranging an annular vibration generating means 17 around the deformable region 16 </ b> A of the thin film 12 having the plurality of nozzles 11 facing the storage portion 14. Compared to a configuration in which the vibration generating means 17A holds the periphery of the thin film 12, the displacement amount of the thin film 12 is relatively large. A plurality of nozzles 11 can be arranged in a relatively large area (φ1 mm or more) where a large amount of displacement can be obtained, and more liquid droplets are stably formed and discharged at a time than the plurality of nozzles 15. Will be able to.

  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 thin film 12 as shown in FIG. 17 is fixed, the basic vibration has a node around the periphery, and the cross section where the displacement ΔL is maximum (ΔLmax) at the center O of the thin film as shown in FIG. 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 more concentric nodes in a circular thin 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 thin film is generated. 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 thin film periodically varies with time, it is a function of time. For example, 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 thin film, and Vm is also a function of position coordinates on the thin film. As described above, the vibration mode of the thin film used in the present invention is an axial object. Therefore, it is substantially a function of the radial coordinate.

As described above, a sound pressure proportional to the vibration displacement speed of the thin film having the distribution 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 thin film that enables droplet formation, a range 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.

When manufacturing the toner of the present invention, as will be described with reference to FIGS. 18 to 20, the maximum value ΔL _max and the minimum value ΔL _mim of the vibration direction displacement ΔL of the thin film near the nozzle generated by the mechanical vibration means. Necessary as a toner fine particle capable of providing a high-quality image by disposing the nozzle in a portion where the ratio R (= ΔL _max / ΔL _min ) of the toner is 2.0 or less. I found out that I could keep it in a different area.

  The conditions of the toner composition liquid were changed, and in the region where the viscosity was 20 mPa · s or less and the surface tension was 20 to 75 mN / m, the satellite generation start region was the same, so the displacement of the sound pressure was 500 kPa or less. It is necessary to be. More preferably, it is 100 kPa or less.

(Thin film with multiple nozzles)
As described above, the thin film having the nozzle is a member in which a solution or dispersion liquid (toner composition liquid 10) of the toner material is discharged to form 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 1 to 40 μm, preferably 3 to 35 μm, is preferable from the viewpoint of generating micro droplets having a very uniform particle size when the 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 can be obtained with a monodisperse particle size distribution by the above-described toner production method. Specifically, the particle size distribution (weight average particle diameter / number average particle diameter) of the toner is preferably in the range of 1.00 to 1.15. Moreover, as a weight average particle diameter, it is preferable that it is 1-20 micrometers.
The toner obtained by the toner manufacturing method can be easily re-dispersed, that is, floated in an air current due to the 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 is characterized by containing a cyclized rubber having a cyclization rate of 50 to 75%, a polyester resin, and a release agent having a melting point of 50 to 85 ° C. The same toner as conventional toner for electrophotography can be used. That is, a toner binder of a cyclized rubber having a cyclization rate of 50 to 75% and a polyester resin (styrene acrylic resin, polyol resin, epoxy resin, etc. may be used in combination) is dissolved in various organic solvents and colored. It is possible to produce the desired toner particles by dispersing the agent and dispersing or dissolving the releasing agent having a melting point of 50 to 85 ° C., and then drying and solidifying it by the toner production method. It is. It is also possible to obtain a target toner by drying and solidifying a liquid obtained by dissolving or dispersing a kneaded material obtained by hot-melting and kneading the above materials in various solvents into fine droplets by the toner production method. is there. By adding acid-modified hydrocarbon wax, which is a release agent, to toner, offset resistance and low-temperature fixability are improved, and the dispersed particle size of the release agent can be reduced and crystal growth can be suppressed. Nozzle clogging can be prevented.

(Toner material)
The toner material contains at least a resin and a colorant, and preferably contains at least one of carnauba wax or paraffin wax as a release agent. If necessary, a charge control agent, a magnetic material, and fluidity improvement. Contains other components such as agents, lubricants, cleaning aids, and resistance adjusters.

(resin)
The cyclized rubber in the present invention is a resin having a cyclic structure within or / and between molecules of natural rubber and synthetic rubber composed of conjugated diene monomers, and these natural rubber and synthetic rubber are acid catalysts. It can obtain by making it react using catalysts, such as.
Examples of natural rubber include natural polyisoprene mainly composed of cis-1,4-polyisoprene. The natural rubber may contain impurities such as non-rubber components as long as it does not affect the effects of the present invention, but it is preferable to use purified natural rubber from the viewpoint of controlling the cyclization rate.

  Synthetic rubber mainly includes polymers obtained by polymerizing conjugated diene monomers alone or in combination of two or more. Examples of the conjugated diene monomer include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, and 2-methyl-1. , 3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene and the like. Among these, 1,3-butadiene and isoprene are preferably used, and in particular, polybutadiene having a cis-1,4-butadiene structure as a main component and polyisoprene having a cis-1,4-isoprene structure as a main component are preferable. Used.

