JP2011081220A - Method for manufacturing toner particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing polymerized toner, capable of acquiring a particulate colorant dispersion liquid-type monomer mixture acquired by dispersing uniformly and finely a colorant into a polymeric monomer. <P>SOLUTION: The method has a dispersion step of acquiring the particulate colorant dispersion liquid-type monomer mixture by dispersing the colorant into the polymeric mixture including the polymeric monomer, synergist, and an electron-donating compound which can coordinate to the synergist. In the dispersion process, liquid is sent to a media type disperser and dispersed. The disperser includes a media particle separation separator 37 and a rotating rotor 35 inside a cylindrical container 2 including a liquid introduction port 29 and a liquid discharge port 30. The cylindrical container is filled with a plurality of media particles 38, and a particle size of the media particles and an aperture ratio of the separation separator satisfy following expression 1 and expression 2: expression 1; 0.20 mm≤(media particle size)≤0.50 mm, expression 2; 5≤(aperture ratio/media particle size)≤49, wherein the aperture ratio is expressed in percents, and the media particle size is expressed in millimeters. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for efficiently producing a polymerized toner in which a colorant is finely and uniformly dispersed.

  In order to obtain a high-definition image using a toner produced by a polymerization method, it is required that the colorant is finely and uniformly dispersed in the toner particles. Therefore, when polymerized toner particles are produced by suspension polymerization, the colorant is finely contained in the polymerizable monomer in the step of dispersing the monomer mixture containing the polymerizable monomer and the colorant. Need to be distributed. If the dispersion of the colorant in the finely divided colorant-dispersed liquid monomer is insufficient, the particle size distribution of the colorant becomes wide, and a coarse colorant exists. In the step of forming a toner particle by dispersing a polymerizable monomer composition obtained by adding a release agent or the like to a fine particle colorant-dispersed liquid monomer mixture in an aqueous dispersion medium, the polymerizable monomer composition is dispersed in the aqueous dispersion medium. It becomes difficult to form uniformly dispersed toner particles of the monomer composition. As a result, the particle size distribution of the toner particles becomes broad, or toner particles that do not contain a colorant are generated in the toner particles, so that the obtained image quality is degraded. Furthermore, even if the colorant is finely and uniformly dispersed, if the familiarity of the polymerizable monomer and the colorant is poor, the dispersion stability of the finely divided colorant-dispersed liquid monomer mixture after the dispersion is reduced, The colorant is easily re-agglomerated.

  Conventionally, as a method of dispersing a colorant in a polymerizable monomer, a method using various media type dispersers has been proposed. In recent years, a fine media particle of less than 0.10 mm is used, and a colorant is used. A method of finely dispersing in a polymerizable monomer has also been studied. The smaller the media particle diameter, the more media particles that can be filled per disperser volume. That is, since the number of collisions between the media particles increases, the colorant in the colorant-dispersed liquid monomer mixture is atomized. However, when the media particle diameter is reduced, the centrifugal force generated in the media particles is reduced with the rotation of the drive shaft of the media type dispersing machine. When the centrifugal force generated on the media particles decreases, when processing a highly viscous product, the force to feed the media particles together with the processed material toward the outlet of the disperser becomes larger than the centrifugal force of the media particles. In the vicinity of the inner outlet, packing of media particles is likely to occur, and the dispersion efficiency is significantly reduced. In addition, when the centrifugal force generated in the media particles is reduced, packing of the media particles is likely to occur in the vicinity of the internal outlet of the disperser as described above unless the feeding amount of the colorant-dispersed liquid monomer mixture to the disperser is reduced. Thus, the dispersion efficiency is significantly reduced. Furthermore, a reduction in the centrifugal force of the media particles means a reduction in the collision force between the media, and in a polymerizable monomer such as a colorant having a strong aggregation or a colorant having a large primary particle size. It becomes difficult to perform fine dispersion.

  In order to solve the above problem, for example, in Patent Document 1, in the dispersion step of dispersing the colorant in the polymerizable monomer, 0.01 mm or more and 0.30 mm or less, preferably 0.05 mm or more and 0.10 mm or less. An example using the following micro media particles is disclosed. In Patent Document 1, the ratio of the aperture ratio and the media particle diameter of the media particle separation screen that separates the fine media particles inside the disperser and the fine colorant-dispersed liquid monomer mixture is defined as 50 or more and less than 260. Thus, it has been suggested that even minute media particles can be dispersed without causing problems such as packing.

  However, even in the above invention, depending on the type of the colorant, as a result of finely dispersing the colorant, the viscosity of the fine colorant-dispersed liquid monomer mixture is increased, and the media particles are packed near the inside outlet of the disperser. There is a case. As a result, the quality of the finely divided colorant-dispersed liquid monomer mixture is deteriorated due to excessive temperature rise, the apparatus is stopped due to an overload of the disperser, and the wear of the disperser and media particles are promoted.

  On the other hand, a colorant dispersant has been studied in order to finely disperse the colorant while suppressing the increase in the viscosity of the fine colorant-dispersed liquid monomer mixture, which is considered to be the cause of the packing. In order to perform its function, the colorant dispersant has a chemical structure that strongly adsorbs to the colorant, and has an affinity for the solvent and resin used to disperse the colorant. A chemical structure that can be a steric hindrance to prevent is needed. As materials that adsorb strongly to the colorant, phthalocyanine colorants and carbon black use phthalocyanine dye derivatives, and quinacridone colorants use quinacridone dye derivatives. Coloring prepared by mixing the above-described materials having an adsorptivity to the colorant and a polymer dispersant that has an affinity for a solvent and a resin and can be sterically hindered, and bonded by acid-base interaction. Agent dispersants are known.

  However, in the case of using these two kinds of colorant dispersants, it is necessary to prepare a colorant dispersion under conditions that do not break the bond due to the acid-base that binds both, and to maintain the conditions. is there. In particular, in the functional group of the resin to be added and the dispersion of the colorant in the aqueous solvent, it is necessary to pay sufficient attention to the pH of the solvent, resulting in restrictions on formulation and manufacturing method (Patent Document 2.3). reference).

JP 2007-206286 A JP 09-005989 A JP-T-2002-514263

  The present invention provides a method for producing a polymerized toner that can solve the above-mentioned problems and can obtain a fine colorant-dispersed liquid monomer mixture in which a colorant is uniformly and finely dispersed in a polymerizable monomer. It is to be.

In order to achieve the above object, the first invention according to the present application,
It has at least a dispersion step of dispersing a colorant in a monomer mixture containing at least a polymerizable monomer, a synergist, and an electron donating compound capable of coordination with the synergist to obtain a fine colorant-dispersed liquid monomer mixture. A method for producing toner particles, wherein the dispersion step is to send the solution to a media-type disperser and perform a dispersion treatment;
The media-type disperser includes a media particle separation separator and a rotating rotor that rotates by rotation of a drive shaft inside a cylindrical container having a liquid introduction port and a liquid discharge port, and the media particle is contained in the cylindrical container. Are filled, and the particle diameter of the media particles and the aperture ratio of the media particle separation separator satisfy the following formulas 1 and 2.
Formula 1:
0.20 mm ≦ (media particle diameter) ≦ 0.50 mm
Formula 2:
5 ≦ opening ratio / media particle size ≦ 49
(In Formula 2, the aperture ratio is a numerical value expressed in% units, and the particle diameter is a numerical value expressed in mm units.)

  According to the present invention, a fine colorant-dispersed liquid monomer mixture is obtained in which a colorant is uniformly and finely dispersed in a polymerizable monomer, and has a high standing stability and suppresses reaggregation of the colorant. It is possible to provide a method for producing a polymerized toner. Furthermore, a large-capacity and low-cost production method can be provided in the production of toner by a polymerization method.

1 is an explanatory diagram of a distributed system 1. FIG. 2 is an explanatory diagram of a distributed system 2. FIG. It is a side view of the disperser of FIG. It is sectional drawing in the casing which follows the A-A 'line of FIG. FIG. 4 is a B-B ′ sectional view of FIG. 3. It is an enlarged view of the rotary rotor used for the disperser of FIG. It is an enlarged view of the media particle separation separator located inside the disperser of FIG. It is sectional drawing in the casing of FIG. FIG. 3 is an enlarged view of a media particle separation separator located inside the disperser of FIG. 2. 2 is an explanatory diagram of a distributed system 3. FIG. It is sectional drawing in the holding tank of FIG. FIG. 11 is an enlarged view of a media particle separation separator located inside the holding tank of FIG. 10.

  Hereinafter, the present invention will be described in detail.

It has at least a dispersion step of dispersing a colorant in a monomer mixture containing at least a polymerizable monomer, a synergist, and an electron donating compound capable of coordination with the synergist to obtain a fine colorant-dispersed liquid monomer mixture. A method for producing toner particles,
The dispersion step is to send the solution to a media-type disperser for dispersion treatment,
The media-type disperser includes a media particle separation separator and a rotating rotor that rotates by rotation of a drive shaft inside a cylindrical container having a liquid introduction port and a liquid discharge port, and the media particle is contained in the cylindrical container. Are filled, and the particle diameter of the media particles and the aperture ratio of the media particle separation separator satisfy the following formulas 1 and 2.
0.20 mm ≦ (media particle diameter) ≦ 0.50 mm Formula 1
5 ≦ opening ratio / media particle size ≦ 49 Formula 2
(In Formula 2, the aperture ratio is a numerical value expressed in% units, and the particle diameter is a numerical value expressed in mm units.)

