JP4523862B2 - Toner manufacturing method and toner manufacturing apparatus - Google Patents

Description

  The present invention relates to a method for producing an electrophotographic toner, and more particularly to a method for producing a toner by polymerization.

  In the developing process, a developer used in electrophotography, electrostatic recording, electrostatic printing, and the like is once attached to an image carrier such as a photoreceptor on which an electrostatic charge image is formed, and then transferred to a transfer process. After being transferred from the photoconductor to a transfer medium such as transfer paper, the toner is fixed on the paper surface in a fixing step. At that time, as a developer for developing an electrostatic charge image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, or a one-component developer not requiring a carrier (magnetic toner) Non-magnetic toner) is known.

  In order to obtain high-quality and high-quality images, improvements have been made by reducing the particle size of the toner. However, as dry toners used in electrophotography, electrostatic recording, electrostatic printing, etc., styrene A toner binder such as resin or polyester is melt-kneaded with a colorant or the like and finely pulverized. In the production method by the usual kneading and pulverizing method, the particle shape is indeterminate, and in the image forming apparatus, stirring with the carrier in the developing unit, and when used as a one-component developer, a developing roller and a toner supply roller, The toner is further pulverized by contact stress caused by a layer thickness regulating blade, a friction charging blade, etc., and fine particles are generated, or a fluidizing agent is embedded in the toner surface, resulting in a phenomenon that the image quality is deteriorated. . Further, because of its shape, the fluidity as a powder is poor, a large amount of fluidizing agent is required, and the filling rate into the toner bottle is low, which is an obstacle to downsizing. Therefore, the current situation is that the merit of reducing the particle size is not utilized.

  In addition, the pulverization method has a lower limit of the particle size that can be prepared, and cannot cope with further reduction in the particle size. Various spherical toner manufacturing methods have been devised to compensate for the disadvantages of such irregular shape effects.

  A commonly used method is a polymer suspension method.

  This method includes a step of emulsifying a toner composition such as a colorant such as a resin, a pigment and the like, and a toner composition such as wax in an organic solvent and dispersing the dispersed oil phase into a toner size droplet in the aqueous phase by mechanical emulsification means. . At this time, if a solid organic fine particle dispersant is used as a stabilizer for emulsified droplets in the aqueous phase, fine droplets having a relatively narrow particle size distribution (Dv / Dn) can be produced.

  As an achievement means for obtaining the above emulsified droplets, the oil phase and the aqueous phase are continuously fed in a certain amount, and the equilibrium reaction of shearing (micronization) and coalescence is repeated within the partial volume of the emulsification mechanism. However, the means for temporarily determining the particle size is used when balanced, and attention is paid to the method of feeding the oil phase or the oil phase / water phase at that time. By supplying the oil phase or oil phase / water phase simultaneously and continuously to the emulsifier through independent paths, the oil phase / water phase can be removed without shearing, which can cause emulsification failure and non-uniform composition. It is possible to avoid the extreme liquid separation phenomenon that occurs when they are mixed, and the generation of coarse particles caused thereby.

  In order to solve such a problem, the following techniques are disclosed.

  Patent Document 1 discloses a method of continuously supplying a dispersed phase component and a continuous phase component to a double pipe from an independent path simultaneously to the vicinity of a rotor when producing a polymer by suspension polymerization of a monomer composition. Is disclosed. By this method, by defining the size of the double tube diameter with respect to the rotor, a dispersion liquid having droplets of a desired size is formed and the polymerization reaction is performed. However, Patent Document 1 only defines the size of the double tube diameter with respect to the rotor, and the positional relationship between the supply mechanism and the rotor, the supply speed of each phase, the speed ratio, or the rotation It does not take into account the premix before shearing by the child.

  Patent Document 2 discloses that one of two liquids forming two phases is a dispersed phase component and the other is a continuous phase component, and both components are passed through a stationary in-tube mixer equipped with a stationary liquid dividing mechanism at high speed. Disclosed is a method in which fine droplets of the dispersed phase component are dispersed in the continuous phase component by passing through a high-speed shear disperser equipped with a rotating liquid shearing mechanism, and resin particles are generated from the droplet. .

  The method described in Patent Document 2 is a system in which a dispersed phase component and a continuous phase component pass through a high-speed shear disperser once to generate fine droplets (one-pass emulsification). However, this one-pass emulsification method cannot be said to be sufficient when considering uniform composition / composition distribution within the particles. The uniform distribution of the particles constituting the toner is considered to strongly affect the electrophotographic characteristics such as the chargeability of the toner, and in this respect, it cannot be said that any patent document has solved the problem. .

  On the other hand, since the color toner reproduces various colors by overlapping toners of different colors as compared with the black toner, the control of the charging condition becomes more problematic. In Patent Document 3, in order to impart excellent charging characteristics, a dissolved or dispersed material is emulsified and dispersed in an aqueous medium in which a surfactant is present, and an interface having a polarity opposite to that of the surfactant is obtained after the emulsified dispersion dispersing step. It has been proposed to add an activator.

However, even in this document, satisfactory electrophotographic characteristics cannot be obtained at present.
Japanese Examined Patent Publication No. 6-102683 JP-A-10-195205 JP 2004-54139 A

  The present invention has been made in view of the above problems, and easily produces a uniform toner having a stable volume average particle diameter and a sharp particle size distribution, and as a result, faithfully develops a latent image. Another object of the present invention is to provide a toner and a manufacturing method that can reproduce a high-quality full-color image. In particular, it is intended to exert an effect on background stains that are easily affected by charging properties.

  In order to solve the above-mentioned problem, as a result of earnest examination, the volume average particle diameter of the composition uniform aim in the emulsification process by setting the oil phase / water phase supply method before being subjected to shearing by the emulsifier, premix conditions, It has been found that a toner having a sharp particle size distribution can be produced.

  That is, this invention solves the said subject by the following (1) thru | or (25).

(1) A step of continuously supplying a dissolved dispersion in which at least two kinds of resins having different molecular weights, a colorant and a release agent are dissolved or dispersed in an organic solvent, and an aqueous medium having water-insoluble resin fine particles. And emulsifying the colored particle aqueous dispersion comprising the dissolved dispersion and the aqueous medium using a shearing means;
A method for producing a toner comprising:
A toner production method, wherein the pre-emulsified colored particle aqueous dispersion and the dissolved dispersion are brought into contact with each other at a distance of 0.2 m or less from the shearing means. Thereby, it is possible to prepare particles uniformly, and it is possible to manufacture a toner with uniform chargeability and suppressed generation of background stains.

(2) A step of continuously supplying a dissolved dispersion in which at least two kinds of resins having different molecular weights, a colorant and a release agent are dissolved or dispersed in an organic solvent, and an aqueous medium having water-insoluble resin fine particles. And emulsifying the colored particle aqueous dispersion comprising the dissolved dispersion and the aqueous medium using a shearing means;
A method for producing a toner comprising:
A method for producing a toner, wherein the pre-emulsified colored particle aqueous dispersion, the dissolved dispersion, and the aqueous medium are contacted at a distance of 0.2 m or less from the shearing means. Thereby, it is possible to prepare particles uniformly, and it is possible to manufacture a toner with uniform chargeability and suppressed generation of background stains.

  (3) The toner production method according to claim 1 or 2, wherein a flow rate for supplying the dissolved dispersion is 0.1 to 1.0 m / s. As a result, it is possible to provide a toner in which each composition is sheared with a relatively uniform composition and excellent in emulsion stability.

  (4) The toner production method according to any one of claims 1 to 3, wherein a flow rate of supplying the aqueous medium is 0.2 to 5.0 m / s. As a result, it is possible to provide a toner in which each composition is sheared with a relatively uniform composition and excellent in emulsion stability.