  The synthetic rubber in the present invention may be a polymer obtained by polymerizing a monomer copolymerizable with a conjugated diene monomer together with the conjugated diene monomer. Examples of the monomer copolymerizable with the conjugated diene monomer include styrene, α-methylstyrene, p-isopropylstyrene, p-phenylstyrene, p-methoxystyrene, p-methoxymethylstyrene, p-tert-butoxystyrene, And aromatic vinyl monomers such as chloromethylstyrene, 2-fluorostyrene, 3-fluorostyrene, pentafluorostyrene, vinyltoluene, vinylnaphthalene and vinylanthracene; olefin monomers such as ethylene, propylene and isobutylene; Among these, styrene and α-methylstyrene are preferably used. The content of the monomer copolymerizable with the conjugated diene monomer in the polymer is not particularly limited, but from the viewpoint of controlling the cyclization rate, it is 60 mol% or less, preferably 40% or less, particularly preferably. 20% or less.

  The cyclized rubber of the present invention can be obtained by reacting the above natural rubber or synthetic rubber with a cyclization catalyst. Examples of the cyclization catalyst include sulfuric acid; organic sulfonic acids such as p-toluenesulfonic acid, monofluoromethanesulfonic acid, difluoromethanesulfonic acid, xylenesulfonic acid, and alkylbenzenesulfonic acid having an alkyl group having 2 to 16 carbon atoms; Organic sulfonic acid compounds such as anhydrides or alkyl esters thereof; boron trifluoride, boron trichloride, tin tetrachloride, titanium tetrachloride, aluminum chloride, diethylaluminum monochloride, aluminum bromide, antimony pentachloride, tungsten hexachloride, Metal halogen compounds such as iron chloride; and the like. These cyclization catalysts may be used alone or in combination of two or more. Among these, an organic sulfonic acid compound is preferable, and p-toluenesulfonic acid is preferably used.

The cyclization rate in the cyclized rubber used in the toner of the present invention represents the ratio of the cyclized portion in the cyclized rubber. The cyclization rate is measured by ¹ H-NMR analysis. When the peak areas of protons derived from double bonds in the polymer before and after the cyclization reaction are measured, the peak area before the cyclization reaction is (C0), and the peak area after the cyclization reaction is (C1). Can be obtained from the following equation (1).
Cyclization rate (%) = {1- (C1 / C0)} × 100 (1)

The cyclization rate of the cyclized rubber in the present invention is preferably 50 to 75%, more preferably 55 to 70%, and particularly preferably 60 to 65%. When it is lower than 50%, the melt viscoelasticity of the resin in the fixing temperature range becomes low, and hot offset tends to occur. On the other hand, if it is higher than 75%, the melt viscoelasticity of the toner in the fixing temperature range becomes high and the low-temperature fixability deteriorates. In addition, as the elastic modulus increases, the kneadability and grindability deteriorate significantly.
The glass transition point (Tg) of the cyclized rubber used in the present invention is preferably 55 to 100 ° C, more preferably 60 to 80 ° C, and particularly preferably 65 to 70 ° C. In the toner of the present invention, when the wax is finely dispersed or compatible with the cyclized rubber, the wax plasticizes a part of the cyclized rubber and exhibits excellent low-temperature fixability. The Tg of some of the cyclized rubber plasticized with wax is lower than the Tg of the cyclized rubber that has not been plasticized. Accordingly, when the Tg of the cyclized rubber is lower than the above-described range, the Tg of the plasticized cyclized rubber is too low, so that the heat resistant storage stability of the toner is deteriorated. On the other hand, when Tg is too high, the amount of wax necessary for plasticizing the cyclized rubber increases, which causes filming. Furthermore, since the Tg of the toner becomes too high, the low-temperature fixability is impaired.

The weight average molecular weight Mw of the cyclized rubber is preferably 1.0 × 10 ^{5 to} 5.0 × 10 ⁵ , more preferably 1.3 × 10 ^{5 to 3.5} × 10 ⁵ . If it is less than 1.0 × 10 ⁵ , the width of the rubber-like flat region in the relaxation elastic modulus characteristic with respect to the temperature of the cyclized rubber is reduced, and the temperature width at which the toner can be fixed is reduced. On the other hand, when it is larger than 5.0 × 10 ⁵ , the elastic modulus of the cyclized rubber becomes too high, so that the low temperature fixability cannot be obtained or the grindability is lowered. Further, it is preferable that the molecular weight distribution width of the cyclized rubber is sharp in order to improve the sharp melt property of the toner. The ratio (Mw / Mn) between the weight average molecular weight Mw and the number average molecular weight Mn is preferably 3.0 or less, more preferably 2.5 or less.

Examples of the monomer constituting the polyester polymer used in combination with the cyclized rubber include the following. Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, or diol obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to bisphenol A, etc. Is mentioned.
In order to crosslink the polyester resin, it is preferable to use a trivalent or higher alcohol together.

