JP4849828B2 - Toner manufacturing method and toner - Google Patents

Description

The present invention relates to substance production using a microchemical process for producing extremely uniform fine particles using a micro through-hole structure.
The present invention relates to a method for producing a toner used as a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing and the like. More particularly, the present invention relates to a method for producing an electrophotographic toner used in a copying machine, a laser printer, a plain paper fax machine, and the like using a direct or indirect electrophotographic developing system. Further, the present invention relates to a full-color copying machine, a full-color laser printer, a full-color plain paper fax machine and the like using a direct or indirect electrophotographic multicolor image developing system, and a manufacturing method thereof.

(Description of electrophotographic process)
The toner image formed by the electrophotographic process is fixed on the paper surface in the fixing step. At that time, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier (magnetic toner, Non-magnetic toners are known.

(Binder resin for dry toner)
Conventionally, as dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like, a toner binder such as a styrene resin and a polyester resin is melt-kneaded together with a colorant and finely pulverized.

(Problems of pulverized toner)
In order to obtain high-quality and high-quality images, improvements have been made to reduce the particle diameter of the toner, but the particle shape is indefinite in the ordinary kneading and pulverization manufacturing method, The toner is further pulverized by contact stress between the developing roller and the toner supply roller, layer thickness regulating blade, friction charging blade, etc. Or the fluidizing agent is embedded in the toner surface, resulting in a phenomenon that the image quality deteriorates.
Further, due to its shape, the fluidity as a powder is poor, a large amount of fluidization 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 limit on the particle size and cannot cope with further reduction in the particle size.
Furthermore, the process of transferring images formed from multicolor toners from a photoconductor to a transfer medium or paper to create a full-color image has become complicated, and the transferability due to an irregular shape such as pulverized toner has been increased. Due to the inconvenience, problems have arisen such that the transferred image is missing and the amount of toner consumed is large to compensate for it.
Therefore, there is an increasing demand for further improving transfer efficiency to reduce toner consumption to obtain a high-quality image without missing images and to reduce running costs. If the transfer efficiency is very good, there is no need for a cleaning unit for removing untransferred toner from the photoreceptor or transfer medium, which has the advantages of reducing the size and cost of the equipment and eliminating waste toner. Because. Various spherical toner manufacturing methods have been devised to compensate for the disadvantages of such irregular shape effects.

However, the spherical toner cannot be removed by a device (for example, a cleaning blade or a cleaning brush) for removing toner remaining on the photosensitive member or the transfer medium, resulting in poor cleaning. In addition, since the toner is spherical, the surface of the toner is exposed to the outside in all directions, and is easily exposed to contact with a charging member such as a carrier or a charging blade, and the toner is not sufficiently melted and fixing is insufficient. appear. From the viewpoint of energy saving and downsizing of the apparatus, a toner having a higher hot offset generation temperature (hot offset resistance) and a lower fixing temperature (low temperature fixing property) is required.
In addition, heat storage stability is required so that the toner is not blocked during storage and at ambient temperature in the apparatus. In particular, in full-color copying machines and full-color printers, the gloss and color mixing of the image are required, so the toner needs to have a lower melt viscosity, and a sharp-melt polyester toner binder is used. ing.
Since such toner tends to cause hot offset, conventionally, in full-color devices, silicone oil or the like is applied to a heat roll. However, the method of applying silicone oil to the hot roll requires an oil tank and an oil application device, and the device is complicated and large. Moreover, it causes deterioration of the heat roll and requires maintenance every certain period. Furthermore, it is inevitable that oil adheres to copy paper, OHP (overhead projector) film, and the like, especially in OHP, there is a problem of deterioration of color tone due to the adhered oil.

(Polymer dissolution suspension method)
As a method for solving these problems, Patent Document 1 (Japanese Patent Laid-Open No. 7-152202) discusses a method involving volume shrinkage called a polymer dissolution suspension method. In this method, a toner material is dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified and formed into droplets in an aqueous medium containing a dispersant, and then the volatile solvent is removed.

(Emulsification process using microchannels)
The polymer dissolution suspension method has a problem that it is difficult to make the particle size of the droplets monodisperse. As a method for solving this problem, a method for producing a droplet using a microchannel is disclosed in Patent Document 2 (Japanese Patent Laid-Open No. 2004-122107), Patent Document 3 (Japanese Patent Laid-Open No. 2004-197083), and Patent Document 4 ( Japanese Patent Laid-Open No. 2004-202476).

In Patent Document 1 (Japanese Patent Laid-Open No. 7-152202), a droplet containing a toner component is produced by a polymer dissolution suspension method. However, since the shearing force of the homogenizer is too strong, the particle size of the droplet is constant. There is a problem of not becoming.
In Patent Document 2 (Japanese Patent Laid-Open No. 2004-122107), droplets are produced using the microchannel shown in FIG. An aqueous medium is used for the continuous phase, and droplets of the organic solvent are produced by a shearing force generated by the flow of the continuous phase. At this time, the organic solvent is pressed against the wall surface of the microchannel as shown in FIG. 1 and is sandwiched between the aqueous medium and the wall surface. Therefore, the solid component contained in the organic solvent adheres to the wall surface on which the organic solvent is pressed. When the solid component adheres, the interfacial tension between the wall surface and the organic solvent changes, that is, the contact angle of the organic solvent with respect to the wall surface changes, which affects the production of droplets. Furthermore, when used for a long time, the adhered solid component reduces the flow of the flow path, and finally clogging occurs. The technique described in Patent Document 2 has the above problems.
In the techniques described in Patent Document 3 (Japanese Patent Laid-Open No. 2004-197083) and Patent Document 4 (Japanese Patent Laid-Open No. 2004-202476), droplets are produced using the microchannel shown in FIG. The difference from the technique described in Patent Document 2 is that, as specified in Patent Document 4, the joining portion where the flow of the lipophilic organic solvent solution that is the dispersed phase and the flow of the aqueous phase that is the continuous phase merges. The liquid droplets are produced by bringing the dispersed phase into contact with the continuous phase so as to sandwich the sheared phase. Therefore, although the problem of patent document 2 is solved to some extent, it may adhere to the upper and lower wall surfaces of the flow path and is not sufficient. In addition, after collecting the formed droplets, it is necessary to remove the organic solvent from the droplets. Droplet preparation and organic solvent removal are different processes, and there is a problem that a new organic solvent removal process is required. It is pointed out in Japanese Patent Application Laid-Open No. 2002-122107 of the above-mentioned Patent Document 2 that a separate “organic solvent removing step” is likely to cause the coalescence of droplets in the dispersion liquid prepared. That's right.