  (5) The toner production method according to any one of claims 1 to 4, wherein the emulsified colored particle dispersion is flowing at 2 to 7 m / s. As a result, it is possible to provide a toner in which each composition is sheared with a relatively uniform composition and excellent in emulsion stability.

  (6) The supplying step is performed by supplying the dissolved dispersion from a central portion of a double tube and supplying the emulsified colored particle dispersion from a hollow portion adjacent to the central portion. The toner production method according to claim 1, 3 or 5. Thereby, the possibility of poor emulsification can be reduced as much as possible, and a toner excellent in emulsification stability can be provided.

  (7) In the supplying step, the dissolved dispersion is supplied from the central portion of the triple tube, the aqueous medium is supplied from the hollow portion adjacent to the central portion, and the triple tube adjacent to the hollow portion. The toner production method according to claim 2, wherein the emulsified colored particle aqueous dispersion is supplied from an outermost hollow portion of the toner. Thereby, the possibility of poor emulsification can be reduced as much as possible, and a toner excellent in emulsification stability can be provided.

  (8) The downstream end wall of the central portion for supplying the dissolved dispersion has a plurality of holes arranged radially with respect to the center of the tube. Toner manufacturing method. Thereby, it is possible to avoid oil phase supply in the rotor axial direction in which the shear peripheral speed becomes low.

  (9) The toner production method according to claim 6, further comprising a step of premixing the dissolved dispersion and the colored particle aqueous dispersion before the emulsification step. As a result, the aqueous phase / oil phase is not locally localized, and the uniformity of each composition is less disturbed.

  (10) The toner production method according to claim 7, further comprising a step of premixing the dissolved dispersion and the aqueous medium before the emulsification step. As a result, the aqueous phase / oil phase is not locally localized, and the uniformity of each composition is less disturbed.

  (11) The toner manufacturing method according to claim 7, further comprising a step of premixing the dissolved dispersion, the aqueous medium, and the colored particle aqueous dispersion before the emulsification step. . As a result, the aqueous phase / oil phase is not locally localized, and the uniformity of each composition is less disturbed.

  (12) The method for producing toner according to any one of claims 9 to 11, wherein the premixing step is performed using a static in-tube mixer provided with a liquid separator in a stationary state. . As a result, the fluid can be reliably homogenized.

  (13) The stationary type in-pipe mixer has one end of the pipe as an inlet and the other end as an outlet, and a guide plate that turns right and a left turn along a central axis while dividing the cross section of the pipe into the pipe. The toner manufacturing method according to claim 12, comprising a structure in which the toner particles are alternately arranged in a direction along the central axis. Thus, the fluid can be surely homogenized, and the toner particle size distribution becomes sharp.

(14) The flow rate of the colored particle aqueous dispersion and the flow rate of the dissolved dispersion in the double tube are:
4 ≦ (flow rate of colored particle aqueous dispersion) / (flow rate of dissolved dispersion) ≦ 30
The toner production method according to claim 6, wherein the toner production method is a toner. As a result, it is possible to provide a toner in which each composition is sheared with a relatively uniform composition and excellent in emulsion stability.

(15) In the triple tube, the flow rate of the colored particle aqueous dispersion, the flow rate of the dissolved dispersion, and the flow rate of the aqueous medium are:
4 ≦ (flow rate of colored particle aqueous dispersion) / (flow rate of aqueous medium) ≦ 25; and 0.5 ≦ (flow rate of aqueous medium) / (flow rate of dissolved dispersion) ≦ 2;
The method for producing a toner according to claim 7 or 10, wherein the toner is a toner. As a result, it is possible to provide a toner in which each composition is sheared with a relatively uniform composition and excellent in emulsion stability.

(16) If the diameter of the central portion is d1, and the distance between the end of the double pipe and the shearing means is D,
0 ≦ D / d1 ≦ 20
The method for producing a toner according to claim 6, 9 or 14. As a result, it is possible to provide a toner in which each composition is sheared with a relatively uniform composition and excellent in emulsion stability.

(17) If the diameter of the central portion is d2, and the distance between the triple tube and the shearing means is D,
0 ≦ D / d2 ≦ 20
The toner production method according to claim 7, 10 or 15. As a result, it is possible to provide a toner in which each composition is sheared with a relatively uniform composition and excellent in emulsion stability.

  (18) A toner manufacturing apparatus for performing the processing of claims 1 to 17. As a result, it is possible to prepare particles uniformly, and it is possible to provide a manufacturing system capable of manufacturing a toner with uniform chargeability and suppressed generation of background stains.

  (19) A toner having a volume average particle diameter (Dv) of 3 to 10 μm of the toner obtained by the toner production method according to any one of claims 1 to 17. As a result, it is possible to obtain high-quality and high-quality toner.

  (20) The volume average particle diameter (Dv) of the toner obtained by the method for producing a toner according to any one of claims 1 to 17 is 3 to 10 μm, and the number average particle diameter of the toner is A toner wherein the ratio of the volume average particle diameter to (Dn) is 1.05 or more and 1.25 or less. As a result, it is possible to obtain high-quality and high-quality toner.

  (21) A developer having the toner according to claim 19 or 20. This makes it possible to obtain a high-quality and high-quality developer.

  (22) An image forming method using the toner according to claim 19 or 20. This makes it possible to obtain a high-quality and high-quality developer.

  (23) An image forming apparatus using the toner according to claim 19 or 20. This makes it possible to obtain a high-quality, high-quality developer.

(24) A step of continuously supplying a dissolved dispersion in which at least two kinds of resins having different molecular weights, a colorant and a release agent are dissolved or dispersed in an organic solvent, and an aqueous medium having water-insoluble resin fine particles. And emulsifying the colored particle aqueous dispersion comprising the dissolved dispersion and the aqueous medium using a shearing means;
A method for producing a toner comprising:
A method for producing a toner, wherein the pre-emulsified colored particle aqueous dispersion and the supplied dissolved dispersion are brought into contact with each other and are agitated within 0.1 to 2 seconds. Thereby, it is possible to prepare particles uniformly, and it is possible to manufacture a toner with uniform chargeability and suppressed generation of background stains.

(25) A step of continuously supplying a dissolved dispersion in which at least two kinds of resins having different molecular weights, a colorant and a release agent are dissolved or dispersed in an organic solvent, and an aqueous medium having water-insoluble resin fine particles. And emulsifying the colored particle aqueous dispersion comprising the dissolved dispersion and the aqueous medium using a shearing means;
A method for producing a toner comprising:
A method for producing a toner, wherein the preliminarily emulsified colored particle aqueous dispersion, the dissolved dispersion, and the aqueous medium are stirred within 0.04 to 1 second. Thereby, it is possible to prepare particles uniformly, and it is possible to manufacture a toner with uniform chargeability and suppressed generation of background stains.

  A toner having a uniform particle size distribution and a uniform dispersion state of the composition can be obtained, and a toner that can provide an image with a constant charge amount distribution and little background stain can be provided.

  In the present invention, the aqueous solvent and the solvent dispersion and the colored particle aqueous dispersion (each of these three components, hereinafter also referred to as each composition) constituting the toner are subjected to shearing a plurality of times, whereby the composition / composition distribution is reduced. The purpose is to equalize.

  Hereinafter, the present invention will be described with reference to the drawings. FIG. 1 is an example of a continuous emulsification apparatus for carrying out a toner production method according to the present invention. The continuous emulsification apparatus shown in FIG. 1 is an oil phase A in which an extender is mixed with a liquid obtained by dissolving or dispersing a toner composition containing at least two kinds of resins having different molecular weights, a colorant, and a release agent in an organic solvent. An oil phase B containing a prepolymer having an isocyanate bond, an aqueous medium containing a solid resin fine particle dispersant (hereinafter referred to as an aqueous phase), a static mixer (hereinafter referred to as STM), a pipe And an emulsifier having a line homomixer (hereinafter PLHM). In addition, although description is abbreviate | omitted about the piping which an emulsion liquid circulates in FIG. 1, the structure of this piping is mentioned later.