<Colorant dispersion step>
As a result of intensive investigations, the present inventors have found that a colorant dispersed in a polymerizable monomer is uniformly and finely dispersed, and has a high standing stability and prevents re-aggregation of the colorant. In order to obtain a monomer mixture, it has been found that the following is important. That is, it has been found that it is necessary to disperse a colorant in a monomer mixture containing at least a polymerizable monomer, a synergist, and an electron donating compound capable of coordination with the synergist.

  In the present invention, a synergist has a van der Waals force with a colorant, or has a common skeleton with the colorant, has a π-π interaction with the colorant, and is strongly adsorbed on the colorant surface. Means a compound. Synergist means a compound that has an affinity for the solvent and resin used when dispersing the colorant, and also has a strong interaction with the polymer dispersant that can cause steric hindrance to prevent re-aggregation of the colorant. .

  In the present invention, a preferred synergist is a compound in which the center of the compound is a metal atom and a phthalocyanine structure is formed around the metal atom. In the present invention, an electron donating compound (polymer dispersing agent) capable of coordinating with a central metal atom of a synergist is not a metal synthesist and a polymer dispersing agent bonded by acid-base interaction as in the prior art. An electron is donated to an atom, and it is strongly bonded by a coordination bond. Therefore, it is possible to bond firmly without being affected by the pH of the solvent or the functional group of the added resin. The electron donor compound capable of coordinating to the synergist exhibits affinity for the dispersion medium and steric hindrance, so that re-aggregation of the colorant is suppressed, the polymerizable monomer and the colorant It becomes possible to reduce the viscosity of the finely divided colorant-dispersed liquid monomer mixture.

  The synergist used in the present invention is a metal phthalocyanine and / or metal phthalocyanine derivative whose central metal is any one of [Cr, Fe, Co, Ni, Zn, Mn, Mg, Al] (hereinafter referred to as “metal phthalocyanines”). Is preferred). A pentacoordinate that can coordinate a ligand in the axial direction to a phthalocyanine ring, which is a macrocyclic compound, carbon black having hexagonal plate crystals, and polycyclic colorants such as quinacridone. It is possible to take a structure or a hexacoordinate structure.

  On the other hand, the electron donating compound that can be coordinated to the synergist used in the present invention is preferably a polymer containing a structural unit derived from a specific polymerizable monomer having an amide group. That is, a polymer containing 0.5 to 20% by mass of a structural unit derived from a polymerizable monomer represented by the following structural formula (1) (hereinafter referred to as “polymer ligand”) is preferable. Since the colorant dispersant has an unshared electron pair, it acts as a polymer ligand for the phthalocyanine ring and the like. Therefore, a polymer complex can be formed by making both coexist.

  In the polymer complex obtained by coordinating a polymer ligand to the metal phthalocyanines used in the present invention, the phthalocyanine ring portion exhibits good affinity with the colorant. In addition, since the polymer portion exhibits affinity with the binder resin and other toner constituent materials and prevents reaggregation due to steric hindrance, it seems that a good dispersion state of the colorant in the toner can be produced. .

  The metal phthalocyanines used in the present invention have a divalent metal, a trivalent or tetravalent substituted metal, or an oxy metal as a central metal because it needs to be a pentacoordinate structure or a hexacoordinate structure. is there. Specifically, it is any selected from the group consisting of [Cr, Fe, Co, Ni, Zn, Mn, Mg, Al]. The central metal of the metal phthalocyanines is preferably [Cr, Fe, Co, Zn, Mn] considering the ease of incorporation of the axial ligand. Furthermore, considering the adsorption ability with the colorant, Zn phthalocyanine (zinc phthalocyanine) having Zn as a central metal capable of taking a five-coordinate structure is particularly preferably selected.

  Known metal phthalocyanines used in the present invention can be used. That is, it is not particularly limited as long as it has a phthalocyanine skeleton. For example, four isoindole moieties into which substituents such as carboxylic acid and sulfonic acid are introduced, aromatics, aliphatics, ethers, alcohols Those introduced with a substituent such as. However, it is not preferable that itself affects the adsorptivity of the phthalocyanine ring and the colorant and the ease of incorporation of the axial ligand.

  In the present invention, the metal phthalocyanines form a polymer complex using a polymer containing a structural unit derived from a specific polymerizable monomer having an amide group, which will be described later, as a polymer ligand. Therefore, the object of the present invention can be achieved with a very small addition amount. The amount is in a range where the effect of the coloring power of the metal phthalocyanines themselves can be ignored. The specific addition amount depends on the kind and addition amount of the colorant used at the same time, but is 0.01 to 0.5 parts by mass, preferably 0.03 to 0.3 parts by mass with respect to 100 parts by mass of the binder resin. Part by mass.

  On the other hand, a polymer containing a structural unit derived from a specific polymerizable monomer having an amide group used as a polymer ligand for the metal phthalocyanines used in the present invention is at least the structural formula (1). Is a polymer containing 0.5 to 20% by mass of a structural unit derived from a polymerizable monomer represented by

  Since such a polymer has an unshared electron pair in at least the molecular structure of the polymerizable monomer represented by the structural formula (1), it is a polymer ligand for the metal phthalocyanines. It forms a polymer complex with the metal phthalocyanines.

In the structural formula (1), R ₁ represents a hydrogen atom or a methyl group. R ₂ and R ₃ each independently represent a hydrogen atom, an aryl group, or a C1 to C10 alkyl group, alkenyl group or alkoxy group, and X ₁ represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or a quaternary ammonium. Represents a salt, and n represents an integer of 1 to 10.

Specific examples of the polymerizable monomer represented by the structural formula (1) include 2- (meth) acrylamide-2-methylpropanesulfonic acid, 2- (meth) acrylamide-n-butanesulfonic acid, 2 -Acrylamide-n-hexanesulfonic acid, 2- (meth) acrylamide-n-octanesulfonic acid, 2- (meth) acrylamide-n-dodecanesulfonic acid, 2- (meth) acrylamide-n-tetradecanesulfonic acid, 2- (Meth) acrylamide-2,2,4-trimethylpentanesulfonic acid, or an alkali metal salt, alkaline earth metal salt, quaternary ammonium salt, or the like thereof. Of these, 2-acrylamido-2-methylpropanesulfonic acid (in the above structural formula (1), R ₁ is a hydrogen atom, R ₂ and R ₃ are methyl groups, X ₁ is a hydrogen atom, and n is 1) And the like are preferably used.

Next, as a result of intensive studies, the present inventors have found that the media-type disperser preferably used in the present invention has a media particle separation separator and a drive shaft in a cylindrical container having a liquid inlet and a liquid outlet. A rotating rotor that rotates by rotation is provided, and the cylindrical container is filled with a plurality of media particles. The particle diameter of the media particles and the aperture ratio of the media particle separation separator are expressed by the following formulas 1 and 2. We found that meeting the requirements was important.
0.20 mm ≦ (media particle diameter) ≦ 0.50 mm Formula 1
5 ≦ opening ratio / media particle size ≦ 49 Formula 2
(In Formula 2, the aperture ratio is a numerical value expressed in% units, and the particle diameter is a numerical value expressed in mm units.)

  An example of a preferable distributed system in the present invention is shown in FIGS.

  The disperser of FIG. 1 includes a cylindrical media particle separation separator having a slit inside the cylindrical container having a first wall surface having the liquid inlet and a second wall surface having the liquid outlet. An inner room and an outer room are provided. And a disperser in which the inner chamber is filled with a rotating rotor and media particles, and the monomer mixture is fed to the media disperser to obtain the fine colorant-dispersed liquid monomer mixture. It is a disperser that is characterized.

  The disperser of FIG. 2 is formed by rotating a drive shaft provided in a horizontal direction inside the cylindrical container having a first wall surface having the liquid inlet and a second wall surface having the liquid outlet. It is filled with a rotatable rotor and media particles. The media particle separation separator that separates the media particles and the monomer mixture is a disperser provided at the center of the rotating rotor, and the monomer mixture is fed to the media type disperser. A disperser characterized in that a fine colorant-dispersed liquid monomer mixture is obtained.

  FIG. 3 is a side view of the disperser of FIG. FIG. 4 is a cross-sectional view inside the casing along the line A-A ′ in FIG. 1. FIG. 5 shows a cross-sectional view along B-B ′ in FIG. 3. FIG. 6 is a perspective view of a rotary rotor used in the disperser of FIG. FIG. 7 is a media particle separation separator that is located inside the disperser of FIG. 1 and separates the media particles and the fine colorant-dispersed liquid monomer mixture.

  FIG. 8 shows a cross-sectional view of the casing 32 in FIG. FIG. 9 is a media particle separation separator 69 that is located inside the disperser of FIG. 2 and separates the media particles and the fine colorant-dispersed liquid monomer mixture.

  A dispersion process using the dispersion system of FIG. 1 will be described below with reference to FIGS. 1 and 3 to 7.

