JP4366211B2 - Toner production method - Google Patents

Description

  The present invention relates to a method for producing a toner, and relates to an improvement in a colorant dispersion technique for producing a toner having excellent electrophotographic characteristics in which a colorant is finely and uniformly dispersed in the toner.

  A number of methods are known for electrophotography. Generally, a photoconductive material is used to form an electric latent image on a photoreceptor by various means, and then the latent image is developed with toner. In this method, a toner image is transferred to a transfer material such as paper as needed, and then fixed by heating, pressure, solvent vapor, or the like (see Patent Document 1). Various methods have been proposed in the past as a method for developing with toner or a method for fixing a toner image, and a method suitable for each image forming process is employed.

  Conventionally, as a toner used for these purposes, generally, a colorant such as a dye and a pigment is melt-mixed in a thermoplastic resin and uniformly dispersed, and then a toner having a desired particle size is produced by a fine pulverizer and a classifier. I have done it.

  While this method of manufacture can produce fairly good toners, it has certain limitations, i.e., limited choice of toner materials. For example, the resin colorant dispersion must be sufficiently brittle and capable of being finely pulverized with economically possible production equipment. However, if the resin colorant dispersion is made brittle to satisfy these requirements, the particle size range of the particles formed when actually pulverized at high speed tends to be widened. It is included in the problem. Further, such a highly brittle material is likely to be further pulverized or powdered when used for development in a copying machine or the like. Also, with this method, it is difficult to completely disperse solid fine particles such as a colorant in the resin, and depending on the degree of dispersion, the increase in fog, the decrease in image density, and the color mixing / transparency may be difficult. Care must be taken to disperse as it will cause defects. Further, exposure of the colorant to the fracture surface may cause a change in development characteristics.

  On the other hand, in order to overcome the problems of the toner by the pulverization method, various polymerization method toners and production methods thereof, including toners by the suspension polymerization method, have been proposed. For example, in the suspension polymerization method, a monomer composition is obtained by uniformly dissolving or dispersing a polymerizable monomer, a colorant, a polymerization initiator and, if necessary, a crosslinking agent, a charge control agent, and other additives. After that, the monomer composition is dispersed in a continuous phase containing a dispersion stabilizer, for example, an aqueous phase by using a suitable stirrer, and at the same time, a polymerization reaction is performed to obtain toner particles having a desired particle size. obtain.

  Since this method does not include a pulverization process, the toner particles do not need to be brittle, and a soft material can be used. In addition, since the classification process can be omitted, energy saving, time Cost reduction effects such as shortening of the process and improvement of process yield are large (see Patent Documents 2 to 4).

  In recent years, there has been a demand for multifunctional toner particles such as higher image quality, full color, and energy saving in copying machines and printers. For example, in the toner particles in order to cope with high-resolution, digital-sized toner particles with a higher image quality, improved transparency of OHP images with full color, and low-temperature fixing with energy saving. There is a demand for the inclusion of a low softening point substance and the formation of toner particles that are effective in improving the transfer efficiency to a transfer material. As means for realizing these demands, a toner by a polymerization method can be mentioned.

  Conventionally, in order to obtain the colorant-containing monomer mixture, a dyno mill (see Patent Document 5) that is commercialized as manufactured by Shinmaru Enterprises Co., Ltd., a coball mill manufactured by Shinko Pantech Co., Ltd. ( It was common to use Patent Document 6).

  FIG. 12 shows a sectional view of the dyno mill main body and a system diagram incorporating the main body. 121 is a main body casing, 122 is a raw material inlet, 123 is an outlet, 124 is an agitator shaft, 125 is a medium, 126 is a circulation pump, 127 is a holding tank, 128 is an agitator disk, and 129 is a motor. The liquid to be dispersed introduced into the holding tank 127 is supplied from the raw material introduction port 123 via the circulation pump 126 and passes through the layer of the medium 125 that repeats the movement by the rotational force of the agitator disk 128 to be dispersed. After being separated, the circulation is performed by repeating the circulation of being discharged from the discharge port 123 and returning to the holding tank 127 again.

  FIG. 13 shows a cross-sectional view of the coball mill main body and a system diagram incorporating the main body. 231 is a main body casing, 232 is a raw material inlet, 233 is an outlet, 234 is a media separator, 235 is a media layer, 236 is a circulation pump, 237 is a holding tank, and 238 is a rotor. The liquid to be dispersed charged into the holding tank 237 is supplied from the raw material inlet 232 via the circulation pump 236, and is dispersed through the narrow media layer 235 that repeats movement by the rotational force of the rotor 238. After being separated from the medium at 234, dispersion is performed by repeating the circulation of discharging from the discharge port 233 and returning to the holding tank 237 again.

  However, in order to obtain a colorant-containing monomer mixture, if the conventional media type dispersers such as these are used, the flow direction of the monomer mixture does not coincide with the centrifugal force direction, so the centrifugal force of the rotor is reduced. When it is stronger than the flow of the monomer mixture, the packing phenomenon in which the media is pressed outward by the centrifugal force of the rotor becomes remarkable, and the media filling layer in the apparatus becomes non-uniform. As a result, there is a problem that the flow of the monomer mixture tends to pass through the thinned portion of the media layer with less resistance, and the efficiency of dispersion is greatly reduced.

  If the centrifugal force of the rotor is inferior to the flow of the monomer mixture, the flow of the monomer mixture will push the media near the discharge port, causing a media blocking phenomenon near the discharge port and making the device stable. It was difficult to drive. Thus, it has been difficult to stably produce the colorant-containing monomer mixture by balancing the centrifugal force caused by the rotation of the rotor and the flow of the monomer mixture.

  Further, when image evaluation is performed with a toner having toner particles obtained by using a colorant-containing monomer mixture in which the dispersion of the colorant and the charge control agent is insufficient, the image density is lowered. When granulation is carried out in an aqueous medium containing a dispersion stabilizer using a colorant-containing monomer mixture that is insufficiently dispersed, there is a problem that the granulation property tends to be lowered. Therefore, in order to obtain a well-dispersed colorant-containing monomer mixture using a media-type disperser, it is necessary to improve media efficiency. In order to improve the media efficiency, the media efficiency is remarkably improved by using a medium having a small diameter, specifically, a medium of 2 mm or less. However, when a medium of 2 mm or less is used, the filling rate is increased, so that the above packing phenomenon and blocking phenomenon are more likely to occur, and stable operation of the apparatus is difficult, and the colorant-containing monomer mixture is stably produced. It was difficult to manufacture.

