JP6094877B2 - Toner production method and resin particle production method - Google Patents

Description

The present invention relates to a method for producing an electrophotographic, electrostatic recording, producing how the toner for developing electrostatic images used for developing an electrostatic charge image in electrostatic printing and the like, the 及 beauty resin particles is there.

  In recent years, electrostatic charge image developing toners used in image forming apparatuses such as copiers, printers, facsimiles, and composite machines based on the electrophotographic recording method have been demanded by the market for speeding up and energy saving of image forming apparatuses. Therefore, there is a demand for a toner that is increasingly larger, has excellent low-temperature fixability, and can provide a high-quality image. In order to achieve the low-temperature fixability of the toner, it is known to use a crystalline resin as a main component for the binder resin of the toner, as disclosed in, for example, Patent Document 1.

  In addition, in order for toner to output a stable image quality for a long time inside the image forming apparatus, it is important to suppress as much as possible the problem that the toner adheres to the members constituting the apparatus and significantly deteriorates the initial performance of those members. is there. Usually, the fine powder component of toner, which has strong adhesion and is difficult to remove, is likely to cause these problems.

  Such a tendency becomes more prominent due to the influence of the crystalline resin having low thermal characteristics in the low-temperature fixing toner having the above-described configuration. In order to solve this problem, it is important to reduce as much as possible the fine powder that easily adheres inside the apparatus, that is, the toner needs to have a narrower particle size distribution than the conventional toner. In order to achieve such a narrow particle size distribution, not only conventional pulverization methods but also suspension polymerization, emulsion aggregation, polymer suspension (polymer aggregation), ester elongation reaction, etc., which are currently in practical use. Even the so-called chemical toner used was insufficient.

  In order to avoid this drawback, a toner manufacturing method called a jet granulation method is known (Patent Documents 2 to 5). In this spray granulation method, a liquid (toner composition liquid) in which a toner raw material is dissolved or dispersed in an organic solvent is discharged into droplets using a droplet spraying means such as a sprayer (atomizer). This is a method for producing a toner by drying and solidifying it to obtain a fine particle toner. Specifically, a toner composition liquid generated by dissolving a fine toner raw material having an average diameter of less than about 0.45 [μm] in an organic solvent is spread under the droplet ejecting means by the droplet ejecting means. Inject into the gas phase space. The droplets of the toner composition liquid travel in the same traveling direction in the gas phase space to form a row of droplets. The droplets are shaped into a substantially spherical shape due to the difference in surface tension between the liquid phase and the gas phase of the toner composition liquid itself, and then dried and solidified to form aggregated fine particles having an average diameter of about 1 to 20 [μm]. Toner is obtained. Thus, the size of the droplets ejected by the droplet ejecting means depends on the diameter of the spray nozzle. For this reason, the obtained toner is likely to have a substantially spherical small particle size, and is characterized by a very narrow particle size distribution.

  However, in the toner production methods described in Patent Documents 2 to 5, an organic solvent capable of dissolving the toner raw material is used. In addition, when a crystalline resin is used as the binder resin as described above, the toner dried during manufacture is extremely adhered to and accumulated on the wall surface, and the yield is reduced. It has been found that the durability within the image forming apparatus is significantly reduced. The reason is considered as follows.

The crystalline resin takes a long time to recrystallize during the drying process of the resin accompanying the removal of the solvent. Even if a crystalline resin having a sufficiently high crystallization rate is used, the above-mentioned jet granulation method has a much slower crystallization rate than the volatilization of the solvent, resulting in insufficient crystallization. Furthermore, among the entire droplets of the toner composition liquid in which the organic solvent is present, the organic solvent in the lower surface portion near the surface of the droplet is volatilized and removed by the drying and solidification treatment, but the organic solvent present in the central portion is removed. The solvent remains without being sufficiently evaporated. The organic solvent present in the central portion can also be removed by performing a treatment in which the binder resin present inside is heated to a temperature at which the binder resin can be softened and depressurized. However, when such a treatment is performed after the drying and solidifying treatment, even if a fluidized bed dryer is used, blocking due to the fusion of the toner particles occurs, and the toner particles become larger than the target size. In the fluidized bed dryer, the drying time and the heating temperature are set in accordance with the target size of the toner particles, so that the removal of the organic solvent in the toner particles larger than the target size becomes insufficient. The organic solvent remains in the central portion of the toner particles, and the binder resin is dissolved in the organic solvent remaining in the toner particles, thereby inhibiting the binding of the molecular chains of the binder resin. These results reduce the degree of crystallinity of the toner.
As described above, when manufacturing a low-temperature fixing toner mainly composed of a crystalline resin having a narrow particle size distribution by the jet granulation method, the wall surface adhesion at the time of manufacture and the durability in the image forming apparatus are insufficient. There was a problem.

The present invention has been made in view of the above problems, and the objects thereof are as follows. Less fine powder using a prilling process, i.e. while ensuring a narrow particle size distribution, a sufficient degree of crystallization of the toner can be obtained belt toner manufacturing how to provide a method for producing 及 beauty resin particles That is.

In order to achieve the above object, the invention of claim 1 is a method for producing a toner containing at least a binder resin, wherein a toner composition liquid obtained by dispersing a raw material of the toner in an aqueous medium is discharged. A droplet forming step for forming droplets; a drying step for drying the aqueous medium in the dropletized toner composition; and an aggregate of fine particles of the raw material of the toner obtained by the drying step in the aqueous medium. And a fusing step of fusing the fine particles to each other by applying heat after being re-dispersed .

The aqueous medium in the toner composition liquid formed into droplets in the droplet forming step is evaporated in the drying step, and the raw material components in the toner particles after drying are concentrated and aggregated. The heating temperature in this drying step is a temperature at which the aqueous medium evaporates, and is not a temperature at which the binder resin contained in the toner particles can be softened. When the toner composition liquid formed into droplets is heated at a temperature at which the binder resin can be softened in the drying process, the binder resin existing on and near the surface of the toner particles is softened, and the binder resins are fused to each other during the drying process. Blocking occurs. As a result, the substantially spherical shape of the toner particles cannot be maintained. Therefore, in the present invention, a toner can be produced without causing blocking or a decrease in crystallinity. In the fusing step, agglomerates of fine particles of toner raw materials are redispersed in an aqueous medium, and then heat is applied to fuse the fine particles. As a result, the fine particles of the binder resin are in a state of sticking in one toner particle while maintaining the crystal state before being formed into droplets, and sufficient stress resistance as a toner can be obtained. Accordingly, while ensuring a narrow particle size distribution can provide a sufficient degree of crystallization of the toner can be obtained belt toner manufacturing how. Moreover, the manufacturing method of the resin particle which can manufacture the resin particle which has sufficient crystallinity can be provided.

FIG. 2 is a schematic diagram illustrating an example of a toner manufacturing apparatus that performs a toner manufacturing method according to an embodiment. It is the schematic diagram which expanded and showed a part of droplet discharge part of the liquid column resonance type droplet discharge apparatus used by embodiment. It is sectional drawing which showed typically a part of liquid column resonance droplet formation part which is the droplet discharge device. (A)-(d) is sectional drawing which illustrated various cross-sectional shapes employable as a cross-sectional shape of the discharge hole of the same liquid column resonance droplet formation part. (A) to (d) show the standing waves of the velocity distribution and the pressure distribution generated in the liquid in the liquid column resonance liquid chamber of the liquid column resonance droplet forming unit when N = 1, 2, and 3. It is explanatory drawing for demonstrating. (A)-(c) is explanatory drawing for demonstrating the mode of the standing wave of the velocity distribution and pressure distribution which arise in the liquid in the same liquid column resonance liquid chamber in the case of N = 4 and 5. FIG. (A)-(d) is explanatory drawing which represented typically the mode of the liquid column resonance phenomenon which arises in the same liquid column resonance liquid chamber. It is explanatory drawing which shows the example which employ | adopted the airflow which goes to a horizontal direction with respect to a droplet discharge direction as a conveyance airflow which conveys the discharged droplet.

Hereinafter, an embodiment of a toner manufacturing apparatus according to the present invention will be described with reference to the drawings.
The toner manufacturing apparatus according to the present exemplary embodiment is configured such that the toner component liquid (particulate-containing liquid) that becomes toner particles (fine particles) when the droplets are solidified is discharged from a plurality of discharge holes that are opened on the discharge surface of the droplet discharge apparatus. The discharge operation for discharging droplets is continued. Then, the discharged droplets are solidified to obtain toner particles. Here, the toner component liquid is a liquid in which the component of the toner to be obtained is dispersed in an aqueous medium as a liquid discharged from the discharge means.

  The droplet discharge device that can be used in the toner manufacturing method of the present embodiment preferably has a narrow particle size distribution of discharged droplets, but is not particularly limited, and a known one can be used. Examples of the droplet discharge device include a one-fluid nozzle, a two-fluid nozzle, a membrane vibration type discharge unit, a Rayleigh split type discharge unit, a liquid vibration type discharge unit, and a liquid column resonance type discharge unit. An example of a membrane vibration type discharge means is disclosed in Japanese Patent Application Laid-Open No. 2008-292976. Further, as a Rayleigh splitting type discharge means, there is one disclosed in Japanese Patent No. 4647506. Moreover, as a liquid vibration type discharge means, there is one disclosed in Japanese Patent Application Laid-Open No. 2010-102195.

  In order to ensure the productivity of the toner with a narrow droplet size distribution, vibration is imparted to the liquid in the liquid column resonance liquid chamber in which a plurality of ejection holes are formed to form a standing wave by liquid column resonance. To do. A liquid column resonance type liquid droplet ejection apparatus that ejects liquid from the ejection holes formed in the region that becomes the antinode of the standing wave is preferable. In the present embodiment, an example in which toner is manufactured using a liquid column resonance type droplet discharge device will be described.

  FIG. 1 is a schematic diagram illustrating an example of a toner manufacturing apparatus that performs the toner manufacturing method according to the present embodiment. The toner manufacturing apparatus 1 mainly includes the above-described liquid column resonance droplet forming unit 10, a dry collection unit 20, and a toner component liquid replenishing unit 30.

  The toner component liquid replenishment unit 30 includes a toner component liquid tank 32 in which the toner component liquid 31 is stored. The toner component liquid tank 32 is connected to the liquid column resonance droplet forming unit 10 via the toner component liquid supply channel 33. A liquid circulation pump 34 that pumps the toner component liquid 31 in the toner component liquid supply flow path 33 is connected to the toner component liquid supply flow path 33. By driving the liquid circulation pump 34, the toner component liquid 31 in the toner component liquid tank 32 is supplied to the liquid column resonance droplet forming unit 10 through the toner component liquid supply channel 33.

  Further, the toner component liquid tank 32 is connected to the liquid column resonance droplet forming unit 10 via a liquid return pipe 35. Among the toner component liquids 31 supplied from the toner component liquid supply channel 33 to the liquid column resonance droplet forming unit 10, there are those that have not been replenished to the liquid column resonance liquid chamber 11 of the liquid column resonance droplet forming unit 10. . It is returned to the toner component liquid tank 32 through the liquid return pipe 35 by driving the liquid circulation pump 34.

  In the present embodiment, the toner component liquid supply flow path 33 is provided with a pressure measuring device P1, and the dry collection unit 20 is provided with a pressure measuring device P2. The liquid feeding pressure to the liquid column resonance droplet forming unit 10 and the pressure in the dry collecting unit 20 are managed based on the measurement results of these pressure measuring devices P1 and P2. At this time, if the pressure of the pressure measuring device P <b> 1 is greater than the pressure of the pressure measuring device P <b> 2, the toner component liquid 31 may ooze out from the discharge hole 12. On the contrary, if the pressure of the pressure measuring device P1 is smaller than the pressure of the pressure measuring device P2, there is a possibility that gas enters the liquid column resonance droplet forming unit 10 and stops the discharge. Therefore, it is desirable that the pressure of the pressure measuring device P1 and the pressure of the pressure measuring device P2 have a substantially equal relationship.

  The dry collection unit 20 is provided with a chamber 21, and the liquid column resonance droplet forming unit 10 is installed in the chamber 21. The chamber 21 is fed with a descending carrier airflow 23 from the carrier airflow inlet 22, and the droplets 13 ejected from the liquid column resonance droplet forming unit 10 are not only gravity but also the carrier airflow 23. , Conveyed downward. The droplets 13 transported downward in the chamber 21 are dried and solidified during the transportation, discharged from the collection outlet 24, sent to the solidified particle collecting means 25, and collected.