  In addition, these Patent Documents 2 to 4 show that the resin melt in the droplets of the dispersed phase in the continuous phase is cross-linked and cured in the channel (flow path). No attempt has been made to aggressively remove organic solvents. Therefore, the purpose of removing the organic solvent from the droplets in the channel is also disclosed to increase the temperature of the aqueous medium and to use an amount of the aqueous medium sufficient to remove the organic solvent to achieve this. Not even. The idea of not only smoothly producing an O / W type or W / O type emulsion having a uniform small particle size in a channel but also removing an organic solvent from the emulsion in a non-open channel is disclosed in Patent Document 2 to 4 are not disclosed.

JP-A-7-152202 JP 2004-122107 A JP 2004 197083 A JP 2004-202476 A

An object of the present invention is to provide an emulsified dispersion by dispersing an organic solvent containing at least a resin and a colorant in an aqueous medium in a flow path in view of the current state of the prior art. An object of the present invention is to provide an electrophotographic toner manufacturing method and an electrophotographic toner for removing and manufacturing an electrophotographic toner.
In particular, an object of the present invention is to provide a method for producing an electrophotographic toner including a specific measure of preparing an emulsified dispersion in a non-open channel and removing an organic solvent from the emulsion.
Another object of the present invention is to provide a method for producing an electrophotographic toner that solves the problem that the particle size of droplets does not become constant because the shearing force is too strong when preparing an emulsified dispersion.

In addition, when preparing the emulsified dispersion, the organic solvent droplets are pressed against the inner wall of the microchannel, and the solid component contained in the organic solvent is prevented from adhering to the wall on which the organic solvent is pressed. The object is to provide a method for producing a photographic toner.
Another object of the present invention is to provide a method for producing an electrophotographic toner in which a separate post-process for removing an organic solvent from a liquid droplet is omitted after the prepared liquid droplets are collected or the burden on the post-process is reduced.

  In addition, the temperature of the aqueous medium in the flow path is increased to increase the removal of the organic solvent from the liquid droplets, and the electrophotographic toner can be removed from the liquid droplets by using a sufficient amount of the aqueous medium in the flow path. An object of the present invention is to provide a method for producing an electrophotographic toner that facilitates the removal of the organic solvent.

  It is another object of the present invention to provide a method for producing an electrophotographic toner including specific measures for using a sufficient amount of an aqueous medium in a flow path.

  It is another object of the present invention to provide a method for producing an electrophotographic toner using a toner production system having a micro-channel having a size capable of producing droplets particularly suitable for such an electrophotographic toner production purpose.

  Furthermore, another object of the present invention is to provide a method for producing an electrophotographic toner using a toner production system in which an appropriate speed of a liquid flowing in such a microchannel is defined.

  It is another object of the present invention to provide a method for producing an electrophotographic toner using a toner production system having a micro-channel having a size capable of flowing an aqueous medium necessary for removing an organic solvent from droplets.

  Furthermore, another object of the present invention is to provide a method for producing an electrophotographic toner using a toner production system having a microchannel with a wall surface suitable for water and having no channel blockage.

  Furthermore, by adopting specific measures to achieve sufficient shear force for droplet generation without using excessive flow rate fluid, the micro flow that can make the droplet size monodisperse. An object of the present invention is to provide a method for producing an electrophotographic toner using a toner production system having a path.

The present inventors have developed a dry toner excellent in uniform charging, powder flowability and transferability when used as a small particle size monodisperse toner, particularly a dry toner excellent in image quality when used in a full-color copying machine, and the like. As a result of intensive studies to develop a dry toner production process having a high yield in the process, no clogging in the emulsification process, and an extremely compact plant configuration, the present invention has been achieved.
The toner comprising the small particle size and monodisperse particles obtained as described above can be developed faithfully to the latent image drawn at high resolution on the photoreceptor.

That is, the said subject is solved by (1)-(11) of this invention.
(1) “A composition obtained by dissolving or dispersing a toner composition containing at least a resin and a colorant in an organic solvent is dispersed in an aqueous medium to obtain an emulsified dispersion, and the organic solvent is removed from the emulsified dispersion. An electrophotographic toner produced by a method for producing an electrophotographic toner,
The organic solvent of the composition liquid in which the toner composition containing the resin and the colorant is dissolved or dispersed has solubility in an aqueous solvent,
1st-3rd flow path which has the part which introduce | transduces a liquid, and 4th flow path which has a part which continues to this 1st-3rd flow path and collect | recovers liquid, 1st flow path The second and third flow paths are symmetrically arranged around the center, and the liquid outlet portion of the first, second, and third flow paths and the liquid inlet portion of the fourth flow path are the first flow path and the fourth flow path. Using microchannels joined so that their channels are on the same axis,
Introducing an organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed into the first flow path;
An aqueous medium is introduced into the second and third flow paths,
Forming droplets of an organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed at the merging portion of the first, second, third and fourth channels,
A method for producing an electrophotographic toner, comprising: removing an organic solvent from a droplet of an organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed in the fourth channel. "
(2) “having a heating mechanism in the fourth flow path,
Increasing the temperature of the aqueous medium by the heating mechanism,
Item (1) is characterized in that the removal of the organic solvent from the droplets of the organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed in the fourth flow path is promoted. Manufacturing method of electrophotographic toner. "
(3) “A composition liquid obtained by dissolving or dispersing a toner composition containing at least a resin and a colorant in an organic solvent is dispersed in an aqueous medium to obtain an emulsified dispersion, and the organic solvent is removed from the emulsified dispersion. In the method for producing an electrophotographic toner and the electrophotographic toner produced by the production method,
The organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed has solubility in an aqueous solvent,
A first to third channel having a portion for introducing a liquid, a fourth channel connected to the first to third channels, a portion for introducing a liquid from the fourth channel, and the A fifth flow path having a portion for collecting the liquid, the second and third flow paths are symmetrically arranged around the first flow path, and the liquid in the first, second, and third flow paths The outlet portion and the liquid inlet portion of the fourth flow path are joined so that the first flow path and the fourth flow path are on the same axis, and the fourth flow path is in the middle of the fifth flow path. Using the micro flow path where the liquid outlet part of
Introducing an organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed into the first flow path;
An aqueous medium is introduced into the second and third flow paths,
Forming droplets of an organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed at the merging portion of the first, second, third and fourth channels,
An electrophotography that promotes removal of an organic solvent from a droplet of an organic solvent in which a toner composition containing the resin and a colorant is dissolved or dispersed in the fourth flow path and the fifth flow path. For manufacturing toner. "
(4) “having a heating mechanism in the fourth channel and the fifth channel,
Increasing the temperature of the aqueous medium by the heating mechanism,
The removal of the organic solvent from the droplets of the organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed in the fourth flow path and the fifth flow path is promoted. (3) A method for producing an electrophotographic toner according to item (3). "
(5) “W1 and D1 are the width and depth of the first channel of the microchannel, and D is the depth of the channel other than the first channel ,
2μm ≦ W1 ≦ 30μm
3 ≦ D1 / W1 ≦ 5
D1 ≒ D
The method for producing an electrophotographic toner according to any one of (1) to (4), wherein a microchannel satisfying the above relationship is used. "
(6) “The viscosity of the aqueous medium is η, the speed of the aqueous medium flowing through the second and third microchannels is Vc1, the speed of the aqueous medium flowing through the fourth microchannel is Vc2, and the first microchannel is Vd is the velocity of the organic solvent flowing to the surface, and σ is the interfacial tension between the aqueous medium and the organic solvent,
0.0001 ≦ η × Vc1 / σ ≦ 0.01
0.0001 × Vc1 ≦ Vd <0.5 × Vc1
Vc1≈Vc2
The method for producing an electrophotographic toner according to any one of (1) to (4), wherein the toner is produced under a condition that satisfies the above relationship. "
(7) “The widths of the fourth and fifth channels of the microchannel are W4 and W5, respectively.
The method for producing an electrophotographic toner as described in (3) or (4) above, wherein a microchannel satisfying the relationship of W4 <W5 is used. "
(8) “The method for producing an electrophotographic toner according to any one of (1) to (4) above, wherein the microchannel is hydrophilic.”
(9) “A vibration component is imparted to the flow of the organic solvent in which the toner composition containing the resin and the colorant is dissolved. Any one of Items (1) to (4)” The manufacturing method of the electrophotographic toner of description. "
(10) “The method for producing an electrophotographic toner according to any one of Items (1) to (4), wherein a vibration component is imparted to the flow of the aqueous medium”.
(11) “An electrophotographic toner produced by the method for producing an electrophotographic toner according to any one of (1) to (10)”.