  Furthermore, in order to obtain a well-dispersed colorant-containing monomer mixture using a conventional media-type disperser while alleviating the above packing phenomenon and blocking phenomenon, a medium larger than 2 mm, preferably a medium larger than 3 mm is used. However, it took a long time to obtain a predetermined dispersion.

  In order to improve this, an apparatus in which the flow direction of the monomer mixture coincides with the direction of centrifugal force is used.

  By using such a system, even when media of 2 mm or less are used, it is possible to operate without causing packing, blocking phenomenon, and short path to the diluted layer of media, and the pigment is efficiently dispersed in the monomer. Has been realized. As a result, a toner having excellent image characteristics in which a colorant is finely and uniformly dispersed in the toner has been produced (see Patent Document 7).

  Furthermore, a method of dispersing using a rotating rotor having a specific shape in an apparatus in which the flow direction of the monomer mixture coincides with the centrifugal force direction has been proposed. By using this method, the pigment is further finely and efficiently dispersed (see Patent Document 8).

  However, the above dispersion methods and toners are not sufficient to cope with further miniaturization and personalization of copiers / printers, etc., and the accompanying increase in restrictions on the devices, and more fine and uniform. There is a need for a toner in which a colorant is dispersed. That is, it is required to perform the dispersion of the colorant in the monomer mixture to a higher degree.

US Pat. No. 2,297,691 Japanese Patent Publication No. 36-10231 Japanese Patent Publication No. 43-10799 Japanese Patent Publication No. 51-14895 Japanese Patent Laid-Open No. 6-11900 JP-A-6-75429 JP 2001-166531 A JP 2003-195561 A

  An object of the present invention is to provide a toner manufacturing method that solves the above-described problems.

  Another object of the present invention is to efficiently and stably produce a toner having a finer and more homogeneous colorant distribution, a sharper particle size distribution, and better image characteristics such as image density in the production of toner by polymerization. An object of the present invention is to provide a manufacturing method for manufacturing automatically.

The present invention is a toner production method including a colorant dispersion step, a granulation step and a polymerization step,
(C) In the dispersion step, an inner chamber is formed by a cylindrical separator having a slit inside a cylindrical container portion having a first wall surface having a liquid supply port and a second wall surface having a liquid discharge port. An outer chamber is provided, and in the inner chamber, a rotating rotor and a plurality of spherical media particles that can be rotated by rotation driving of a drive shaft are incorporated,
The rotor has a disk shape having a plurality of stators in the drive shaft direction and a plurality of double-sided through portions, and a means for dispersing the media particle agitation type wet disperser in which the rotor center portion is connected in the direction perpendicular to the drive shaft. Use as
(D) While rotating the rotating rotor by rotationally driving the drive shaft, a colorant is introduced into the central portion of the inner chamber together with the liquid monomer mixture from the liquid supply port,
While the colorant is dispersed in the liquid monomer mixture by centrifugal force and media particles generated by the rotation of the rotary rotor, the liquid monomer mixture and colorant are separated from the inner chamber by the centrifugal force generated by the rotation of the rotary rotor. transported to the outer chamber through the toner colorant, characterized in that the liquid monomer mixture is dispersed is discharged from the outer chamber through the liquid outlet, obtaining a colorant-containing monomer mixed compound It relates to the manufacturing method.

The present inventor has conducted extensive studies, a disc shape having a plurality of stator shaft drive direction, comprising a rotating rotor the rotor central portion is connected to the drive shaft and the vertical direction, the liquid monomer mixture When the colorant is dispersed in the liquid monomer mixture using a media-type disperser in which the direction of flow and the direction of the centrifugal force generated by the rotation of the rotating rotor coincide, stable dispersion is achieved in a shorter time than before. It was also found that fine and homogeneous colorant dispersion can be achieved.

  Furthermore, it has been found that a toner having excellent image characteristics can be obtained with a more uniform and fine dispersion of the colorant in the toner than ever before.

  In the present invention, it is possible to provide a production method for efficiently and stably producing a toner having finer and homogeneous colorant dispersion, sharper particle size distribution, and better image characteristics such as image density. It is.

Media particle agitation type wet-dispersion machine two will be described in the drawings as a disperser 2 preferably used in the disperser 1, the present invention shown for reference. However, the disperser used in the present invention is not limited to this.

Drawings showing the disperser 1 are FIG. 1, FIG. 2, FIG. 3, FIG. 5, FIG. 8, FIG.
Drawings showing the disperser 2 are FIGS. 1, 2, 4, 6, 6, 7, and 11. FIG.

Figure 1 shows a distributed system incorporating the disperser 1 or disperser 2 which is media particle agitation type wet-dispersion machine, Figure 2 shows a body side view of a distributed machine 1 or 2. 1 and 2 are common to the disperser 1 and the disperser 2.

  3 and 5 are cross-sectional views of the main body of the disperser 1, which are a cross-sectional view taken along the line B-B 'in FIG. 2 and a cross-sectional view taken along the line A-A' in FIG. 8 and 9 are perspective views of the rotating rotor of the disperser 1. FIG.

  4 and 6 and 7 are cross-sectional views of the main body of the disperser 2, which are a cross-sectional view taken along the line B-B 'in FIG. 2 and a cross-sectional view taken along the line A-A' in FIG. FIG. 10 is a perspective view of the rotating rotor of the disperser 2. FIG. 11 is a perspective view of the separator, which is common to the disperser 1 and the disperser 2.

  The disperser 1 includes a rotating rotor (3a, 3b) for stirring the media particles in the casing 2, and a separator 4 having a slit for separating the media particles 5 and the liquid monomer mixture on the outer periphery thereof. When the rotating rotor (3a, 3b) having the protrusions is rotated, a centrifugal force is generated, and the centrifugal force causes the media particles 5 to form a layer on the outer separator 4, and the rotating rotor (3a 3b), a rotational movement is also performed, so that a strong shearing force is generated and the colorant is dispersed.

Incidentally, as shown in FIG. 3, the diameter A of the rotary rotor, indicates the length of the tip of the projection which faces the tip of the projection. Further, the height B of the projection is the sum of the height of the projection (for example, B1) and the height of the projection (for example, B2) facing the projection.

Moreover, the diameter C of the core part of the rotating rotor indicates the length obtained by subtracting the height B of the protrusion from the diameter A of the rotating rotor, and the separator diameter D indicates the inner diameter of the separator.