  The lines between these units are as shown in FIG. 1, and from oil phase A and oil phase B, independent lines heading to STM are respectively connected, and each line is an upstream portion of STM. Merge and pipe to STM. From STM, it is further piped to an emulsifier. A line piped from the aqueous phase is connected to a line between the STM and the emulsifier. Further piping is provided from the emulsifier and connected to the PLHM.

  Next, a continuous emulsification process using the continuous emulsification apparatus of FIG. 1 will be described. The oil phase A and the oil phase B merge at the upstream portion of the STM and are mixed by the STM to form an oil phase. The oil phase joins with the aqueous phase before being introduced into the emulsifier, and then introduced into the partial retention volume of the emulsification mechanism, where it is sheared and emulsified by a pipeline homomixer (hereinafter PLHM) within this volume. (Emulsified liquid is obtained). Part of the resulting emulsified liquid is discharged, and the other part is further circulated through the circulation path and subjected to shearing. A part of the discharged amount is discharged and overflowed by the amount newly supplied into the circulation path. FIG. 7 shows the relationship between the emulsified liquid that stays and circulates and the newly supplied oil phase / water phase.

  In general, when the oil phase is present in the emulsion without being sheared by the emulsifier, the particles in the emulsion in contact with the oil phase are adsorbed to the oil phase and emulsified locally. Defects occur. Once a poor emulsification occurs, the newly fed emulsion that has been emulsified will also be defective due to a chain action through the circulation path.

(Distance to shearing means)
In order to avoid this phenomenon, when emulsifying the emulsified liquid and the oil phase using the above-described PLHM, it is preferable that the emulsified liquid and the oil phase first come into contact with each other at a distance of 0.2 m from the PLHM. Further, this distance is more preferably 0.01 to 0.1 m, and most preferably 0.01 to 0.05 m. If it is larger than 0.2 m, the state in which the unsheared oil phase and the aqueous phase are mixed with each other continues for a long time, the O / W balance is locally disturbed, and particle uniformity and composition uniformity are obtained. As a result, the chargeability between the particle surfaces or between the particles is not uniform, and soiling occurs.

  The aqueous phase may be configured to contact the oil phase and / or the emulsion in any order. However, as described above, when the emulsion and the oil phase are in contact with each other for the first time, the aqueous phase is configured to be in contact. Also good. That is, when emulsifying the emulsified liquid, the aqueous phase, and the oil phase using the above-described PLHM, the emulsified liquid, the aqueous phase, and the oil phase may first contact each other at a distance of 0.2 m from the PLHM. preferable. Further, this distance is more preferably 0.01 to 0.1 m, and most preferably 0.01 to 0.05 m. The critical significance related to this numerical limitation is the same as described above.

  Next, with reference to FIG. 2 thru | or 9, the structure of piping which supplies an emulsion liquid, a water phase, and an oil phase is demonstrated.

(Multiple pipe)
FIG. 2 is an example of a method of supplying an emulsion, an aqueous phase and an oil phase to a continuous emulsifier using a double tube. In this example, the emulsified liquid circulating in the emulsifier is brought into contact with the aqueous phase, and then sent to the hollow part in contact with the outer diameter of the pipe having the double pipe structure in the upstream part of the emulsifier. On the other hand, the oil phase is supplied through the central portion of the double pipe structure. At this time, the emulsion fed as described above and the oil phase fed through the center of the double pipe are in a state of being separated by the double pipe wall structure, and the emulsion and the oil phase are separated from each other. There is no contact. Thereafter, the fed emulsion solution contacts the oil phase fed as described above for the first time at the end of the double-pipe structure (part B in FIG. 2). The emulsion, water phase, and oil phase that have been contacted in this way are then fed into the emulsifier.

  By adopting such a double tube structure, supplying the oil phase through the central part and supplying the emulsion through the outer diameter part, the possibility of poor emulsification is reduced as much as possible and the emulsion stability is improved. An excellent toner can be provided.

FIG. 3 shows an example of a method of supplying an emulsion, an aqueous phase and an oil phase to a continuous emulsifier using a triple tube. In this example, emulsion circulating emulsification machine, in the upstream portion of the emulsifying machine, is fed to the outermost hollow portion in contact with the outer diameter of the pipe having a triple tube structure. On the other hand, the oil phase is supplied through the central portion of the double pipe structure. The aqueous phase is supplied through a hollow portion between the outermost hollow portion to which the emulsion is supplied and the central portion to which the oil phase is supplied. At this time, the emulsion, the oil phase, and the aqueous phase fed as described above are in a state of being separated by the triple tube wall structure, and the emulsion, the oil phase, and the aqueous phase are not in contact with each other. . Thereafter, the fed emulsion, the oil phase, and the aqueous phase are in contact with each other for the first time at the end of the triple tube structure (C portion in FIG. 3). Thereafter, the contacted emulsion, water phase and oil phase are fed into the emulsifier.

  Adopting such a triple pipe structure, supplying an oil phase through the central part, supplying an emulsion in the outermost hollow part, and supplying an aqueous phase through the hollow part, The possibility can be reduced as much as possible, and a toner excellent in emulsion stability can be provided.

  By using a multiple tube such as a double tube or a triple tube, the composition can be made uniform, emulsification failure is prevented, and the particle size distribution of the obtained toner becomes sharp.

  2 and 3, the diameters of the center portions of the double tube structure and the triple tube structure are d1 and d2, respectively, and the distance between the end of the double tube structure and the triple tube structure and the PLHM of the emulsifier Is D.

(End structure of pipe)
As above-mentioned, when sending an oil phase through the center part of a double tube and / or a triple tube, you may have a some hole in the wall which defines the center part of these tubes. The outline is shown in FIG. By adopting such an end configuration, it becomes possible to supply the oil phase radially from the center of the rotor shaft, and as a result, it is possible to avoid the oil phase supply in the rotor shaft direction that reduces the shear peripheral speed, The toner particle size distribution is sharpened, or the composition of the toner is uniform.

(Pre-mixing process)
In addition, the aqueous phase, the oil phase and the emulsion may be mixed in advance before being supplied to the emulsifier and subjected to a shearing treatment. Hereinafter, this mixing is referred to as premixing or premixing step.

  FIG. 4 is an example of a method of supplying an emulsion, an aqueous phase and an oil phase to a continuous emulsifier using a double tube and a mixer. The continuous emulsification device according to this example has a stationary in-tube mixer between the end of the double tube (B portion in FIG. 2) and the emulsifier. Other configurations are the same as those in FIG. A space where the emulsion, the aqueous phase and the oil phase can come into contact exists between the end of the double tube and the mixer.

  FIG. 5 shows an example of a method of supplying an emulsion, an aqueous phase and an oil phase to a continuous emulsifier using a triple tube and a mixer. The continuous emulsification device according to this example has a static in-tube mixer in contact with the end of the triple tube (C portion in FIG. 3). Other configurations are the same as those in FIG.

  FIG. 6 shows another example of a method for supplying an emulsion, an aqueous phase and an oil phase to a continuous emulsifier using a triple tube and a mixer. The continuous emulsifier according to this example has a stationary in-tube mixer so as to come into contact with the end of the triple tube (C portion in FIG. 3) and the emulsifier inlet. Other configurations are the same as those in FIG.