  The method for producing a toner of the present invention includes a step of forming a continuous surface by applying heat treatment at least in the binder resin aggregate obtained by collection. Specifically, in a process performed using the “droplet solidifying means”, heat is applied as a first method to form a continuous surface, or toner particles collected as a second method are further recycled to an aqueous medium. Disperse and heat with stirring. In the first method, for example, by drying and solidifying using a heated conveying air flow 23, the binding of the binder resin aggregates in one toner particle can be promoted to form a continuous layer. At this time, the temperature of the carrier airflow is preferably in the range from the melting peak shoulder temperature to the melting peak temperature indicated by the DSC method of the crystalline resin used as the binder resin. If the airflow temperature is lower than this range, a sufficient continuous layer may not be formed and the toner strength may be insufficient. If the airflow temperature is higher than the above range, not only the toner particles but also the binding between the toner particles may occur. It is promoted to easily cause blocking. Moreover, the wall surface adhesion of the collection part is likely to deteriorate.

  In the second method, after the solidified particles are collected, they are redispersed by being immersed and stirred in an aqueous medium, and from the viewpoint of shortening the process, the solidified particle collecting part is filled with the aqueous medium, and is simultaneously immersed and redispersed. Particularly preferred is a method of making them. In this case, for example, in the solidified particle collecting means 25, the aqueous medium is redispersed in the collected toner particles through the aqueous medium supply pipe 26 and heated while stirring. Steam generated by heating is discharged from the steam exhaust port 27. Thereby, the continuous layer of binder resin can be formed.

  The dispersion of the toner liquid discharged with a uniform particle diameter concentrates the dispersoid by evaporation of water in the air stream. During this process, the toner material aggregates to form an aggregate of toner material having a uniform particle size. The toner material aggregates are dipped and dispersed again in an aqueous medium pre-filled in the cyclone collecting section. When re-dispersing the aggregate in the aqueous medium, it is necessary to disperse the aggregate in such a degree that the aggregate structure obtained by droplet drying is not destroyed. In order to improve the wettability between the toner material aggregate and the aqueous medium, it is preferable to add a surfactant in the aqueous medium.

  The fine particles taken into the aqueous medium are then heated under stirring, whereby the binder resin as the toner material is softened to form a continuous surface. The heating temperature at this time is preferably at least the shoulder temperature of the melting peak obtained by the DSC method of the crystalline resin used as the binder resin.

  The aqueous dispersion of toner thus obtained is then subjected to removal of the surfactant by washing with water, and further, a slurry containing fine particles is obtained by a known powder collecting means such as a filter press or centrifugal separation. Can be obtained. By using a general known drying means such as fluidized bed drying or vacuum drying, moisture can be dried. Moreover, even if the means for forming the continuous surface is the first method, it is possible to perform the above-described water cleaning in order to remove excess surfactant.

  When the ejected droplets come into contact with each other before drying, a phenomenon called coalescence in which the droplets coalesce into one large particle occurs, and the toner particle size distribution spreads. Therefore, in order to obtain toner particles having a narrow particle size distribution, it is necessary to secure the distance between the discharged droplets. However, the ejected droplets have a constant initial velocity, but gradually become stalled due to air resistance. For this reason, the liquid droplets discharged later may catch up with the stalled liquid droplets, and there is a possibility that coalescence occurs. Since such a coalescence phenomenon occurs constantly, when the particles are collected, the particle size distribution is greatly deteriorated. In order to prevent such a coalescence phenomenon, in the present embodiment, a drop in the velocity of the droplet is prevented by the carrier airflow 23 of the descending airflow so that the droplets do not come into contact with each other.

  In this embodiment, the carrier airflow 23 of the descending airflow is directed downward, but as shown in FIG. 8 to be described later, a carrier airflow 23 extending in the lateral direction with respect to the droplet discharge direction can also be employed. However, in this case, it is desirable to form the transport airflow 23 so that the loci of the droplets 13 transported by the transport airflow 23 from the ejection holes 12 do not overlap. The direction of the carrier airflow may not be transverse to the droplet ejection direction, but may be oblique to the droplet ejection direction, but has an angle such that the ejected droplets are separated. It is desirable.

  Further, in the present embodiment, both the prevention of coalescence and the conveyance to the solidified particle collecting means 25 are realized by the downdraft carrier airflow 23, but the first airflow for preventing the coalescence, You may form separately the 2nd airflow for conveying to the solidified particle collection means 25. FIG. In this case, it is desirable that the flow rate of the first air stream is equal to or higher than the moving speed of the droplets during discharge. If the flow velocity of the first air stream is slower than the droplet moving speed at the time of ejection, there is a possibility that the function of preventing contact between the droplets, which is the original purpose of the first air stream, may not be performed. About the other characteristic of 1st airflow, you may add suitably the conditions that droplets do not contact, and it does not necessarily need to be the same as the characteristic of 2nd airflow. For example, a chemical substance that promotes solidification of the droplets may be mixed in the first air stream, or a physical action may be performed so as to promote solidification of the droplets.

  The carrier airflow 23 of the descending airflow of the present embodiment may be, for example, a laminar flow, a swirl flow, a turbulent flow, or the like. There is no particular limitation on the type of gas constituting the carrier airflow 23 of the downdraft, and it may be air or a nonflammable gas such as nitrogen. Further, the temperature of the carrier airflow 23 of the descending airflow can be adjusted as appropriate, and it is desirable that there is no fluctuation during production. Also, means for changing the airflow state of the carrier airflow 23 of the descending airflow may be provided in the chamber 21. Further, the carrier airflow 23 of the descending airflow may be used not only to prevent the droplets from contacting each other but also to prevent them from adhering to the inner wall of the chamber 21.

  As shown in FIG. 1, in the present embodiment, when the amount of residual solvent contained in the toner particles collected by the solidified particle collecting means 25 is large, drying means are used as necessary to reduce this. Secondary drying is performed by 28. As the secondary drying, general known drying means such as fluidized bed drying or vacuum drying can be used. When the organic solvent remains in one particle of the toner, not only the toner characteristics such as heat-resistant storage property, fixing property, and charging property are changed with time, but also the organic solvent is volatilized at the time of heat-fixing during the image forming operation. For this reason, the possibility of adverse effects on various devices in the image forming apparatus is increased, and it is desired to perform sufficient drying.

FIG. 2 is an enlarged schematic view showing a part of a droplet discharge portion of a liquid column resonance type droplet discharge device used in the present embodiment.
The liquid droplet ejection unit of the present embodiment includes a liquid column resonance liquid chamber 11, and this liquid column resonance liquid chamber 11 is one side wall portion (opening side wall) among the side wall portions at both ends in the longitudinal direction (left-right direction in the figure). The liquid common supply path 14 communicates with the liquid common supply path 14. Further, the liquid column resonance liquid chamber 11 has a plurality of discharge holes 12 for discharging the droplets 13 to one wall portion (the bottom wall portion on the lower side in the drawing) of the wall portions connecting the side wall portions at both ends in the longitudinal direction. It has. Further, vibration generating means 15 for generating high-frequency vibrations is provided on the side of the upper wall portion facing the discharge hole 12 in the liquid column resonance liquid chamber 11 in order to form a liquid column resonance standing wave. The vibration generating means 15 is connected to a high frequency power source (not shown).

FIG. 3 is a cross-sectional view schematically showing a part of the liquid column resonance droplet forming unit 10 which is the droplet discharge device of the present embodiment. 3 is viewed from above or below in FIG.
In the present embodiment, the liquid discharged from the droplet discharge unit is a fine particle-containing liquid in a state where the components of the fine particles to be manufactured are dissolved or dispersed. Since this embodiment is an example of manufacturing toner, this fine particle-containing liquid will be described as a toner component liquid. The toner component liquid 31 passes through the liquid supply pipe by a liquid circulation pump (not shown) and flows into the liquid common supply path 14 of the liquid column resonance droplet forming unit 10, and the liquid column resonance liquid chamber 11 of each droplet discharge unit. It is replenished.

  In the toner component liquid 31 filled in the liquid column resonance liquid chamber 11, a pressure distribution is formed by the liquid column resonance standing wave generated by the vibration generating unit 15. Then, the droplet 13 is ejected from the ejection hole 12 disposed in the region that is the antinode of the liquid column resonance standing wave (the region where the amplitude is large and the pressure fluctuation is large). The region that becomes the antinode of the standing wave due to the liquid column resonance means a region other than the node of the standing wave. Preferably, it is a region where the pressure fluctuation of the standing wave has an amplitude large enough to discharge the liquid, and more preferably ± from the position where the amplitude of the standing wave is maximized to the position where the amplitude is minimized. The range is a quarter wavelength. If the region is an antinode of a standing wave, even if the plurality of discharge holes 12 are formed in one liquid column resonance liquid chamber 11 as in the present embodiment, the size is almost uniform from each. Can be discharged. When the amount of liquid in the liquid column resonance liquid chamber 11 decreases due to the discharge of the droplet 13, a suction force due to the action of the liquid column resonance standing wave in the liquid column resonance liquid chamber 11 acts, and the liquid common resonance supply channel 14 The flow rate of the supplied liquid increases, and the liquid is replenished in the liquid column resonance liquid chamber 11.

  The liquid column resonance liquid chamber 11 of the droplet discharge unit is formed by joining frames formed of a material such as a metal, ceramics, or silicon having such a high rigidity that does not affect the resonance frequency of the liquid at the driving frequency. Has been. Further, as shown in FIG. 2, the length L between the side wall portions at both ends in the longitudinal direction of the liquid column resonance liquid chamber 11 is determined based on the liquid column resonance principle as described later. Further, as shown in FIG. 3, the length (width) W between the side walls at both ends in the short direction of the liquid column resonance liquid chamber 11 is set so as not to give an extra frequency to the liquid column resonance. It is desirable to be less than half the length L of 11.

  In order to improve productivity, it is preferable that a plurality of liquid column resonance liquid chambers 11 are arranged with respect to one liquid column resonance droplet forming unit 10. Therefore, in this embodiment, one liquid column resonance droplet is used. A configuration in which a plurality of liquid column resonance liquid chambers 11 are arranged with respect to the forming unit 10 is adopted. The number of liquid column resonance liquid chambers 11 provided for one liquid column resonance droplet forming unit 10 is not particularly limited. However, one liquid column resonance liquid chamber having 100 to 2000 liquid column resonance liquid chambers 11 is provided. The droplet forming unit 10 is preferable because both operability and productivity can be realized. In the present embodiment, a plurality of liquid column resonance liquid chambers 11 communicate with one liquid common supply path 14.

Further, the vibration generating means 15 in the droplet discharge section is not particularly limited as long as it can be driven at a predetermined frequency, but has a structure in which an elastic plate 15B is attached to the piezoelectric body 15A as in the present embodiment. preferable. The elastic plate 15B is provided so as to isolate the piezoelectric body 15A from the liquid column resonance liquid chamber 11 so that the piezoelectric body 15A does not come into contact with the liquid. As the piezoelectric body 15A, for example, piezoelectric ceramics such as lead zirconate titanate (PZT) can be cited. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO _{3, and the} like can be given. Furthermore, it is desirable that the vibration generating means 15 is arranged so that it can be individually controlled for each liquid column resonance liquid chamber 11. For example, a configuration in which one piezoelectric material is divided into a plurality of piezoelectric bodies in accordance with the arrangement of the liquid column resonance liquid chamber 11 and each liquid column resonance liquid chamber can be individually controlled by each piezoelectric body is preferable.

  The outlet side diameter of the discharge hole 12 is desirably in the range of 1 [μm] to 40 [μm]. If it is smaller than 1 [μm], the formed droplets will be very small, and toner may not be obtained. In particular, when solid fine particles such as a pigment are contained as a constituent component of the toner, the solid fine particles may block the discharge holes 12, which may reduce toner productivity. On the other hand, when the particle diameter is larger than 40 [μm], the droplet diameter is large. Therefore, when it is dried and solidified to obtain a toner particle diameter of 3 [μm] or more and 6 [μm] or less, the toner composition is formed with an organic solvent. Needs to be diluted to a very dilute solution. In this case, a large amount of drying energy is required to obtain a certain amount of toner, which is inconvenient.