Diameter A and the protrusions of the rotating rotor height B,
0.10 ≦ B / A ≦ 0.3, preferably 0.13 ≦ B / A ≦ 0.25
Use a rotor that satisfies the following conditions. When this rotor is used, the layer of the media particles 5 formed on the outer peripheral separator 4 can be efficiently stirred, and a large rotational motion and a very strong shearing force can be applied.

  Further, by using the above-described rotor, a high-speed vortex is formed by the liquid monomer mixture in the crushing chamber 24 formed between the protrusions 25 and the media particles 5 move vigorously along with the flow. Therefore, the dispersion of the colorant is further promoted.

  When a rotor of 0.10> B / A that deviates from the above range is used, the stirring efficiency of the media particles 5 is lowered, which is not preferable. Further, when a rotor of 0.3 <B / A is used, it is not preferable because a vortex flow in the crushing chamber 24 between the protrusions is not efficiently formed and packing of the media particles 5 is induced.

In addition , a rotor in which the diameter C and the separator diameter D of the cylindrical portion of the rotating rotor satisfy the condition of 0.5 ≦ C / D ≦ 0.85, preferably 0.65 ≦ C / D ≦ 0.80. It is good to use. When this rotor is used, the space formed between the separator 4 and the rotor can be expanded. Therefore, a large amount of the media particles 5 can be filled, and the thickness of the media particle layer can be increased, thereby enabling more uniform and fine dispersion. Furthermore, in the above range, it is possible to use a rotor having a relatively high protrusion, and it has both the effects of improving dispersibility by being able to fill a large amount of media particles and improving dispersibility by the protrusion described above. it can.

  When a rotor of 0.5> C / D that deviates from the above range is used, the formed media particle layer may be thicker than necessary, resulting in a portion where the movement of the media particles 5 is retained. Therefore, it is not preferable. Further, when a rotor of 0.85 <C / D is used, it is not preferable because the height of the protrusion 25 cannot be sufficiently secured and the thickness of the media particle layer becomes insufficient.

Furthermore, the properties of the liquid Jotan monomer mixture, there is a case where swirl in the crushing chamber 24 formed between the projection 25 and the projection 25 can not be efficiently formed, the media particles 5 are packing. In order to solve this problem, as shown in FIG. 9, a rotor 3b having a groove in the protrusion 25 may be used. Thereby, in addition to effective vortex formation, the media particles 5 can move between the crushing chambers 24 and packing can be suppressed in some cases.

  On the other hand, the disperser 2 has a rotating rotor for stirring the media particles inside the casing 5 and a separator 4 having a slit 4a for separating the media particles 5 and the liquid monomer mixture on the outer periphery thereof. When a disk-shaped rotary rotor 27 having a plurality of stators 26 is rotated, a centrifugal force is generated, and the centrifugal force causes the media particles 5 to form a layer on the outer separator 4.

  This disperser can be filled with a large number of media particles 5 and can form a very thick media particle layer. In addition, the plurality of stators 26 provided in the drive shaft direction can uniformly and efficiently stir the media particle layer in the rotor rotation direction regardless of the thick media particle layer.

  Therefore, a very high degree of dispersion can be achieved because the liquid monomer mixture passes through a vigorously moving thick media particle layer and the colorant is more likely to be sheared by the media particles 5.

  In addition, the media particles 5 can move more and more vigorously because the double-sided through portion 28 provided between the stators 26 of the disc-shaped rotor 27 allows the media particles 5 to come and go between the two sides separated by the disc-shaped rotor 27. it can. Therefore, dispersion of the colorant can be further promoted.

  Furthermore, in the present invention, as shown in FIG. 7, a stator 26 may be provided in the casing. Depending on the properties of the material put into the disperser, a stronger shearing force may be applied to improve dispersibility.

  In the disperser 1 or the disperser 2, the liquid monomer mixture charged into the holding tank 8 is supplied from the raw material charging port 6 through the circulation pump 10, and the outer periphery of the rotor is caused by the centrifugal force generated by the rotation of the rotating rotor 3. It is surely finely dispersed through the media layer formed in the part. Thereafter, the liquid monomer mixture is separated from the media particles 5 by the separator 4, discharged from the liquid discharge port 7, and returns to the holding tank 8 through the cooling means 11. The monomer mixture in the holding tank 8 is uniformly and efficiently dispersed in the liquid monomer mixture while repeating the circulation of the cycle between the disperser 1 or the disperser 2 and the holding tank 8. Done.

  The circulation of returning the liquid monomer mixture returned to the holding tank 8 to the raw material inlet 6 of the disperser 1 is repeated.

  A polymerizable monomer, a colorant, a charge control agent, and the like may be charged directly into the holding tank 8, but may be charged into the holding tank 8 after preliminary mixing in advance.

  In addition, since heat is generated during dispersion and the monomer mixture is likely to be adversely affected, a heat exchanger may be installed as a cooling means in the circulation system line to perform operation while performing heat exchange. In that case, it is preferable to adjust the liquid temperature of a monomer mixture to 10-40 degreeC (more preferably 15-35 degreeC).

  In the disperser 1 and the disperser 2, the diameter of the media particles 5 is preferably used in the range of 0.1 mm to 2 mm from the viewpoint of dispersibility of the colorant in the liquid monomer mixture.

  From the viewpoint of dispersibility of the colorant, wear of the media particles 5, and stable operation of the apparatus itself, it is preferable to use a peripheral speed of the tip of the rotary rotor in the range of 5 to 20 m / s, and further 7 to 17 m / s. It is more preferable to use within the range of s.

  In the present invention, a viscometer 25 is installed between the liquid discharge port 7 and the liquid supply port 6 in order to prevent wear of media particles, achieve stable continuous operation of the apparatus itself, and reduce power consumption. The viscosity of the fine colorant-containing monomer mixture that varies depending on the colorant and the degree of dispersion is measured, and the peripheral speed of the rotating rotor tip is controlled in the range of 5 to 20 m / s depending on the viscosity value. It is preferable to control within a range of 7 to 17 m / s.

  Specific examples of such viscometers include a vibratory viscometer FUM-80A shield type (manufactured by Yamaichi Electric Co., Ltd.) and MIVI6001 ADF type (manufactured by Soflaser). In order to disperse the inside of the disperser while applying pressure, it is more preferable to provide a valve 19 on the downstream side of the discharge port 7 because the dispersibility of the colorant is good and a short pass can be prevented.