  The disperser 1 in FIG. 1 has a rotating rotor 35 for stirring the media particles 38 inside the main casing 2 and a slit 36 for separating the media particles 38 and the fine colorant-dispersed liquid monomer mixture on the outer periphery thereof. There is a media particle separation separator 37 having. When the rotary rotor 35 is rotated by the drive shaft 31, centrifugal force is generated, and the media particles 38 form a layer on the media particle separator 37 on the outer periphery, and also perform rotational motion by the rotational force of the rotary rotor 35. A strong shearing force is generated to disperse the colorant.

  Thereafter, the fine colorant-dispersed liquid monomer mixture is separated from the media particles 38 by the media particle separation separator 37 and then discharged from the liquid discharge port 30 and returns to the holding tank 21 via the cooling means 11. The finely divided colorant-dispersed liquid monomer mixture in the holding tank 21 is uniformly and efficiently dispersed in the polymerizable monomer while repeating the circulation between the disperser and the holding tank 21. Done.

  The diameter of the media particles used in the present invention is preferably in the range of 0.20 mm to 0.50 mm.

  When the diameter of the media particles is less than 0.20 mm, the amount of media particles per volume of the disperser increases, so the number of collisions between the media particles increases. As a result, the final reached particle diameter of the colorant becomes fine, while the centrifugal force generated in the media particles decreases in inverse proportion to the weight. Therefore, when coarse particles are contained in the colorant or the cohesive force of the colorant is large, the dispersion time is increased and the dispersion efficiency is remarkably lowered.

  Further, since the centrifugal force decreases as the media particles become smaller, the media particles are pushed away by the processed material, and are easily packed near the media particle separation separator (dispersing machine outlet). Therefore, in order to prevent packing, the amount of liquid to be processed must be limited to the extent that the media particles do not pack, and the dispersion time increases and the dispersion efficiency decreases significantly.

  When the diameter of the media particles exceeds 0.50 mm, the centrifugal force generated in the media particles is sufficiently dispersible even when coarse particles are included in the colorant or the cohesive force of the colorant is large. . However, since the amount of media particles per volume of the disperser decreases, the number of collisions between the media particles also decreases, and the time until the final reached particle size increases, which is not preferable.

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

  In the present invention, the aperture ratio / media particle diameter is preferably in the range of 5 to 49.

  In order to increase the aperture ratio when the media particle size is constant, increasing the aperture width increases the possibility of media particle leakage, so the slits or wires that make up the media particle separator must be thinned. Don't be.

  However, when the aperture ratio / media particle diameter exceeds 49, the linear shape of slits or wires constituting the media particle separation separator becomes too thin. As a result, wear of the media particle separation separator and contamination into the fine colorant-dispersed liquid monomer mixture due to wear, and further leakage of media particles, etc. are not preferable. Generally, a metal such as stainless steel is used as a component inside the disperser. However, if the media particle separator or the like is heavily worn, the metal is contaminated in the toner particles and affects the charging characteristics of the toner. End up. In particular, since charges easily leak from the toner, image defects such as fogging tend to deteriorate.

  When the aperture ratio / media particle diameter is less than 5, it is a fine low-viscosity fine colorant-dispersed liquid monomer mixture containing a polymerizable monomer, a synergist, and an electron donor compound capable of coordination with the synergist. However, since the aperture ratio is too small, clogging is likely to occur. As the internal pressure of the disperser increases due to clogging, the product temperature of the processed product also fluctuates, which is not preferable because the quality of the toner is lowered. Also, if the internal pressure of the disperser rises due to clogging, the pressure by which the processed material pushes the media particles to the media particle separation separator increases, so that the media particles tend to be packed and the damage due to wear inside the disperser becomes severe. Absent.

  In the present invention, in order to prevent clogging of the colorant between the slits of the media particle separation separator or between the wires, pressure is applied from the liquid outlet 30 of the media type dispersing machine to the liquid inlet 29 for a certain period of time. It is preferable to carry out dispersion while preventing the above. In order to prevent clogging, a check valve 9 is installed between the liquid inlet 29 and the pump 10. The check valve 9 can prevent media particles from flowing into the pump and damaging the pump.

  As a procedure for preventing clogging, while the pump 10 is stopped during the dispersion or after the dispersion is completed, the pressure source and the disperser direction are opened by the three-way valve 3, and the processed material is supplied from the liquid outlet 30 to the liquid inlet 29. Extrude in the direction to remove clogging of the media particle separator. The pressure source is preferably air, preferably an inert gas such as nitrogen gas. The pressure from the liquid discharge port 30 to the liquid introduction port 29 of the media type dispersing machine is preferably equal to or lower than the internal pressure of the shaft seal liquid tank 22, preferably about 0.10 MPa lower than the internal pressure of the shaft seal liquid tank 22. . When the pressure is high by the shaft seal liquid tank 22, the processed material enters the shaft seal and the device is damaged, which is not preferable.

  As described above, according to the present invention, it is possible to prevent a decrease in dispersion efficiency due to the packing of media particles and an increase in the temperature of the processed product due to an increase in the internal pressure of the disperser due to clogging of the media particle separator. That is, it is possible to prevent the toner quality from being lowered, and the colorant can be finely dispersed with uniform quality.

  The filling rate of the media of the disperser in the present invention is preferably 70 to 130%. Here, the media filling rate indicates the ratio of the total volume of media particles to the space volume between the rotary rotor 35 and the media particle separation separator 37.

  When the media filling rate is less than 70%, the number of media particles with respect to the internal volume of the disperser is too low, so the number of collisions between the media particles decreases, and the dispersion efficiency decreases. On the other hand, if it exceeds 130%, the number of media particles with respect to the internal volume of the disperser is too large, and the packing feels so undesirably that the movement of the media particles decreases and the dispersion efficiency decreases.

  The total volume of media particles is accurately measured by putting the media particles into a graduated cylinder.

  From the viewpoint of dispersibility of the colorant, wear of the media particles, and stable operation of the apparatus itself, it is preferable to use the peripheral speed of the tip of the rotary rotor in the range of 8 to 25 m / s, and more preferably 12 to 20 m / s. It is more preferable to use within a range.

  When the peripheral speed deviates from the above range and is smaller than 8 m / s, the media particle centrifugal force is reduced, so that the dispersion efficiency is remarkably deteriorated. Moreover, since the bad movement of the media hinders the flow of the monomer composition, it induces an excessive increase in the pressure in the apparatus. On the other hand, when the peripheral speed exceeds 25 m / s, the wear between the media particles and the wear between the media particles and the apparatus become so severe that the image performance deteriorates due to the mixing of the media particle fragments.

  Next, the case where the distributed system of FIG. 2 is used will be described below. FIG. 8 is a cross-sectional view inside the casing in FIG. FIG. 9 is a media particle separation separator that is located inside the disperser of FIG. 2 and separates the media particles and the fine colorant-dispersed liquid monomer mixture.

  The disperser 41 shown in FIG. 2 is arranged in a cylindrical vessel coaxially with the vessel, and can be rotated by a drive shaft 71, and a media particle 72 and a fine colorant-dispersed liquid monomer mixture. A media particle separation separator 70 is provided for separating the particles. The media particles filled in the disperser are vigorously stirred by the action of the rotor pin 73 installed on the rotating cylindrical rotor 69 and the vessel pin 74 installed on the vessel. The finely divided colorant-dispersed liquid monomer mixture is passed through the crushing chamber 75 to promote fine dispersion and crushing. Thereafter, the fine colorant-dispersed liquid monomer mixture that has passed through the crushing chamber 75 passes through the media particle separator 70 and is discharged from the liquid discharge port 77. At this time, the media particles 72 that have flowed in the vicinity of the media particle separation separator 70 together with the flow of the fine colorant-dispersed liquid monomer mixture pass through the media particle outlet 79 due to the centrifugal force generated by the rotation of the cylindrical rotor 69. And returned to the crushing chamber 75. By this centrifugal separation action, the fine colorant-dispersed liquid monomer mixture can be circulated at a large flow rate, and efficient dispersion of the colorant is achieved.

  In the case of the dispersion system of FIG. 2, the diameter of the media particles used in the present invention is preferably in the range of 0.20 mm to 0.50 mm, as in the dispersion system of FIG.

  Also, the aperture ratio / media particle diameter is preferably in the range of 5 to 49 as in the dispersion system of FIG.

  In the present invention, in order to prevent clogging of the colorant between the media particle separators, a pressure is applied from the liquid outlet 77 of the media type dispersing machine in the direction of the liquid inlet 76 for a certain time to disperse while preventing clogging. Is preferably performed. In order to prevent clogging, a check valve 49 is installed between the liquid inlet 76 and the pump 50. The check valve 49 can prevent media particles from flowing into the pump and damaging the pump.

  As a clogging prevention procedure, with the pump 50 stopped, the pressure source and the disperser direction are opened by the three-way valve 60, the processed material is pushed out from the liquid discharge port 77 toward the liquid inlet port 76, and the media particles are separated. The clogging of the separator 70 is removed. The pressure source is preferably air, preferably an inert gas such as nitrogen gas. The pressure from the liquid discharge port to the liquid introduction port of the media type dispersing machine is preferably equal to or lower than the internal pressure of the shaft seal liquid tank 62, preferably about 0.1 MPa lower than the internal pressure of the shaft seal liquid tank 62. When the pressure is high by the shaft seal liquid tank 62, the processed material enters the shaft seal and the device is damaged, which is not preferable.