(Operational effect on claim 1)
In claim 1, an organic solvent containing at least a resin and a colorant is dispersed in an aqueous medium using a microchannel to obtain an emulsified dispersion, and the organic solvent is removed from the emulsified dispersion to obtain an electron. Since the photographic toner is produced, the toner diameter can be monodispersed.
Furthermore, since the second and third flow paths are symmetrically arranged on both sides of the first flow path, and the organic solvent is sandwiched between the aqueous media, droplets are formed. Can be made the same, and a droplet can be formed at the center of the fourth flow path. Accordingly, the droplet does not contact the wall surface, and the solid component in the organic solvent does not adhere to the wall surface. Here, “symmetric” means a symmetrical position or a position that is substantially symmetrical enough to form an aqueous medium flow that disperses droplets by sandwiching an organic solvent containing a resin and a colorant. Although it depends on the flow velocity and flow rate, it means a position deviation range within 5 mm.
Further, since the organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed is at least partially soluble in the aqueous solvent, the organic solvent is dropped in the fourth channel. To the aqueous medium, and the organic solvent is removed from the droplets. The organic solvent is preferably one that is not completely soluble or miscible with the aqueous solvent (for O / W type or W / O type emulsion formation). Therefore, the droplet formation and the removal of the organic solvent from the droplet can be performed with the same apparatus, and the process can be simplified.

(Operational effect on claim 2)
According to the second aspect, since the heating mechanism is provided in the fourth flow path and the temperature of the aqueous medium is increased, the degree of removal of the organic solvent from the droplets can be made better than that of the first aspect.

(Operational effect on claim 3)
According to the third aspect, when the drying of the liquid droplet is not completed in the fourth flow path, the fourth flow path is connected to the fifth flow path in which the aqueous medium flows, so that the organic solvent Can be further removed.

(Operational effect on claim 4)
In claim 4, since the heating mechanism is provided in the fourth flow path and the fifth flow path, and the temperature of the aqueous medium is increased, the degree of removal of the organic solvent from the droplets is higher than that in claim 3. Can be better.

(Operational effect on claim 5)
In claim 5, since the width W1 of the first flow path is 2 μm ≦ W1 ≦ 30 μm, the diameter of the formed droplet is approximately 2 μm ≦ W1 ≦ 35 μm, and the toner particle size suitable for the electrophotographic toner Can be obtained.
Further, since the aspect ratio of the first flow path is 3 ≦ D1 / W1 ≦ 5, and the depth of the second flow path is equal to the depth of the first flow path, the formed droplets The depth of the flow path becomes larger than the diameter of the liquid crystal, so that the droplets do not contact the upper and lower wall surfaces of the flow path, and solid components in the organic solvent can be prevented from adhering to the wall surfaces.

(Operational effect on claim 6)
In claim 6, the viscosity of the aqueous medium is η, the speed of the aqueous medium flowing through the second and third microchannels is Vc1, the speed of the aqueous medium flowing through the fourth microchannel is Vc2, and the first microflow Vd is the velocity of the organic solvent flowing in the road, and σ is the interfacial tension between the aqueous medium and the organic solvent,
0.0001 ≦ η × Vc1 / σ ≦ 0.01
0.0001 × Vc1 ≦ Vd <0.5 × Vc1
Vc1≈Vc2
Since the conditions satisfy the above relationship, droplets can be formed stably.

(Operational effect on claim 7)
In claim 7, since the relationship between the widths W4 and W5 of the fourth and fifth flow paths is W4 <W5, a larger amount of continuous phase than the continuous phase flowing in the fourth flow path is used as the fifth flow path. The organic solvent can be sufficiently removed from the droplets that can be flowed.

(Operational effect on claim 8)
According to the eighth aspect of the present invention, since the microchannel is hydrophilic, it is difficult for the organic solvent to come into contact with the wall surface of the microchannel, and solid components in the organic solvent can be prevented from adhering to the wall surface.

(Operational effect on claim 9)
According to the ninth aspect of the invention, since the vibration component is added to the flow of the organic solvent, the formation speed of the organic solvent droplets can be increased.

(Operational effect on claim 10)
According to the tenth aspect, since the vibration component is added to the flow of the aqueous medium, the formation speed of the organic solvent droplets can be increased.

(Volume shrinkage)
Obtained by volume shrinkage at a shrinkage rate of 10% to 90% in an aqueous medium, the volume average particle diameter is 1 to 10 μm, the ratio of the volume average particle diameter to the number average particle diameter is 1.10 to 1.25, circular The dry toner with a degree of 0.93-0.99 excels in heat-resistant storage stability, low-temperature fixability, and hot-offset resistance, especially when used in full-color copiers, etc. Furthermore, with a two-component developer, even if a long-term balance of the toner is performed, fluctuations in the particle size of the toner in the developer are reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. It is done. 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 thinned. 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. It was also clarified that the same applies when the volume average particle diameter / number average particle diameter is larger than 1.25.
Further, when the volume average particle size / number average particle size is smaller than 1.10, 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. As a result, it became clear that the cleaning property may be deteriorated.
Particularly in the present invention, in order to give an appropriate shape, it is important to use a solid fine particle dispersant in a production method having a volume shrinkage step of 10 to 90% in volumetric shrinkage in an aqueous medium. Here, the volume shrinkage is Vo, the volume of the oil phase (dispersed phase) in which the toner composition before being emulsified and dispersed in the aqueous medium is Vo, and the volume of the dispersed phase after removing the emulsified dispersion and volatile components is Vt. Then, volumetric shrinkage rate = (1−Vt / Vo) × 100
The change in characteristics before emulsification and after granulation is measured. Specifically 1) A method of measuring the weight and true specific gravity of the oil phase before emulsification and the obtained toner 2) Measure the average particle size of the particles after removing the liquid droplets and volatile components after emulsification in an aqueous medium, It can be determined by a method such as a volume conversion method.