  Examples of the material for the media particles used in the disperser include glass, steel, chromium alloy, alumina, zirconia, zircon, and titania. Among the above-mentioned media materials, zirconia or titania is more preferable in terms of wear resistance. preferable.

  The toner of the present invention contains at least a resin and a colorant, but may contain a release agent, a charge control agent, or the like, which is a fixability improving agent, if necessary. Further, an external additive composed of inorganic fine particles or organic fine particles may be added to the toner particles containing the resin and the colorant as main components.

  For the toner of the present invention, a suspension polymerization method or a so-called seed polymerization method in which a monomer is further adsorbed to the obtained polymer particles and then polymerized using a polymerization initiator can be suitably used.

  Although it does not specifically limit as a manufacturing method of suspension polymerization method, The following manufacturing methods can be mentioned.

  That is, various constituent materials such as a colorant and, if necessary, a release agent, a charge control agent, and a polymerization initiator are added to the polymerizable monomer, and then a homogenizer, a sand mill, a sand grinder, an ultrasonic disperser, etc. Various constituent materials are dissolved or dispersed in the polymerizable monomer. The polymerizable monomer in which these various constituent materials are dissolved or dispersed is dispersed in oil droplets having a desired size as a toner in an aqueous medium containing a dispersion stabilizer using a homomixer or a homogenizer. Then, it transfers to the reaction apparatus which has a stirring mechanism, and a polymerization reaction is advanced by heating. After completion of the reaction, the dispersion stabilizer is removed, filtered, washed, and dried to prepare the toner of the present invention.

  Examples of the polymerizable monomer that can be used in the polymerized toner include styrene monomers such as styrene, o (m-, p-)-methylstyrene, m (p-)-ethylstyrene; methyl (meth) acrylate. , Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, (Meth) acrylate monomers such as 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate; butadiene, isoprene, cyclohexene, (meth) acrylonitrile, acrylic Vinyl monomers such as acid amides are preferably used. Moreover, it may be preferably used in combination of two or more as required.

  In the present invention, it is particularly preferable to add a polar resin in addition to the outer shell resin in order to encapsulate the low softening point substance in the outer shell resin. As the polar resin used in the present invention, a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a saturated polyester resin, and an epoxy resin are preferably used. The polar resin is particularly preferably one containing no unsaturated group capable of reacting with the outer shell resin or the monomer. In the case of containing a polar resin having an unsaturated group, a cross-linking reaction occurs with the monomer forming the outer shell resin layer, and as a full color toner, it becomes extremely high molecular weight, which is disadvantageous for the color mixture of four color toners, which is not preferable. .

  The low softening point substance used in the present invention is preferably a compound having a main maximum peak value measured in accordance with ASTM D3418-8 of 40 to 90 ° C. When the maximum peak is less than 40 ° C., the self-aggregation force of the low softening point substance becomes weak, and as a result, the high temperature offset resistance becomes weak, which is not preferable for a full color toner. On the other hand, when the maximum peak exceeds 90 ° C., the fixing temperature becomes high, and it becomes difficult to appropriately smooth the surface of the fixed image, which is not preferable from the viewpoint of mixing properties. Furthermore, in the case of obtaining a toner by direct polymerization, granulation and polymerization are carried out in an aqueous system, so if the temperature of the maximum peak value is high, a low softening point substance mainly precipitates during granulation and inhibits the suspension system. Therefore, it is not preferable. Specifically, paraffin wax, polyolefin wax, Fischer-Tropsch wax, amide wax, higher fatty acid, ester wax and derivatives thereof, or graft / block compounds thereof can be used.

  As the colorant used in the present invention, a black colorant that is toned in black using carbon black, a magnetic material, and the following yellow / magenta / cyan colorant is used.

  As the yellow colorant, compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168, etc. are preferably used.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like can be used particularly preferably.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin.

  When a magnetic material is used as the black colorant, 40 to 150 parts by mass are added to 100 parts by mass of the resin, unlike other colorants.

  As the charge control agent used in the present invention, known ones can be used. However, a charge control agent that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable. Further, when the direct polymerization method is used in the present invention, a charge control agent having no polymerization inhibition and no solubilized product in an aqueous system is particularly preferable. Specific examples of the negative compounds include salicylic acid, naphthoic acid, dicarboxylic acid metal compounds, sulfonic acid, polymer compounds having carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds, calixarene, and the like. As a positive system, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, an imidazole compound, and the like are preferably used. The charge control agent is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin. However, in the present invention, it is not essential to add a charge control agent. When a two-component development method is used, frictional charging with a carrier is used, and even when a non-magnetic one-component blade coating development method is used, the blade It is not always necessary to include a charge control agent in the toner by actively utilizing frictional charging with the member or the sleeve member.

  Examples of the polymerization initiator that can be used in the polymerized toner according to the present invention include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1 ′. -Azo or diazo polymerization initiators such as azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide; Peroxide polymerization initiators such as methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide are used. The addition amount of the polymerization initiator varies depending on the target degree of polymerization, but generally 0.5 to 20% by mass is added to the monomer. The kind of the polymerization initiator varies slightly depending on the polymerization method, but can be used alone or in combination with reference to the 10-hour half-life temperature.

  In order to control the degree of polymerization, a known crosslinking agent, chain transfer agent, polymerization inhibitor and the like can be further added and used.

  In the polymerized toner according to the present invention, particularly when using suspension polymerization using a dispersant, the dispersant used is an inorganic compound such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate. , Magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina and the like. As organic compounds, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and its salts, starch and the like can be dispersed in an aqueous phase. These stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Among these stabilizers, when an inorganic compound is used, a commercially available one may be used as it is, but in order to obtain fine particles, the inorganic compound may be produced in a dispersion medium. For example, in the case of tricalcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed under high stirring.

  Moreover, you may use 0.001-0.1 mass part surfactant for fine dispersion | distribution of these stabilizers. This is to promote the desired action of the above dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, lauric acid. Examples thereof include sodium, potassium stearate, calcium oleate and the like.

  In the toner manufacturing method of the present invention, the toner can be specifically manufactured by the following manufacturing method.