  As described above, according to the present invention, it is possible to prevent a decrease in dispersion efficiency due to the packing of media particles and an increase in the temperature of the processed product due to an increase in the internal pressure of the disperser due to clogging of the media particle separator. That is, it is possible to prevent the toner quality from being lowered, and the colorant can be finely dispersed with uniform quality.

  The peripheral speed of the cylindrical rotor 69 of the disperser in the present invention is preferably in the range of 8 to 25 m / s. When the peripheral speed that deviates from the above range is less than 8 m / s, the collision probability between the media particles and the colorant is lowered, so that the dispersion efficiency is deteriorated. Further, if it exceeds 25 m / s, the wear between the media particles and the wear between the media particles and the apparatus become so severe that the image performance deteriorates due to the mixing of the media particle fragments.

  The filling rate of the media particles of the disperser in the present invention is preferably 60 to 90%. The media particle filling rate referred to here indicates the ratio of the total volume of media particles to the volume of the grinding chamber. The total volume of media particles is accurately measured by putting the media particles into a graduated cylinder.

  When the media filling rate is less than 60%, the number of media particles with respect to the internal volume of the disperser is too low, so the number of collisions between the media particles decreases, and the dispersion efficiency decreases. On the other hand, if it exceeds 90%, the number of media particles with respect to the internal volume of the disperser is too large, which makes packing seem to be unsatisfactory.

  The material of the cylindrical rotor and vessel in the disperser is preferably stainless steel, cemented carbide, carbon steel, alumina, ceramic, or zirconia from the viewpoint of strength. Moreover, it is more preferable to use stainless steel or carbide from the viewpoint of wear.

  As described above, the colorant can be finely dispersed in the polymerizable monomer by the dispersion system of FIG. 1 or the dispersion system of FIG.

  In addition, the heat generated during dispersion tends to adversely affect the fine colorant-dispersed liquid monomer mixture. Therefore, a heat exchanger is installed as a cooling means in the circulation system line for heat exchange. It is preferable to do. It is preferable to install a heat exchanger in the disperser or the path after passing through the disperser. At that time, the liquid temperature of the fine colorant-dispersed liquid monomer mixture is preferably adjusted to 10 to 50 ° C.

  If the liquid temperature of the fine colorant-dispersed liquid monomer mixture is lower than 10 ° C, moisture due to condensation may be mixed in the fine colorant-dispersed liquid monomer mixture, which may reduce the dispersion efficiency. This is not preferable. When the liquid temperature exceeds 50 ° C., the polymerizable monomer may be deteriorated by thermal polymerization, which causes a problem in image characteristics.

≪Toner production method≫
The method for producing a polymerization method toner of the present invention can be suitably used for a suspension polymerization method and an emulsion aggregation method. An example of the suspension polymerization method will be described below.

  In the dispersing step, at least the colorant is dispersed in the polymerizable monomer by the above dispersion method to obtain a fine colorant-dispersed liquid monomer mixture.

  In the adjusting step of mixing the fine colorant-dispersed liquid monomer mixture obtained in the dispersing step with additives such as a release agent, a polymerizable monomer composition is obtained. The polymerizable monomer composition obtained in the adjusting step is dispersed in an aqueous phase containing a dispersion stabilizer by a stirrer having a high shearing force such as Claremix or a homomixer. At this time, the stirring speed and time are adjusted and granulated so that the droplets of the polymerizable monomer composition have a desired toner size.

  In the suspension polymerization method, it is usually preferable to use 100 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the polymerizable monomer composition. After that, since the particle state is maintained by the action of the dispersion stabilizer, stirring may be performed to such an extent that the particles do not settle.

  The polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. Further, the temperature may be raised in the latter half of the polymerization reaction for the purpose of obtaining a desired molecular weight distribution. Further, in order to remove unreacted polymerizable monomers, by-products, etc. The partial aqueous medium may be distilled off by distillation. The distillation operation can be performed under normal pressure or reduced pressure. After completion of the polymerization reaction or subsequent distillation operation, the produced toner particles are filtered / washed, and the dispersion stabilizer on the obtained particulate surface is removed by acid and / or alkali treatment before or after this step. You can also. The toner particles finally separated from the liquid phase are dried, classified, and externally added by a known method.

  The material used suitably by this invention is demonstrated below.

[Colorant]
As the colorant used in the present invention, a known colorant can be used.

  Examples of organic pigments or organic dyes as cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, the following are mentioned. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue.

  Examples of the organic pigment or organic dye as the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specifically, the following are mentioned. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  Examples of the organic pigment or organic dye as the yellow colorant include compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following are mentioned. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.

  Black colorants include carbon black, aniline black, nonmagnetic ferrite, and magnetite. Examples thereof include those prepared by adjusting the color to black using the yellow colorant / magenta colorant / cyan colorant.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner. The colorant is preferably used by adding 1 part by mass or more and 20 parts by mass or less to 100 parts by mass of the polymerizable monomer or binder resin.

  In the present invention, when a toner is obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and water phase migration property of the colorant, and preferably, the hydrophobic treatment with a substance that does not inhibit polymerization is colored. It is better to apply to the agent. In particular, since dye-based colorants and carbon black have many polymerization-inhibiting properties, care must be taken when using them.

  In addition, as a method for suppressing the polymerization inhibitory property of the dye-based colorant, a method of polymerizing a polymerizable monomer in the presence of these dyes in advance can be mentioned, and the obtained colored polymer is composed of a polymerizable monomer composition. Add to product.

  Moreover, about carbon black, you may process with the substance (for example, polyorganosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.

(Polymerizable monomer)
As the polymerizable monomer used in the toner of the present invention, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene derivatives such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2 -Ethylhexyl acrylate acrylic polymerizable monomers such as n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; Methacrylic polymerizable monomer in which acrylate of the above acrylic polymerizable monomer is replaced with methacrylate; methylene aliphatic monocarboxylic acid ester; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate, etc. Vinyl esters; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl Ketones such as vinyl, and the like.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Acrylate polymerizable monomers such as diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate; tetramethylolmethane tetraacrylate, the above acrylic Methacrylate polymerizable monomer in which acrylate of the polymerizable monomer is replaced with methacrylate; divinylbenzene, divinylnaphthalene, divinyl ester Tel and the like.

  In the present invention, the above monofunctional polymerizable monomers are used alone or in combination of two or more, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. To do. Among the above-mentioned monomers, styrene or a styrene derivative is preferably used alone or in combination, or in combination with other monomers from the viewpoint of toner development characteristics and durability.

[Low molecular weight resin]
In the production of the toner of the present invention, for the purpose of improving the shape of the toner, the dispersibility and fixing properties of the material, and the image characteristics, the polymerization can be carried out by adding a resin to the polymerizable monomer composition. For example, when a monomer component containing a hydrophilic functional group that cannot be used because it is soluble in an aqueous suspension and causes emulsion polymerization because the monomer is water-soluble, the following procedure is performed. That is, it can be used in the form of a copolymer such as a random copolymer, a block copolymer, and a graft copolymer of the above hydrophilic functional group-containing monomer component and a vinyl compound such as styrene or ethylene. It is. Further, it can be used in the form of the above-mentioned monomer component containing a hydrophilic functional group and a polycondensate such as polyester and polyamide, or an addition polymer such as polyether and polyimine. Examples of hydrophilic functional groups include amino groups, carboxylic acid groups, hydroxyl groups, sulfonic acid groups, glycidyl groups, and nitrile groups.

  In addition to the above, examples of the low molecular weight resin that can be added to the polymerizable monomer composition include the following. Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene- Ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate Copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer , Styrene-butadi Copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene copolymer such as styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, Polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin. In addition, the said low molecular weight resin can be used individually or in mixture.

  Among these low molecular weight resins, the glass transition point of the low molecular weight resin is preferably 40 ° C. or higher and 100 ° C. or lower. When the glass transition point is less than 40 ° C., the strength of the whole toner is lowered, and the transferability and development characteristics are liable to be lowered during a multi-endurance test. Furthermore, the toner aggregates in a high-temperature and high-humidity environment, resulting in a problem that storage stability is lowered. On the other hand, if the glass transition point exceeds 100 ° C., the problem of poor fixing tends to occur.

  The glass transition point of the low molecular weight resin is preferably 40 ° C. or higher and 70 ° C. or lower, more preferably 40 ° C. or higher and 65 ° C. or lower, from the viewpoint that low temperature fixability and a high gloss image can be obtained.

[Polar resin]
In the case of a polymerization method using an aqueous dispersion medium such as suspension polymerization, the inclusion of a release agent can be promoted by adding a polar resin to the polymerizable monomer composition. When a polar resin is present in the polymerizable monomer composition in the aqueous medium, the polar resin tends to move near the interface between the aqueous medium and the polymerizable monomer composition due to the difference in hydrophilicity. Polar resin will be unevenly distributed. As a result, the toner has a core-shell structure, and even when a large amount of the release agent is contained, the inclusion property of the release agent is improved.

  As the polar resin, a polyester resin is particularly preferable since the fluidity of the polar resin itself can be expected when it is unevenly distributed on the toner surface to form a shell.