(Circularity measurement method)
It is important that the toner in the present invention has a specific shape and distribution of the shape. When the average circularity is less than 0.95 and the amorphous shape is too far from the spherical shape, there is no satisfactory transferability and dust. A high-quality image cannot be obtained. As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. A toner with an average circularity of 0.95 or more, which is a value obtained by dividing the perimeter of an equivalent circle with the same projected area obtained by this method by the perimeter of the actual particle, is a high-definition image with a reproducibility of an appropriate density. It was found to be effective in forming. More preferably, the average circularity is 0.96 to 0.98. This value can be measured as an average circularity by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance. About 0.1 to 0.5 g. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

(Glass transition point measurement method)
In the DSC measurement in the present invention, since the heat exchange of the toner is measured and the behavior is observed, it is necessary to measure with a differential scanning calorimeter of high accuracy internal heat type input compensation type from the measurement principle. For example, DSC-200 manufactured by Seiko Electronics Co., Ltd. can be used.
The measurement method is performed according to ASTM D3418-82. The DSC curve used in the present invention is the DSC curve measured when the temperature is lowered once and the temperature is raised in the range of a temperature rate of 10 ° C./min and a temperature of 0 to 200 ° C. after raising the temperature once and taking a previous history. Specifically, the measurement is performed according to the following procedure.
(1). The sample is pulverized, a weight of 10 ± 1 mg is weighed into an aluminum sample container, and an aluminum lid is crimped from above.
(2). The glass transition point (Tg) is measured by DSC method in a nitrogen atmosphere.
Here, after heating the sample from room temperature to 200 ° C. at a rate of temperature increase of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, cooled to 0 ° C. at a temperature decrease rate of 50 ° C./min and left for 10 min. DSC measurement is performed by heating again to 200 ° C. at a rate of temperature increase of 10 ° C./min. At this time, Tg is the temperature at which the curve is clearly separated from the baseline at the time of temperature rise, that is, the differential value of the peak curve is positive, and the temperature at which the differential value starts to increase or the differential value from negative to positive Temperature.

(Molecular weight measurement method)
The molecular weight distribution of the toner binder component of the present invention is measured by the following method. After about 1 g of toner is carefully evaluated in an Erlenmeyer flask, 10 to 20 g of THF (tetrahydrofuran) is added to obtain a THF solution having a binder concentration of 5 to 10%. The column is stabilized in a heat chamber at 40 ° C., and THF as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min, and 20 μl of the THF sample solution is injected. The molecular weight of the sample is calculated from the relationship between the retention value and the logarithmic value of a calibration curve prepared from a monodisperse polystyrene standard sample. A calibration curve is created using a polystyrene standard sample. As a monodisperse polystyrene standard sample, the thing of the range of molecular weight 2.7 * 10 < ² > -6.2 * 10 < ⁶ > by Tosoh Corporation is used, for example. A refractive index (RI) detector is used as the detector. As the column, for example, TSKgel, G1000H, G2000H, G2500H, G3000H, G4000H, G5000H, G6000H, G7000H, GMH manufactured by Tosoh Corporation are used in combination.
The main peak molecular weight is usually 1000 to 30000, preferably 1500 to 10000, more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 30000, low-temperature fixability will deteriorate. The content of components having a molecular weight of 30000 or more is 1 to 10%, preferably 3 to 6%. If it is less than 1%, sufficient hot offset resistance cannot be obtained, and if it is 10% or more, glossiness and transparency are deteriorated. The value of Mw / Mn is preferably 5 or less. When it is 5 or more, the sharp melt property is lacking and the glossiness is impaired.

(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 10 μm standard particles, and the aperture current was set at an automatic setting. As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary 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 electrolyte solution in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number distribution of the toner particles of 2 μm or more are measured by 50,000 counts using a 100 μm aperture tube. And calculated. Then, 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.

(Coloring agent)
It is important that the toner in the present invention has a specific shape and distribution of the shape. When the average circularity is less than 0.95 and the amorphous shape is too far from the spherical shape, there is no satisfactory transferability and dust. A high-quality image cannot be obtained. As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. A toner with an average circularity of 0.95 or more, which is a value obtained by dividing the perimeter of an equivalent circle with the same projected area obtained by this method by the perimeter of the actual particle, is a high-definition image with a reproducibility of an appropriate density. More preferably, the average circularity is 0.96 to 0.98, which has been found to be effective to form. This value can be measured as an average circularity by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance. About 0.1 to 0.5 g. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

(Release agent)
Further, a wax can be contained together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention, such as 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. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, 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.

(resin)
The resin constituting the toner in the present invention is, for example, a heavy polymer that contains at least one selected from a styrene monomer, a (meth) acrylic monomer, and a (meth) acrylic acid ester monomer as an essential component. It is preferable that it is composed of coalescence. Examples of the styrene monomer that can be used include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,3-dimethylstyrene, 2, 4-dimethylstyrene, pn-butylstyrene, pt-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn -Dodecyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, 3,4-dichloro styrene, etc. can be mentioned. These monomers may be used alone or in combination of two or more.

  Examples of the acrylic ester or methacrylic ester that can be used include methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, propyl acrylate, octyl acrylate, dodecyl acrylate, lauryl acrylate, and acrylic acid. Acrylate esters such as 2-ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate; for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate , Isobutyl methacrylate, octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacryl Dimethylaminoethyl methacrylate esters such as diethylaminoethyl methacrylate; and the like.

Further, a polyester resin, an epoxy resin, or a polyol resin may be used as a resin constituting the toner. The polyhydric alcohol constituting the polyester resin includes an ethylene oxide adduct of bisphenol A, a propylene oxide adduct of bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,5-pentanediol, Examples of 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene glycol, 1,4-cyclohexanedimethanol and trifunctional or higher alcohols include trimethylolpropane and pentaerythritol. Polyester acids constituting the polyester resin include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, paraphenylene dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, glutaric acid, adipic acid, and suberin. Examples of the acid, azelaic acid, sebacic acid, dodecanedioic acid, and trifunctional or higher acid components include trimellitic acid and pyromellitic acid. If a trihydric or higher polyhydric alcohol or polyvalent carboxylic acid is used, the resin may be cross-linked, which may be advantageous for offset resistance.
Examples of the epoxy resin and polyol resin include resins made from bisphenol A and epichlorohydrin, polyol glycidyl ester type, and polyacid glycidyl ester type.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.
In the present invention, the amount of charge control agent used is determined 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.