  That is, a release agent composed of a low softening point substance, a colorant, a charge control agent, a polymerization initiator and other additives are added to the polymerizable monomer, and the mixture is uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser or the like. The monomer system is dispersed in an aqueous phase containing a dispersion stabilizer by a usual stirrer or CLEARMIX, homomixer, homogenizer or the like. Preferably, granulation is performed by adjusting the stirring speed and time so that the monomer droplets have a desired toner particle size. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. The polymerization is preferably carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. In addition, the temperature may be raised in the second half of the polymerization reaction, and further, the second half of the reaction or the completion of the reaction to remove unreacted polymerizable monomers and by-products that cause odor during toner fixing. A part of the aqueous medium may be distilled off later. After completion of the reaction, the produced toner particles are recovered by washing and filtration and dried by the drying method of the present invention. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by mass of water as a dispersion medium with respect to 100 parts by mass of the monomer system.

  In the present invention, the Tg of the toner particles obtained in this way is adjusted to be 40 to 75 ° C. When the temperature is lower than 40 ° C., there is a problem in terms of storage stability of the toner and durability of the developer. On the other hand, when the temperature exceeds 75 ° C., the fixing point is increased. Insufficient color mixing results in poor color reproducibility, and further reduces the transparency of the OHP image, which is undesirable from the standpoint of high image quality.

  The particle size distribution of the toner can be measured by various methods, and was performed using a Coulter Multisizer based on the Coulter method.

  A Coulter Multisizer (manufactured by Coulter Inc.) was used as a measuring device, and an interface for outputting the number average distribution and volume average distribution (manufactured by Nikka) and a PC9801 personal computer (manufactured by NEC) were connected to the electrolyte. Is used to prepare a 1% NaCl aqueous solution.

  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 with an ultrasonic disperser, and the particle size distribution of particles of 2 to 40 μm on the basis of the number is used with the Coulter Multisizer using a 100 μm aperture as the aperture. Measure and then determine various values.

  In the present invention, since the fine colorant is finely and uniformly dispersed in the monomer mixture, the weight average particle size is 4 to 10 μm (more preferably 4 to 9 μm), and the number distribution varies. A toner having a sharp particle size distribution with a coefficient of 35% or less (more preferably 30% or less) can be produced efficiently and with high yield.

The coefficient of variation in the number distribution is calculated from the following equation.
Coefficient of variation (%) = [S / D1] × 100
[In the formula, S represents the standard deviation in the number distribution of toner particles, and D1 represents the number average particle diameter (μm) of the toner particles. ]

  Hereinafter, the present invention will be specifically described based on examples.

  First, in the present invention, 1. 1. Evaluation method of colorant-containing styrene monomer mixture (hereinafter referred to as dispersion) 2. Toner granulating evaluation method The image density evaluation method will be described below.

Evaluation 1. The dispersion state of the colorant in the dispersion liquid in the dispersion step was measured by measuring the gloss (glossiness) of the dispersion liquid. The gloss of the dispersion was measured after the dispersion was uniformly applied to art paper and sufficiently dried. When the fine colorant is well dispersed, smoothness and gloss are generated on the coated surface and the gloss value is increased. On the contrary, when the dispersion of the fine colorant is poor, the unevenness remains on the coating surface, and the gloss value becomes low because it becomes dull. For measurement of gloss (glossiness), a VG-10 glossiness meter manufactured by Nippon Denshoku Co., Ltd. was used. For measurement, set it to 6V with a constant voltage device, then adjust the light projection angle and light reception angle to 60 ° C, use zero point adjustment and a standard plate, and stack three blank sheets on the sample stage after standard setting. Then, the coated sample was placed thereon for measurement, and the numerical value shown in the marking part was read in% units. As evaluation criteria, when the gloss value is 50% or more, good dispersibility is exhibited. When the gloss value is 40% or more and less than 50%, there is a slight problem in the image, but there is no problem in practical use. Dispersibility which is quite severe and is undesirable on the product.

  2. About the granulation property in the granulation step, a part of the slurry after polymerization was sampled, further washed and dried, and examined by the number variation coefficient measured by the above-mentioned Coulter Multisizer. When the number variation coefficient is less than 35%, good granulation property is exhibited. When the coefficient of variation is 35% or more and less than 40%, there is a slight problem in the image, but there is no problem in practical use. The effect is quite severe and the product exhibits undesirable granulation properties.

3. Evaluation Method of Toner Image Density To 100 parts by mass of the toner obtained after drying, 1.7 parts by mass of hydrophobic silica having a specific surface area of 200 m ² / g by BET method was externally added to obtain a toner. Using this developer, an image was performed in an environment of 30 ° C./80% RH using a modified LBP2510 (manufactured by Canon).

  The obtained image was subjected to reflection density measurement using an SPI filter of Macbeth RD918 type (the same is true for the subsequent image density measurement methods). The results are shown in Table 1. As an evaluation standard, when the Macbeth density value is 1.2 or more, a good image density is shown. If it is less than 1, the influence on the image is considerably severe, and an image density unfavorable on the product is exhibited.

[Production Example of Dispersion 1]
The dispersion | distribution process was performed using the disperser 1 (rotary rotor: 3a). In the distributed system, in the holding tank,
-Styrene monomer 100 parts by mass-Carbon black 10 parts by mass-E-88 (manufactured by Orient Chemical Co., Ltd.) 5 parts by mass-T-77 (manufactured by Hodogaya Chemical) 2.5 parts by mass are introduced and stirred. A styrene monomer mixture containing a carbon black colorant was prepared. At that time, the liquid temperature of the styrene monomer mixture was adjusted to about 18 ° C. by introducing and discharging cooling water into the jacket.

The prepared styrene monomer mixture was introduced into a media particle agitation type wet disperser 1 filled with 49.6 kg of spherical media particles (zirconia spherical particles having a diameter of 0.5 mm) by a circulation pump. The internal configuration of the media type dispersing machine 1 is as follows:
Rotor diameter A: 450 mm
Projection height B: 134 mm
Diameter C of rotor core tube part: 316 mm
Separator diameter D: 464 mm
And
Peripheral speed: 14.1 m / s
Flow rate: 4.8m ³ / hr
The operation was performed for 4 hours under the conditions of The temperature of the styrene monomer mixture after the operation was 34 ° C.

[Production Example of Dispersion 2]
The internal configuration of the media-type disperser 1 is
Rotor diameter A: 352 mm
Projection height B: 36 mm
Diameter C of rotor core tube part: 316 mm
Separator diameter D: 464 mm
Except that, Dispersion 2 was prepared in the same manner as Dispersion 1. The temperature of the styrene monomer mixture after the operation was 28 ° C.