  Examples of polar resins that can be used in this toner include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Acidic monomers such as camphoric acid, cyclohexanedicarboxylic acid, trimellitic acid; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butane Alkylene glycols such as diol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane and polyalkylene glycols, bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, bisphenol A pro Alkylene oxide adducts, glycerol, trimethylolpropane, and such as pentaerythritol polyhydric alcohol monomer may be mentioned those condensation polymerization.

(Polymerization initiator)
The following are mentioned as a polymerization initiator used when manufacturing a toner with a polymerization method. 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy carbonate, cumene hydroperoxide, 2,4- Peroxide polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 20% by mass relative to the polymerizable monomer, and may be used alone or in combination.

〔Release agent〕
Examples of the wax component that can be used in the toner according to the present invention include the following. Paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof by Fischer-Tropsch method, polyolefin wax and derivatives thereof such as polyethylene and polypropylene, carnauba wax, candelilla Natural waxes such as waxes and derivatives thereof, and derivatives include oxides, block copolymers with vinyl monomers, graft modified products, fatty acids such as higher aliphatic alcohols, stearic acid, palmitic acid, or compounds thereof, Acid amide wax, ester wax, ketone, hydrogenated castor oil and derivatives thereof, plant wax, animal wax, silicone resin.

[Charge control agent]
The toner of the present invention may contain a charge control agent.

  Known charge control agents can be used. For example, organometallic compounds and chelate compounds are effective for controlling the toner to be negatively charged, and monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic compounds are effective. There are metal compounds of acids and aromatic dicarboxylic acids. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol.

  Also, urea derivatives, metal-containing salicylic acid compounds, quaternary ammonium salts, calixarene, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-acrylic-sulfonic acid copolymers, nonmetal carboxyls Examples include acid compounds.

  Examples of toners that are controlled to be positively charged include modified products of nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, And onium salts such as phosphonium salts and analogs thereof, and lake lake pigments, triphenylmethane dyes and lake pigments thereof (metal salts of higher fatty acids; diorganotins such as dibutyltin oxide, dioctyltin oxide, and dicyclohexyltin oxide) Tin oxides; diorganotin borates such as dibutyl tin borate, dioctyl tin borate, dicyclohexyl tin borate, etc., and these can be used alone or in combination of two or more. Shin-based, such as charge control agent quaternary ammonium salt is preferably used.

  These charge control agents may be used in an amount of 0.01 to 20 parts by mass (more preferably 0.5 to 10 parts by mass) with respect to 100 parts by mass of the resin component.

[Crosslinking agent]
Examples of the crosslinkable monomer include the following as a bifunctional crosslinking agent. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and the above acrylates replaced with methacrylate of.

  Moreover, the following are mentioned as a polyfunctional crosslinking | crosslinked monomer. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate and the like. A preferable addition amount of the crosslinking agent is 0.001 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

(Dispersion stabilizer)
As a dispersion stabilizer for satisfactorily dispersing the polymerizable monomer composition in an aqueous medium, for example, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, which are inorganic oxides, Examples thereof include magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina, titania, magnetic substance, and ferrite. As the organic compound, for example, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, starch and the like are used dispersed in an aqueous phase. The dispersion stabilizer is preferably used in an amount of 0.2 to 10.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  Commercially available dispersion stabilizers may be used as they are, but in order to obtain dispersed particles having a fine and uniform particle size, the inorganic compound can also be produced under high-speed stirring in a dispersion medium. For example, in the case of tricalcium phosphate, a dispersant suitable for the suspension polymerization method can be obtained by introducing and mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution into water under high-speed stirring. Further, 0.001 to 0.1 parts by mass of a surfactant may be used in combination for miniaturization of these dispersants. Specifically, commercially available nonionic, anionic and cationic surfactants can be used, such as sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, olein. Acid calcium or the like is preferably used.

(External additive)
In using the toner produced according to the present invention, an external additive can be used for the purpose of imparting various properties. The external additive preferably has a particle diameter of 1/10 or less of the weight average diameter of the toner from the viewpoint of durability when added to the toner. The particle size of the additive means the average particle size obtained from observation with an electron microscope. As an external additive, for example,
Metal oxide (aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide, etc.), nitride (silicon nitride, etc.), carbide (silicon carbide, etc.), metal salt (sulfuric acid) Calcium, barium sulfate, calcium carbonate, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.), carbon black, silica, etc. are used.

  These external additives are used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the toner. The external additives may be used singly or in combination of two or more, but those subjected to hydrophobic treatment are more preferable.

  The toner of the present invention can be used in any developing system as a one-component or two-component developer. For example, in the case of a magnetic toner in which a magnetic material is contained in the toner as the one-component developer, there is a method of transporting and charging the magnetic toner using a magnet built in the developing sleeve. When non-magnetic toner containing no magnetic material is used, there is a method in which a blade and a fur brush are used to forcibly charge by a developing sleeve, and the toner is attached to the sleeve and conveyed.

  On the other hand, when used as a two-component developer that is generally used, a carrier is used together with the toner of the present invention. Although it does not specifically limit as a carrier used for this invention, It is comprised by the single and composite ferrite state which mainly consist of iron, copper, zinc, nickel, cobalt, manganese, and a chromium element. Further, it may be a magnetic fine particle dispersed resin carrier in which a magnetic material is dispersed in a resin. The carrier shape is also important from the viewpoint that the saturation magnetization and electric resistance can be controlled in a wide range. For example, it is preferable to select a spherical shape, a flat shape, an indeterminate shape, etc., and also to control the fine structure of the carrier surface state, for example, surface unevenness .

  A system in which the surface of the carrier is coated with a resin or the like is particularly preferable. As the method, any of conventionally known methods such as a method in which a coating material such as a resin is dissolved or suspended in a solvent and applied and adhered to a carrier, or a method of simply mixing with a powder can be applied.

  The treatment amount of the above compound is generally 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the carrier as a total amount.

  These carriers have an average particle size of 10 to 100 μm, preferably 20 to 50 μm.

  When a two-component developer is prepared by mixing with the toner of the present invention, the mixing ratio is usually 2 to 15 parts by mass, preferably 4 to 13 parts by mass as the toner concentration in the developer. Results. If the toner concentration is less than 2 parts by mass, the image density is low and impractical, and if it exceeds 15 parts by mass, fog and in-machine scattering increase and the useful life of the developer is shortened.

Further, the magnetic properties of the carrier are preferably as follows. The magnetization strength (σ1000) at 1000 Oersted after magnetic saturation is required to be ³⁰ to 300 emu / cm ³ . Further, in order to achieve high image quality, it is preferably 100 to 250 emu / cm ³ . When it is greater than 300 emu / cm ^3, it becomes difficult to obtain a high-quality toner image. When it is less than ³⁰ emu / cm ³ , the magnetic binding force is also reduced, so that carrier adhesion is likely to occur.

<Disperser stability evaluation>
When the colorant is dispersed, the smaller the opening ratio of the media particle separator is, the more easily the media particle separator is clogged, and the change in the internal pressure of the disperser at the start of dispersion and after the end of dispersion increases. The larger the pressure change, the more the media particles are packed, and the media particle separator separator becomes more worn out. Regarding the evaluation, in the colorant dispersion step, the disperser internal pressure at the start of dispersion and the disperser internal pressure at the end of dispersion were measured and evaluated. That is, the smaller the pressure difference between the start of dispersion and the end of dispersion, the more stable dispersion is preferable.
Evaluation criteria: (pressure difference = pressure at the end of dispersion−pressure at the start of dispersion, unit: MPa)
Rank A: Less than 0.10 Rank B: 0.10 or more and less than 0.15 Rank C: 0.15 or more and less than 0.20 Rank D: 0.20 or more

<Gloss (glossiness) measurement>
The dispersion state of the pigment in the fine colorant dispersed liquid monomer mixture in the colorant dispersion step was measured by measuring the gloss (glossiness) of the fine colorant dispersed liquid monomer mixture. Gloss of fine colorant-dispersed liquid monomer mixture is applied on top of super art paper <Kinto 180 kg 80 x 160 (made by Seven Dos Co., Ltd.) on a straight line, and then uniformly on the art paper using a wire bar (# 10). Apply. After sufficiently drying, the coated sample was placed on a smooth glass plate and measured. In the measurement, three points were measured using GLOSS CHECKER IG320 manufactured by HORIBA, and the average value was defined as the gloss (glossiness) of the fine colorant-dispersed liquid monomer mixture.