(Organic solvent)
The organic solvent used in the present invention is preferably an organic solvent that can dissolve the resin component and dissolve or disperse additive components such as a colorant, a release product, and a charge control agent. Furthermore, the organic solvent must be dissolved in the aqueous medium described in claim 1. Specifically, dichloromethane, ethanol, butanol, tetrahydrofuran, methyl acetate, ethyl acetate, isopropyl acetate, acetone, methyl ethyl ketone, diacetone alcohol, cyclohexanone, benzyl alcohol and the like can be used alone or in combination of two or more. A partially soluble solvent such as ethyl acetate and a solvent having high solubility or miscibility such as tetrahydrofuran can be mixed and used, and the solubility in an aqueous solvent can be adjusted by the mixing ratio. The usage-amount of an organic solvent is 0-300 weight part normally with respect to 10 weight part of resin components, Preferably it is 0-100 weight part, More preferably, it is 10-70 weight part.

(Aqueous medium)
The aqueous medium used in the present invention may be water alone, or 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.

(Micro channel: depth)
3 and 4 are plan views of the microchannel, but the depth of the microchannel needs to be deeper than the width of the first channel. The droplet diameter of the organic solvent formed in the micro flow path is generally determined by the smaller one of the width and the depth of the first flow path. If the depth of the first channel is made larger than the width as in the present invention, the droplet diameter of the organic solvent is smaller than the depth, so that the droplet is less likely to contact the upper and lower wall surfaces of the microchannel. . Thereby, the solid component in the organic solvent does not adhere to the wall surface, and the clogging of the microchannel can be prevented. Preferably, the depth is between 3 and 5 as in claim 5. That is, when the aspect ratio is 3 or less, the solid component adheres to the upper and lower wall surfaces because the depth is insufficient. When the aspect ratio is 5 or more, the organic solvent droplets are not formed well.

(Micro channel: width)
The width of the first flow path is determined in consideration of the volume shrinkage rate of the organic solvent. For example, when producing toner having a diameter of 5 μm, if the volume shrinkage of the organic solvent is 90%, the required width of the first flow path is about 10 μm. The diameter of the organic solvent formed in the micro flow path is substantially equal to the width of the first flow path or slightly larger than the width of the first flow path. Since the required toner diameter is about 2 to 15 μm and the volume shrinkage is 10 to 90%, the width of the first flow path is 2 to 30 μm as shown in claim 5.

(Micro channel: granulation)
An organic solvent in which a toner composition containing a resin and a colorant is dissolved or dispersed is introduced into the first channel. An aqueous medium is introduced into the second and third flow paths. Since the second and third flow paths are symmetrically arranged in the first flow path, the shearing force applied by the aqueous medium to the organic solvent is also applied symmetrically. Therefore, droplet formation is also symmetric and good. In addition, since the droplet is formed and flows at the center of the fourth flow path, the liquid droplet does not contact the wall surface of the fourth flow path, and clogging can be prevented. In the microchannel, the flow velocity near the wall surface is close to zero, and the flow velocity in the central portion is maximized. Therefore, the liquid droplet does not contact the wall surface by moving along the flow in the central portion of the microchannel.
Further, the formation of droplets depends on the capillary number Ca of the aqueous medium. Capillary number Ca is η × Vc1 where η is the viscosity of the aqueous medium, Vc1 is the speed of the aqueous medium in the second and third microchannels, and σ is the interfacial tension between the aqueous medium and the organic solvent. / Σ. Generally, when the number of capillaries Ca is small, a shearing force necessary for forming a droplet cannot be obtained, and a droplet cannot be formed. When the capillary number Ca is large, the shearing force becomes too strong, the formation of the droplet becomes unstable, and the diameter of the droplet does not become constant.
In addition, the formation of droplets depends on the speed Vc1 of the aqueous medium in the second and third microchannels and the speed Vd of the organic solvent in the first microchannel. Generally, when the velocity Vc1 of the aqueous medium and the velocity Vd of the organic solvent are substantially equal, a laminar flow occurs and no droplet is formed. When the speed Vc1 of the aqueous medium is higher than the speed Vd of the organic solvent, droplets of the aqueous medium are formed.
The formation of the liquid droplets depends on the speed Vc1 of the aqueous medium in the second and third microchannels and the speed Vc2 of the aqueous medium in the fourth microchannel. In general, when the width of the fourth microchannel is sufficiently larger than the width of the first to third microchannels, the velocity Vc2 of the aqueous medium in the fourth microchannel is the second and third It becomes too small with respect to the velocity Vc1 of the aqueous medium in the microchannel. For this reason, the shearing force is also reduced and droplets cannot be formed. When the width of the fourth microchannel is sufficiently smaller than the width of the first to third microchannels, the velocity Vc2 of the aqueous medium in the fourth microchannel is in the second and third microchannels. It becomes too large for the speed Vc1 of the aqueous medium. For this reason, the shearing force also increases, the formation of the droplet becomes unstable, and the diameter of the droplet does not become constant. For example, when using a micro flow channel in which the outlets of the first to third flow channels as shown in FIG. 10 are opened, droplets could not be formed. In addition, when a micro flow channel having a fourth flow channel width about half of the second and third flow channel widths was used, the dispersion value of the liquid droplets deteriorated.

As a result of the experiment, it was found that organic solvent droplets can be stably formed under the following conditions. The experimental results are shown in FIGS.
0.0001 ≦ η × Vc1 / σ ≦ 0.01
0.0001 × Vc1 ≦ Vd <0.5 × Vc1
Vc1≈Vc2

(Micro channel: organic solvent removal)
After the formation of the organic solvent droplets, the droplets are carried along the flow of the aqueous medium through the fourth channel as shown in FIG. In the present invention, since the organic solvent that dissolves in water is used, the organic solvent dissolves in the aqueous medium, the solid component concentration in the droplet increases, and finally only the solid component is obtained. When the volume shrinkage is small or the solubility of the organic solvent in water is large, the organic solvent can be completely removed by the method shown in FIG.
However, when the volumetric shrinkage rate is large or the solubility of the organic solvent in water is not so high, the organic solvent that dissolves in the aqueous medium in the fourth flow path reaches saturation and does not dissolve any more. In this case, as shown in FIG. 4, a fifth channel is newly provided, and the organic solvent is removed in the aqueous medium of the fifth channel. The width of the fifth channel is made larger than the width of the fourth channel so that the organic solvent in the aqueous medium does not reach saturation. Moreover, as shown in FIG. 5, a heating part is provided, the temperature of an aqueous medium is raised, and the solubility of an organic solvent is enlarged.