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

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

  When the binder resin is a polyester resin, at least one peak exists in the molecular weight region of 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component. Further, as the THF soluble component, a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100% is preferable, and at least one peak exists in a region having a molecular weight of 5,000 to 20,000. A binder resin is more preferable.

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

In addition, a conventionally known styrene- (meth) acrylic resin can be mixed in the toner.
Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, and pn-amyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, Examples thereof include styrene such as p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof.

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

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

  In the toner of the present invention, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic vinyl vinyl compounds such as divinylbenzene and divinylnaphthalene. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6. And xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of these compounds with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate. Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond. Examples of polyester diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

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

  These cross-linking agents are preferably used in an amount of 0.01 to 10 parts by mass, and 0.03 to 5 parts by mass, with respect to 100 parts by mass of the other monomers forming the vinyl polymer or copolymer. More preferred. Among these crosslinkable monomers, diacrylates bonded to a toner resin by a bond chain containing one aromatic divinyl compound (especially divinylbenzene), one aromatic group and an ether bond from the viewpoint of fixability and offset resistance. Preferred examples include compounds. Among these, a combination of monomers that becomes a styrene copolymer or a styrene-acrylic copolymer is preferable.

  Examples of the polymerization initiator used in the production of the vinyl polymer or copolymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1 , 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2 ′ , 4′-dimethyl-4′-methoxyvaleronitrile, 2,2′-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, Ketone peroxides such as rohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl Hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide , Lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylpero Xidicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclo Hexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexarate, tert-butyl peroxylaurate, tert-butyl-oxybenzoate, tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisophthalate, tert-butylperoxyallyl carbonate, isoamylperoxy-2-ethylhexanoate, di- tert- butylperoxy to hexa hydro terephthalate, tert- butylperoxy azelate, and the like.

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

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

In the present invention, the molecular weight distribution of the binder resin is measured by gel permeation chromatography (GPC) using THF as a solvent.
As the binder resin that can be used in the toner of the present invention, a resin containing a monomer component capable of reacting with both of these resin components in at least one of the vinyl polymer component and the polyester resin component can also be used. . Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
Moreover, when using together a polyester polymer, a vinyl polymer, and another binder resin, what has 60 mass% or more of resin whose acid value of the whole binder resin has 0.1-50 mgKOH / g is preferable.

In the present invention, the acid value of the binder resin component of the toner composition is determined by the following method. The basic operation conforms to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 (ml) beaker, and a mixed solution 150 (ml) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The usage amount of the KOH solution at this time is set to S (ml), the blank is measured at the same time, the usage amount of the KOH solution at this time is set to B (ml), and the following calculation formula (2) is used. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (2)

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

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

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

  The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. 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.
Further, 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, and an acid value of 20 mgKOH / g or less and an amine value of 10 It is more preferable that the coloring agent 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. Further, 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 a 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 preferable. In particular, 5,000 to 50,000 are preferable, and 5,000 to 30,000 are most preferable. When the molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant decreases. There are things to do.

  The addition amount of the dispersant is preferably 1 to 50 parts by mass, and more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the colorant. If it is less than 1 part by mass, the dispersibility may be lowered, and if it exceeds 50 parts by mass, the chargeability may be lowered.

(Release agent)
In the present invention, a cyclized isoprene resin is moderately dissolved in each other to promote softening of the resin, while a polyester resin and an incompatible wax are used. In the present invention, a release agent having a melting point of 50 to 85 ° C. is contained as a release agent for the purpose of offset resistance during fixing and low-temperature fixability. As such a releasing agent, conventionally known waxes can be used, but among them, it is preferable to contain at least one of carnauba wax and paraffin wax.
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.

  As described above, low-melting paraffin wax is used as the hydrocarbon wax to achieve low-temperature fixability and offset resistance as a toner, and further stable dispersion in the dispersion by maleic anhydride modification. As a result, clogging of the nozzle can be prevented in the manufacturing method in which the toner composition liquid is periodically discharged by mechanical vibration means to form droplets. Further, stable low-dispersion in the toner can achieve further low-temperature fixability and offset resistance.

  In the present invention, the release agent preferably has an acid value of 1 to 90 KOHmg / g, and more preferably 5 to 50 KOHmg / 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.

Still
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
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
Measurement 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
Steppes 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
Potentialial 2 No
Stop for revaluation No

Specifically, 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 0.1N potassium hydroxide alcohol solution that has been standardized to obtain a titration amount X [ml], the following formula: acid value = X × N × 56.1 / sample weight [KOHmg / g]
Therefore, an acid value is calculated | required. In the above formula, N is a factor of an alcohol solution of 0.1N potassium hydroxide.

  In the present invention, the release agent preferably has a melt viscosity at 120 ° C. of 1.0 to 30 mPa · cm, and more preferably 1.0 to 10 mPa · cm, from the viewpoints of fixability and offset resistance. When the melt viscosity is less than 1.0 mPa · cm, the fluidity of the toner may be inferior, and when it exceeds 30 mPa · second, the offset resistance may be deteriorated. The melt viscosity is measured using a Brookfield rotary viscometer.