  Further, in the present embodiment, as shown in FIG. 3, the row of the discharge holes in which the plurality of discharge holes 12 are arranged (see FIG. 2) is arranged in the width direction in the liquid column resonance liquid chamber 11 (the horizontal direction in FIG. 3). ) Are arranged in parallel. With such a configuration, more liquid droplets can be ejected by a single ejection operation, which increases production efficiency. Since the liquid column resonance frequency varies depending on the arrangement of the discharge holes 12, it is desirable that the liquid column resonance frequency is appropriately determined while confirming the discharge of the droplet.

  4A to 4D are cross-sectional views illustrating various cross-sectional shapes that can be adopted as the cross-sectional shape of the discharge hole 12. In the present embodiment, the case where the cross-sectional shape of the discharge hole 12 is a tapered shape whose diameter decreases toward the outlet side as shown in FIG. 2 is illustrated, but this cross-sectional shape is appropriately selected. can do.

  The cross-sectional shape of the discharge hole 12 shown in FIG. 4A is a cross-sectional shape in which the diameter becomes narrower while having a round shape (curved shape) from the inlet side to the outlet side of the discharge hole 12. This cross-sectional shape maximizes the pressure applied to the liquid near the outlet of the discharge hole 12 when the discharge hole thin film 16 constituting the bottom wall portion of the liquid column resonance liquid chamber 11 in which the discharge hole 12 is formed vibrates. For this reason, it is a preferable shape for the stabilization of discharge.

  The cross-sectional shape of the discharge hole 12 shown in FIG. 4 (b) is a cross-sectional shape having a taper shape such that the diameter becomes narrower with a certain angle from the inlet side to the outlet side of the discharge hole 12. The embodiment is employed. In this cross-sectional shape, since it is a tapered shape, like the cross-sectional shape shown in FIG. 4A, the liquid is applied near the outlet of the discharge hole 12 when the discharge hole thin film 16 vibrates. The pressure can be increased. The nozzle angle 17 which is the taper angle can be changed as appropriate, but is preferably in the range of more than 60 ° and 90 ° or less. This is because when the nozzle angle 17 is 60 ° or less, it is difficult to apply pressure to the liquid, and further, it is difficult to process the discharge hole thin film 16. On the other hand, when the nozzle angle 17 is 90 °, the cross-sectional shape as shown in FIG. 4C is obtained, but since it is difficult for pressure to be applied near the outlet of the discharge hole 12, a suitable angle range of the nozzle angle 17 is obtained. As a result, 90 ° is the maximum value. When the nozzle angle 17 is larger than 90 °, no pressure is applied near the outlet of the discharge hole 12, so that the droplet discharge becomes very unstable.

  The sectional shape of the discharge hole 12 shown in FIG. 4D is a combination of the sectional shape shown in FIG. 4A and the sectional shape shown in FIG. In this way, the cross-sectional shape may be changed step by step.

Next, the mechanism of droplet formation by the liquid column resonance droplet forming unit 10 will be described.
First, the principle of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber 11 in the droplet discharge section shown in FIG. 2 will be described.
When the sound velocity of the toner component liquid in the liquid column resonance liquid chamber is “c” and the driving frequency given to the toner component liquid as a medium from the vibration generating unit 15 is “f”, the wavelength λ at which the liquid resonance occurs is It can be calculated from the following equation (1).
λ = c / f (1)

In the present embodiment, the side wall (opening side wall) of the liquid column resonance liquid chamber 11 in which the communication path for communicating with the liquid common supply path 14 is formed is the opposite side wall (where the communication path is not formed) ( It can be considered that it is equivalent to the closed side wall. In this case, when the length L in the longitudinal direction of the liquid column resonance liquid chamber 11 coincides with an even multiple of 1/4 of the wavelength λ, the liquid in the liquid column resonance liquid chamber 11 is changed by the vibration of the vibration generating means 15. Resonant vibration occurs most efficiently. The optimum liquid column resonance condition in which such liquid column resonance occurs most efficiently can be expressed by the following equation (2). Note that the optimum condition of the liquid column resonance shown in the above equation (2) holds true even when the both side walls in the longitudinal direction of the liquid column resonance liquid chamber 11 are completely opened.
L = (N / 4) × λ (2)

  On the other hand, when one of the longitudinal side walls of the liquid column resonance liquid chamber 11 is open and the other is closed, the length L of the liquid column resonance liquid chamber 11 is the wavelength. Liquid column resonance is most efficiently formed when it coincides with an odd multiple of λ. In other words, the optimum condition for liquid column resonance in this case is expressed by an odd number of “N” in the above formula (2).

The driving frequency f with the highest liquid column resonance efficiency is represented by the following equation (3) from the above equations (1) and (2). However, in reality, since the liquid has a viscosity that attenuates resonance, the vibration is not amplified infinitely. It has a Q value and, as shown in equations (4) and (5) described later, the above equation Resonance also occurs at a frequency in the vicinity of the most efficient drive frequency f shown in (3).
f = N × c / (4L) (3)

FIGS. 5A to 5D are explanatory diagrams for explaining the standing wave of the velocity distribution and the pressure distribution generated in the liquid in the liquid column resonance liquid chamber 11 when N = 1, 2, and 3. FIG.
However, FIG. 5A is an example in the case of N = 1, where one of the longitudinal ends of the liquid column resonance liquid chamber 11 is open and the other is closed. . FIG. 5B shows an example where N = 2 and both ends in the longitudinal direction of the liquid column resonance liquid chamber 11 are closed. Further, FIG. 5C shows an example in which N = 2 and both end portions in the longitudinal direction of the liquid column resonance liquid chamber 11 are open. FIG. 5D is an example in the case of N = 3, where one of the longitudinal ends of the liquid column resonance liquid chamber 11 is open and the other is closed. .

FIGS. 6A to 6C are explanatory diagrams for explaining the standing wave of the velocity distribution and the pressure distribution generated in the liquid in the liquid column resonance liquid chamber 11 when N = 4 and 5. FIG. FIG.
However, FIG. 6A shows an example where N = 4 and both end portions in the longitudinal direction of the liquid column resonance liquid chamber 11 are closed. FIG. 6B shows an example in which N = 4 and both end portions in the longitudinal direction of the liquid column resonance liquid chamber 11 are open. Further, FIG. 6C is an example in the case of N = 5, where one of the longitudinal ends of the liquid column resonance liquid chamber 11 is open and the other is closed. .

  In FIGS. 5 and 6, the solid line represents the velocity standing wave, and the dotted line represents the pressure standing wave. In addition, the wave generated in the liquid in the liquid column resonance liquid chamber 11 is actually a sparse wave (longitudinal wave), but in FIG. 5 and FIG. 6, this is expressed in the form of a sine wave (cosine wave). . For example, when looking at the velocity distribution of FIG. 5A, it can be intuitively understood that the amplitude of the velocity distribution becomes zero at the closed side wall portion that is closed, and the amplitude becomes maximum at the opened side wall portion, Since it is easy to understand, sine wave notation is used here. Since the standing wave pattern differs depending on the open / closed state of the both side walls in the longitudinal direction (combination pattern of the open end and the fixed end), in FIG. 5 and FIG. The combination pattern of the open end and the fixed end that do not match 11 is also shown.

  As will be described in detail later, the end condition is determined by the state of the opening of the discharge hole 12 and the opening of the communication path that connects the liquid column resonance liquid chamber 11 and the liquid common supply path 14. In acoustics, at the open end (open end), the moving speed of the medium (liquid) in the longitudinal direction is maximum, and the pressure is zero. On the other hand, at the fixed end (closed end), on the contrary, the moving speed of the medium becomes zero and the pressure becomes maximum. The fixed end (closed end) is considered as an acoustically hard wall, and on the assumption that the wave is completely reflected, if the end is ideally completely closed or open, the wave is overlapped. It is assumed that a standing wave as shown in FIG. 6 is generated. If there are openings such as the discharge holes 12 and the communication passages as in the liquid column resonance liquid chamber 11 of the present embodiment, the number of the discharge holes 12, the positions of the discharge holes 12, the size and position of the communication passages, and the like. However, the standing wave pattern fluctuates. Therefore, the actual resonance frequency appears at a position shifted from the ideal resonance frequency obtained from the above equation (3). However, even if there is such a shift, there is no problem because the drive frequency may be adjusted as appropriate while confirming the actual discharge state.

  1200 [m / s] is used as the sound velocity c of the liquid, and the longitudinal length L of the liquid column resonance liquid chamber 11 is 1.85 [mm]. In the case of N = 2 resonance mode equivalent to a model in which walls are present at both ends in the longitudinal direction and both ends are fixed ends, it is most efficient for the liquid in the liquid column resonance liquid chamber 11 from the above equation (2). The ideal resonance frequency that causes liquid column resonance is derived as 324 [kHz]. On the other hand, 1200 [m / s] is used as the sound velocity c of the liquid, and the longitudinal length L of the liquid column resonance liquid chamber 11 is 1.85 [mm]. In the case of N = 4 resonance mode equivalent to a model in which walls are present at both ends and both ends are fixed ends, the liquid in the liquid column resonance liquid chamber 11 is most efficiently liquidated from the above equation (2). The ideal resonance frequency that causes column resonance is derived as 648 [kHz]. Thus, higher-order resonance can be used also in the liquid column resonance liquid chamber 11 having the same configuration.

  The liquid column resonance liquid chamber 11 of the present embodiment has a configuration in which both ends in the longitudinal direction are equivalent to the closed end, or a configuration that can be described as an acoustically soft wall due to the opening of the discharge hole 12. It is preferable for increasing the resonance frequency. However, the configuration is not limited thereto, and for example, a configuration in which both ends in the longitudinal direction are equivalent to the open ends may be employed. The influence of the opening of the discharge hole 12 here means that the acoustic impedance is reduced, and in particular, the compliance component is increased. As shown in FIG. 3, the discharge hole 12 provided in the liquid column resonance liquid chamber 11 of the present embodiment is disposed so as to be close to one end side in the longitudinal direction (the side opposite to the liquid common supply path 14). Therefore, the one end side can be regarded as an open end (open end) due to the influence of the opening of the discharge hole 12. As a result, when both end walls in the longitudinal direction of the liquid column resonance liquid chamber 11 are equivalent to closed ends as shown in FIGS. 5B and 6A, only the resonance mode in which both ends are fixed ends is used. It is also possible to use a resonance mode in which one end is an open end and the other end is a fixed end.

  In addition, the number of ejection holes 12, the arrangement of the ejection holes 12, and the cross-sectional shape of the ejection holes 12 are also factors that determine the driving frequency, and the driving frequency can be appropriately determined according to this. For example, the closer the arrangement of the discharge holes 12 is to the one end side in the longitudinal direction, the looser the restraint by the wall portion of the liquid column resonance liquid chamber 11 at the end portion in the longitudinal direction. Therefore, as the arrangement of the ejection holes 12 is moved closer to one end in the longitudinal direction, the end in the longitudinal direction is almost close to the opening end, and the drive frequency is changed. Further, for example, when the number of the discharge holes 12 is increased, the restriction by the wall portion of the liquid column resonance liquid chamber 11 becomes loose at one end in the longitudinal direction where the arrangement of the discharge holes 12 is approached, and the end in the longitudinal direction is almost the open end. It is changed so that the drive frequency becomes high in a state close to. In addition, for example, when the cross-sectional shape of the discharge hole 12 is changed or the dimension of the discharge hole 12 is changed, the drive frequency needs to be changed.