(Micro channel: Hydrophilization)
The flow path of the present invention is surface-treated so that the wall surface becomes hydrophilic. As the surface treatment means, hydrophilicity such as sputtering treatment of SiO ₂ and thermal oxidation treatment of a metal substrate is preferable. FIG. 6 shows a method for producing a hydrophilic channel. A SiO ₂ sputtering process is performed on the surfaces of the glass substrate on which the microchannel is formed and the glass substrate on which the through hole for introducing or collecting the liquid in the microchannel is formed. Thereafter, the two glass substrates are bonded together to obtain the flow path of the present invention.
The definition of hydrophilicity required in the present invention will be described with reference to FIG. This is explained by the contact angle between the glass substrate surface and the aqueous medium. The contact angle between the aqueous medium and the substrate is desirably 30 degrees or less. More desirably, it is 10 degrees or less.
By making the wall surface of the microchannel hydrophilic as in the present invention, the droplets of the organic solvent do not come into contact, and the solid component in the organic solvent does not adhere to the wall surface. Therefore, clogging of the microchannel can be prevented.

(Micro channel: Vibration)
The reason why vibration is necessary in the present invention will be described.
As described in the prescribed part of the width of the flow path, the aqueous medium can be stably granulated within a certain flow velocity range. When the flow rate of the aqueous medium is less than a certain flow rate F1, granulation cannot be performed because the shearing force is too small. In addition, when the flow rate of the aqueous medium is equal to or higher than a certain flow rate F2, the shearing force is too strong and stable granulation cannot be performed. As a result, the increase in the average particle size and the deterioration of the particle size distribution become remarkable, and it becomes impossible to obtain a toner that gives high image quality. The upper and lower limits of the flow rate F1 and F2 of the aqueous medium can be uniquely determined because it varies depending on various parameters such as the viscosity of the organic solvent and the aqueous medium, the interfacial tension, the contact angle between the flow path wall surface and the micro flow path size. is not.
In the present invention, vibration is applied to the organic solvent or the aqueous medium in order to increase the upper and lower limits of the flow rates F1 and F2 of the aqueous medium. That is, the upper limit value F2 of the flow rate of the aqueous medium is increased, and it becomes possible to granulate a larger flow rate organic solvent.
As a means for imparting vibration, as shown in FIG. 8, the organic solvent that passes through the pipe by a mechanism in which a part of the pipe for introducing the organic solvent into the microchannel can mechanically impart vibration from the outside is used. The linear velocity can be changed. The vibration can be controlled in frequency and amplitude by a pulse generator. In the organic solvent, a vibration component is added to the linear velocity in the microchannel, and shearing is promoted according to the cycle. The vibration period is preferably 5 to 10 kHz, but more preferably 10 to 1 kHz.

(Micro channel: integration)
An example in which the microchannels used in the present invention are integrated is shown in FIG. By laminating a plurality of glass substrates on which microchannels are formed, they can be integrated in the thickness direction. Integration is possible without increasing the number of pipes for introducing and recovering liquid.

(Other dispersants used at the time of emulsification or added later)
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, alkyltrimethylammonium salts, Nonionic interfaces such as dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, quaternary ammonium salt type cationic surfactants such as benzethonium chloride, fatty acid amide derivatives, polyhydric alcohol derivatives, etc. Activators include amphoteric surfactants such as alanine, dodecyl di (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. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is 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 (Daikin Kogyo Co., Ltd.), Mega-Fac F-l0, F-l20, 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).

  Examples of cationic surfactants include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, benza Luconium 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) , Megafac 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, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having nitrogen atoms or heterocyclic rings thereof, polyoxyethylene, polyoxypropylene, polymers 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 may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

  The elongation and / or cross-linking reaction time is selected depending on the reactivity 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. is there. 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.

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 lower the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron Examples include a system (manufactured by Kawasaki Heavy Industries, Ltd.) and an automatic mortar.

(External additive)
When preparing the developer, in order to improve the flowability, storage stability, developability, and transferability of the developer, the hydrophobic silica fine powder listed above in addition to the developer produced as described above, etc. Inorganic fine particles 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.

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, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

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

  Such 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 with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of carrier. Part 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 chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexa Fluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro such as terpolymers of emission and 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 Hereinafter, although an Example and a comparative example demonstrate this invention further, this invention is not limited to this.
(Particle size)
As an apparatus for measuring the particle size distribution of toner particles by the Coulter counter method, there are Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using first grade sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 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 treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter of the toner can be obtained.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

(saturation)
A solid image having an adhesion amount of 1.00 ± 0.05 mg / cm ^{2 on} a copy paper (TYPE 6000 <70W> manufactured by Ricoh Co., Ltd.) was created at a fixing roller surface temperature of 160 ± 2 ° C. using immagio Neo 450 manufactured by Ricoh. The saturation (C *) of the monochromatic solid image was measured by X-Rite 938, and was ranked in five stages according to the following criteria. Here, the higher the saturation, the brighter the color is without turbidity.
A: 76 or more O: 72-76
Δ: 64-72
X: Less than 64

Example 1
In a sealed pot, 10 parts by weight of polyester resin (Mn = 14,000) is dissolved in 100 parts by weight of ethyl acetate, 2 parts by weight of carbon black and 2 parts by weight of carnauba wax are added, and 5 mmφ zirconia beads are used. Ball mill dispersion is performed for 24 hours to prepare a composition liquid of the toner composition. 5 parts by weight of sodium dodecylbenzenesulfonate is completely dissolved in 1000 parts by weight of water to obtain an aqueous medium.
The composition liquid of the toner composition and the aqueous medium are introduced into the microchannel according to claim 4. The widths of the first to fifth channels are 10 μm, 10 μm, 10 μm, 20 μm, and 40 μm, respectively, and the depth is 40 μm. The velocity Vd in the first flow path of the composition liquid of the toner composition is 0.005 m / s, and the speed Vc1 in the second and third flow paths of the aqueous medium is 0.1 m / s. Liquid feeding is performed using a syringe pump. The speed of the aqueous medium in the fourth channel is approximately 0.1 m / s. Under such conditions, droplets of the composition liquid of the toner composition are formed, and the fourth and fifth flow paths are heated with a heater to dissolve ethyl acetate in the aqueous medium. The average particle diameter Dm of the dispersoid in the dispersion thus obtained is 5.3 μm.
Thereafter, the operation of adding pure water to the dispersion and filtering is repeated twice to prepare a uniform slurry. The slurry is dried by a spray dryer to produce a granular material. Toner particles having a volume average particle diameter of 5.0 μm and a dispersion value of 6.0% were obtained.