In the present invention, the cyclized isoprene resin compatible with the wax is plasticized by the wax, and the thermal properties of the resin change depending on the blending ratio, the melting point of the wax, the Tg and molecular weight of the resin, and the cyclization rate.
This phenomenon is observed so that the Tg and the softening temperature of the resin seem to change. In particular, the melting point of the wax is a factor that greatly changes the properties of the resin. If the melting point of the wax is too low, the toner tends to agglomerate during high-temperature storage, or the image surface may stick. On the other hand, when a wax having a high melting point is used, the expected low-temperature fixability cannot be obtained. The melting point of the wax is preferably 50 to 85 ° C.
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 is performed 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. When the melting point is less than 50 ° C., blocking tends to occur during the production of the toner or when the toner is stored, and the heat resistant storage stability may be lowered. On the other hand, if the melting point exceeds 90 ° C., the low-temperature fixability and the offset resistance may deteriorate.

  In this invention, it is preferable that the addition amount of a mold release agent is 0.1-20 mass parts with respect to 100 mass parts of binder resin, and 0.5-10 mass parts is further more preferable. If the amount added is less than 0.1 parts by mass, the effect of the release agent may not be sufficiently obtained, and offset resistance may decrease. If the amount added exceeds 20 parts by mass, the fluidity of the toner may decrease. , It may stick to the developing device.

(Magnetic material)
The toner of the present invention may contain a magnetic material as necessary.
Examples of the magnetic material that can be used in the present invention include (1) iron oxide containing magnetic iron oxide such as magnetite, maghemite, and ferrite, and other metal oxides, and (2) metals such as iron, cobalt, and nickel, or Alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, (3) and these A mixture of
Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , _{PbFe 12 O, NiFe 2 O 4} , NdFe 2 O, BaFe 12 O 19, MgFe 2 O 4, MnFe 2 O 4, LaFeO 3, iron powder, cobalt powder, nickel powder, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of triiron tetroxide and γ-iron trioxide are particularly preferable.

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

  The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | 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.
All known charge control agents can be used, such as 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 a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry 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 (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 primarily by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. Although it is not a thing, Preferably it is used in 0.1-10 mass parts with respect to 100 mass parts of binder resin. Preferably, the range of 0.2-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, and the image density 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, fluororesin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder unoxidized titanium, fine powder unalumina. , 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 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.

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

  Examples of 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.

(Two-component developer)
The toner of the present invention may be used as a one-component developer, or may be used as a two-component developer by mixing the toner and a carrier. When used as a two-component developer, the carrier can be a normal carrier such as ferrite or magnetite or a resin-coated carrier.
The resin-coated carrier comprises a carrier core particle and a coating material that is a resin that coats (coats) the surface of the carrier core particle.
Examples of the resin used for the coating material include styrene-acrylic ester copolymers, styrene-acrylic ester copolymers 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 a 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 is simply mixed in a powder state Is applicable.
The ratio of the resin coating material to the resin-coated carrier may be appropriately determined, but is preferably 0.01 to 5% by mass and more preferably 0.1 to 1% by mass with respect to the resin-coated carrier.

Examples of use in which a magnetic material is coated with a coating agent of two or more kinds of mixtures include (1) dimethyldichlorosilane and dimethyl silicon oil (mass ratio 1: 5) with respect to 100 parts by mass of fine titanium oxide powder. Those treated with 12 parts by mass of the mixture, and (2) those treated with 20 parts by mass of a mixture of dimethyldichlorosilane and dimethylsilicone oil (mass ratio 1: 5) with respect to 100 parts by mass of the silica fine powder.
Among the resins, a styrene-methyl methacrylate copolymer, a mixture of a fluorine-containing resin and a styrene copolymer, and a silicone resin are preferably used, and a silicone resin is particularly preferable.

  Examples of the mixture of the fluorine-containing resin and the styrene copolymer include, for example, a mixture of polyvinylidene fluoride and a styrene-methyl methacrylate copolymer, a mixture of polytetrafluoroethylene and a styrene-methyl methacrylate copolymer, Vinylidene fluoride-tetrafluoroethylene copolymer (copolymer mass ratio 10:90 to 90:10), styrene-2-ethylhexyl acrylate copolymer (copolymer mass ratio 10:90 to 90:10) and styrene A mixture with 2-ethylhexyl acrylate-methyl methacrylate copolymer (copolymer mass ratio 20 to 60: 5 to 30:10:50) is mentioned.

  Examples of the silicone resin include modified silicone resins produced by reacting a nitrogen-containing silicone resin and a nitrogen-containing silane coupling agent with a silicone resin.

Examples of the magnetic material for the carrier core include oxides such as ferrite, iron-rich ferrite, magnetite, and γ-iron oxide, metals such as iron, cobalt, and nickel, or alloys thereof.
Examples of elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium. It is done. Among these, copper-zinc-iron-based ferrites mainly composed of copper, zinc, and iron components, and manganese-magnesium-iron-based ferrites mainly composed of manganese, magnesium, and iron components are preferable.