When an AC voltage is applied to the vibration generating means 15 at the drive frequency determined in this way, the piezoelectric body 15A of the vibration generating means 15 is deformed according to the voltage fluctuation, and thereby the elastic plate 15B is displaced. As a result, vibration corresponding to the drive frequency is applied to the liquid in the liquid column resonance liquid chamber 11, and a liquid column resonance standing wave is generated in the liquid in the liquid column resonance liquid chamber 11. However, if the liquid column resonance standing wave has a frequency close to the drive frequency at which it is most efficiently generated, the liquid column resonance standing wave is generated. Specifically, when the distance between the longitudinal wall on the liquid common supply path 14 side and the discharge hole arranged closest to the liquid common supply path 14 is Le, the length of the liquid column resonance liquid chamber is defined as Le. The length L between the directional walls is used. The range of the driving frequency f for generating the liquid column resonance standing wave can be defined by, for example, the following equations (4) and (5). By vibrating the vibration generating means 15 using a drive waveform whose main component is the drive frequency f within the range determined by these equations (4) and (5), liquid column resonance is induced to cause the droplet to It is possible to discharge appropriately from the discharge hole 12. However, the ratio of L to Le is preferably Le / L> 0.6.
N × c / (4L) ≦ f ≦ N × c / (4Le) (4)
N × c / (4L) ≦ f ≦ (N + 1) × c / (4Le) (5)

  In the present embodiment, using the principle of the liquid column resonance phenomenon described above, a liquid column resonance pressure standing wave is formed in the liquid column resonance liquid chamber 11 shown in FIG. Thus, continuous droplet discharge is caused from the discharge hole 12. Therefore, it is preferable to dispose the discharge hole 12 at a position where the standing wave of the pressure fluctuates the most, because the discharge efficiency is increased and the drive voltage can be further suppressed.

  Further, one discharge hole 12 may be provided for one liquid column resonance liquid chamber 11, but it is preferable from the viewpoint of productivity that a plurality of discharge holes 12 be arranged for one liquid column resonance liquid chamber 11 as described above. Specifically, it is preferably between 2 and 100. When the number exceeds 100, if the droplets are to be appropriately ejected from the respective ejection holes 12, it is necessary to set a high drive voltage to the vibration generating means 15, and the behavior of the piezoelectric body 15A of the vibration generating means 15 is changed. Prone to instability.

  Moreover, when forming the several discharge hole 12 with respect to one liquid column resonance liquid chamber 11, it is preferable that the pitch between discharge holes is 20 [micrometers] or more. When the pitch between the discharge holes is smaller than 20 [μm], there is a high probability that the liquid droplets discharged from the adjacent discharge holes come into contact with each other to form large liquid droplets, and the toner particle size distribution deteriorates. This is because the possibility increases.

Next, the state of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber 11 in the droplet discharge unit in the liquid column resonance droplet forming unit 10 will be described.
FIGS. 7A to 7D are explanatory views schematically showing the state of the liquid column resonance phenomenon that occurs in the liquid column resonance liquid chamber 11.
7 indicates the velocity distribution obtained by plotting the velocity at an arbitrary measurement position in the longitudinal direction of the liquid column resonance liquid chamber 11. The direction from the closed side wall portion on the left side in the figure to the open side wall portion on the right side in the figure is positive, and the opposite direction is negative. Further, the dotted line shown in the liquid column resonance liquid chamber 11 in FIG. 7 shows the pressure distribution obtained by plotting the pressure value at an arbitrary measurement position in the longitudinal direction of the liquid column resonance liquid chamber 11. Positive pressure is positive with respect to atmospheric pressure, negative pressure is negative.

  In this embodiment, as shown in FIG. 2, the height h1 (= from the bottom surface of the liquid column resonance liquid chamber 11 in the droplet discharge section to the lower end of the communication path communicating with the common liquid supply path 14 in FIG. About 80 [μm]) is set to about twice the height h2 (= about 40 [μm]) of the communication port. Therefore, the liquid column resonance liquid chamber 11 of the present embodiment can be approximately considered that both ends in the longitudinal direction are substantially fixed ends. 7A to 7D show temporal changes in the velocity distribution and the pressure distribution under such an idea.

  FIG. 7A shows a pressure waveform and a velocity waveform in the liquid column resonance liquid chamber 11 when droplets are discharged. At this time, the pressure of the liquid portion on the closed side wall portion side in the liquid column resonance liquid chamber 11, that is, the liquid portion in the liquid chamber region where the discharge hole 12 is provided (liquid in the vicinity of the discharge hole) becomes maximum. . As a result, the meniscus pressure increases, and the liquid comes out from each discharge hole 12. Thereafter, as shown in FIG. 7B, the pressure of the liquid in the vicinity of the discharge hole 12 decreases, and the liquid droplet 13 is discharged from the discharge hole 12 by shifting in the negative pressure direction.

  Thereafter, as shown in FIG. 7C, the pressure of the liquid in the vicinity of the ejection hole 12 becomes minimum. From this time, replenishment of the toner component liquid from the liquid common supply path 14 to the liquid column resonance liquid chamber 11 starts. Then, as shown in FIG. 7D, the pressure of the liquid in the vicinity of the discharge hole 12 gradually increases and shifts in the positive pressure direction. At this time, the replenishment of the toner component liquid is completed, and the pressure of the liquid near the discharge hole 12 of the liquid column resonance liquid chamber 11 again becomes a maximum as shown in FIG.

  As described above, in the liquid near the discharge hole 12 in the liquid column resonance liquid chamber 11, a standing wave due to the liquid column resonance is generated by the high frequency driving of the vibration generating means 15, and the pressure is the position where the pressure fluctuates most greatly. Discharge holes 12 are arranged at locations corresponding to antinodes of standing waves due to liquid column resonance. From these things, the droplet 13 is continuously discharged from the discharge hole 12 according to the period of the belly.

  The toner of the present invention contains at least a binder resin, and optionally contains a colorant, a wax, a charge adjusting agent, an additive, and other components.

(Binder resin)
One feature of the toner production method of the present invention is that a toner raw material containing at least a binder resin is dispersed in an aqueous medium. This production method is not particularly defined and includes a generally used apparatus having a wet crushing function. For example, batch type emulsifiers such as homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (manufactured by Akihara Seisakusho), TK Philmix, TK pipe Line homomixer (manufactured by Koki Kogyo Kogyo Co., Ltd.), colloid mill (manufactured by Shinko Pantech Co., Ltd.), thrasher, trigonal wet pulverizer (manufactured by Mitsui Miike Chemical Co., Ltd.), Cavitron (manufactured by Eurotech Co., Ltd.), fine Continuous emulsifiers such as Flow Mill (manufactured by Taiheiyo Kiko Co., Ltd.), Microfluidizer (manufactured by Mizuho Kogyo Co., Ltd.), Nanomizer (manufactured by Nanomizer Co., Ltd.), APV Gaurin (manufactured by Gaulin Co., Ltd.) ), Nanovaita (Yoshida Kikai Kogyo Co., Ltd.) and other high-pressure emulsifiers, membrane emulsifiers Membrane emulsifiers such as Chilling Industries Co., Ltd., vibratory emulsifiers such as Vibro mixer (Chilling Industries Co., Ltd.), ultrasonic emulsifiers such as ultrasonic homogenizer (Branson Co., Ltd.), Starmill (Ashizawa Fine) Media type pulverizers such as a bead mill, a ball mill, and a paint shaker. Among these, an apparatus having a mechanism that pushes and collides against the pores with a plunger pump at a high pressure is excellent in terms of processing efficiency and crushability. Examples of such devices include Starburst made by Sugino Machine and Nanovaita made by Yoshida Kikai Kogyo. By using the apparatus, the binder resin can be crushed and refined without being dissolved in an organic solvent. In this crushing and dispersing process, heating and cooling may be performed as necessary.

  Specific examples of such toner binder resins are not particularly limited, and can be appropriately selected from those known as toner binder resins. For example, vinyl polymers such as styrene monomers, acrylic monomers, methacrylic monomers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins , Silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, terpene resin, coumarone indene resin, polycarbonate resin, petroleum resin, and the like.

Among these, when the main component of the adhesive base material in the toner is a polyester resin, compatibility is improved at the time of fixing, and glossiness is improved when used in a low-temperature fixing property or a full-color image forming apparatus. In this respect, a polyester resin is preferable. The polyester resin used in the present invention preferably contains both an amorphous polyester resin and a crystalline polyester resin, and the contents Ta and Tc with respect to the total amount T of the binder resin preferably satisfy the following relationship.
0.5 <Ta / T <0.97
0.03 <Tc / T <0.50
By satisfying this relationship, it is possible to provide a low-temperature fixing toner that exhibits the effects of the sharp melt property of the crystalline polyester resin and the heat resistance of the amorphous polyester resin, and is excellent in heat-resistant storage stability.

As the amorphous polyester resin used in the present invention, the general formula (1)
A- (OH) m (1)
[Wherein, A represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, or an aromatic group or heterocyclic aromatic group which may have a substituent. m represents an integer of 2 to 4. And one or more polyols represented by the general formula (2)
B- (COOH) n (2)
[Wherein, B represents an alkyl group having 1 to 20 carbon atoms, an alkylene group, or an aromatic group or heterocyclic aromatic group which may have a substituent. n represents an integer of 2 to 4. ] One or two or more kinds of polycarboxylic acids represented by the following formula:

  Specific polyols represented by the general formula (1) include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol. 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2 , 3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2- Tylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide Examples include adducts, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct, and the like.

  Specific polycarboxylic acids represented by the general formula (2) include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid. Azelaic acid, malonic acid, n-dodecenyl succinic acid, isooctyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, Isooctyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5 -Hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxyprop 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, Examples include butanetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and ethylene glycol bis (trimellitic acid).

  There is no restriction | limiting in particular as crystalline polyester resin used by this invention, Although it can select suitably according to the objective, A divalent alcohol (diol) component and a divalent acid (dicarboxylic acid) component are the main components. A linear resin synthesized as is preferable in that crystallinity is easily obtained.

  There is no restriction | limiting in particular as a bivalent alcohol, According to the objective, it can select suitably according to the objective, For example, a C2-C12 saturated aliphatic diol compound etc. are mentioned. These may be used alone or in combination of two or more. Specific examples of the divalent alcohol include 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, and derivatives thereof. Is mentioned.

  There is no restriction | limiting in particular as a bivalent acid, According to the objective, it can select suitably according to the objective, For example, C2-C12 dicarboxylic acid which has a double bond (C = C bond), Examples thereof include saturated dicarboxylic acids having 2 to 12 carbon atoms. These may be used alone or in combination of two or more.

  Specific examples of the divalent acid include fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1,12-dodecane. Examples thereof include diacids and derivatives thereof. The method for synthesizing the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method in which an alcohol component and an acid component are subjected to a polycondensation reaction under an appropriate catalyst. It is done.

  There is no restriction | limiting in particular as melting | fusing point of crystalline polyester resin, Although it can select suitably according to the objective, 50 [degrees C]-130 [degrees C] are preferable, and 50 [degrees C]-100 [degrees C] are more preferred. . If the melting point of the crystalline polyester resin is less than 50 [° C.], the storage stability of the toner may be deteriorated, and if it exceeds 130 [° C.], fixing may be impossible at a low temperature.

The melting point can be measured by differential scanning calorimetry (DSC).
Specifically, about 10 mg of a sample is placed in an aluminum sample container, placed on a holder unit, and set in an electric furnace. First, after heating from room temperature to 150 [° C.] at a heating rate of 10 [° C./min], left at 150 [° C.] for 10 minutes, cooled to room temperature, left for 10 minutes, and again under a nitrogen atmosphere. DSC measurement is performed by heating to 150 [° C.] at a heating rate of 10 [° C./min]. Melting | fusing point is made into melting | fusing point by calculating | requiring the melting peak temperature of crystalline polyester using the analysis system of a differential scanning calorimeter. The crystalline polyester resin has a crystal structure in which molecules are regularly arranged to a certain degree below the melting point temperature. When the temperature is higher than the melting point temperature, this crystal structure collapses, takes a random structure, and becomes a molten state. Therefore, in differential scanning calorimetry (DSC), it indicates a clear endothermic peak, not a stepwise endothermic change.

  There is no restriction | limiting in particular as an acid value of binder resin, Although it can select suitably according to the objective, 0 mgKOH / g-70 mgKOH / g are preferable, and 1.0 mgKOH / g-50 mgKOH / g are more preferable. If the acid value exceeds 70 mgKOH / g, the environmental fluctuation of charging may become large.