(Example 2)
In a sealed pot, 30 parts by weight of polyester resin (Mn = 14,000) is dissolved in 100 parts by weight of methyl ethyl ketone, 4 parts by weight of carbon black and 4 parts by weight of carnauba wax are added, and 24 mm of 5 mmφ zirconia beads are used. A ball mill dispersion is performed for a time to prepare a composition liquid of the toner composition. 5 parts by weight of sodium dodecylbenzenesulfonate is completely dissolved in 1000 parts by weight of water to obtain an aqueous medium.
The composition liquid of the toner composition and the aqueous medium are introduced into the microchannel according to claim 3. The widths of the first to fifth channels are 6 μm, 10 μm, 10 μm, 20 μm, and 40 μm, respectively, and the depth is 30 μm. The velocity Vd in the first flow path of the composition liquid of the toner composition is 0.001 m / s, and the speed Vc1 in the second and third flow paths of the aqueous medium is 0.1 m / s. Liquid feeding is performed using a syringe pump. The speed of the aqueous medium in the fourth channel is approximately 0.1 m / s. Under such conditions, droplets of the composition liquid of the toner composition are formed, and methyl ethyl ketone is dissolved in the aqueous medium. The average particle diameter Dm of the dispersoid in the dispersion thus obtained is 5.0 μm. Although heating is performed in Example 1, heating is not performed in Example 2. This is because the solubility of methyl ethyl ketone in water is higher than that of ethyl acetate in Example 1, so that it dissolves in an aqueous medium without heating.
Thereafter, the operation of adding pure water to the dispersion and filtering is repeated twice to prepare a uniform slurry. The slurry is dried by a spray dryer to produce a granular material. Toner particles having a volume average particle diameter of 4.6 μm and a dispersion value of 6.0% were obtained.

(Example 3)
In a sealed pot, 80 parts by weight of a polyester resin (Mn = 14,000) is dissolved in 100 parts by weight of tetrahydrofuran, 8 parts by weight of carbon black and 8 parts by weight of carnauba wax are added, and 24 mm of 5 mmφ zirconia beads are used. A ball mill dispersion is performed for a time to prepare a composition liquid of the toner composition. 5 parts by weight of sodium dodecylbenzenesulfonate is completely dissolved in 1000 parts by weight of water to obtain an aqueous medium.
The composition liquid of the toner composition and the aqueous medium are introduced into the microchannel according to claim 1 and claim 9. The widths of the first to fourth channels are 5 μm, 10 μm, 10 μm, and 20 μm, respectively, and the depth is 20 μm. The velocity Vd in the first flow path of the composition liquid of the toner composition is 0.0001 m / s, and the speed Vc1 in the second and third flow paths of the aqueous medium is 0.1 m / s. Liquid feeding is performed using a syringe pump. The speed of the aqueous medium in the fourth channel is approximately 0.1 m / s. Further, a vibration of about 1000 Hz is applied to the composition liquid of the toner composition. The content of the polyester resin relative to tetrahydrofuran is large and the viscosity is high. By applying vibration to the composition liquid of the toner composition, droplet formation is facilitated. Under such conditions, droplets of the composition liquid of the toner composition are formed, and tetrahydrofuran is dissolved in the aqueous medium. The average particle diameter Dm of the dispersoid in the dispersion thus obtained is 5.0 μm.
Thereafter, the operation of adding pure water to the dispersion and filtering is repeated twice to prepare a uniform slurry. The slurry is dried by a spray dryer to produce a granular material. Toner particles having a volume average particle diameter of 4.8 μm and a dispersion value of 5.5% were obtained.

Example 4
In a sealed pot, 80 parts by weight of a polyester resin (Mn = 14,000) is dissolved in 100 parts by weight of tetrahydrofuran, 8 parts by weight of carbon black and 8 parts by weight of carnauba wax are added, and 24 mm of 5 mmφ zirconia beads are used. A ball mill dispersion is performed for a time to prepare a composition liquid of the toner composition. 5 parts by weight of sodium dodecylbenzenesulfonate is completely dissolved in 1000 parts by weight of water to obtain an aqueous medium.
The composition liquid of the toner composition and the aqueous medium are introduced into the microchannel according to claims 1 and 10. The widths of the first to fourth channels are 5 μm, 10 μm, 10 μm, and 20 μm, respectively, and the depth is 20 μm. The velocity Vd in the first flow path of the composition liquid of the toner composition is 0.0001 m / s, and the speed Vc1 in the second and third flow paths of the aqueous medium is 0.3 m / s. Liquid feeding is performed using a syringe pump. The speed of the aqueous medium in the fourth channel is approximately 0.3 m / s. In addition, a vibration of about 1000 Hz is applied to the aqueous medium. Since the content of the polyester resin with respect to tetrahydrofuran is large and the viscosity is high, a large shearing force is required for forming droplets, and Vc1 is large. When Vc1 increases, droplet formation becomes unstable and the dispersion value increases. Drop formation is stabilized by applying vibration to the aqueous medium. Under such conditions, droplets of the composition liquid of the toner composition are formed, and tetrahydrofuran is dissolved in the aqueous medium. The average particle diameter Dm of the dispersoid in the dispersion thus obtained is 4.8 μm.
Thereafter, the operation of adding pure water to the dispersion and filtering is repeated twice to prepare a uniform slurry. The slurry is dried by a spray dryer to produce a granular material. Toner particles having a volume average particle diameter of 4.6 μm and a dispersion value of 5.5% were obtained.

(Comparative Example 1)
In a sealed pot, 10 parts by weight of polyester resin (Mn = 14,000) is dissolved in 100 parts by weight of ethyl acetate, 2 parts by weight of carbon black and 2 parts by weight of carnauba wax are added, and 5 mmφ zirconia beads are used. Ball mill dispersion is performed for 24 hours to prepare a composition liquid of the toner composition. 5 parts by weight of sodium dodecylbenzenesulfonate is completely dissolved in 1000 parts by weight of water to obtain an aqueous medium.
Next, the aqueous medium is stirred at a rotation speed of 100 rpm using a TKL homomixer, and the toner composition liquid is dropped at a rate of 50 to 100 g / min. Do. Thereafter, the liquid is brought to 55-58 ° C. and stirred at 400 rpm for 20 minutes to remove ethyl acetate and prepare a dispersion. The average particle diameter Dm of the dispersoid in the obtained dispersion is 9.5 μm.
After cooling, pure water is added to the dispersion and decantation is performed twice. Further, washing with water (cleaning with pure water) and filtration are repeated 5 times at room temperature. Thereafter, the separated dispersoid is placed in pure water at 50 ° C., stirred for about 1 hour, and further filtered twice. Thereafter, the obtained filtrate (toner cake) is stirred and mixed in a 50 wt% aqueous methanol solution to prepare a uniform slurry, which is dried by a spray dryer to produce a granular material. Toner particles having a volume average particle diameter of 9.0 μm and a dispersion value of 40% were obtained.