(Mixer)
By using the continuous emulsification apparatus having the configuration shown in FIGS. 4 to 6, it is possible to eliminate the inhomogeneous portion generated in the fluid without causing any disturbance in the composition of the local oil phase and water phase. → "Emulsification", which is advantageous for uniform shearing. By performing pre-mixing, the particle size distribution becomes sharp, which is more advantageous.

  In the continuous emulsification apparatus shown in FIGS. 4 to 6, a static in-tube mixer is used as a mixer for performing the pre-mixing step. However, various means are used as long as they are known mixers in this technical field. be able to.

  Among these, in the present invention, a static in-tube mixer is preferably used. The static mixer has a cutting means and has a structure in which elements are arranged vertically and horizontally and alternately. By adopting such a configuration, the action of “dividing action → converting action → reversing action” of the two liquids or the three liquids is continuously repeated, so that the fluid can be reliably homogenized. In addition, the shape may be simple, and there is almost no fluid retention portion, and there is no viscosity unevenness that can cause sharpening of the particle size distribution or uniform composition.

(Flow rate)
On the other hand, the speed at which the aqueous phase, the oil phase and the emulsion are supplied into the emulsifier, that is, the flow rate, is the toner that is finally obtained by stirring (shearing) in which the ratio of the supply amount of the oil phase to the supply amount of the aqueous phase is uniform. It is important from the viewpoint of affecting the physical properties. The flow rate of the oil phase supplied to the emulsifier is preferably 0.1 to 1.0 m / s, more preferably 0.2 to 0.8 m / s, and most preferably 0.4 to 0.5 m / s. It is. Similarly, the flow rate of the aqueous phase is 0.2 to 5.0 m / s, more preferably 0.5 to 4 m / s, and most preferably 0.5 to 2 m / s. Further, the flow rate of the emulsion flowing in the emulsifier is 2 to 7 m / s, more preferably 3 to 5 m / s, and most preferably 4 to 5 m / s.

(Flow rate ratio between each composition)
As described above, when a double tube / triple tube is employed in the continuous emulsification apparatus according to the present invention, not only the flow rate of each composition but also the flow rate ratio between the compositions is an important factor. For example, when adopting a double pipe, the ratio of the flow rate of the emulsion and the flow rate of the oil phase is
4 ≦ (flow rate of colored particle aqueous dispersion) / (flow rate of dissolved dispersion) ≦ 30
It is preferable that More preferably, this ratio is 5-20, most preferably 5-10.

In addition, when a triple pipe is used, the flow rate of the emulsion, the flow rate of the aqueous phase, and the flow rate of the oil phase are:
4 ≦ (flow rate of colored particle aqueous dispersion) / (flow rate of aqueous medium) ≦ 25; and 0.5 ≦ (flow rate of aqueous medium) / (flow rate of dissolved dispersion) ≦ 2;
It is preferable that In particular, the ratio of (flow rate of aqueous medium) / (flow rate of dissolved dispersion) is more preferably 0.5 to 1.5, and most preferably 0.8 to 1.0.

(Distance between multiple pipe diameter and shearing means)
In the continuous emulsification apparatus of the present invention, when a multiple tube such as a double tube / triple tube is employed, the diameter of the tube supplying each composition, particularly the diameter of the central portion supplying the oil phase, and the end of the multiple tube It was also found that it is effective to define the distance between the shearing means and the shearing means. For example, when a double pipe is employed, the diameter of the central portion (d1 in FIG. 2 above) and the distance between the end of the double pipe and the shearing means (D in FIG. 2 above) are:
0 ≦ D / d1 ≦ 20
It is preferable that This D / d1 is more preferably 0 to 10, and most preferably 0 to 5.

On the other hand, when a triple pipe is employed, the diameter of the central portion (d2 in FIG. 3 above) and the distance between the end of the triple pipe and the shearing means (D in FIG. 3 above) are:
0 ≦ D / d2 ≦ 20
It is preferable that This D / d2 is more preferably 0 to 10, and most preferably 0 to 5.

When larger than the upper limit of these ranges, it is inconvenient in the point which disperse | distributes each composition uniformly and the stability point of the emulsion obtained from each composition .

  Next, the toner obtained by the production method according to the present invention and the components relating to each composition constituting the toner will be described in more detail.

(Dry toner)
In a dry toner containing at least a polyester-based resin as a toner binder, the dry toner having a Dv of 3 to 10 μm and a Dv / Dn of 1.05 to 1.25 can be used for heat-resistant storage, low-temperature fixability, Excellent hot-offset resistance, especially when used in full-color copiers, etc., excellent in image glossiness. In addition, in a two-component developer, even if the toner balance for a long time is performed, The variation in the particle diameter of the toner is reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Even when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner is filmed on the developing roller and the toner is made thin. The toner was not fused to a member such as a blade, and good and stable developability and images were obtained even when the developing device was used (stirred) for a long time.

  In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced, When used as an agent, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.

  Further, these phenomena are the same for the toner having a fine powder content larger than the range of the present invention.

  On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high resolution and high quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. The same applies when Dv / Dn is greater than 1.25.

  Further, when Dv / Dn is smaller than 1.05, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and equalizing the charge amount, but the toner cannot be sufficiently charged or the cleaning property is deteriorated. .

(Particle size distribution measurement method)
The average particle size and particle size distribution of the toner were analyzed using a Coulter Multisizer III (manufactured by Coulter), connected to a personal computer (manufactured by IBM) and using dedicated analysis software (manufactured by Coulter). The Kd value was set using standard particles of 10 μm, and the aperture current was set with an automatic setting. As the electrolytic solution, a 1% NaCl aqueous solution was prepared using first grade sodium chloride. In addition, ISOTON-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion process for about 1 to 3 minutes using an ultrasonic disperser, and a volume average particle diameter (by measuring 50,000 counts of the volume and number of toners of 2 μm or more using a 100 μm aperture tube. Dv) and the number average particle diameter (Dn) were calculated. Based on this calculated value, the volume-based volume average particle size obtained from the volume distribution according to the present invention and the number-based number average particle size obtained from the number distribution were obtained. The closer the Dv / Dn is to 1.0, the sharper the particle size distribution.

  As the resin used in the present invention, any resin can be used as long as it is a resin used for ordinary toners such as styrene acrylic resin, polyol resin, and polyester resin. Particularly from the viewpoint of fixability, a polyester resin is suitable for reproducing a full-color image.

(Modified polyester resin)
The polyester resin suitable for the present invention may be a modified polyester resin. The modified polyester resin has a functional group contained in a monomer unit such as acid or alcohol and a bonding group other than an ester bond in the polyester resin, or a resin component having a different configuration in the polyester resin is covalently bonded. Or resin bound by ionic bonds.

  For example, the resin which introduce | transduced bonds other than an ester bond to the terminal of a polyester resin is mentioned. Specifically, a resin in which a functional group such as an isocyanate group that reacts with an acid group or a hydroxyl group is introduced at the terminal of the polyester resin and then further reacted with an active hydrogen compound to modify the terminal or undergo an extension reaction is also included.

  Further, if the compound has a plurality of active hydrogen groups, a resin in which the polyester ends are bonded to each other is also included (such as urea-modified polyester and urethane-modified polyester).

  In addition, a reactive group such as a double bond is introduced into the polyester main chain and radical polymerization is performed at this introduction site, and a graft component of a carbon-carbon bond is introduced as a side chain, or double bonds are cross-linked. (Styrene-modified, acrylic-modified polyester, etc.).

  Further, it may be a resin obtained by copolymerizing resin components having different structures in the main chain of the polyester or reacting with a terminal carboxyl group or hydroxyl group. For example, those obtained by copolymerization with a silicone resin having a terminal modified with a carboxyl group, a hydroxyl group, an epoxy group, or a mercapto group (such as a silicone-modified polyester) are also included. Hereinafter, the modified polyester will be specifically described.