When the colorant is well dispersed, the coated surface becomes smooth, gloss is increased, and the gloss value is increased. On the contrary, when the dispersion of the colorant is poor, the unevenness remains on the coating surface, and the gloss value becomes low because it becomes dull.
Evaluation criteria:
Rank A: 80 or more Rank B: Less than 80 72 or more Rank C: Less than 72 65 or more Rank D: Less than 65

<Durable image density measurement>
A modified machine (process speed: 190 mm / sec, fixing temperature: 190 ° C.) of a full color laser beam printer (LBP-2510, manufactured by Canon) is used. With this printer, 350 g of toner was set on a process cartridge in an environment of normal temperature and normal humidity (24 ° C./60% RH), printed out and evaluated. Specifically, up to 15000 sheets of recording paper (75 mg / cm ² ) were printed out with an image with a printing ratio of 2%, and the solid image density at the initial and 15000 sheet output was evaluated.
Evaluation criteria:
Rank A: 1.40 or more Rank B: Less than 1.40 1.30 or more Rank C: Less than 1.30 1.20 or more Rank D: Less than 1.19

<Measurement of fogging>
A modified machine (process speed: 190 mm / sec, fixing temperature: 190 ° C.) of a full color laser beam printer (LBP-2510, manufactured by Canon) is used. In an endurance test under an H / H environment, fog after 7000 endurance was measured. As a method, the average reflectance Dr (%) of plain paper before image printing was measured with a reflectometer ("REFLECTOMETER ODEL TC-6DS" manufactured by Tokyo Denshoku Co., Ltd.) equipped with a green filter. On the other hand, a solid white image was drawn on plain paper, and then the reflectance Ds (%) of the solid white image was measured. The fog (%) is expressed by the following formula: Fog (%) = Dr (%) − Ds (%)
Calculate from
Evaluation criteria:
Rank A: Very good (less than 1.1%)
Rank B: Good (1.1% to less than 2.5%)
Rank C: Normal (2.5% or more to less than 4.0%)
Rank D: Bad (over 4%)

  Hereinafter, the present invention will be described in more detail with specific production methods, examples, and comparative examples, but this does not limit the present invention in any way. In addition, all the parts in the following mixing | blending are a mass part.

  A method for preparing a fine colorant-dispersed liquid monomer mixture in the colorant-dispersing step will be described.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 1]
A colorant dispersion step was performed using the dispersion system of FIG. 3 is a side view of the disperser of FIG. FIG. 4 is a cross-sectional view inside the casing along the line AA ′ in FIG. 1. FIG. 5 is a cross-sectional view taken along the line BB ′ in FIG. FIG. 6 is a perspective view of a rotary rotor used in the disperser of FIG. FIG. 7 is a media particle separation separator that is located inside the disperser of FIG. 1 and separates the media particles and the fine colorant-dispersed liquid monomer mixture.

  As a disperser, a media dispersion type SC100 (manufactured by Mitsui Mining Co., Ltd.) was used.

First, in the holding tank 21,
-Styrene monomer 400 parts-Copper phthalocyanine (CI Pigment Blue 15: 3) 70 parts-St-2EHA copolymer containing 2-acrylamido-2-methylpropanesulfonic acid (1% by mass) as a constituent component 8 parts / Zinc phthalocyanine A monomer mixture was prepared by introducing 40 kg of a monomer mixture containing copper phthalocyanine as a colorant at a ratio of 0.4 part and stirring. At that time, the temperature of the monomer composition was adjusted to about 20 ° C. by introducing and discharging cooling water into the jacket. Dispersion was carried out by repeating the circulation of the holding tank 21, the circulation pump 10, and the disperser by sending the prepared monomer mixture with the circulation pump 10. Further, the internal pressure of the disperser was constantly monitored by the disperser inlet pressure gauge 5, and dispersion was performed while monitoring the clogged state of the media particle separation separator 21.

The device configuration and distribution conditions of the disperser in the distributed system of FIG. 1 are as follows.
・ Media diameter: 0.30mm beads (Material: Zirconia)
Media particle separation separator slit width: 2.00 mm
-Media particle separation separator opening width: 0.180 mm
-Media particle separation separator opening ratio: 8.3%
Opening ratio / media particle diameter: 28
・ Rotating rotor peripheral speed: 15 m / s
・ Media filling rate: 90%
・ Disperser back pressure: 0.1 MPa
-Circulation flow rate: 5 L / min.
・ Dispersion time: 120 min

  Dispersion was performed under the above conditions to prepare a fine colorant-dispersed liquid monomer mixture 1. Then, 20 batch dispersion | distribution processes were performed continuously by the same condition, and the 20th batch fine colorant dispersion liquid monomer mixture 1 was sent to the next process. In addition, the pressure source (nitrogen gas: 0.3 MPa) and the disperser direction are opened by the three-way valve 3 every three batches, and the fine colorant-dispersed liquid monomer mixture 1 is supplied from the liquid outlet 62 to the liquid inlet. Extruding in the 61 direction, the clogging of the media particle separation separator 37 was removed. The pressure after the end of the 1 batch dispersion and the end of the 20 batch dispersion was almost the same, and the media particle separation separator was not clogged.

  Table 1 shows the physical properties and dispersion conditions of the disperser fine colorant-dispersed liquid monomer mixture 1.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 2]
Dispersion process conditions ・ Media diameter: 0.20 mm beads (Material: Zirconia)
Media particle separator separator slit width: 12.00mm
-Media particle separation separator opening width: 0.120 mm
-Media particle separation separator opening ratio: 1.0%
Opening ratio / media particle diameter: 5
The finely divided colorant-dispersed liquid monomer mixture 1 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 1, and the 20th batch of finely divided colorant-dispersed liquid monomer mixture 2 is obtained. The solution was sent to the next step. The physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 2 are shown in Table 1.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 3]
Dispersion process conditions ・ Media diameter: 0.20 mm beads (Material: Zirconia)
Media particle separation separator slit width: 1.15 mm
-Media particle separation separator opening width: 0.125 mm
-Media particle separation separator opening ratio: 9.8%
Opening ratio / media particle diameter: 49
The finely divided colorant-dispersed liquid monomer mixture 1 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 1, and the 20th batch of finely divided colorant-dispersed liquid monomer mixture 3 is obtained. The solution was sent to the next step. The physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 3 are shown in Table 1.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 4]
Dispersion process conditions-Media diameter: 0.50 mm beads (Material: Zirconia)
Media particle separator separator slit width: 12.00mm
-Media particle separation separator opening width: 0.310 mm
-Media particle separation separator opening ratio: 2.5%
Opening ratio / media particle diameter: 5
The finely divided colorant-dispersed liquid monomer mixture 1 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 1, and the 20th batch of finely divided colorant-dispersed liquid monomer mixture 4 is obtained. The solution was sent to the next step. The physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 4 are shown in Table 1.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 5]
Dispersion process conditions-Media diameter: 0.50 mm beads (Material: Zirconia)
Media particle separation separator slit width: 1.15 mm
-Media particle separation separator opening width: 0.370 mm
-Media particle separation separator opening ratio: 24.3%
Opening ratio / media particle diameter: 49
The finely divided colorant-dispersed liquid monomer mixture 1 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 1, and the 20th batch of finely divided colorant-dispersed liquid monomer mixture 5 is obtained. The solution was sent to the next step. The physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 5 are shown in Table 1.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 6]
The colorant dispersion step was performed using the dispersion system of FIG. FIG. 8 is a cross-sectional view inside the casing in FIG. FIG. 9 is a media particle separation separator that is located inside the disperser of FIG. 2 and separates the media particles and the fine colorant-dispersed liquid monomer mixture.

  As a disperser, a media dispersion type star mill LMZ type 2 (manufactured by Ashizawa Finetech) was used.

First, in the holding tank 51,
-Styrene monomer 400 parts-Copper phthalocyanine (CI Pigment Blue 15: 3) 70 parts-St-2EHA copolymer containing 2-acrylamido-2-methylpropanesulfonic acid (1% by mass) as a constituent component 8 parts / Zinc phthalocyanine A monomer mixture was prepared by introducing 40 kg of a monomer mixture containing copper phthalocyanine as a colorant at a ratio of 0.4 part and stirring. At that time, the temperature of the monomer mixture was adjusted to about 13 ° C. by introducing and discharging cooling water into the jacket. Dispersion was carried out by repeating the circulation of the holding tank, the circulation pump and the disperser by sending the prepared monomer mixture with the circulation pump 40. Further, the internal pressure of the disperser was constantly monitored by the disperser inlet pressure gauge 35, and dispersion was performed while monitoring the clogged state of the media particle separation separator.

The device configuration and distribution conditions of the disperser in the distributed system of FIG. 2 are as follows.
・ Rotating rotor peripheral speed: 15 m / s
・ Media diameter: 0.30mm beads (Material: Zirconia)
Media particle separation separator wedge wire width: 1.00 mm
-Media particle separation separator opening width: 0.090 mm
-Media particle separation separator opening ratio: 8.3%
Opening ratio / media particle diameter: 28
・ Media filling rate: 80%
・ Disperser back pressure: 0.1 MPa
-Circulation flow rate: 5 L / min.
・ Dispersion time: 120 min

  Dispersion was performed under the above conditions to prepare a fine colorant-dispersed liquid monomer mixture 6. Thereafter, 20 batch dispersion steps were continuously performed in the same manner as above, and the 20th batch of fine colorant-dispersed liquid monomer mixture 6 was fed to the next step. The physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 6 are shown in Table 1.