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

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

  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 further in detail, this invention is limited to the following Example at all and is not interpreted.
In the following examples and comparative examples, “cyclization rate of cyclized rubber”, “glass transition temperature (Tg) of resin”, “weight average molecular weight Mw of resin, number average molecular weight Mn”, and “melting point of wax” are The measurement was performed as follows.

(Cyclization rate of cyclized rubber)
The cyclization rate of the cyclized rubber was measured using ¹ H-NMR (manufactured by JEOL Ltd., JOEL JNM400 FT NMR SYSTEM). Put each 1wt% deuterated chloroform solution of the polymer before and after the cyclization reaction into a sample tube (manufactured by WILMAD, high-precision NMR sample tube). It was measured. The peak area before the cyclization reaction was (C0), the peak area after the cyclization reaction was (C1), and the cyclization rate was determined using the formula (1).

(Glass transition temperature (Tg) of resin)
The glass transition temperature (Tg) of the resin was measured using a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation). 10 mg of a sample was weighed into an aluminum sample pan, and while performing a nitrogen flow (flow rate 50 mL / min), the temperature was increased from 20 ° C. to 200 ° C. at a rate of temperature increase of 10 ° C./min. After the temperature was lowered at min, the DSC curve was measured when the temperature was raised from 20 ° C. to 200 ° C. at a rate of temperature rise of 10 ° C./min. From the obtained DSC curve, the temperature of the intersection of the extended line of the base line below the endothermic peak temperature and the tangent showing the maximum inclination from the peak rising portion to the peak apex was determined and used as the glass transition temperature (Tg).

(Weight average molecular weight Mw, number average molecular weight Mn of resin)
The molecular weight distribution of the resin was measured with a GPC (gel permeation chromatography) measuring device (manufactured by Tosoh Corporation, HLC-8220 GPC). A TSK-GEL H type (manufactured by Tosoh Corporation) was used for the column. The column was stabilized in a heat chamber at 40 ° C., and HFIP (hexafluoro-2-propanol) or THF (tetrahydrofuran) as a solvent was allowed to flow through the column at this temperature at a flow rate of 1 ml / min. Measurement was carried out by injecting 50 to 200 μl of a resin sample solution prepared to ˜0.6 mass%. Here, HFIP was used as the solvent for the cyclized rubber, and THF was used as the solvent for the other resins. In measuring the weight average molecular weight Mw and the number average molecular weight Mn, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Or a molecular weight of 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , manufactured by Toyo Soda Kogyo Co., Ltd. 9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ were used. An RI (refractive index) detector was used as the detector.

(Melting point of wax)
The melting point of the wax was measured using a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation). 10 mg of a sample was weighed into an aluminum sample pan, and while performing a nitrogen flow (flow rate 50 mL / min), the temperature was increased from 20 ° C. to 200 ° C. at a rate of temperature increase of 10 ° C./min. The temperature at the peak top, which is the maximum peak of the endothermic peak of the wax measured when the temperature was raised from 20 ° C. to 200 ° C. at a rate of temperature rise of 10 ° C./min after the temperature was lowered at min, was defined as the melting point of the wax.

(Production example 1 of cyclized rubber A)
Nitrogen inlet, reflux condenser, stirrer, and a four-necked flask equipped with a thermometer, polyisoprene (weight average molecular ^{weight: Mw3.0 × 10 5, Mw /} Mn ratio: 2.1, cis -1, 4 structures 86%, trans-1,4 structures 7%, 3,4 structures 7%) 120 parts by mass and toluene 1000 parts by mass were charged and dissolved, then 6 parts by mass of p-toluenesulfonic acid was added, and nitrogen atmosphere was added. The cyclization reaction was carried out at 85 ° C. for 2 hours. Thereafter, 40 parts of a 10% sodium carbonate solution was added and stirred for 1 hour to stop the cyclization reaction. The reaction solution was poured into a large amount of methanol solution, and the precipitate was collected and dried under reduced pressure to obtain cyclized polyisoprene A. Table 1 shows the physical properties of the obtained cyclized polyisoprene A.

(Production example 2 of cyclized rubber B)
A cyclized polyisoprene B was obtained in the same manner as in the cyclized rubber production example 1 except that the cyclization reaction time was changed to 4 hours in the cyclized rubber production example 1 described above. Table 1 shows the physical properties of the obtained cyclized polyisoprene B.

(Production example 3 of cyclized rubber C)
A cyclized polyisoprene C was obtained in the same manner as in the cyclized rubber production example 1 except that the cyclization reaction time was changed to 6 hours in the cyclized rubber production example 1. Table 1 shows the physical properties of the obtained cyclized polyisoprene C.