The acid value can be measured, for example, by the following method according to JIS K-0070 for basic operation.
(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 [g] to 2.0 [g] is precisely weighed, and the weight of the polymer component is defined as W [g]. 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 in a 300 [mL] beaker, and 150 [mL] of a mixed solution of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 [mol / L] KOH.
(4) The amount of KOH solution used at this time is set to S [mL], a blank is measured at the same time, and the amount of KOH solution used at this time is set to B [mL]. However, f is a factor of KOH.
Acid value [mgKOH / g] = [(SB) × f × 5.61] / W

(Aqueous medium)
In the present invention, the toner liquid is constituted by crushing or dispersing the material constituting the toner in an aqueous medium. The aqueous medium is not particularly limited as long as it contains at least water, and can be appropriately selected according to the purpose. However, it contains at least a surfactant from the viewpoint of wettability and dispersion stability of the toner material. Is preferred. Specific examples of the surfactant include, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. Among these, an anionic surfactant is preferably used for controlling the chargeability and cohesion of the toner.

  Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, anionic surfactants having a fluoroalkyl group, and those having a fluoroalkyl group are preferred. Can be mentioned. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, perfluorooctanesulfonyl glutamate disodium, 3- [omega-fluoroalkyl (6 to 6 carbon atoms). 11) Sodium oxy] -1-alkyl (3 to 4 carbon atoms) sulfonate, sodium 3- [omega-fluoroalkanoyl (6 to 8 carbon atoms) -N-ethylamino] -1-propanesulfonate, fluoroalkyl ( Carbon number 11-20) carboxylic acid or metal salt thereof, perfluoroalkyl carboxylic acid (carbon number 7-13) or metal salt thereof, perfluoroalkyl (carbon number 4-12) sulfonic acid or metal salt thereof, perfluorooctane Sulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Chill) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC -129 (manufactured by Sumitomo 3M Co., Ltd.); Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F-191, F-812, F- 833 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); 100, F150 (manufactured by Neos) and the like.

  The material constituting the toner in the present invention is not particularly limited as long as the toner can be formed, and can be appropriately selected according to the purpose. For example, in addition to the binder resin, a colorant and a wax may be included, and, if necessary, other components such as a wax dispersant and a charge control agent are included. Here, these materials may be introduced into the binder resin in advance, or may be added to the aqueous medium as an aqueous dispersion. Examples of means for introducing the binder resin into the binder resin in advance include a method of mixing or kneading the binder resin and one or more of these toner constituting materials by applying a high shear force. In this case, for example, the binder resin and the powder of the toner constituting material are mechanically mixed using a normal mixer using a rotating blade, and the mixture is then charged into a kneader and melt-kneaded. As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. It is important that this melt-kneading is performed under appropriate conditions that do not cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature should be performed with reference to the softening point of the binder resin. If the temperature is too low than the softening point, cutting is severe, and if the temperature is too high, dispersion does not proceed.

  Examples of means for preparing an aqueous dispersion include a method in which one or two or more of these toner constituent materials are dispersed in an aqueous phase containing at least a surfactant. As this dispersion treatment method, for example, a batch type emulsifier such as a homogenizer (manufactured by IKA), polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (manufactured by Aihara Seisakusho) , TK Philmix, TK Pipeline Homomixer (manufactured by Special Machine Industries Co., Ltd.), Colloid Mill (manufactured by Shinko Pantech Co., Ltd.), Thrasher, Trigonal Wet Fine Crusher (manufactured by Mitsui Miike Chemical Industries, Ltd.), Cavitron ( Eurotech), continuous emulsifiers such as Fine Flow Mill (Pacific Kiko Co., Ltd.), Microfluidizer (Mizuho Kogyo Co., Ltd.), Nanomizer (Nanomizer Co., Ltd.), APV Gaurin (Gaulin Inc.), Star Burst (manufactured by Sugino Machine Co., Ltd.), Nanovaita (manufactured by Yoshida Machine Industry Co., Ltd.) High-pressure emulsifiers such as membrane emulsifiers such as membrane emulsifiers (made by Chilling Industries Co., Ltd.), vibratory emulsifiers such as Vibro mixers (made by Chilling Industries Co., Ltd.), ultrasonic homogenizers (made by Branson), etc. Media type pulverizers such as a bead mill such as an ultrasonic emulsifier and a star mill (manufactured by Ashizawa Finetech Co., Ltd.), a ball mill, and a paint shaker are included, but not limited thereto.

[Colorant]
There is no restriction | limiting in particular as a coloring agent, The coloring agent normally used as a toner can be selected suitably, and can be used.

  The content of the colorant is preferably 1 to 15 [% by mass] and more preferably 3 to 10 [% by mass] based on the toner.

<Wax>
The toner component liquid used in the present invention can contain a wax together with a binder resin and a colorant.
The wax is not particularly limited and can be appropriately selected from commonly used ones such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, and sazol wax. Oxides of aliphatic hydrocarbon waxes such as aliphatic hydrocarbon waxes, polyethylene oxide waxes or block copolymers thereof, plant waxes such as candelilla wax, carnauba wax, wood wax, jojoba wax, beeswax, lanolin Waxes mainly composed of fatty acid esters such as animal waxes such as whale wax, mineral waxes such as ozokerite, ceresin, and petrolatum, and montanic acid ester waxes and castor waxes. Deoxidized carnauba wax and other fatty acid esters that have been partially or wholly deoxidized are included.

  The melting point of the wax is preferably 70 to 140 [° C.] and more preferably 70 to 120 [° C.] in order to balance the fixability and the offset resistance. If it is less than 70 [° C.], the blocking resistance may be lowered, and if it exceeds 140 [° C.], the offset resistance effect may be difficult to be exhibited.

  The total content of the wax is preferably 0.2 to 20 parts by mass and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

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

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

  In the toner according to the present invention, as other additives, protection of the electrostatic latent image carrier / carrier, improvement of cleaning properties, adjustment of thermal characteristics, electrical characteristics and physical characteristics, resistance adjustment, softening point adjustment, fixing rate For the purpose of improvement, various metal soaps, fluorosurfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductivity imparting agents, and inorganic such as titanium oxide, aluminum oxide, alumina A fine powder or the like can be added as necessary. These inorganic fine powders may be hydrophobized as necessary. In addition, lubricants such as polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, strontium titanate, anti-caking agents, white particles and black particles having opposite polarity to the toner particles, Can also be used in small amounts as a developability improver.

  These additives have a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicons for the purpose of charge control and the like. It is also preferable to treat with a treating agent such as a compound or various treating agents.

  As the additive, inorganic fine particles can be preferably used. As inorganic fine particles, for example, known ones such as silica, alumina and titanium oxide can be used.

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

  Such an external additive can be made hydrophobic by the surface treatment agent and prevent deterioration of the external additive itself even under high humidity. Examples of the surface treatment agent include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. Are preferable.

The primary particle diameter of the external additive is preferably 5 [nm] to 2 [μm], and more preferably 5 [nm] to 500 [nm]. Moreover, as a specific surface area by BET method, it is preferable that it is 20-500 [m < ² > / g]. The use ratio of the inorganic fine particles is preferably 0.01 to 5 [% by weight] of the toner, and more preferably 0.01 to 2.0 [% by weight].

  Examples of the cleaning property improver for removing the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymethyl methacrylate. There may be mentioned polymer fine particles produced by soap-free emulsion polymerization such as fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 [μm].

  Further, the toner obtained in the present invention needs to have a total concentration of organic solvents capable of dissolving the binder resin determined by the gas chromatography method of 30 [ppm] or less. As a method for measuring this concentration, for example, in the case of ethyl acetate, it is specifically determined by the following procedure.

Measuring equipment condition measuring device: GC? 2010 (Gas Chromatograph manufactured by Shimadzu Corporation), injection amount: 2.0 [μL], sample vaporization chamber injection mode: split vaporization chamber temperature: 180 ° C., carrier gas: He, pressure: 40. 2 [kPa], total flow rate: 56.0 [mL / min], column flow rate: 1.04 [mL / min], linear velocity: 20.0 [cm / sec], purge flow rate: 3.0 [mL / min min], split ratio: 50.0, column column name: ZB? 50, liquid phase film thickness: 0.25 [μm], length: 30.0 [m], inner diameter: 0.32 [mm], ID Column upper limit temperature: 340 [° C.], column oven column temperature: 60 [° C.], column oven temperature program: 60 [° C.] hold 6 [min] → heating rate 60 “° C./min”→230 [° C.] hold 5 [min], detector Detector temperature: 250 [° C.], makeup gas: N2 / Air, makeup flow rate: 30.0 [mL / min], H ₂ flow rate: 47.0 [mL / min], Air flow rate: 400 [mL / min], adjustment of standard solution in measurement method: Toluene 4 [g] is weighed into a volumetric flask and diluted to 500 [mL] with DMF. Preparation of measurement sample: After diluting 1.5 [g] of the emulsion to be measured to about 50 [mL] with DMF, the internal standard solution 10 [mL] is collected and introduced with a whole pipette. After stirring the measurement sample with a stirrer at 400 rpm for 4 minutes, the sample is set in the autosampler of the measuring instrument GC and measurement is performed. After the measurement, the amount of ethyl acetate in the toner is calculated by the internal standard method from the ratio of toluene and ethyl acetate as the internal standard material.

  EXAMPLES The present invention will be specifically described below with reference to examples of the present invention, but the present invention is not limited to these examples.

(Synthesis Example 1: Synthesis of crystalline polyester resin 1)
1,6-hexanediol 0.8 mol and 1,5-pentanediol 0.2 mol as the alcohol component, fumaric acid 1 mol as the carboxylic acid component, tin octylate as the esterification catalyst, nitrogen introduction tube, dehydration Place in a 5 liter four-necked flask equipped with a tube, stirrer, and thermocouple. Then, after a polycondensation reaction is performed at 170 [° C.] for 4 hours in a nitrogen atmosphere, the temperature is raised to 200 [° C.] and the reaction is performed for 1 hour, and further the reaction is performed at 8 [kPa] for 1 hour. Polyester resin 1 was synthesized. The compounds used for the synthesis of the crystalline polyester resin 1 are summarized in Table 1 below.

(Synthesis Example 2: Synthesis of crystalline polyester resin 2)
In Synthesis Example 1, the alcohol component was changed to 0.8 mol of 1,6-hexanediol and 0.2 mol of 1,5-pentanediol, and instead of 0.1 mol of 1,5-pentanediol, 1,4-butane A crystalline polyester resin 2 was synthesized in the same manner as in Synthesis Example 1 except that 0.9 mol of diol was used and 1 mol of 1,8-octanedicarboxylic acid was used instead of 1 mol of fumaric acid. . The compounds used for the synthesis of the crystalline polyester resin 2 are summarized in Table 1 below.

(Synthesis Example 3: Synthesis of crystalline polyester resin 3)
In Synthesis Example 1, the alcohol component was replaced with 0.8 mol of 1,6-hexanediol and 0.2 mol of 1,5-pentanediol, and 1 mol of 1,6-hexanediol was used. A crystalline polyester resin 3 was synthesized in the same manner as in Synthesis Example 1 except that 0.9 mol of fumaric acid and 0.1 mol of 1,8 octanedicarboxylic acid were used instead of 1 mol of acid. The compounds used for the synthesis of the crystalline polyester resin 3 are summarized in Table 1 below.

(Synthesis Example 4: Synthesis of Amorphous Polyester Resin 1)
In Synthesis Example 1, the alcohol component was replaced with 0.8 mol of 1,6-hexanediol and 0.2 mol of 1,5-pentanediol, and 0.7 mol of BPA-PO and 0.3 mol of BPA-EO were used. Amorphous polyester resin 1 was synthesized in the same manner as in Synthesis Example 1 except that 0.9 mol of terephthalic acid and 0.07 mol of trimetic anhydride were used instead of 1 mol of fumaric acid. The compounds used for the synthesis of the amorphous polyester resin 1 are summarized in Table 1 below.

<Confirmation of physical properties>
Number average molecular weight (Mn), weight average molecular weight (Mw) of crystalline polyester resins 1 to 3 and amorphous polyester resin 1 synthesized in Synthesis Examples 1 to 4, flow tester T1 / 2, melting point, and glass transition point ( Tg) was measured by the following method.

(Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw))
Each resin synthesized in Synthesis Examples 1 to 6 was added to hexafluoroisopropanol (HFIP) [concentration 0.005 M (mol / L) -CF ₃ COONa / HFIP] to which sodium trifluoroacetate (CF ₃ COONa) was added. After dissolving at 06% (wt / vol), the solution was filtered through a 0.45 [μm] -Millex-LH (Millipore) filter to prepare a GPC sample. The sample thus prepared was measured using GPC under the following conditions. The results are shown in Table 2 below.
[GPC measurement conditions]
Apparatus: Gel permeation chromatograph GPC-7 (manufactured by Waters)
Column: Shodex HFIP-806M (inner diameter 8.0 mm / length 30 cm) × 2 (manufactured by Showa Denko KK)
Flow rate: 0.5 [mL / min]
Temperature: 23 [° C]
Injection volume: 300 [μL]
Detector: Differential refractive index detector R-401 (manufactured by Waters)
Molecular weight calibration: Monodisperse polymethyl methacrylate (PMMA) standard sample (manufactured by Showa Denko KK)

(Measurement of flow tester T1 / 2)
The flow tester T1 / 2 is the melting temperature in the 1/2 method.
A pellet-like sample is produced by pressure molding using 1.0 g of each of the resins synthesized in Synthesis Examples 1-6. And using a flow tester (elevated flow tester CFT500 type, manufactured by Shimadzu Corporation), the softening point (Tf1 / 2), the difference between the outflow start temperature (Tfb) and the outflow end temperature (Tend) (Tend−Tfb) ) Was measured under the following conditions. The results are shown in Table 2 below.
[Flow tester measurement conditions]
Load: 30 [kg / cm ² ]
Temperature increase rate: 3.0 [° C./min]
Die diameter: 0.50 [mm]
Die length: 1.0 "mm"
Tf1 / 2 calculation method: 1/2 method

(Measurement of melting point and glass transition point)
The melting point of each resin synthesized in Synthesis Examples 1 to 3 and the glass transition point of the resin synthesized in Synthesis Example 4 are each 10 [mg] and packed into an aluminum cell. And it measured on condition of the following using the differential scanning calorimeter (DSC) (automatic differential scanning calorimeter DSC-60A, Shimadzu Corporation make). The melting point was the endothermic peak of the DSC curve at the second temperature rise, and the glass transition temperature was the endothermic start temperature of the endothermic shoulder (the temperature of the tangent before the endotherm and the intersection point after the endotherm). The results are shown in Table 2 and Table 3 below.
[Differential scanning calorimeter measurement conditions]
Measurement temperature: 0 [° C.] to 200 [° C.]
Temperature increase rate: 10 [° C./min]

(Adjustment Example 1-1 Adjustment of Crystalline Polyester Dispersion 1)
In a container in which a stirring blade and a thermometer are set, 20 parts by mass of crystalline polyester 1, 78 parts by mass of ion-exchanged water, and 2 parts by mass of an anionic surfactant (Eleminol MON-7: manufactured by Sanyo Kasei) are charged. Then, the mixture was heated to 85 [° C.] and stirred for 20 minutes to dissolve the crystalline polyester 1, and then rapidly cooled to precipitate the fine particles of the crystalline polyester 1. This dispersion was further finely crushed and dispersed by treating for 3 hours using a bead mill (LMZ06, manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconia beads having a diameter of 0.3 [mm]. The volume average particle size of the obtained dispersion was measured using a laser diffraction / scattering particle size distribution analyzer (LA-950, manufactured by HORIBA, Ltd.) and found to be 0.38 [μm] and 1 [μm]. The above particles were not confirmed.

(Adjustment Examples 1-2 to 1-3 Adjustment of Crystalline Polyester Dispersions 2-3)
Crystalline polyester dispersions 2-3 were prepared in the same manner except that the crystalline polyester 1 in Preparation Example 1-1 was changed to crystalline polyesters 2-3. The particle size distribution measurement results of the obtained crystalline polyester dispersion are summarized in Table 4 below.

(Adjustment Example 1-4 Preparation of Crystalline Polyester Solution 1)
In a container in which a stirring blade and a thermometer are set, 20 parts by mass of crystalline polyester 1 and 80 parts by mass of ethyl acetate are added, heated to 85 [° C.] and stirred for 20 minutes to dissolve crystalline polyester 1. Then, it was gradually cooled with stirring to 30 [° C.] to obtain a crystalline polyester solution 1. The obtained crystalline polyester solution was transparent, and no resin was deposited.

(Adjustment Examples 1-5 to 1-6 Adjustment of Crystalline Polyester Solution 2-3)
Crystalline polyester solutions 2 to 3 were prepared in the same manner except that the crystalline polyester 1 in Preparation Example 1-4 was changed to crystalline polyesters 2 to 3. The obtained crystalline polyester solution 2 to 3 was transparent, and no resin deposition was observed.

(Adjustment Example 2-1 Adjustment of Amorphous Polyester Dispersion 1)
Amorphous polyester 1 was finely pulverized with an ACM pulverizer (manufactured by Hosokawa Micron Corporation). The obtained pulverized product was passed through a sieve having a mesh opening of 75 [μm], and the passing part of the sieve was collected to obtain a pulverized product of amorphous polyester 1. 20 parts by mass of the obtained pulverized amorphous polyester 1 and 71 parts by mass of ion-exchanged water and 2 parts by mass of an anionic surfactant (Eleminol MON-7: manufactured by Sanyo Kasei) were used as a pH adjuster. 7 parts by mass of a mass% aqueous sodium hydroxide solution is added and heated to 85 [° C.]. Then, an amorphous polyester dispersion 1 was obtained by passing 50 passes at a pressure of 180 [MPa] with a collision type generator using a high-pressure emulsification / pulverization apparatus (Nano Veita: manufactured by Yoshida Kikai Kogyo Co., Ltd.). At this time, the pipe after passing through the generator was immersed in a chiller filled with a refrigerant, so that the dispersion was always circulated in a range of 70 [° C.] to 90 [° C.]. The particle size distribution measurement results of the obtained amorphous polyester dispersion 1 are summarized in Table 4 below.

(Adjustment Example 2-2 Adjustment of Amorphous Polyester Dispersion 2)
Amorphous polyester 1 was finely pulverized with an ACM pulverizer (manufactured by Hosokawa Micron Corporation). The obtained pulverized product was passed through a sieve having a mesh opening of 75 [μm], and the passing part of the sieve was collected to obtain a pulverized product of amorphous polyester 1. 20 parts by weight of the obtained pulverized amorphous polyester 1 and 71 parts by weight of ion-exchanged water and 2 parts by weight of an anionic surfactant (Eleminol MON-7: manufactured by Sanyo Chemical Co., Ltd.) were added as pH adjusters. 7 parts by mass of a mass% aqueous sodium hydroxide solution is added and heated to 85 [° C.]. And it was made to disperse | distribute for 45 minutes at 10,000 [rpm] at flow volume 3 [L / m] using the emulsification apparatus (Cabitron CD1010 by Taiheiyo mechanism), and the amorphous polyester dispersion liquid 2 was obtained. The particle size distribution measurement results of the obtained amorphous polyester dispersion 2 are summarized in Table 4 below.

(Adjustment Example 2-3 Preparation of Amorphous Polyester Solution 1)
Amorphous polyester solution by adding 20 parts by mass of amorphous polyester 1 and 80 parts by mass of ethyl acetate to a container in which a stirring blade and a thermometer are set, and stirring for 5 hours to dissolve amorphous polyester 1 1 was obtained. The obtained amorphous polyester solution was transparent, and no insoluble resin or precipitate was observed.

(Adjustment Example 3-1 Adjustment of Colorant Dispersion Liquid 1)
10 parts of carbon black (Regal 400, manufactured by Cabot) 88 parts of water 2 parts of sodium dodecyl sulfate was mixed as a surfactant, and dispersion treatment was performed for 2 minutes with an ultrasonic homogenizer. Next, this dispersion was used with a bead mill Ultra Visco Mill (manufactured by Imex Co., Ltd.) with a liquid feeding speed of 1 [kg / hour], a disk peripheral speed of 6 [m / sec] and a particle size of 0.5 [mm]. A colorant dispersion 1 was obtained by performing 10 passes under the condition of filling 80% by volume of zirconia beads. The particle size distribution measurement results of the obtained colorant dispersion 1 are summarized in Table 4 below.

(Adjustment Example 3-2 Adjustment of Colorant Dispersion Liquid 2)
10 parts by mass of amorphous polyester 1 finely pulverized with an ACM pulverizer (manufactured by Hosokawa Micron) and 10 parts of carbon black (Rega 1400, manufactured by Cabot) were uniformly mixed using a Henschel mixer. Next, the mixed material was melt-kneaded with an open roll kneader to obtain a master batch of a colorant. 20 parts by mass of the obtained master batch and 80 parts by mass of ethyl acetate were mixed and dissolved by stirring for 5 hours to obtain a colorant dispersion 2. The particle size distribution measurement results of the obtained colorant dispersion 1 are summarized in Table 4 below.

(Adjustment Example 4-1 Adjustment of wax dispersion 1)
Carnauba wax: 10 parts, water: 88 parts, 2 parts of sodium dodecyl sulfate as a surfactant are mixed in a container equipped with a stirring blade and a thermometer, heated to 85 [° C.], stirred for 20 minutes and waxed Dissolve completely. Thereafter, the mixture was rapidly cooled with stirring to prepare a dispersion liquid in which wax was finely precipitated. Next, this dispersion was used with a bead mill Ultra Visco Mill (manufactured by Imex Co., Ltd.) with a liquid feeding speed of 1 [kg / hour], a disk peripheral speed of 6 [m / sec] and a particle size of 0.5 [mm]. Wax dispersion 1 was obtained by performing 20 passes under the condition of filling 80% by volume of zirconia beads. The particle size distribution measurement results of the obtained wax dispersion 1 are summarized in Table 4 below.

(Adjustment Example 4-2 Adjustment of Wax Dispersion 2)
A container equipped with a stirring blade and a thermometer was charged with 10 parts of carnauba wax and 90 parts by mass of ethyl acetate, heated to 85 [° C.] and stirred for 20 minutes to dissolve the carnauba wax. Fine particles were precipitated. Next, this dispersion was used with a bead mill Ultra Visco Mill (manufactured by Imex Co., Ltd.) with a liquid feeding speed of 1 [kg / hour], a disk peripheral speed of 6 [m / sec] and a particle size of 0.5 [mm]. The wax dispersion 2 was obtained by performing 35 passes under the condition of filling 80% by volume of zirconia beads. The particle size distribution measurement results of the obtained wax dispersion 2 are summarized in Table 4 below.

(Adjustment Examples 5-1 to 5-13 Adjustment of Toner Composition Liquids 1 to 18)
Into a container in which a stirring blade and a thermometer were set, the respective liquids were charged in the blending amounts shown in Table 4 below, and toner compositions 1 to 18 were obtained by stirring and mixing in a state heated to 30 [° C.]. In any of the toner composition liquids, pigments and wax particles did not aggregate due to shock caused by solvent dilution.

(Toner production equipment)
The toner production apparatus 1 having the configuration shown in FIG. 1 was used, and toner was produced by using several ejection means as ejection means. The size and conditions of each component are shown below.

(Liquid column resonance droplet discharge means)
The length L between the longitudinal ends of the liquid column resonance liquid chamber 18 is 1.85 [mm], N = 2 resonance mode, and the first to fourth discharge holes are N = 2 mode pressure standing. The thing which has arrange | positioned the discharge hole in the position of the antinode of the wave was used. The drive signal generation source was a NF company function generator WF 1973, which was connected to the vibration generation means with a polyethylene-coated lead wire. The driving frequency at this time is 340 [kHz] according to the liquid resonance frequency.

(Toner collecting part)
The inside diameter of the chamber 61 is φ400 [mm] and the height is 2000 [mm] and is fixed vertically, the upper end and the lower end are narrowed, and the diameter of the carrier air flow inlet is φ50 [mm]. The diameter of the carrier airflow outlet is φ50 [mm]. The droplet discharge means 2 is disposed at the center of the chamber 61 at a height of 300 [mm] from the upper end in the chamber 61. The carrier airflow was 10.0 [m / s] and 40 [° C.] nitrogen.