(Urea-modified polyester resin)
One type of modified polyester resin includes a modified polyester (i) having a urea bond. Examples of the polyester (i) include a reaction product of a polyester prepolymer (A) having an isocyanate group and amines (B). Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group further reacted with a polyisocyanate (3). It is done. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2), (1-1) alone or a mixture of (1-1) and a small amount of (1-2). Is preferred. Diol (1-1) is alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F) Bisphenol S, etc .; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; bisphenol Alkylene oxide Le ethers (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of (2) -2) is preferred. Dicarboxylic acid (2-1) is alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, Naphthalenedicarboxylic acid and the like). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.). The polycarboxylic acid (2) may be reacted with the polyol (1) using the above acid anhydrides or lower alkyl esters (such as methyl ester, ethyl ester, isopropyl ester).

  The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Polyisocyanate (3) is an aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanate (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates with phenol derivatives, oximes, caprolactams, etc. Blocked; and combinations of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  The amines (B) are diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), amino mercaptan (B4), amino acid (B5), and B1-B5 amino groups blocked ( B6) and the like. Diamine (B1) is aromatic diamine (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamine (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophorone) Diamine, etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the blocked B1-B5 amino group (B6) include ketimine compounds and oxazoline compounds obtained from the amines of B1-B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates. In the present invention, the polyester (i) modified with a urea bond may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

  The urea-modified polyester (i) of the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the urea-modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. (I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

(Unmodified polyester resin)
In the present invention, not only the polyester (i) modified with a urea bond but also the polyester (ii) not modified can be included as a toner binder component together with the (i). By using (ii) in combination, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to the single use. Examples of (ii) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (i), and the preferred one is also the same as (i). Further, (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, for example, may be modified with a urethane bond. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Therefore, the polyester component (i) and (ii) preferably have similar compositions. When (ii) is contained, the weight ratio of (i) to (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. When the weight ratio of (i) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (ii) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (ii) is usually 1-30, preferably 5-20. By having an acid value, it tends to be negatively charged.

In the present invention, the glass transition point (Tg) of the toner binder is usually 50 to 70 ° C., preferably 55 to 65 ° C. If the temperature is less than 50 ° C., the heat-resistant storage stability of the toner is deteriorated. Due to the coexistence of the urea-modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners. As the storage elastic modulus of the toner binder, the temperature (TG ′) at which 10000 dyne / cm ² is obtained at a measurement frequency of 20 Hz is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner binder, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or lower, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, from the viewpoint of achieving both low temperature fixability and hot offset resistance, TG ′ is preferably higher than Tη. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

(Coloring agent)
As the colorant of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide , Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow ( 5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithobon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

  The masterbatch in the present invention may be prepared by mixing and kneading a masterbatch resin and a colorant under high shearing force. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
In addition to the toner binder and the colorant, a release agent such as wax may be contained. As the release agent of the present invention, known ones can be used, for example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sazol wax, etc.); carbonyl group-containing wax, etc. It is done. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18 -Octadecanediol distearate, etc.); polyalkanol esters (trimellitic acid tristearyl, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenylamide, etc.); polyalkylamides (trimellitic acid tristearylamide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. Any known charge control agent can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified) Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine dye Bontron 03, Quaternary ammonium salt Bontron P-51, Metal-containing azo dye Bontron S-34, Oxynaphthoic acid metal complex E-82, Salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (above, Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP 1415 (above, Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

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

(Toner production method in aqueous medium)
As an aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The toner binder can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group. Further, (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond. When (3) is reacted and (A) and (B) are reacted, a solvent can be used as necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to the isocyanate (3), such as tetrahydrofuran (such as tetrahydrofuran). When polyester (ii) not modified with urea bond is used in combination, (ii) is produced in the same manner as polyester having a hydroxyl group, and this is dissolved in the solution after completion of the reaction of (i) and mixed. To do.

  In order to lower the viscosity of the oil phase of the toner composition and make it emulsifiable, a volatile solvent in which the modified polyesters (i) and (A) are soluble is used. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. In addition, the toner shape can be further adjusted by using a solvent that can be dissolved in an aqueous medium such as alcohol or water. The amount of solvent used with respect to 100 parts of the toner composition is usually 10 to 900 parts.

  The toner particles may be formed by reacting, for example, a dispersion in a volatile organic solvent composed of an isocyanate group-containing prepolymer (A) and other toner compositions in an aqueous medium with (B), A modified polyester (i) produced in advance may be used. As a method for stably forming a dispersion comprising a modified polyester (i) or prepolymer (A) and a toner composition in an aqueous medium, the urea-modified polyester (i) or prepolymer (A) can be used in an aqueous medium. And a method of adding a toner raw material composition to be dispersed by a shearing force. The prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials), a colorant masterbatch, a release agent, a charge control agent, an unmodified polyester resin, etc. are dispersed in an aqueous medium. It may be mixed at the time of formation, but it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. For the dispersion, an ordinary agitating mixer, more preferably a homogenizer having a high-speed rotating body and a stator, a high-pressure homogenizer, a disperser using a medium such as a ball mill, a bead mill, a sand mill, or the like is used. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. The emulsifier having rotating blades is not particularly limited, and any emulsifier and disperser that are generally commercially available can be used. For example, Ultra Thalax (manufactured by IKA), Polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK pipeline homomixer , TK homomic line flow (manufactured by Special Machine Industries Co., Ltd.), colloid mill (manufactured by Shinko Pantech Co., Ltd.), slasher, trigonal wet pulverizer (manufactured by Mitsui Miike Chemical Co., Ltd.), Cavitron (Eurotech Co., Ltd.) ), Fine flow mill (manufactured by Taiheiyo Kiko Co., Ltd.) and other continuous emulsifiers, CLEARMIX (manufactured by MTechnic Co., Ltd.), fill mix (manufactured by Tokushu Kika Kogyo Co., Ltd.) and other batch or continuous emulsifiers Etc.

  When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 10 to 98 ° C. Higher temperatures are preferred in that the dispersion made of the modified polyester (i) or the prepolymer (A) has a low viscosity and is easily dispersed.

  The amount of the aqueous medium used relative to 100 parts of the toner composition containing the urea-modified polyester (i) and the prepolymer (A) is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.

  Solid fine particles are dispersed in the aqueous medium, but as described above, other dispersants can be used in combination to adjust the adsorptivity of the solid dispersant to the droplets. Other dispersants can be added before emulsification of the toner composition or when volatile components are removed after emulsification.

(Solid resin fine particle dispersant (hereinafter referred to as solid fine particle dispersant)
The solid fine particle dispersant is present in a solid state hardly soluble in water in an aqueous medium, and is preferably fine particles having an average particle diameter of 0.01 to 1 μm.

  Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  More preferably, tricalcium phosphate, calcium carbonate, colloidal titanium oxide, colloidal silica, hydroxyapatite and the like can also be used. In particular, hydroxyapatite synthesized by reacting sodium phosphate and calcium chloride in water under a basic condition is preferable.

  As organic solid particulate dispersants, low molecular weight organic compound microcrystals and polymer fine particles, such as soap-free emulsion polymerization, suspension polymerization, copolymerization with a monomer having a carboxyl group such as methacrylic acid obtained by dispersion polymerization Polystyrene particles such as polystyrene, methacrylic acid ester, acrylic acid ester copolymer, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resin.