(Production example 4 of cyclized rubber D)
A cyclized polyisoprene D was obtained in the same manner as in the cyclized rubber production example 1 except that the cyclization reaction time was changed to 8 hours in the cyclized rubber production example 1. Table 1 shows the physical properties of the obtained cyclized polyisoprene D.

(Production example 5 of cyclized rubber E)
Cyclic polyisoprene E was obtained in the same manner as in Cyclic rubber production example 1 except that the cyclization reaction temperature was changed to 75 ° C. and the reaction time was changed to 1 hour. The physical properties of the obtained cyclized polyisoprene E are shown in Table 1.

(Production example of polyester resin)
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermometer, 150 parts by mass of terephthalic acid, 207 parts by mass of bisphenol A (2,2) propylene oxide, bisphenol A (2,2) ethylene oxide 127 parts by mass and 2.5 parts by mass of dibutyltin oxide as an esterification catalyst were added and subjected to a condensation polymerization reaction at 230 ° C. for 15 hours in a nitrogen atmosphere, and then reacted at 230 ° C. and 8.0 kPa for 1 hour. . After cooling to 180 ° C., 115 parts by weight of trimellitic anhydride was added, the temperature was raised to 210 ° C. over 3 hours, and the reaction was carried out at normal pressure (101.3 kPa) for 10 hours, and then 210 ° C., 20 kPa. For 3 hours to synthesize polyester resin A (Mw 1.5 × 10 ⁴ , Mw / Mn 4.6, Tg 60 ° C.).

(Example of master batch production)
A cyclized rubber and a polyester resin having the following composition were mixed and kneaded by two rolls. First, the roll temperature was set to 80 ° C., the polyester was charged first, and then the roll temperature was raised to 130 ° C. and the cyclized rubber was charged. Furthermore, a wax having the following formulation was added and dispersed for 30 minutes to prepare a master batch 1. The prepared master batch is shown in Table 2.
[Masterbatch 1]
Cyclized rubber A 30 parts by mass Polyester resin A 63 parts by mass Wax F 7 parts by mass The same as the formulation of masterbatch 1 described above, except that in the formulation of masterbatch 1, the wax shown in Table 2 was used and the cyclized rubber was used. Master batches of master batches 2 to 11 were prepared by replacing A and the polyester resin with those shown in Table 3. Table 3 shows all the master batches 1 to 11 created.

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

-Preparation of dispersion with added resin and wax-
In a container in which a stirring blade and a thermometer are set, 10 parts by mass of polyester resin A prepared in the above-described production example of polyester resin as a binder resin, 10 parts by mass of paraffin wax (wax F: mp = 81 ° C.), 80 ethyl acetate A mass part was charged, heated to 85 ° C. and stirred for 20 minutes, and then rapidly cooled to precipitate fine particles of paraffin wax. This dispersion was further finely dispersed by a strong shearing force using a dyno mill to obtain a [resin / wax dispersion].

-Preparation of resin and cyclized rubber dispersion-
20 parts by mass of [Masterbatch 1] described above were dissolved in 80 parts by mass of ethyl acetate using a mixer having stirring blades. The obtained liquid is finely dispersed with a strong shearing force using a dyno mill and passed through a stainless steel 400 mesh to completely remove aggregates [resin / cyclized rubber dispersion] Was prepared.

-Preparation of toner composition liquid-
30 parts by mass of [carbon black dispersion], 70 parts by mass of [resin / wax dispersion] and 490 parts by mass of [resin / cyclized rubber dispersion] were mixed using a mixer having stirring blades.
The obtained toner composition liquid (toner composition preparation liquid) was further diluted with ethyl acetate to a solid content of 6.0% to prepare [toner composition liquid].

-Preparation of toner-
The obtained [toner composition solution] was supplied to the ring-type vibrator head of the toner production 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 from 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, a laminate of lead zirconate titanate (PZT) was used, and the vibration frequency was 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 the device 30.0 L / min Temperature in the device: 27 to 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 Co., Ltd.), and black toner a (simply referred to as “toner a” ”). The particle size of the obtained toner a was measured. As shown in Table 5, 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 (organostriction silicone): 100 parts by mass Toluene: 100 parts by mass γ- (2-aminoethyl) aminopropyltrimethoxysilane: 5 parts by mass Carbon black: 10 parts by mass The above mixture is a homomixer -For 20 minutes to prepare a coating layer forming solution. The above mixture was dispersed with a homomixer for 20 minutes to prepare a coat layer forming solution. This coating layer forming liquid was coated on the surface of 1000 parts by mass of spherical magnetite having a particle diameter of 50 μm using a fluidized bed type coating apparatus to obtain a magnetic carrier A.

-Preparation of two-component developer-
96 parts by mass of the magnetic carrier A was mixed with 4 parts by mass of the toner a using a ball mill to prepare [Two-component developer 1], and cold offset property, hot offset property and filming property were evaluated. The evaluation results are shown in Table 5. As shown in Table 5, the two-component developer 1 was good in cold offset property, hot offset property and filming property. Moreover, evaluation of each characteristic shown in Table 5 was performed according to the following evaluation method. These evaluation results are also shown in Table 5.