[Production Example of Dispersion 3]
The internal configuration of the media-type disperser 1 is
Rotor diameter A: 367 mm
Projection height B: 51 mm
Diameter C of rotor core tube part: 316 mm
Separator diameter D: 464 mm
Except that, the dispersion 3 was produced in the same manner as the production method of the dispersion 1. The temperature of the styrene monomer mixture after the operation was 30 ° C.

[Production Example of Dispersion 4]
The internal configuration of the media-type disperser 1 is
Rotor diameter A: 416 mm
Projection height B: 100 mm
Diameter C of rotor core tube part: 316 mm
Separator diameter D: 464 mm
A dispersion 4 was produced in the same manner as the production method of the dispersion 1, except that The temperature of the styrene monomer mixture after the operation was 32 ° C.

[Production Example of Dispersion 5]
68.4 kg of spherical media particles (zirconia spherical particles having a diameter of 0.5 mm) are filled in the media particle agitation type wet disperser 1, and the internal configuration of the media type disperser 1 is
Rotor diameter A: 279 mm
Projection height B: 42 mm
Diameter C of rotor core tube part: 237 mm
Separator diameter D: 464 mm
Except that, the dispersion 5 was produced in the same manner as the production method of the dispersion 1. The temperature of the styrene monomer mixture after the operation was 25 ° C.

[Production Example of Dispersion 6]
34.7 kg of spherical media particles (zirconia spherical particles having a diameter of 0.5 mm) are filled in the media particle agitation type wet disperser 1, and the internal configuration of the media type disperser 1 is
Rotor diameter A: 432 mm
Projection height B: 65 mm
Diameter C of rotor core tube: 367 mm
Separator diameter D: 464 mm
A dispersion 6 was produced in the same manner as the production method of the dispersion 1 except that. The temperature of the styrene monomer mixture after the operation was 33 ° C.

[Production Example of Dispersion 7]
27.2 kg of spherical media particles (zirconia spherical particles having a diameter of 0.5 mm) are filled in the media particle agitation type wet disperser 1, and the internal configuration of the media type disperser 1 is
Rotor diameter A: 459 mm
Projection height B: 69 mm
Diameter C of rotor core tube part: 390 mm
Separator diameter D: 464 mm
A dispersion 7 was produced in the same manner as the production method of the dispersion 1 except that. The temperature of the styrene monomer mixture after the operation was 35 ° C.

[Production Example of Dispersion 8]
52.3 kg of spherical media particles (zirconia spherical particles having a diameter of 0.5 mm) are filled in the media particle agitation type wet disperser 1, and the internal configuration of the media type disperser 1 is
Rotor diameter A: 360 mm
Projection height B: 54 mm
Diameter C of rotor cylinder part: 306 mm
Separator diameter D: 464 mm
A dispersion 8 was produced in the same manner as the production method of the dispersion 1 except that The temperature of the styrene monomer mixture after the operation was 29 ° C.

[Production Example of Dispersion 9]
Dispersion 9 was prepared in the same manner as Dispersion 3, except that 49.6 kg of zirconia spherical particles having a diameter of 0.1 mm were charged in media particle agitation type wet disperser 1. In addition, since the temperature of the styrene monomer mixture reached 40 ° C. after 2 hours, the flow rate was increased while the temperature of the cooling water flowing into the jacket was decreased. The temperature of the styrene monomer mixture after the operation was 39 ° C.

[Production Example of Dispersion 10]
Dispersion 10 was prepared by the same method as Dispersion 3 except that 49.6 kg of zirconia spherical particles having a diameter of 2 mm were charged in media particle agitation type wet disperser 1. The temperature of the styrene monomer mixture after the operation was 28 ° C.

[Production Example of Dispersion 11]
Dispersion 11 was prepared in the same manner as Dispersion 3 except that the peripheral speed of the rotating rotor was 20 m / s. In addition, since the temperature of the styrene monomer mixture reached 40 ° C. after 2 hours, the flow rate was increased while the temperature of the cooling water flowing into the jacket was decreased. The temperature of the styrene monomer mixture after the operation was 40 ° C.

[Production Example of Dispersion 12]
Dispersion 12 was prepared in the same manner as Dispersion 3 except that the peripheral speed of the rotating rotor was 5 m / s. The temperature of the styrene monomer mixture after the operation was 24 ° C.

[Production Example of Dispersion 13]
In the media type agitator / disperser 1, a rotating rotor 3 b having a groove in a protrusion as shown in FIG. 9 is used, and the internal configuration of the disperser 1 is
Rotor diameter A: 367 mm
Projection height B: 51 mm
Diameter C of rotor core tube part: 316 mm
Separator diameter D: 464 mm
Except that, the dispersion 13 was prepared in the same manner as the manufacturing method of the dispersion 3. The temperature of the styrene monomer mixture after the operation was 29 ° C.

[Production Example of Dispersion 14]
Spherical media particles (zirconia spherical particles having a diameter of 0.5 mm) are filled in 38 kg of the media particle agitation type wet disperser 1, and the internal configuration of the media type disperser 1 is
Rotor diameter A: 422 mm
Projection height B: 66 mm
Diameter C of rotor cylinder part: 356 mm
Separator diameter D: 464 mm
Peripheral speed: 15.9m / s
A dispersion 14 was produced in the same manner as the production method of the dispersion 1, except that The temperature of the styrene monomer mixture after the operation was 31 ° C.

[Production Example of Dispersion 15]
The internal configuration of the media-type disperser 1 is
Rotor diameter A: 450 mm
Projection height B: 94 mm
Diameter C of rotor cylinder part: 356 mm
Separator diameter D: 464 mm
Peripheral speed: 17 m / s
A dispersion 15 was produced in the same manner as the production method of the dispersion 14 except that. The temperature of the styrene monomer mixture after the operation was 32 ° C.

[Production Example of Dispersion 16]
In the media type agitator / disperser 1, a rotating rotor 3 b having a groove in a protrusion as shown in FIG. 9 is used, and the internal configuration of the disperser 1 is
Rotor diameter A: 422 mm
Projection height B: 66 mm
Diameter C of rotor cylinder part: 356 mm
Separator diameter D: 464 mm
The dispersion liquid 16 was produced by the same method as the manufacturing method of the dispersion liquid 14 except that. The temperature of the styrene monomer mixture after the operation was 30 ° C.