  After adjusting the solid fine particle dispersant in water, an inorganic substance that can be dissolved in an acid such as tricalcium phosphate is partially dissolved by adding a necessary amount of hydrochloric acid or the like in advance. The addition amount of the acid is preferably 0.01% to 10%, more preferably 0.1% to 5% of the amount capable of completely dissolving the inorganic substance.

  When using a compound that can be dissolved in alkali, such as polymer fine particles copolymerized with (meth) acrylic acid having a carboxyl group, as the solid fine particle dispersant, add a necessary amount of base such as sodium hydroxide, To dissolve. The amount of alkali added is preferably 0.01% to 10%, more preferably 0.1% to 5% of the amount capable of completely dissolving the inorganic substance.

(Other dispersants used at the time of emulsification or added later)
In the toner production method according to the present invention, a dispersant may be added during or after emulsification. Dispersants include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, and alkyltrimethyl. Ammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, quaternary ammonium salt type cationic surfactants such as benzethonium chloride, fatty acid amide derivatives, polyhydric alcohol derivatives, etc. Nonionic surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6- C11) Sodium oxy] -1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) Carboxylic acid and metal salt, perfluoroalkylcarboxylic acid (C7 to C13) and its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid and its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl- N- (2-hydroxyethyl) perful Olooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-ll0, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF- 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  In addition, as the cationic surfactant, an aliphatic primary, secondary or secondary amine acid that has a right fluoroalkyl group, an aliphatic quaternary ammonium salt such as a perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) ), Megafuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.

  The stabilization of the dispersed droplets may be adjusted by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or esters of compounds containing vinyl alcohol and carboxyl groups For example, vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine Homopolymers or copolymers such as those having a nitrogen atom or its heterocyclic ring, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, after the elongation and / or cross-linking reaction, it is better to dissolve and wash away the remaining solid fine particle dispersant. From the aspect, it is preferable.

  The elongation and / or crosslinking reaction time is selected depending on the reactivity depending on the combination of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. It is. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

  When the particle size distribution at the time of emulsification dispersion is wide, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.

  In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying, but it is preferably performed in a liquid in terms of efficiency. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.

  The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

  By mixing the resulting dried toner powder with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle.

  Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

  In addition, when preparing the developer, in order to improve the fluidity, storage stability, developability, and transferability of the developer, the hydrophobic silica fine particles listed above are further listed in the developer produced as described above. Inorganic fine particles such as powder may be added and mixed.

  For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and vice versa.

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

  To further adjust the shape of the resulting toner, a toner binder, a method of adjusting the shape mechanically using a hybridizer, mechanofusion, etc. A so-called spray drying method is a method in which a toner material is dissolved and dispersed in a solvent in which a toner binder is soluble, and then a solvent is removed using a spray drying apparatus to obtain a spherical toner. Moreover, although the method of making it spherical by heating in an aqueous medium is mentioned, it is not limited to this.

(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resin Examples include polymer particles.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

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

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing it with a magnetic carrier. Part by weight is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resin such as vinyl, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

  Examples according to the present invention will be described below. Note that the present invention is not limited to this. Hereinafter, a part shows a weight part.

Example 1
1. Preparation of each component of oil phase A (1) Synthesis of low molecular weight polyester In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2 mol adduct, 3 mol of bisphenol A propylene oxide Add 529 parts of adduct, 208 parts of terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide, react for 8 hours at 230 ° C. under normal pressure, and further react for 5 hours under reduced pressure of 10-15 mmHg. Was added 44 parts of trimellitic anhydride and reacted at 180 ° C. under normal pressure for 2 hours to obtain [Low molecular weight polyester 1]. [Low molecular polyester 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, Tg of 43 ° C., and an acid value of 25.

(2) Synthesis of MB 1200 parts of water, 540 parts of carbon black (Printex 35; manufactured by Dexa) [DBP oil absorption = 42 ml / 100 mg, pH = 9.5] and 1200 parts of polyester resin were added, and Henschel mixer (Mitsui Mining Co., Ltd.). ), The mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1]. In addition, PY155 (manufactured by Clariant) was used instead of carbon black, and [Masterbatch 2] was obtained through the same process.

(3) Synthesis of ketimine (extending agent) 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged in a reaction vessel equipped with a stirrer and a thermometer, and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. . The amine value of [ketimine compound 1] was 418.

2. Preparation of oil phase A In a container equipped with a stirrer and a thermometer, 378 parts of [Low molecular weight polyester 1], 110 parts of Carnauba WAX, 22 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), 947 parts of ethyl acetate The mixture was charged, heated to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1]. [Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80% by volume. Carbon black and WAX were dispersed under conditions of filling and 3 passes. Next, 1324 parts of 65% ethyl acetate solution of [low molecular weight polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1] (solid content of [Pigment / WAX Dispersion 1] The concentration (130 ° C., 30 minutes) was 50%). 749 parts of [Pigment / WAX Dispersion 1] and 2.9 parts of [Ketimine Compound 1] were placed in a container and mixed with a homodisper (made by Tokushu Kika) at 5,000 rpm for 1 minute to obtain an oil phase A.

3. Preparation of oil phase B In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2 mol adduct, 81 parts of bisphenol A propylene oxide 2 mol adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.

  Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%.

4). Preparation of aqueous phase In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30; manufactured by Sanyo Chemical Industries), 83 parts of styrene, methacrylic acid When 83 parts of acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred for 15 minutes at 400 rpm, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). A dispersion [fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 105 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 150,000. 83 parts of this [fine particle dispersion 1], 990 parts of water, 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. As a result, a milky white liquid was obtained. This is designated as [Aqueous Phase 1].

5). Emulsification step 60.4 parts of oil phase A, 7.4 parts of oil phase B, and 101.6 parts of aqueous phase obtained as described above were introduced into the continuous emulsification apparatus shown in Fig. 1 and emulsified. The emulsification conditions are as follows.

(1) Flow rate of the solution or dispersion to the circulation path:
0.5 m / s (hereinafter referred to as oil phase flow rate)
(2) Flow rate of liquid flow to the water phase circulation path:
1 m / s (hereinafter referred to as water phase flow velocity)
(3) Flow rate in the circulation path of the colored particle aqueous dispersion: 5 m / s (hereinafter referred to as emulsion flow rate)
(4) Oil / water phase supply mechanism: Double pipe use (terminal structure is shown in Fig. 8)
(5) Emulsified liquid flow rate / oil phase flow rate = 10
(6) Emulsion flow rate / water phase flow rate = 5
(7) Water phase flow rate / oil phase flow rate = 2
(8) Pre-mixing means: Use FIG. 4 (9) Ratio (D1) between the diameter (d1) of the center portion of the double pipe and the distance (D) between the end of the double pipe and the emulsifier shear blade (hereinafter, D / d1) = 10

  The solvent removal process was performed by the following method. The temperature was raised to 45 ° C., and the solvent was removed at an outer peripheral edge peripheral speed of 10.5 m / s under atmospheric pressure (101.3 kPa). The solvent removal time required 20 hours. Thereafter, the toner of Example 1 was obtained after filtration, washing, and drying. Next, 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84 manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (made by Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was adjusted to 50 m / Set to sec, 5 cycles of 2 minutes of operation and 1 minute of rest were performed for a total treatment time of 10 minutes. Furthermore, 0.5 part of hydrophobic silica (H2000, manufactured by Clariant Japan) was added, the peripheral speed was 15 m / sec, mixing for 30 seconds and resting for 1 minute were performed for 5 cycles. Furthermore, 0.5 part of hydrophobic silica and 0.5 part of hydrophobized titanium oxide were mixed with a Henschel mixer, and coarse particles were removed with a screen having an opening of 37 μm to obtain black toner and yellow toner.