[Evaluation methods]
<Particle size distribution>
The weight average particle diameter (D4) and number average particle diameter (Dn) of the toner of the present invention were measured with an aperture diameter of 100 μm using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.), and analysis software ( Analysis was performed with a Beckman Coulter Mutizer 3 Version 3.51). Specifically, 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, 0.5 g of each toner is added, and the mixture is stirred with a micropartel. 80 ml of ion exchange 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 .35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Particles with a particle size of 2.00 μm to less than 40.30 μm were used using 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm. 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.

The prepared toner was mounted on a BK unit of a composite machine Imagio NeoC285 manufactured by Ricoh Co., Ltd., and a printing test was performed. Evaluation was performed as follows.
(Fixability)
<Low temperature fixability>
An evaluator modified so that the fixing temperature can be adjusted was used. A single-color solid image with a toner adhesion amount of 0.85 ± 0.1 mg / cm ² is created on a thick transfer paper (manufactured by NBS Ricoh Co., Ltd., copy printing paper <135>), and the temperature of the fixing belt using an external power source Fixing was performed by changing. The obtained fixed image surface was drawn with a ruby needle (tip radius 260 to 320 μmR, tip angle 60 degrees) and a load of 50 g using a drawing tester (AD-401, manufactured by Ueshima Seisakusho), and fibers (Hanicot # 440, The drawing surface was rubbed strongly 5 times with Hanilon Co., Ltd., and the fixing belt temperature at which image shaving was almost eliminated was defined as the minimum fixing temperature, and the low-temperature fixing property was evaluated according to the following criteria. The solid image was created on the transfer paper at a position of 3.0 cm from the front end in the paper passing direction.
〔Evaluation criteria〕
A: Fixing lower limit temperature is 110 ° C. or less ○: Fixing lower limit temperature is 111 ° C. or more and 120 ° C. or less Δ: Fixing lower limit temperature is 121 ° C. or more and 135 ° C. or less ×: Fixing lower limit temperature is 136 ° C. or more and 140 ° C. or less XX: Fixing lower limit temperature Temperature is 141 ℃ or more

<Hot offset resistance>
Using the evaluation machine, a monochrome solid image with a black toner adhesion amount of 0.85 ± 0.1 mg / cm ² was created on a plain paper transfer paper (type 6200, manufactured by Ricoh Co., Ltd.), and the temperature of the fixing roller or belt A fixing test was conducted by changing the temperature and the presence or absence of hot offset was visually evaluated. The upper limit temperature at which hot offset did not occur was defined as the upper limit fixing temperature, and hot offset resistance was evaluated according to the following criteria. The solid image was created on the transfer paper at a position of 3.0 cm from the front end in the paper passing direction. Further, the worst result among the measurement results of the four colors of each toner was used as the evaluation value of the toner.
〔Evaluation criteria〕
A: Fixing upper limit temperature is 220 ° C. or more. ○: Fixing upper limit temperature is 210 ° C. or more and less than 220 ° C. Δ: Fixing upper limit temperature is 190 ° C. or more and less than 210 ° C. ×: Fixing upper limit temperature is 180 ° C. or more and less than 190 ° C. Temperature is less than 180 ° C

(Fixing releasability)
Using the evaluation machine, a solid image with a toner adhesion amount of 0.85 ± 0.1 mg / cm ² was prepared on a plain paper transfer paper (Ricoh Co., Ltd., type 6200 (longitudinal)), and the fixing roller or belt This occurs when a fixed image discharged in the A4 size is contacted with a separation claw arranged to separate the fixing paper and the fixing belt in the vicinity of the fixing nip exit. The degree of scars on the fixed image was visually evaluated. The extent of the scar was evaluated in five stages using a rank sample, and an upper limit temperature at which no scar or jam was generated was used as an index for fixing releasability. The solid image was created on the transfer paper at a position 0.5 cm from the front end in the paper passing direction.
〔Evaluation criteria〕
◎: Upper limit temperature is 200 ° C or higher ○: Upper limit temperature is 190 ° C or higher and lower than 200 ° C △: Upper limit temperature is 170 ° C or higher and lower than 190 ° C ×: Upper limit temperature is 160 ° C or higher and lower than 170 ° C XX: Upper limit temperature is lower than 160 ° C

(Carrier contamination)
The carrier contamination property is a characteristic that serves as an index of toner carrier contamination. The higher the mechanical strength of the toner, the less the carrier contamination.
As an evaluation method, specifically, using the above-mentioned evaluation machine, the developer after 100 sheets running output of an image chart of 50% image area and 30,000 sheets running output was extracted in the monochrome mode, and the developer was removed. An appropriate amount was put in a gauge with a mesh having a mesh size of 32 μm, and air blowing was performed to separate the toner and the carrier. 1.0 g of the obtained carrier was put in a 50 ml glass bottle, 10 ml of chloroform was added, and the mixture was shaken 50 times and allowed to stand for 10 minutes. Thereafter, the supernatant chloroform solution was placed in a glass cell, and the transmittance of the chloroform solution was measured using a turbidimeter, and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Transmittance is 95% or more ○: Transmittance is 90% or more and 94% or less △: Transmittance is 80% or more and 89% or less ×: Transmittance is 70% or more and 79% or less XX: Transmittance is 69% or less