[Production Example of Dispersion 17]
In the media type agitator / disperser 1, a rotating rotor 3 b having a groove in a protrusion as shown in FIG. 9 is used, and the internal configuration of the disperser 1 is
Rotor diameter A: 450 mm
Projection height B: 94 mm
Diameter C of rotor cylinder part: 356 mm
Separator diameter D: 464 mm
The dispersion liquid 17 was produced by the same method as the manufacturing method of the dispersion liquid 14 except that. The temperature of the styrene monomer mixture after the operation was 31 ° C.

[Production Example of Dispersion 18]
Using the disperser 2, the dispersion process was performed. In the distributed system, in the holding tank,
-Styrene monomer 100 parts by mass-Carbon black 9 parts by mass-E-88 (made by Orient Chemical Industry Co., Ltd.) 5.5 parts by mass-T-77 (made by Hodogaya Chemical Co., Ltd.) 3.0 parts by mass are introduced and stirred. A styrene monomer mixture containing a carbon black colorant was prepared. At that time, the liquid temperature of the styrene monomer mixture was adjusted to about 18 ° C. by introducing and discharging cooling water into the jacket.

  The prepared styrene monomer mixture was introduced into a media particle agitation type wet disperser 2 filled with 49 kg of spherical media particles (zirconia spherical particles having a diameter of 0.5 mm) by a circulation pump.

Peripheral speed: 14.1 m / s
Flow rate: 4.8m ³ / hr
The operation was performed for 4 hours under the conditions of The temperature of the styrene monomer mixture after the operation was 28 ° C.

[Production Example of Dispersion 19]
Dispersion 19 was prepared in the same manner as Dispersion 18 except that 49 kg of zirconia spherical particles having a diameter of 0.1 mm were filled in media particle agitation type wet disperser 2. Since the temperature of the styrene monomer mixture reached 39 ° C. after 2 hours had elapsed, the flow rate was increased while the temperature of the cooling water flowing into the jacket was decreased. The temperature of the styrene monomer mixture after the operation was 30 ° C.

[Production Example of Dispersion 20]
Dispersion 20 was prepared in the same manner as Dispersion 18 except that 49 kg of zirconia spherical particles having a diameter of 2 mm were filled in media particle agitation type wet disperser 2. The temperature of the styrene monomer mixture after the operation was 26 ° C.

[Production Example of Dispersion 21]
Dispersion 21 was produced in the same manner as the dispersion 18 except that the peripheral speed of the rotating rotor was 20 m / s. In addition, since the temperature of the styrene monomer mixture reached 40 ° C. after 2 hours, the flow rate was increased while the temperature of the cooling water flowing into the jacket was decreased. The temperature of the styrene monomer mixture after the operation was 40 ° C.

[Production Example of Dispersion 22]
Dispersion 22 was prepared in the same manner as the dispersion 18 except that the peripheral speed of the rotating rotor was 4 m / s. The temperature of the styrene monomer mixture after the operation was 23 ° C.

[Production Example of Dispersion 23]
The dispersion liquid 18 is used except that an apparatus having an internal structure in which a stator is provided on the casing wall surface so as not to interfere with the stator of the rotating rotor as shown in FIG. Dispersion liquid 23 was produced in the same manner as in the production method. The temperature of the styrene monomer mixture after the operation was 30 ° C.

[Production Example of Dispersion 24]
22 kg of spherical media particles (zirconia spherical particles having a diameter of 0.5 mm) are filled in the media particle agitation type wet disperser 1, and the internal configuration of the media type disperser 1 is
Rotor diameter A: 448 mm
Projection height B: 42 mm
Diameter C of rotor core tube part: 406 mm
Separator diameter D: 464 mm
The dispersion liquid 24 was produced by the same method as the manufacturing method of the dispersion liquid 1 except that. The temperature of the styrene monomer mixture after the operation was 34 ° C.

[Production Example of Dispersion 25]
39 kg of spherical media particles (zirconia spherical particles having a diameter of 0.5 mm) are filled in the media particle agitation type wet disperser 1, and the internal configuration of the media type disperser 1 is
Rotor diameter A: 390 mm
Projection height B: 34 mm
Diameter C of rotor cylinder part: 356 mm
Separator diameter D: 464 mm
A dispersion 25 was produced in the same manner as the production method of the dispersion 1, except that The temperature of the styrene monomer mixture after the operation was 31 ° C.

[Production Example of Dispersion 26]
The dispersion | distribution process was performed using the disperser 3. FIG. In the distributed system, in the holding tank,
-Styrene monomer 100 parts by mass-Carbon black 10 parts by mass-E-88 (manufactured by Orient Chemical Co., Ltd.) 5 parts by mass-T-77 (made by Hodogaya Chemical Co., Ltd.) 2.5 parts by mass are introduced and stirred. A styrene monomer mixture containing a carbon black colorant was prepared. At that time, the liquid temperature of the styrene monomer mixture was adjusted to about 18 ° C. by introducing and discharging cooling water into the jacket.

The prepared styrene monomer mixture was charged with 42 kg of spherical media particles (diameter 0.5 mm) by a circulation pump, and supplied at 1 m ³ / hr via the pump. A dispersion liquid 26 was prepared by dispersing in a rotor circumferential speed of 13 m / s and a circulation system for 4 hours.

[Production Example of Dispersion 27]
The dispersion process was performed using the disperser 4. In the distributed system, in the holding tank,
-Styrene monomer 100 parts by mass-Carbon black 10 parts by mass-E-88 (manufactured by Orient Chemical Co., Ltd.) 5 parts by mass-T-77 (made by Hodogaya Chemical Co., Ltd.) 2.5 parts by mass are introduced and stirred. A styrene monomer mixture containing a carbon black colorant was prepared. At that time, the liquid temperature of the styrene monomer mixture was adjusted to about 18 ° C. by introducing and discharging cooling water into the jacket.

The prepared styrene monomer mixture was filled with 2.6 kg of spherical media particles (diameter 0.5 mm) by a circulation pump, and fed through the pump at 2.25 × 10 ⁻³ m ³ / hr. Dispersion was performed using a rotor circumferential speed of 13 m / s and a circulation system of 4 hours to prepare dispersion liquid 27.

[Production Example of Dispersion 28]
The dispersion process was performed using a medialess disperser Ebara Milder (manufactured by Ebara Corporation). In the distributed system, in the holding tank,
-Styrene monomer 100 parts by mass-Carbon black 10 parts by mass-E-88 (manufactured by Orient Chemical Co., Ltd.) 5 parts by mass-T-77 (made by Hodogaya Chemical Co., Ltd.) 2.5 parts by mass are introduced and stirred. A styrene monomer mixture containing a carbon black colorant was prepared. At that time, the liquid temperature of the styrene monomer mixture was adjusted to about 18 ° C. by introducing and discharging cooling water into the jacket.