Example 1
Preparation of Toner 1 Using the above-described toner manufacturing apparatus, toner component liquid 1 was continuously discharged for 1 hour, and the discharged toner solution was dried and solidified in a chamber, and toner particles were collected by a cyclone collector. In the cyclone collecting unit, 1 [kg] of the aqueous medium was added, and the toner particles after drying were dispersed again in water. As an aqueous medium, 10 [g] of Eleminol MON-7 (manufactured by Sanyo Kasei) was added as a surfactant to 1 [kg] of pure water. The obtained aqueous dispersion of toner particles was heated at 63 [° C.] with stirring and held for 1 hour, whereby a continuous layer was formed between the binder resins that are aggregates of the toner composition. . Next, the mixture was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the obtained filter cake, and the mixture was mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered twice. To the obtained filter cake, 20 parts of a 10% by mass aqueous sodium hydroxide solution was added, mixed at 12,000 [rpm] for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered twice. 20 parts of 10% by mass hydrochloric acid was added to the obtained filter cake, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered twice to obtain a filter cake. The obtained filter cake was dried at 40 [° C.] for 36 hours using a circulating dryer, and sieved with a mesh having an opening of 75 [μm], whereby toner base particles 1 were produced. 100 parts of the obtained toner base particles 1 and 1.0 part of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive were used at a peripheral speed of 30 using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Mix at [m / sec] for 30 seconds. Then, after 5 cycles of a treatment for 1 minute of rest, sieving with a mesh having an opening of 35 [μm], toner 1 of Example 1 was produced.

  The particle size distribution of the toner was measured with a flow type particle image analyzer (Sysmex Corp. FPIA-3000) under the following measurement conditions. When this was repeated three times, the average of the volume average particle diameter (Dv) was 5.5 [μm], the average of the number average particle diameter (Dn) was 5.2 [μm], and the average of Dv / Dn was 1.06. A measurement method using a flow particle image analyzer (Flow Particle Image Analyzer) will be described below. The measurement of toner, toner particles and external additives using a flow type particle image analyzer can be performed using, for example, a flow type particle image analyzer FPIA-3000 manufactured by Toa Medical Electronics Co., Ltd.

In the measurement, fine dust is removed through a filter, and as a result, the number of particles in a measurement range (for example, an equivalent circle diameter of 0.60 [μm] or more and less than 159.21 [μm]) in 10 ⁻³ [cm ³ ] water. A few drops of nonionic surfactant (preferably Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.) is added to 10 [ml] of 20 or less water. Further, 5 [mg] of the measurement sample is added, and dispersion treatment is performed for 1 minute under the conditions of 20 [kHz] and 50 [W / 10 cm < ³ >] using UH-50 manufactured by STM. Further, a dispersion treatment was performed for a total of 5 minutes, and a sample dispersion liquid having a particle concentration of 4000 to 8000 [pieces / 10 ⁻³ cm ³ ] (for particles having a diameter equivalent to the measurement circle) as a target was set to 0. The particle size distribution of particles having an equivalent circle diameter of 60 [μm] or more and less than 159.21 [μm] is measured.

  The sample dispersion is passed through a flat and flat transparent flow cell (thickness: about 200 [μm]) flow path (spread along the flow direction). In order to form an optical path that passes across the thickness of the flow cell, the strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter.

  In about 1 minute, the equivalent circle diameter of 1200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 [μm] into 226 channels (divided into 30 channels for one octave). In actual measurement, particles are measured in a range where the equivalent circle diameter is 0.60 [μm] or more and less than 159.21 [μm].

(Examples 2-9)
Preparation of Toners 2 to 9 Toners 2 to 9 were prepared in the same manner as in Example 1 except that the toner composition liquid 1 of Example 1 was replaced with toner composition liquids 1 to 9. The particle size distribution of the obtained toner was determined in the same manner as in Example 1. The results are shown in Table 4 above.

(Example 10 )
Production of Toner 10 In the toner manufacturing apparatus having the configuration shown in FIG. 1, the toner component liquid 1 is used under the same conditions as in Example 1 except that the air flow is 10.0 [m / s] and 55 [° C.] nitrogen. Was continuously discharged for 1 hour. The discharged toner solution was dried and solidified in the chamber, and the toner base particles were collected by a cyclone collector. In addition, 1 kg of an aqueous medium was put into the cyclone collecting part, and the toner base particles after drying were dispersed in water again. As an aqueous medium, 10 g of Eleminol MON-7 (manufactured by Sanyo Kasei) was added as a surfactant to 1 kg of pure water. The obtained aqueous dispersion of toner particles was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the obtained filter cake, and the mixture was mixed at 12,000 [rpm] for 10 minutes using a TK homomixer. Filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered twice. To the obtained filter cake, 20 parts of a 10% by mass aqueous sodium hydroxide solution was added, mixed at 12,000 [rpm] for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered twice. 20 parts of 10% by mass hydrochloric acid was added to the obtained filter cake, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice to obtain a filter cake. Using a circulating dryer, the obtained filter cake was dried at 40 [° C.] for 36 hours, and sieved with a mesh having an opening of 75 [μm] to prepare toner base particles. 100 parts of the obtained toner base particles and 1.0 part of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive were added to a peripheral speed of 30 [ m / sec] was mixed for 30 seconds and rested for 1 minute for 5 cycles, and then sieved with a mesh having an opening of 35 [μm] to prepare toner 10 of Example 10 . The particle size distribution of the obtained toner was determined in the same manner as in Example 1. The results are shown in Table 4 above.

(Examples 11 to 12 )
Each toner component liquid 1 toner component liquid 2 in Preparation Example 10 of the toner 11 to 12 produce the toner 11 to 12 Other than changing the toner component liquid 3 in the same manner as in Example 10 Examples 11-12 did. The particle size distribution of the obtained toner was determined in the same manner as in Example 1. The results are shown in Table 4 above.

(Comparative Example 1)
Preparation of Toner 13 Using the above-described toner manufacturing apparatus, the toner composition liquid 10 prepared using at least ethyl acetate as an organic solvent was discharged, and the toner particles dried and solidified in the chamber were collected by a cyclone collector. . The toner was taken out from the toner storage container and further dried at 40 [° C.] for 36 hours to obtain toner mother particles 10. 100 parts of the obtained toner base particles 1 and 1.0 part of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive were used at a peripheral speed of 30 using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). Mix at [m / sec] for 30 seconds. Then, after 5 cycles of the treatment of resting for 1 minute, sieving with a mesh having an opening of 35 [μm], the toner 13 of Comparative Example 1 was produced. The particle size distribution measurement results of this toner are shown in Table 4 above.

(Comparative Examples 2 to 8)
Except for changing the toner composition liquid 10 Preparation Comparative Example 1 of toner 14-20 in the toner constituent liquid 12 to 17 in the same manner as in Comparative Example 1 to produce a toner 14-20. The particle size distribution results of the obtained toner are shown in Table 4 above.

(Comparative Example 9)
Production of Toner 21 Using the above-described toner production apparatus, the toner composition liquid 18 was continuously discharged for 1 hour, and the discharged toner solution was dried and solidified in a chamber, and the toner particles were collected by a cyclone collector. In addition, the aqueous medium 1 [kg] was put in the cyclone collecting part, and the toner particles after drying were dispersed again in water. As an aqueous medium, 10 [g] of Eleminol MON-7 (manufactured by Sanyo Kasei) was added as a surfactant to 1 [kg] of pure water. The obtained aqueous dispersion of toner particles was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 [° C.] for 8 hours. Next, the mixture was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the obtained filter cake, and the mixture was mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered twice. To the obtained filter cake, 20 parts of a 10% by mass aqueous sodium hydroxide solution was added, mixed at 12,000 [rpm] for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered twice. 20 parts of 10% by mass hydrochloric acid was added to the obtained filter cake, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 [rpm] using a TK homomixer, and then filtered twice to obtain a filter cake. Using a circulating dryer, the obtained filter cake was dried at 40 [° C.] for 36 hours, and sieved with a mesh having an opening of 75 [μm] to prepare toner base particles.

100 parts of the obtained toner base particles and 1.0 part of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive were added to a peripheral speed of 30 [ m / sec] for 30 seconds. Then, after 5 cycles of the treatment of resting for 1 minute, sieving with a mesh having an opening of 35 [μm], the toner 21 of Comparative Example 9 was produced.
(Comparative Example 10)
Preparation of toner 22
In the toner manufacturing apparatus 1 having the configuration shown in FIG. 1, the water was collected without putting the aqueous medium into the cyclone collecting part. At this time, the carrier airflow was set to 10.0 [m / s] and 55 [° C.] nitrogen. Otherwise, the conditions were the same as in Example 1. Using this apparatus, the toner component liquid 1 was continuously discharged for 1 hour, and the discharged toner solution was dried and solidified in the chamber and heated by an air flow, and the toner base particles were collected by a cyclone collector. Further, secondary drying was performed at 40 [° C.] for 48 hours to obtain toner base particles 10. 100 parts of the obtained toner base particles and 1.0 part of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive were added to a peripheral speed of 30 [ m / sec] was mixed for 30 seconds and rested for 1 minute for 5 cycles, and then sieved with a mesh having an opening of 35 [μm] to prepare toner 22 of Comparative Example 10. The particle size distribution of the obtained toner was determined in the same manner as in Example 1. The results are shown in Table 4 above.
(Comparative Examples 11-12)
Preparation of toners 23 to 24
Toners 23 to 24 of Comparative Examples 11 to 12 were produced in the same manner as Comparative Example 10 except that the toner component liquid 1 was changed to the toner component liquid 1 and the toner component liquid 2 in Comparative Example 10, respectively. The particle size distribution of the obtained toner was determined in the same manner as in Example 1. The results are shown in Table 4 above.

<Creation of carrier>
To 100 parts of toluene, 100 parts of a silicone resin (organostraight silicone), 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black are added. Then, it was dispersed for 20 minutes with a homomixer to prepare a resin layer coating solution. Using a fluid bed type coating apparatus, the resin layer coating solution was applied to the surface of 1.000 parts of spherical magnetite having a volume average particle size of 50 [μm] to prepare a carrier.

<Production of developer>
Each developer of Examples 1 to 12 and Comparative Examples 1 to 12 was prepared by mixing 5 parts of toner 1 to 24 and 95 parts of carrier.

<Measurement of the amount of residual ethyl acetate>
The amount of residual ethyl acetate was measured by a hot extraction gas chromatograph mass spectrometry (GC-MS) method. The apparatus used was QP2010 manufactured by Shimadzu Corporation, the data analysis software used was GCMSsolution manufactured by Shimadzu Corporation, and the heat extraction apparatus used was Py2020D manufactured by Frontier Laboratories. The heat extraction conditions were extraction: 150 [° C.] × 10 minutes and Clarion trap: −190 [° C.]. The results are summarized in Table 4 above. The total concentration of residual ethyl acetate in toners 1 to 9 was all 30 ppm or less. On the other hand, the total concentration of residual ethyl acetate in toners 10 to 12 exceeded 30 [ppm].

<Evaluation of clogged discharge holes>
When the toner base particles were produced, the droplet discharge head was observed with a CCD camera, and it was confirmed whether or not the discharged droplets were ejected from the discharge port, and the clogging of the discharge port was evaluated. The results are shown in Table 4 above.
[Evaluation criteria]
○: Continuous droplet formation was possible without clogging the discharge holes for 3 hours.
Δ: Clogging occurred in less than 50% of the discharge holes in 1 hour.
X: Clogging occurred in 50% or more of the discharge holes in 1 hour.
Further, for each developer, (a) fixing lower limit, (b) hot offset property, (c) heat-resistant storage property, (d) toner filming, (e) background stain, (f) toner Scatterability was measured. The results are shown in Table 4 above.