(Example 2)
The emulsification step was performed in the same manner as in Example 1 except that the emulsification conditions shown in “5. Emulsification step” described in Example 1 were as follows.

(1) Oil phase flow rate: 1 m / s
(2) Water phase flow velocity: 1 m / s
(3) Emulsified liquid flow rate: 5 m / s
(4) Oil / water phase supply mechanism: Use of triple pipe (terminal structure is shown in FIG. 8)
(5) Emulsified liquid flow rate / oil phase flow rate = 5
(6) Emulsion flow rate / water phase flow rate = 5
(7) Water phase flow rate / oil phase flow rate = 1
(8) Pre-mixing means: Use FIG. 5 (9) Ratio (D2) between the diameter (d2) of the center portion of the triple pipe and the distance (D) between the end of the triple pipe and the emulsifier shear blade (hereinafter referred to as D / d2) = 10

(Example 3)
The emulsification step was performed in the same manner as in Example 1 except that the emulsification conditions shown in “5. Emulsification step” described in Example 1 were as follows.

(1) Oil phase flow rate: 1 m / s
(2) Water phase flow velocity: 1 m / s
(3) Emulsified liquid flow rate: 5 m / s
(4) Oil / water phase supply mechanism: Use of triple pipe (terminal structure is shown in FIG. 8)
(5) Emulsified liquid flow rate / oil phase flow rate = 5
(6) Emulsion flow rate / water phase flow rate = 5
(7) Water phase flow rate / oil phase flow rate = 1
(8) Pre-mixing means: using FIG. 6 (9) D / d2 = 10

Example 4
The emulsification step was performed in the same manner as in Example 1 except that the emulsification conditions shown in “5. Emulsification step” described in Example 1 were as follows.

(1) Oil phase flow rate: 1 m / s
(2) Water phase flow velocity: 1 m / s
(3) Emulsified liquid flow rate: 5 m / s
(4) Oil / water phase supply mechanism: Use of triple pipe (terminal structure is shown in FIG. 8)
(5) Emulsified liquid flow rate / oil phase flow rate = 5
(6) Emulsion flow rate / water phase flow rate = 5
(7) Water phase flow rate / oil phase flow rate = 1
(8) Pre-mixing means: using FIG. 5 (9) D / d2 = 25

(Example 5)
The emulsification step was performed in the same manner as in Example 1 except that the emulsification conditions shown in “5. Emulsification step” described in Example 1 were as follows.

(1) Oil phase flow rate: 1 m / s
(2) Water phase flow velocity: 1 m / s
(3) Emulsified liquid flow rate: 5 m / s
(4) Oil / water phase supply mechanism: Use of a triple pipe (Figure 8 shows the outlet structure)
(5) Emulsified liquid flow rate / oil phase flow rate = 5
(6) Emulsion flow rate / water phase flow rate = 5
(7) Water phase flow rate / oil phase flow rate = 1
(8) Pre-mixing means: using FIG. 3 (9) D / d2 = 25

(Example 6)
The emulsification step was performed in the same manner as in Example 1 except that the emulsification conditions shown in “5. Emulsification step” described in Example 1 were as follows.

(1) Oil phase flow rate: 1 m / s
(2) Water phase flow velocity: 2.5 m / s
(3) Emulsified liquid flow rate: 5 m / s
(4) Oil / water phase supply mechanism: Use of a triple pipe (Figure 8 shows the outlet structure)
(5) Emulsified liquid flow rate / oil phase flow rate = 5
(6) Emulsion flow rate / water phase flow rate = 2
(7) Water phase flow rate / oil phase flow rate = 2.5
(8) Pre-mixing means: using FIG. 3 (9) D / d2 = 30

(Example 7)
The emulsification step was performed in the same manner as in Example 1 except that the emulsification conditions shown in “5. Emulsification step” described in Example 1 were as follows.

(1) Oil phase flow rate: 1 m / s
(2) Water phase flow velocity: 2.5 m / s
(3) Emulsified liquid flow rate: 5 m / s
(4) Oil / water phase supply mechanism: Use of a triple pipe (Figure 9 shows the outlet structure)
(5) Emulsified liquid flow rate / oil phase flow rate = 5
(6) Emulsion flow rate / water phase flow rate = 2
(7) Water phase flow rate / oil phase flow rate = 2.5
(8) Pre-mixing means: using FIG. 3 (9) D / d2 = 30

(Comparative Example 1)
The emulsification step was performed in the same manner as in Example 1 except that the emulsification conditions shown in “5. Emulsification step” described in Example 1 were as follows.

(1) Oil phase flow rate: 2 m / s
(2) Water phase flow velocity: 0.1 m / s
(3) Emulsion flow rate: 0.3 m / s
(4) Oil / water phase supply mechanism: FIG.
(5) Emulsified liquid flow rate / oil phase flow rate = 0.15
(6) Emulsified liquid flow rate / aqueous phase flow rate = 0.3
(7) Water phase flow rate / oil phase flow rate = 0.05
(8) Pre-mixing means: None

(Comparative Example 2)
The emulsification step was performed in the same manner as in Example 1 except that the emulsification conditions shown in “5. Emulsification step” described in Example 1 were as follows.

(1) Oil phase flow rate: 10 m / s
(2) Water phase flow velocity: 25 m / s
(3) Emulsion flow rate: 10 m / s
(4) Oil / water phase supply mechanism: FIG.
(5) Emulsion flow rate / oil phase flow rate = 1
(6) Emulsified liquid flow rate / water phase flow rate = 0.4
(7) Water phase flow rate / oil phase flow rate = 2.5
(8) Pre-mixing means: None

  Table 1 shows the evaluation results regarding the toners manufactured as in Examples 1 to 7 and Comparative Examples 1 and 2.

  Table 1

  As shown in Table 1, in the examples using the present invention, the toner charge amount was appropriate and the image evaluation was good as compared with the comparative examples.

  Each evaluation method is as follows.

(Emulsified particle size)
The emulsified particle size was measured before the converging tank in FIG.

(Toner particle size)
The toner obtained as described above was subjected to data analysis using a Coulter Multisizer III (manufactured by Coulter), connected to a personal computer (manufactured by IBM) and using dedicated analysis software (manufactured by Coulter). The Kd value was set using standard particles of 10 μm, and the aperture current was set with an automatic setting. As the electrolytic solution, a 1% NaCl aqueous solution was prepared using first grade sodium chloride.

(Regarding the amount of charge)
A developer was prepared by mixing 60 g of the above ferrite carrier and 3 g of toner, 6 g of the developer was weighed, charged into a metal cylinder that could be sealed, and blown to determine the charge amount. The toner concentration is adjusted to 4.5 to 5.5% by weight. The optimum range is −35 ± 4 μC / g.

(About evaluation method of fine line reproducibility)
Fine line reproducibility is obtained by using the developer obtained in the above (with respect to the charge amount) and putting it in a remodeling machine from which the fixing oil portion of an intermediate transfer type commercial color copying machine (IMAGIO COLOR 5000; manufactured by Ricoh) is removed. Running was performed using 6000 paper manufactured by Ricoh with a printing rate of 7% occupation. Compare the original 10th image and the 30,000th image thin line with the original, zoom in with an optical microscope at a magnification of 100x, and evaluate the line omission in 5 stages while comparing it with the stage sample. did. An evaluation of 1 to 5 gave 5 the best, and 3.5 or more was considered acceptable.