The prepared styrene monomer mixture was fed through a pump at a feed rate of 0.2 m ³ / hr. Dispersion was performed by a rotor rotation speed of 5000 rpm (circumferential speed: 15 m / s) and a circulation system for 4 hours to prepare dispersion liquid 28.

  Table 1 shows the physical properties of the above dispersions.

( Reference Example 1)
After adding 450 parts by mass of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution to 710 parts by mass of ion-exchanged water and heating to 60 ° C., using Claremix (M Technique Co., Ltd.), 3,500 revolutions / Stir in minutes. To this was added 68 parts by mass of a 1.0 mol / liter-CaCl ₂ aqueous solution to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Then, as a dispersoid system,
-80 parts by weight of styrene monomer-20 parts by weight of 2-ethylhexyl acrylate-10 parts by weight of saturated polyester-40 parts by weight of paraffin wax (melting point 72 ° C) 117.5 parts by weight of dispersion 1 Add the above formulation to 60 ° C Warmed and dissolved and mixed for 30 minutes. In this, 10 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was put into the aqueous dispersion medium and granulated for 15 minutes while maintaining the rotation speed. Then, the stirrer was changed from the high-speed stirrer to the propeller stirring blade, the internal temperature was raised to 80 ° C., and the polymerization was continued for 10 hours at 50 rpm. After completion of the polymerization, the slurry was cooled, diluted hydrochloric acid was added, and Ca ₃ (PO ₄ ) ₂ was dissolved, followed by filtration, washing with water, crushing and drying to obtain a toner. The obtained toner particles were evaluated according to the above-described evaluation method of granulation property and image density. The results are shown in Table 1.

( Reference Examples 2-17, Examples 1-6 )
The same operations as in Reference Example 1 were carried out except that the dispersion liquid in the dispersoid system formulation of Reference Example 1 was changed as shown in Table 1 to obtain a toner. Table 1 shows the evaluation results of granulation properties and image density.

( Reference Comparative Examples 1-2, Comparative Examples 1-3 )
The same operations as in Reference Example 1 were carried out except that the dispersion liquid in the dispersoid system formulation of Reference Example 1 was changed as shown in Table 1 to obtain a toner. Table 1 shows the evaluation results of granulation properties and image density.

1. Dispersibility of dispersion liquid Gloss of dispersion liquid: 50% or more ・ ・ ・ ・ A Good
: 40% or more and less than 50% ··· B slightly inferior (no product problem)
: Less than 40% ··· C bad 2. Granulation in granulation process Number variation coefficient: less than 35%
: 35% or more and less than 40% ··· B slightly inferior (no product problems)
: 40% or more. Toner image density
Concentration value: 1.2 or higher ... A good
: 1.0 or more and less than 1.2 ··· B slightly inferior (no problem in product)
: Less than 1.0 ... C bad

It is explanatory drawing of the dispersion | distribution process using a media particle stirring wet disperser, a cooling means, a holding tank, and a circulation pump. It is a side view of a disperser. It is sectional drawing in the casing which follows the B-B 'line in FIG. It is sectional drawing in the casing which follows the B-B 'line in FIG. It is sectional drawing in the casing which follows the A-A 'line in FIG. It is sectional drawing in the casing which follows the A-A 'line in FIG. It is sectional drawing in the casing which follows the A-A 'line in FIG. It is a perspective view of a rotation rotor. It is a perspective view of a rotation rotor. It is a perspective view of a rotation rotor. It is a perspective view of a separator. It is explanatory drawing which shows an example of the conventional dispersion | distribution process. It is explanatory drawing which shows an example of the other conventional dispersion | distribution process.

Explanation of symbols

1. 1. Media type disperser Casing (container)
3a. Rotating rotor 3b. Rotating rotor (with grooves)
4). Separator 4a. Slit 5. Media particles6. 6. Liquid supply port Liquid outlet 8. Holding tank 10. Circulation pump 11. Cooling means 12. Thermometer 13. Stirring motors 14, 16. Cooling water supply ports 15, 17. Cooling water outlet 18. Jacket 19. Valve 20. Three-way valve 21. Drive shaft 22. Inner room 23. Outside room 24. Grinding chamber 25. Protrusion 26. Stator 27. Disc shaped rotor 28. Double-sided penetration

Claims (5)

A toner manufacturing method including a colorant dispersion step, a granulation step, and a polymerization step,
(C) In the dispersion step, an inner chamber is formed by a cylindrical separator having a slit inside a cylindrical container portion having a first wall surface having a liquid supply port and a second wall surface having a liquid discharge port. An outer chamber is provided, and in the inner chamber, a rotating rotor and a plurality of spherical media particles that can be rotated by rotation driving of a drive shaft are incorporated,
The rotor has a disk shape having a plurality of stators in the drive shaft direction and a plurality of double-sided through portions, and a means for dispersing the media particle agitation type wet disperser in which the rotor center portion is connected in the direction perpendicular to the drive shaft. Use as
(D) While rotating the rotating rotor by rotationally driving the drive shaft, a colorant is introduced into the central portion of the inner chamber together with the liquid monomer mixture from the liquid supply port,
While the colorant is dispersed in the liquid monomer mixture by centrifugal force and media particles generated by the rotation of the rotary rotor, the liquid monomer mixture and colorant are separated from the inner chamber by the centrifugal force generated by the rotation of the rotary rotor. And a liquid monomer mixture in which a colorant is dispersed is discharged from the outer chamber through a liquid discharge port to obtain a colorant-containing monomer mixture. Method. While repeating the circulation of the liquid monomer mixture by supplying the liquid monomer mixture to the media particle agitation type wet disperser and discharging the liquid monomer mixture from the media particle agitation type wet disperser method for producing a toner according to claim 1 for dispersing the colorant in the liquid monomer mixture. The method for producing a toner according to claim 1 or 2 , wherein the media particle diameter of the media particle agitation type wet disperser is in the range of 0.1 to 2 mm. The method for producing a toner according to any one of claims 1 to 3 , wherein the peripheral speed of the tip of the rotary rotor of the media particle agitation type wet disperser is controlled in a range of 5 to 20 m / s. The method for producing a toner according to any one of claims 1 to 4 , wherein the liquid temperature of the liquid monomer mixture dispersed with the agitation type wet disperser of media particles is adjusted to 10 to 40 ° C.

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