(Comparative Example 2)
In a sealed pot, 10 parts by weight of polyester resin (Mn = 14,000) is dissolved in 100 parts by weight of ethyl acetate, 2 parts by weight of carbon black and 2 parts by weight of carnauba wax are added, and 5 mmφ zirconia beads are used. Ball mill dispersion is performed for 24 hours to prepare a composition liquid of the toner composition. 5 parts by weight of sodium dodecylbenzenesulfonate is completely dissolved in 1000 parts by weight of water to obtain an aqueous medium.
The composition liquid of the toner composition and the aqueous medium are introduced into the microchannel shown in FIG. 1 to form droplets of the composition liquid of the toner composition. Since the solubility of ethyl acetate in water is 8.08% at room temperature and normal pressure, ethyl acetate dissolves in an aqueous medium. Although the initial stage of forming the droplet can be satisfactorily formed, the toner composition adheres to the wall surface of the micro-channel when used for a long time, and the diameter of the droplet is not constant. Furthermore, clogging occurs in the microchannel when used for a long time.
Table 1 shows the evaluation results of Examples and Comparative Examples. The dispersion value is a value obtained by dividing the standard deviation of the particle diameter by the average particle diameter.

It is a figure which shows an example of the conventional microchannel. It is a figure which shows an example of the conventional microchannel. It is a figure which shows an example of the microchannel of this invention. It is a figure which shows the other example of the microchannel of this invention. It is a figure which shows the other example of the microchannel of this invention. It is a figure which shows the creation method of the channel made hydrophilic. It is a figure for demonstrating the definition of hydrophilicity. It is a figure which shows the other example of the microchannel of this invention. It is a figure which shows the other example of the microchannel of this invention. It is a figure which shows the other example of a microchannel. It is a figure which shows the conditions which can form an organic solvent droplet stably. It is a figure which shows the conditions which can form an organic solvent droplet stably.

Claims (11)

A composition liquid obtained by dissolving or dispersing a toner composition containing at least a resin and a colorant in an organic solvent is dispersed in an aqueous medium to obtain an emulsified dispersion, and the organic solvent is removed from the emulsified dispersion for electrophotography. An electrophotographic toner produced by a method for producing a toner,
The organic solvent of the composition liquid in which the toner composition containing the resin and the colorant is dissolved or dispersed has solubility in an aqueous solvent,
1st-3rd flow path which has the part which introduce | transduces a liquid, and 4th flow path which has a part which continues to this 1st-3rd flow path and collect | recovers liquid, 1st flow path The second and third flow paths are symmetrically arranged around the center, and the liquid outlet portion of the first, second, and third flow paths and the liquid inlet portion of the fourth flow path are the first flow path and the fourth flow path. Using microchannels joined so that their channels are on the same axis,
Introducing an organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed into the first flow path;
An aqueous medium is introduced into the second and third flow paths,
Forming droplets of an organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed at the merging portion of the first, second, third and fourth channels,
A method for producing an electrophotographic toner, comprising: removing an organic solvent from a droplet of an organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed in the fourth channel. A heating mechanism in the fourth flow path;
Increasing the temperature of the aqueous medium by the heating mechanism,
2. The electrophotography according to claim 1, wherein the removal of the organic solvent from the droplets of the organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed in the fourth flow path is promoted. For manufacturing toner. A composition liquid obtained by dissolving or dispersing a toner composition containing at least a resin and a colorant in an organic solvent is dispersed in an aqueous medium to obtain an emulsified dispersion, and the organic solvent is removed from the emulsified dispersion for electrophotography. In a toner production method and an electrophotographic toner produced by the production method,
The organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed has solubility in an aqueous solvent,
A first to third channel having a portion for introducing a liquid, a fourth channel connected to the first to third channels, a portion for introducing a liquid from the fourth channel, and the A fifth flow path having a portion for collecting the liquid, the second and third flow paths are symmetrically arranged around the first flow path, and the liquid in the first, second, and third flow paths The outlet portion and the liquid inlet portion of the fourth flow path are joined so that the first flow path and the fourth flow path are on the same axis, and the fourth flow path is in the middle of the fifth flow path. Using the micro flow path where the liquid outlet part of
Introducing an organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed into the first flow path;
An aqueous medium is introduced into the second and third flow paths,
Forming droplets of an organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed at the merging portion of the first, second, third and fourth channels,
An electrophotography that promotes removal of an organic solvent from a droplet of an organic solvent in which a toner composition containing the resin and a colorant is dissolved or dispersed in the fourth flow path and the fifth flow path. Of manufacturing toner. A heating mechanism is provided in the fourth channel and the fifth channel,
Increasing the temperature of the aqueous medium by the heating mechanism,
The removal of the organic solvent is promoted from the droplet of the organic solvent in which the toner composition containing the resin and the colorant is dissolved or dispersed in the fourth channel and the fifth channel. 4. A method for producing an electrophotographic toner according to 3. The width and depth of the first channel of the microchannel are W1 and D1, respectively, and the depth of channels other than the first channel is D,
2μm ≦ W1 ≦ 30μm
3 ≦ D1 / W1 ≦ 5
D1 ≒ D
5. The method for producing an electrophotographic toner according to claim 1, wherein a microchannel satisfying the above relationship is used. The viscosity of the aqueous medium is η, the speed of the aqueous medium flowing through the second and third microchannels is Vc1, the speed of the aqueous medium flowing through the fourth microchannel is Vc2, and the organic solvent flowing through the first microchannel Vd, and σ the interfacial tension between the aqueous medium and the organic solvent,
0.0001 ≦ η × Vc1 / σ ≦ 0.01
0.0001 × Vc1 ≦ Vd <0.5 × Vc1
Vc1≈Vc2
5. The method for producing an electrophotographic toner according to claim 1, wherein the toner is produced under a condition satisfying the relationship: The widths of the fourth and fifth channels of the micro channel are W4 and W5, respectively.
5. The method for producing an electrophotographic toner according to claim 3, wherein a microchannel satisfying a relationship of W4 <W5 is used. 5. The method for producing an electrophotographic toner according to claim 1, wherein the microchannel is hydrophilic. 5. The method for producing an electrophotographic toner according to claim 1, wherein a vibration component is imparted to a flow of an organic solvent in which the toner composition containing the resin and the colorant is dissolved. The method for producing an electrophotographic toner according to claim 1, wherein a vibration component is imparted to the flow of the aqueous medium. An electrophotographic toner produced by the method for producing an electrophotographic toner according to claim 1.

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