(A) Evaluation of minimum fixing temperature Each prepared two-component developer is put in a commercially available copying machine (Imagiono 455, manufactured by Ricoh Co., Ltd.), and the fixing temperature is increased from 100 ° C. to 10 ° C. Images were output to type 6000 paper (manufactured by Ricoh Co., Ltd.). The output image was rubbed by hand, and the temperature at which the toner could not be peeled was evaluated as the minimum fixing temperature. The results are shown in Table 4 above.
(B) Evaluation of hot offset property Each prepared two-component developer is put in a commercially available copying machine (Imagiono 455, manufactured by Ricoh Co., Ltd.), and paper (type 6000 paper, Ricoh) is changed while changing the fixing temperature from low temperature to high temperature. The image was output to (made by Co., Ltd.) The temperature at which the glossiness of the output image decreased or the temperature at which the offset image was recognized in the image was defined as the offset generation temperature, and the hot offset property was evaluated based on the following evaluation criteria. The results are shown in Table 4 above.
[Evaluation criteria]
○: Offset generation temperature is 200 ° C or more ×: Offset generation temperature is less than 200 ° C

(C) Heat-resistant storage stability (Penetration)
Each toner was filled in a glass container of 50 [ml] and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 [° C.], and the penetration (mm) was measured by a penetration test (JIS K2235-1991) and evaluated based on the following criteria. In addition, it shows that heat resistance preservability is excellent, so that the value of the said penetration degree is large, and when it is less than 5 [mm], possibility that a problem in use will generate | occur | produce is high.
〔Evaluation criteria〕
◎: Needle penetration 25 mm or more ○: Needle penetration 15 mm or more and less than 25 mm △: Needle penetration 5 mm or more and less than 15 mm ×: Needle penetration less than 5 mm

(D) Toner Filming Using each of the produced developers using a tandem color image forming apparatus (Imagio Neo450, manufactured by Ricoh Co., Ltd.), a chart of 20% image area becomes an image density of 1.4 ± 0.2. In this way, 200,000 sheets are output while controlling the toner density. The amount of change in the charge amount [μc / g] of the electrophotographic developer thereafter (charge amount decrease after 200,000 sheets run / charge amount at the initial stage of the run), compared with the initial value before output, is as follows. Evaluated by criteria. The charge amount was measured by a blow-off method.
〔Evaluation criteria〕
◎: Less than 15% ○: 15% or more and less than 30% △: 30% or more and less than 50% ×: 50% or more When the toner is filmed on the electrophotographic carrier, the composition of the outermost surface of the electrophotographic carrier changes. As a result, the charge amount decreases. It is determined that the smaller the change in the charge amount before and after the run, the less the degree of filming of the toner onto the electrophotographic carrier.

(E) Knowledge stain Using each developer obtained, when 200,000 sheets of a chart with an image area ratio of 5% were continuously output by a tandem type color image forming apparatus (Imagio Neo 450, manufactured by Ricoh Co., Ltd.) The degree of soiling of the background portion was visually evaluated according to the following criteria.
〔Evaluation criteria〕
○: No background stain on the image background. △: Slight background stain on the image background, but no problem in actual use. ×: Background stain in the image background, which is a problem in actual use. Is

(F) Toner scattering property 200,000 charts with an image area ratio of 5 [%] were continuously output from each developer obtained using a tandem color image forming apparatus (Imagio Neo 450, manufactured by Ricoh Co., Ltd.). . The degree of toner contamination in the machine at that time was visually evaluated in four stages according to the following criteria.
〔Evaluation criteria〕
A: There is no toner contamination in the image forming apparatus and it is in a good state. ○: There is no toner contamination in the image forming apparatus and it is in a good state. Δ: There is toner contamination in the image forming apparatus, but it is actually used. Possible level ×: Toner contamination in the image forming apparatus is severe and is not practically usable.

As shown in Table 4 above, the toners of Examples 1 to 12 that do not use a solvent in the production process have good fixability and toner strength, and not only resistance to heat blocking but also stirring stress in the developing device. It was confirmed that a good image can be obtained over a long period of time. On the other hand, it was confirmed that the toners of Comparative Examples 1 to 8 had a large amount of the remaining organic solvent despite a sufficient drying time, and deteriorated the strength and filming resistance of the toner. This was presumed to be because a small amount of organic solvent was held inside the resin in the process of drying and solidifying the binder resin dissolved in the organic solvent, thereby reducing the heat resistance of the binder resin. The toner of Comparative Example 9 was a toner obtained by dissolving in an organic solvent, but the residual solvent could be reduced by re-dispersing in an aqueous medium during collection. However, the residual ethyl acetate concentration was higher than that of the example using no solvent, resulting in insufficient durability. Further, all of the toners of the comparative examples collected by being dissolved in an organic solvent had a great adhesion to the inner wall of the cyclone, whereas the toners of the examples collected by being dispersed in an aqueous medium were all deposited on the inner wall of the cyclone. It was confirmed that the adhesion was suppressed and the yield was improved.

  The embodiment described above is an example of producing toner particles for electrophotography. However, in addition to the toner particles for electrophotography, spacer particles for liquid crystal panels and for electronic paper are used as resin particles that require uniformity. These are used in various ways, such as colored particles, resin particles as drug carriers for pharmaceuticals, and the like. These resin particles are also produced by the production apparatus and production method of the above embodiment, and the same effect can be obtained.

What has been described above is merely an example, and the present invention has a specific effect for each of the following modes.
(Aspect 1)
A method for producing a toner containing at least a binder resin, a droplet forming step for discharging a toner composition liquid in which a raw material of toner is dispersed in an aqueous medium to form droplets, and a droplet toner composition A drying process for drying the aqueous medium in the liquid, and agglomerates of fine particles of the toner raw material obtained by the drying process are redispersed in the aqueous medium, and heat is applied to fuse the fine particles together. A fusion process. According to this, as described in the above embodiment, the toner can be manufactured without causing blocking or a decrease in crystallinity. In the fusing step, agglomerates of fine particles of toner raw materials are redispersed in an aqueous medium, and then heat is applied to fuse the fine particles. As a result, the fine particles of the binder resin are in a state of sticking in one toner particle while maintaining the crystal state before being formed into droplets, and sufficient stress resistance as a toner can be obtained. Therefore, a sufficient toner crystallinity can be obtained while ensuring a narrow particle size distribution .
( Aspect 2 )
In (Aspect 1), the fusing step is performed by applying heat at a temperature higher than that during the drying step to the aggregate in the gas phase continuously following the drying step. According to this, as described in the above embodiment, the toner can be manufactured without causing blocking or a decrease in crystallinity. The fine particles are fused to each other by applying heat at a temperature higher than that in the drying step to the aggregate in the gas phase continuously following the drying step. As a result, the fine particles of the binder resin are in a state of sticking in one toner particle while maintaining the crystal state before being formed into droplets, and sufficient stress resistance as a toner can be obtained. Therefore, a sufficient toner crystallinity can be obtained while ensuring a narrow particle size distribution.
(Aspect 3 )
Oite in (Aspect 1) or (Embodiment 2), as a binder resin comprises a crystalline resin. According to this, as described in the above embodiment, a toner having excellent heat-resistant storage stability can be provided.
(Aspect 4 )
In any one of (Aspect 1) to (Aspect 3 ), 50% or more of the binder resin is a resin having crystallinity. According to this, as described in the above embodiment, a low-temperature fixing toner that can exhibit the respective effects of the sharp melt property of the crystalline polyester resin and the heat resistance of the amorphous polyester resin and has excellent heat-resistant storage stability is provided. can do.
(Aspect 5 )
In any one of (Aspect 1) to (Aspect 4 ), in the droplet formation step, vibration is imparted to the toner composition liquid in the liquid column resonance chamber in which at least one discharge port is formed, thereby causing liquid column resonance. A standing wave is formed, and the toner composition liquid is ejected from an ejection port arranged in a region where the standing wave becomes an antinode. According to this, as described in the above embodiment, the droplets are continuously ejected from the ejection holes in accordance with the anti-node period of the standing wave, the droplet size distribution is narrow, and the toner productivity is reduced. Can be secured.
(Aspect 6 )
In any one of (Aspect 1) to (Aspect 5 ), the volume average particle diameter Dv by the laser diffraction method of the dispersion in the toner composition liquid is 0.5 [μm] or less, and the particle ratio is 1 [μm] or more. Is 0 [%]. According to this, as described in the above embodiment, the particle size distribution of the droplets is narrow, and the toner productivity can be ensured.
(Aspect 7 )
In (Aspect 3 ), the crystalline resin is a crystalline polyester resin. According to this, as described in the above embodiment, since the crystalline resin is a crystalline polyester resin, the compatibility point at the time of fixing, and when used in a low-temperature fixing property or a full-color image forming apparatus. Glossiness is improved.
(Aspect 8 )
In (Aspect 3 ), the crystalline resin has a urethane bond and / or a urea bond. According to this, as described in the above embodiment, since the crystalline resin has a urethane bond and / or a urea bond, the compatibility point at the time of fixing, low temperature fixability, and full color image forming apparatus can be used. If this happens, the glossiness is improved.
(Aspect 9 )
In (Aspect 8 ), the crystalline resin is a block polymer of polyester and polyurethane. According to this, as described in the above embodiment, since the crystalline resin has a urethane bond and / or a urea bond, the compatibility point at the time of fixing, low temperature fixability, and full color image forming apparatus can be used. If this happens, the glossiness is improved .
( Aspect 10 )
A method for producing resin particles containing at least a resin, comprising: a droplet forming step of discharging a resin particle composition liquid in which a raw material of resin particles is dispersed in an aqueous medium to form droplets; and a dropletized resin A drying step of drying the aqueous medium in the particle composition liquid, and agglomerates of the fine particles of the raw material of the resin particles obtained by the drying step are redispersed in the aqueous medium, and then heat is applied to the fine particles. A fusing process for fusing. According to this, as described in the above embodiment, the binder resin particles adhere to each other in one resin particle while maintaining the crystal state before being formed into droplets, and the resin particle has a narrow particle size distribution. Sufficient crystallinity of the resin particles can be obtained while ensuring.

DESCRIPTION OF SYMBOLS 1 Toner manufacturing apparatus 10 Liquid column resonance droplet formation part 11 Liquid column resonance liquid chamber 12 Discharge hole 13 Droplet 14 Liquid common supply path 15 Vibration generating means 16 Discharge hole thin film 17 Nozzle angle 20 Drying collection part 21 Chamber 22 Conveyance Airflow inlet 23 Carrying airflow 24 Collection outlet 25 Solidified particle collecting means 26 Aqueous medium supply pipe 27 Water vapor exhaust port 28 Powder collecting means 29 Dunbar part 30 Toner component liquid replenishing part 31 Toner component liquid 32 Toner component liquid tank 33 Toner component liquid supply passage 34 Liquid circulation pump 35 Liquid return pipe P1: Liquid pressure gauge P2: In-chamber pressure gauge

JP 2002-72567 A Japanese Patent No. 3786034 Japanese Patent No. 3786035 JP-A-57-201248 Japanese Patent No. 4660729

Claims (10)

A method for producing a toner containing at least a binder resin,
A droplet forming step of discharging a toner composition liquid in which the raw material of the toner is dispersed in an aqueous medium to form droplets;
A drying step of drying the aqueous medium in the dropletized toner composition liquid;
And a fusing step of fusing the fine particles to each other by re-dispersing the aggregates of the fine particles of the raw material of the toner obtained in the drying step in an aqueous medium. Toner manufacturing method . The method of manufacturing a toner 請 Motomeko 1,
The method for producing a toner, wherein the fusing step is performed by applying heat at a temperature higher than that in the drying step to the aggregate in a gas phase continuously from the drying step. In the toner production method according to claim 1 or 2 ,
A toner production method comprising a crystalline resin as the binder resin. In the manufacturing method of the toner in any one of Claims 1-3 ,
A method for producing a toner, wherein 50% or more of the binder resin is a resin having crystallinity. In the manufacturing method of the toner in any one of Claims 1-4 ,
In the droplet forming step, a standing wave due to liquid column resonance is formed by applying vibration to the toner composition liquid in the liquid column resonance chamber in which at least one or more discharge ports are formed. A toner manufacturing method, wherein the toner composition liquid is discharged from the discharge port arranged in a region to be. The method of manufacturing a toner according to any one of claims 1 to 5
A volume average particle diameter Dv by a laser diffraction method of a dispersion of raw materials in the toner composition liquid is 0.5 [μm] or less, and a particle ratio of 1 [μm] or more is 0 [%]. Toner manufacturing method. The toner production method according to claim 3, wherein:
A toner manufacturing method, wherein the crystalline resin is a crystalline polyester resin. The toner production method according to claim 3, wherein:
A method for producing a toner, wherein the crystalline resin has a urethane bond and / or a urea bond. The toner production method according to claim 3, wherein:
A method for producing a toner, wherein the crystalline resin is a block polymer of polyester and polyurethane . A process for producing a resin particle comprising a resin even without low,
A droplet forming step of discharging a resin particle composition liquid obtained by dispersing the raw material of the resin particles in an aqueous medium into droplets;
A drying step of drying the aqueous medium in the droplet-formed resin particle composition liquid;
And a fusing step of fusing the fine particles of the resin particles obtained by the drying step together by re-dispersing them in an aqueous medium and then applying heat. A method for producing resin particles.

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