(Photoreceptor filming property)
Using the evaluation machine, the toner filming state on the photosensitive member was visually evaluated after running 100 sheets of 50% image area image chart and outputting 50,000 sheets in monochrome mode. Considering the presence or absence of abnormality in the output image, the determination was made in the following five stages.
〔Evaluation criteria〕
A: No image abnormality and no toner filming on the photoreceptor.
◯: There is no image abnormality at all, but a slight toner filming is seen on the photoreceptor.
Δ: Some abnormal image is seen, and clear toner filming is also seen on the photoreceptor.
X: Clear image abnormality was observed, toner filming on the photosensitive member was severe, and there was a problem level.
XX: Clear image abnormality is observed, toner filming on the photoconductor is severe, and a normal image cannot be obtained.

(Initial image quality)
The initial image quality was evaluated by using the evaluator to output an image evaluation chart in the BK single color mode, and checking for the presence of gradation defects, fogging, image density, blurring, and the like. The presence / absence of abnormality and the rank evaluation of the image quality were visually evaluated and judged in the following five stages.
〔Evaluation criteria〕
A: Image abnormality is not observed at all and is good.
○: Compared with the original image, a slight difference in color tone, image density, background stain, etc. is observed, but it is satisfactory in practical use.
Δ: Slightly felt gradation, image density, background stains, etc.
X: Gradation defects, density changes, background stains, etc. are obvious and cause problems.
XX: Gradation failure, density change, background stain, etc. are severe and a normal image cannot be obtained.

(Time-lapse image quality)
Using the evaluation machine, after running 50,000 image charts with an 80% image area in BK single color mode, the same evaluation as the initial image quality evaluation is performed, and the initial image is compared. evaluated.
〔Evaluation criteria〕
A: Image abnormality is not observed at all and is good.
○: Compared with the initial image, slight differences in gradation, image density, background stain, and the like are observed, but the level is not problematic under normal temperature and humidity conditions.
Δ: Compared with the initial image, there is a slight change in gradation, image density, background stains, and the like.
X: Compared with the initial image, gradation changes, density changes, background stains, etc. are obvious and cause problems.
XX: Compared with the initial image, the gradation change, density change, background stain, etc. are severe, and a normal image cannot be obtained.

[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 ejection holes were provided only in a range of about 5 mmφ at the center of the nozzle plate in a staggered pattern so that the distance between the ejection holes was 100 μm. 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 mass 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.
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.
A developer was prepared using the same carrier as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 4.

[Examples 3-7 and Comparative Examples 1-5]
Thereafter, a toner was prepared in the same manner as in Example 2 using the materials shown in Table 4 below. Similarly, the results of the evaluation are shown in Table 4.

  The toner 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 has low temperature fixability and offset resistance. Since it is excellent, 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 mechanical longitudinal vibration means for manufacturing toner 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.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 2 Droplet injection 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 Storage portion 15 Channel member 16 Droplet forming means 16A Deformable region 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 Fixed portion

Claims (10)

A toner obtained by solidifying a toner composition liquid, in which a toner composition having at least a binder resin, a colorant, and a release agent is dissolved or dispersed in an organic solvent, into droplets in a gas phase, ,
The toner according to claim 1, wherein the binder resin includes at least a polyester resin and a cyclized rubber having a cyclization rate of 50 to 75%, and a melting point of the release agent is 50 to 85 ° C.   The toner according to claim 1, wherein the droplet formation is performed by vibrating a nozzle plate having ejection holes and continuously ejecting the toner composition liquid from the ejection holes.   The droplet formation is performed by causing a thin film formed with a plurality of nozzles provided in a storage portion for storing the toner composition liquid to vibrate by a vibrating means to periodically discharge the toner composition liquid from each of the nozzles. The toner according to claim 1, wherein the toner is used.   The toner according to claim 3, wherein the vibration unit is a vibration generation unit formed in an annular shape in a peripheral region where the nozzles of the nozzle plate are provided.   4. The toner according to claim 3, wherein the vibration means has a vibration surface parallel to the thin film, and the vibration surface vibrates in the vertical direction.   The toner according to claim 3, wherein a vibration frequency of the vibration unit is 20 kHz or more and less than 2.0 MHz.   The toner according to claim 3, wherein the vibration unit is a horn-type vibrator.   The toner according to claim 2, wherein an opening diameter of the nozzle is 1 to 40 μm.   The toner according to claim 1, wherein the solidification after the droplet formation is performed by removing a solvent from the droplet-formed toner composition liquid.   A developer comprising the toner according to claim 1 and a carrier.

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