1 is an example of a continuous emulsification apparatus for performing a toner production method according to the present invention. It is an example of the method of supplying an emulsified liquid, an aqueous phase, and an oil phase to a continuous emulsifier using a double tube. It is an example of the method of supplying an emulsion, an aqueous phase, and an oil phase to a continuous emulsification device using a triple pipe. It is an example of the method of supplying an emulsified liquid, an aqueous phase, and an oil phase to a continuous emulsifier using a double tube and a mixer. It is an example of the method of supplying an emulsified liquid, an aqueous phase, and an oil phase to a continuous emulsifier using a triple tube and a mixer. It is another example of the method of supplying an emulsion liquid, an aqueous phase, and an oil phase to a continuous emulsifier using a triple tube and a mixer. It is an example of the method of supplying an emulsion liquid, an aqueous phase, and an oil phase to a continuous emulsification apparatus. It is an example of the edge part structure of the pipe | tube which supplies an oil phase. It is another example of the edge part structure of the pipe | tube which supplies an oil phase.

Claims (23)

A step of continuously supplying a dissolved dispersion in which at least two kinds of resins having different molecular weights, a colorant and a release agent are dissolved or dispersed in an organic solvent, and an aqueous medium having resin fine particles insoluble in water; A method for producing a toner comprising a step of emulsifying a colored particle aqueous dispersion comprising a dissolved dispersion and the aqueous medium using a shearing means,
Supplying the dissolved dispersion from the center of the double tube;
Supplying the aqueous medium and the emulsified colored particle aqueous dispersion from a hollow portion adjacent to the central portion;
The dissolved dispersion supplied from the central part, the aqueous medium supplied from the hollow part, and the emulsified colored particle aqueous dispersion are brought into contact with each other, and then emulsified using the shearing means. A method for producing toner.   2. The toner according to claim 1, wherein the contacted dissolved dispersion, the aqueous medium, and the emulsified colored particle aqueous dispersion are premixed and then emulsified using the shearing unit. Production method.   The method for producing toner according to claim 2, wherein the pre-mixing is performed using a static in-tube mixer provided with a liquid divider in a stationary state.   The stationary in-tube mixer has one end of the tube as an inlet and the other end as an outlet, and a guide plate that turns right and a left-turn guide plate along the central axis is divided into the tube in half. The toner manufacturing method according to claim 3, comprising a structure in which the layers are alternately arranged in a direction along the axis.   5. The ratio of the flow rate of supplying the emulsified colored particle aqueous dispersion to the flow rate of supplying the dissolved dispersion in the double tube is 4 or more and 30 or less. The method for producing the toner according to item. A step of continuously supplying a dissolved dispersion in which at least two kinds of resins having different molecular weights, a colorant and a release agent are dissolved or dispersed in an organic solvent, and an aqueous medium having resin fine particles insoluble in water; A method for producing a toner comprising a step of emulsifying a colored particle aqueous dispersion comprising a dissolved dispersion and the aqueous medium using a shearing means,
Supplying the dissolved dispersion from the central part of the triple tube;
Supplying the aqueous medium from a hollow portion adjacent to the central portion;
Supplying the emulsified colored particle aqueous dispersion from the outermost hollow portion adjacent to the hollow portion;
After contacting the dissolved dispersion supplied from the central part, the aqueous medium supplied from the hollow part, and the emulsified colored particle aqueous dispersion supplied from the outermost hollow part, A method for producing a toner, comprising emulsifying using a shearing means.   7. The toner according to claim 6, wherein the contacted dissolved dispersion, the aqueous medium, and the emulsified colored particle aqueous dispersion are premixed and then emulsified using the shearing unit. Manufacturing method. The method for producing toner according to claim 7 , wherein the pre-mixing is performed using a stationary in-tube mixer provided with a liquid divider in a stationary state. The stationary in-tube mixer has one end of the tube as an inlet and the other end as an outlet, and a guide plate that turns right and a left-turn guide plate along the central axis is divided into the tube in half. The toner manufacturing method according to claim 8 , comprising a structure in which the layers are alternately arranged in a direction along the axis. The ratio of the flow rate of supplying the emulsified colored particle aqueous dispersion to the flow rate of supplying the aqueous medium in the triple tube is 4 or more and 25 or less,
Production of the toner according to any one of claims 6 to 9, wherein the flow rate of supplying the aqueous medium for the flow rate of supplying the dissolved dispersion in the triple pipe is 0.5 to 2 Method. The dissolution dispersion flow rate for supplying the method for producing a toner according to any one of claims 1 to 10, characterized in that a 0.1~1.0m / s. Flow rate supplying the aqueous medium, method for producing a toner according to any one of claims 1 to 11, characterized in that the 0.2~5.0m / s. Flow rate supplying the emulsified colored particle dispersion, method for producing a toner according to any one of claims 1 to 12, characterized in that a 2~7m / s. The central portion has a plurality of holes radially arranged with respect to the center of the tube in a wall at an end portion on the downstream side with respect to a direction in which the dissolved dispersion is supplied. The method for producing a toner according to any one of 1 to 13 . A supply means for continuously supplying at least two kinds of resins having different molecular weights, a colorant and a release agent dissolved or dispersed in an organic solvent, and an aqueous medium having resin particles insoluble in water; An apparatus for producing a toner having a shearing means for emulsifying a colored particle aqueous dispersion composed of the dissolved dispersion and the aqueous medium,
The supply means has a double pipe composed of a central portion for supplying the dissolved dispersion, and a hollow portion adjacent to the central portion for supplying the aqueous medium and the emulsified colored particle aqueous dispersion.
The shearing means emulsifies a liquid in which the dissolved dispersion supplied from the central portion, the aqueous medium supplied from the hollow portion, and the emulsified colored particle aqueous dispersion are in contact with each other. Toner manufacturing equipment. A premixing means for premixing the contacted liquid;
The toner manufacturing apparatus according to claim 15 , wherein the shearing unit emulsifies the premixed liquid. 17. The toner manufacturing apparatus according to claim 16 , wherein the pre-mixing means is a static in-pipe mixer provided with a liquid separator in a stationary state. The stationary in-tube mixer has one end of the tube as an inlet and the other end as an outlet, and a guide plate that turns right and a left-turn guide plate along the central axis is divided into the tube in half. 18. The toner manufacturing apparatus according to claim 17 , further comprising a structure in which the layers are alternately arranged in a direction along the axis. A supply means for continuously supplying at least two kinds of resins having different molecular weights, a colorant and a release agent dissolved or dispersed in an organic solvent, and an aqueous medium having resin particles insoluble in water; An apparatus for producing a toner having a shearing means for emulsifying a colored particle aqueous dispersion composed of the dissolved dispersion and the aqueous medium,
The supply means includes a central part for supplying the dissolved dispersion, a hollow part for supplying the aqueous medium, the hollow part for supplying the aqueous medium, and the emulsified colored particle aqueous dispersion for supplying the aqueous medium. Having a triple pipe consisting of the outermost hollow part to be supplied,
In the shearing means, the dissolved dispersion supplied from the central portion, the aqueous medium supplied from the hollow portion, and the emulsified colored particle aqueous dispersion supplied from the outermost hollow portion are in contact with each other. A toner production apparatus for emulsifying the obtained liquid. A premixing means for premixing the contacted liquid;
The toner manufacturing apparatus according to claim 19 , wherein the shearing unit emulsifies the premixed liquid. 21. The toner manufacturing apparatus according to claim 20 , wherein the pre-mixing means is a static in-pipe mixer provided with a liquid separator in a stationary state. The stationary in-tube mixer has one end of the tube as an inlet and the other end as an outlet, and a guide plate that turns right and a left-turn guide plate along the central axis is divided into the tube in half. The toner manufacturing apparatus according to claim 21 , further comprising: a structure alternately arranged in a direction along the axis. The central portion has a plurality of holes radially arranged with respect to the center of the tube in a wall at an end portion on the downstream side with respect to a direction in which the dissolved dispersion is supplied. The toner production apparatus according to any one of 15 to 22 .

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