[Production Example of Fine Particle Colorant-Dispersed Liquid Monomer Mixture 7]
Dispersion process conditions ・ Media diameter: 0.20 mm beads (Material: Zirconia)
Media particle separation separator wedge wire width: 6.00 mm
-Media particle separation separator opening width: 0.060 mm
-Media particle separation separator opening ratio: 1.0%
Opening ratio / media particle diameter: 5
The finely divided colorant-dispersed liquid monomer mixture 6 was dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 6 except that The solution was sent to the next step. Table 1 shows the physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 7.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 8]
Dispersion process conditions ・ Media diameter: 0.20 mm beads (Material: Zirconia)
Media media separator separator wedge wire width: 0.60 mm
Media media separator separator opening width: 0.065mm
-Media particle separation separator opening ratio: 9.8%
Opening ratio / media particle diameter: 49
The finely divided colorant-dispersed liquid monomer mixture 6 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 6 except that The solution was sent to the next step. The physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 8 are shown in Table 1.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 9]
Dispersion process conditions-Media diameter: 0.50 mm beads (Material: Zirconia)
Media particle separation separator wedge wire width: 6.00 mm
-Media particle separation separator opening width: 0.150 mm
-Media particle separation separator opening ratio: 2.4%
Opening ratio / media particle diameter: 5
The finely divided colorant-dispersed liquid monomer mixture 6 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 6, and the 20th batch of finely divided colorant-dispersed liquid monomer mixture 9 is obtained. The solution was sent to the next step. It was. The physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 9 are shown in Table 1.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 10]
Dispersion process conditions-Media diameter: 0.50 mm beads (Material: Zirconia)
Media media separator separator wedge wire width: 0.60 mm
-Media particle separation separator opening width: 0.195 mm
-Media particle separation separator opening ratio: 24.5%
Opening ratio / media particle diameter: 49
The finely divided colorant-dispersed liquid monomer mixture 6 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 6 except that the 20th batch of finely divided colorant-dispersed liquid monomer mixture 10 is obtained. The solution was sent to the next step. Table 1 shows the physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 10.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 11]
The colorant dispersion step was performed using the dispersion system of FIG. FIG. 11 is a sectional view of the inside of the holding tank 90 in FIG. FIG. 12 is a media particle separation separator that is located inside the pulverization tank 81 of FIG. 10 and separates the media particles and the fine colorant-dispersed liquid monomer mixture.

  A media dispersion type handy mill (Mitsui Mining Co., Ltd.) was used as the disperser.

First, in the holding tank 90,
-Styrene monomer 400 parts-Copper phthalocyanine (CI Pigment Blue 15: 3)
70 parts 2-St-2-EHA copolymer containing 2-acrylamido-2-methylpropanesulfonic acid (1% by mass) as a constituent 8 parts-Zinc phthalocyanine 0.4 parts copper phthalocyanine as a colorant 40 kg of the monomer mixture is introduced. The liquid temperature of the monomer mixture was adjusted to about 13 ° C. by introducing and discharging cooling water to and from the jacket while stirring the monomer mixture by the rotation of the main stirring member 86. The inlet 82 and the outlet 83 were opened, and the prepared monomer mixture was sent by the circulation pump 40, whereby the circulation between the holding tank and the circulation pump was repeated to perform dispersion.

The device configuration and distribution conditions of the disperser in the distributed system of FIG. 10 are as follows.
・ Main stirring member 86 peripheral speed: 13 m / s
・ Media diameter: 0.30mm beads (Material: Zirconia)
Media particle separation separator slit width: 2.00 mm
-Media particle separation separator opening width: 0.180 mm
-Media particle separation separator opening ratio: 8.3%
Opening ratio / media particle diameter: 28
・ Media filling rate: 60%
-Circulation flow rate: 5 L / min.
・ Dispersion time: 120 min

  Dispersion was performed under the above conditions to prepare a fine colorant-dispersed liquid monomer mixture 11. The physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 11 are shown in Table 1.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 12]
Dispersion was carried out using the same apparatus configuration and conditions as in the production example of the fine colorant-dispersed liquid monomer mixture 1 except that 20 batches were dispersed continuously without removing the clogging of the media particle separator 69. The 20th batch of fine colorant-dispersed liquid monomer mixture 10 was fed to the next step.

  Pressure at the end of 1 batch: Compared to 0.14 MPa, the pressure after the end of 50 batches has increased to 0.35 MPa, and the internal pressure of the disperser is reduced due to clogging of the colorant and the like in the media particle separation separator. It seems to have risen.

  The physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 12 are shown in Table 1.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 13]
Zinc phthalocyanine: Dispersed in the same apparatus configuration and conditions as in the production example of fine colorant-dispersed liquid monomer mixture 1 except that 0.4 part was changed to 0.4 part of iron phthalocyanine: 20 batches The fine colorant-dispersed liquid monomer mixture 13 of the eyes was fed to the next step.

  Table 1 shows the physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 13.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 14]
Zinc phthalocyanine: 0.4 parts were changed to aluminum coupling agent (alkyl acetoacetate aluminum diisopropylate; Ajinomoto Fine Techno Co., Ltd., trade name “AL-M”): 0.4 parts. Except for the above, the dispersion is performed in the same apparatus configuration and conditions as in the production example of the fine colorant-dispersed liquid monomer mixture 1, and the 20th batch of fine colorant-dispersed liquid monomer mixture 14 is used as the next step. Liquid was sent.

  Table 2 shows the physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 14.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 15]
Dispersion process conditions ・ Media diameter: 0.05mm beads (Material: Zirconia)
Media particle separation separator slit width: 2.00 mm
-Media particle separation separator opening width: 0.030 mm
-Media particle separation separator opening ratio: 1.5%
Opening ratio / media particle diameter: 30
The finely divided colorant-dispersed liquid monomer mixture 1 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 1, The solution was sent to the next step.

  When the gloss was measured after the dispersion was finished, the art paper was rough and the gloss value was 58. This is probably because the media particles were too small, so the centrifugal force of the media particles was insufficient and the coarse particles could not be dispersed sufficiently.

  Table 2 shows the physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 15.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 16]
Dispersion process conditions-Media diameter: 0.60 mm beads (Material: Zirconia)
Media particle separation separator slit width: 2.00 mm
-Media particle separation separator opening width: 0.390 mm
-Media particle separation separator opening ratio: 16.3%
Opening ratio / media particle diameter: 27
The finely divided colorant-dispersed liquid monomer mixture 1 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 1, The solution was sent to the next step.

  When the gloss was measured after the dispersion was finished, the art paper was rough and the gloss value was 61. Since the media particles are too large, the number of collisions between the media particles is insufficient, and it seems that the dispersion was insufficient.

  Table 2 shows the physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 16.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 17]
Dispersion process conditions-Media diameter: 0.30 mm beads (Material: Zirconia)
Media particle separation separator slit width: 20.00 mm
-Media particle separation separator opening width: 0.150 mm
-Media particle separation separator opening ratio: 0.7%
Opening ratio / media particle size: 2
The finely divided colorant-dispersed liquid monomer mixture 1 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 1, and the 20th batch of finely divided colorant-dispersed liquid monomer mixture 17 is obtained. The solution was sent to the next step.

  The pressure at the start of dispersion was 0.14 MPa, whereas the pressure at the end of dispersion was increased to 0.36 MPa, which is considered to be because the opening ratio of the media particle separation separator was too small. Further, after the dispersion was completed, the disperser was disassembled and cleaned, and the inside of the disperser was confirmed. As a result, the media particle separator was severely worn. This is probably because the inside of the disperser was pressurized and the media particles were packed. In addition, since the media particle separator was worn out violently, it seems that stainless steel (material of the media particle separator) was contaminated into the fine colorant-dispersed liquid monomer mixture.

  Table 2 shows the physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 17.

[Production Example of Fine Particle Colorant-Dispersed Liquid Monomer Mixture 18]
Dispersion process conditions-Media diameter: 0.30 mm beads (Material: Zirconia)
-Media particle separator separator slit width: 0.70 mm
-Media particle separation separator opening width: 0.150 mm
-Media particle separation separator opening ratio: 17.6%
Opening ratio / media particle diameter: 59
The finely divided colorant-dispersed liquid monomer mixture 1 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 1, The solution was sent to the next step.

  After the dispersion was completed, the disperser was disassembled and cleaned, and the inside of the disperser was checked. As a result, the media particle separator was severely worn, and the slit of the media particle separator was too thin. It is.

  In addition, since the media particle separator was worn out violently, it seems that stainless steel (material of the media particle separator) was contaminated into the fine colorant-dispersed liquid monomer mixture. Table 2 shows the physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 18.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 19]
Dispersion process conditions ・ Media diameter: 0.05mm beads (Material: Zirconia)
Media particle separation separator wedge wire width: 1.00 mm
・ Media particle separator opening width: 0.015 mm
-Media particle separation separator opening ratio: 1.5%
Opening ratio / media particle diameter: 30
The finely divided colorant-dispersed liquid monomer mixture 19 was dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 6 except that The solution was sent to the next step.

  When the gloss was measured after the dispersion was finished, the art paper was rough and the gloss value was 60. This is probably because the media particles were too small, so the centrifugal force of the media particles was insufficient and the coarse particles could not be dispersed sufficiently.

  Table 2 shows the physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 19.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 20]
Dispersion process conditions-Media diameter: 0.60 mm beads (Material: Zirconia)
Media particle separation separator wedge wire width: 1.00 mm
・ Media particle separator opening width: 0.200mm
-Media particle separation separator opening ratio: 16.7%
Opening ratio / media particle diameter: 28
The finely divided colorant-dispersed liquid monomer mixture 6 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 6 except that The solution was sent to the next step.

  When the gloss was measured after the dispersion was finished, the art paper was rough and the gloss value was 62. Since the media particles are too large, the number of collisions between the media particles is insufficient, and it seems that the dispersion was insufficient.

  Table 2 shows the physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 20.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 21]
Dispersion process conditions-Media diameter: 0.30 mm beads (Material: Zirconia)
Media particle separation separator wedge wire width: 15.00mm
-Media particle separation separator opening width: 0.090 mm
-Media particle separation separator opening ratio: 0.6%
Opening ratio / media particle size: 2
The finely divided colorant-dispersed liquid monomer mixture 6 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 6, and the 20th batch of finely divided colorant-dispersed liquid monomer mixture 21 is obtained. The solution was sent to the next step.

  The pressure at the start of dispersion was 0.12 MPa, whereas the pressure at the end of dispersion was increased to 0.35 MPa, which is considered to be because the opening ratio of the media particle separation separator was too small. Further, after the dispersion was completed, the disperser was disassembled and cleaned, and the inside of the disperser was confirmed. As a result, the media particle separator was severely worn. This is probably because the inside of the disperser was pressurized and the media particles were packed. In addition, since the media particle separator was worn out violently, it seems that stainless steel (material of the media particle separator) was contaminated into the fine colorant-dispersed liquid monomer mixture.

  Table 2 shows the physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 21.

[Production Example of Fine Colorant-Dispersed Liquid Monomer Mixture 22]
Dispersion process conditions-Media diameter: 0.30 mm beads (Material: Zirconia)
-Media particle separation separator wedge wire width: 0.40 mm
-Media particle separation separator opening width: 0.090 mm
Media media separator separator opening ratio: 18.4%
Opening ratio / media particle diameter: 61
The finely divided colorant-dispersed liquid monomer mixture 6 is dispersed in the same apparatus configuration and conditions as in the production example of the finely divided colorant-dispersed liquid monomer mixture 6, and the 20th batch of finely divided colorant-dispersed liquid monomer mixture 22 is obtained. The solution was sent to the next step.

  After the dispersion was completed, the disperser was disassembled and cleaned, and the inside of the disperser was checked. As a result, the media particle separator was severely worn, and the slit of the media particle separator was too thin. It is.

  In addition, since the media particle separator was worn out violently, it seems that stainless steel (material of the media particle separator) was contaminated into the fine colorant-dispersed liquid monomer mixture. Table 2 shows the physical properties and dispersion conditions of the fine colorant-dispersed liquid monomer mixture 22.

<Example 1>
5 parts of Na3PO4 · 12H2O was added to 332 parts of ion-exchanged water, heated to 60 ° C., and then stirred at 3,500 revolutions / minute using CLEARMIX (M Technique). To this was added 27 parts of a 1.0 mol / liter-CaCl2 aqueous solution to obtain an aqueous medium containing Ca3 (PO4) 2.

Then, as a dispersoid system,
Styrene monomer 30 parts n-Butyl acrylate 30 parts Saturated polyester resin 5 parts <Polycondensation product of propylene oxide modified bisphenol A (2 mole adduct) and terephthalic acid (polymerization molar ratio 10:12), Tg = 68 ° C., Mw = 10000, Mw / Mn = 5.12>
Low molecular styrene resin (Mw: 3200, Mw / Mn: 1.25, Tg: 53 ° C.)
10 parts Fischer-Tropsch wax: melting point 78.0 ° C 12 parts fine particle colorant dispersion liquid monomer mixture 1 45 parts The above formulation was heated to 60 ° C and dissolved and mixed for 30 minutes. In this, 8 parts 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 medium, and stirred at 4500 rpm for 15 minutes with Claremix in an N2 atmosphere at 60 ° C. to granulate the polymerizable monomer mixture.

  Thereafter, while stirring with a full zone stirring blade (manufactured by Shinko Pantech Co., Ltd.), the temperature was raised to 70 ° C. and reacted for 10 hours. After completion of the polymerization reaction, saturated steam (pure steam / steam pressure 205 kPa / temperature 120 ° C.) was introduced while stirring was continued with a full zone stirring blade. Twenty minutes after the start of the introduction of saturated steam, the temperature of the contents in the container reached 100 ° C., and a distillation fraction began to come out. Residual monomers were distilled off by obtaining a predetermined amount of fractions, and cooled to obtain a toner particle dispersion.

  Hydrochloric acid was added to the toner particle dispersion to dissolve the calcium phosphate salt on the surface of the toner particles, followed by filtration, washing with water, crushing and drying to obtain toner particles. The obtained toner particles were evaluated according to the image density evaluation method described above. The results are shown in Table 1.

<Examples 2 to 13>
A toner was obtained in the same manner as in Example 1 except that the monomer composition was changed as shown in Table 1 in the dispersoid formulation of Example 1. Table 1 shows the evaluation results of the image density.

<Comparative Examples 1 to 9>
The same procedure as in Example 1 was performed except that the monomer composition was changed as shown in Table 2 in the dispersoid system formulation of Example 1 to obtain a toner. Table 2 shows the evaluation results of the image density.

1: Disperser, 2: Casing, 3: Three-way valve, 4: Disperser inlet pressure adjustment valve, 5: Disperser inlet pressure gauge, 6: Strainer, 7: Disperser inlet thermometer, 8: Disperser outlet thermometer 9: Back valve, 10: Circulation pump, 11: Cooling means, 12: Disperser outlet pressure gauge, 13: Stirrer motor, 14, 16: Cooling water supply port, 15, 17: Cooling water discharge port, 18: Cooling jacket, 19: Disperser back pressure adjustment valve, 20: Three-way valve, 21: Holding tank, 22: Shaft seal liquid tank, 23: Air pressure gauge, 24: Regulator, 25: Air inlet, 26: Shaft seal liquid Tank pressure gauge, 27: shaft seal liquid injection line, 28: shaft seal liquid return line, 29: liquid inlet, 30: liquid outlet, 31: drive shaft, 32: inner chamber, 33: outer chamber, 34: dispersion Machine rotating rotor projection, 35: Spatter rotor, 36: slit, 37: media particle separator, 38: media particle, 41: disperser, 42: casing, 43: three-way valve, 44: disperser inlet pressure adjustment valve, 45: disperser inlet pressure Total: 46: Strainer, 47: Disperser inlet thermometer, 48: Disperser outlet thermometer, 49: Back exit valve, 50: Circulation pump, 51: Cooling means, 52: Disperser outlet pressure gauge, 53: Stirring motor 54, 55: Cooling water supply port, 56, 57: Cooling water discharge port, 58: Cooling jacket, 59: Dispersing machine back pressure adjusting valve, 60: Three-way valve, 61: Holding tank, 62: Shaft seal liquid tank, 63: Air pressure gauge, 64: Regulator, 65: Air inlet, 66: Shaft seal liquid tank pressure gauge, 67 Shaft seal liquid injection line, 68: Shaft seal liquid return line, 69 : Cylindrical rotor, 70: Media particle separation separator (centrifugation screen), 71: Drive shaft, 72: Media particles, 73: Rotor pin, 74: Vessel pin, 75: Crushing chamber, 76: Liquid inlet, 77: Liquid Discharge port, 78: wedge wire, 79: media particle discharge port, 81: grinding tank, 82: inflow port, 83: outflow port, 84: media particle, 85: drive shaft, 86: main stirring member, 87: media particle Separation separator, 88: support shaft, 89: lifting blade, 90: holding tank, 91: cooling jacket, 92: cooling water supply port, 93: cooling water discharge port, 94: three-way valve, 95: circulation pump, 96: Dispersing machine, 97: thermometer, 98: pressure gauge, 99: slit

Claims (5)

It has at least a dispersion step of dispersing a colorant in a monomer mixture containing at least a polymerizable monomer, a synergist, and an electron donating compound capable of coordination with the synergist to obtain a fine colorant-dispersed liquid monomer mixture. A method for producing toner particles,
The dispersion step is to send the solution to a media-type disperser for dispersion treatment,
The media-type disperser includes a media particle separation separator and a rotating rotor that rotates by rotation of a drive shaft inside a cylindrical container having a liquid introduction port and a liquid discharge port, and the media particle is contained in the cylindrical container. A method for producing toner particles, wherein a plurality of particles are filled, and the particle diameter of the media particles and the opening ratio of the media particle separation separator satisfy the following formulas 1 and 2.
Formula 1:
0.20 mm ≦ (media particle diameter) ≦ 0.50 mm
Formula 2:
5 ≦ opening ratio / media particle size ≦ 49
(In Formula 2, the aperture ratio is a numerical value expressed in% units, and the particle diameter is a numerical value expressed in mm units.)   The media-type disperser includes a cylindrical media particle separation separator having a slit inside the cylindrical container having a first wall surface having the liquid inlet and a second wall surface having the liquid discharge port. An inner chamber and an outer chamber are provided, a disperser in which the inner chamber is filled with a rotating rotor and media particles, and the monomer mixture is fed to the media type disperser and the fine particulate colorant The method for producing toner particles according to claim 1, wherein a dispersion liquid monomer mixture is obtained. The media-type disperser is rotated by a drive shaft provided in a horizontal direction inside the cylindrical container having a first wall surface having the liquid inlet and a second wall surface having the liquid outlet. Filled with rotatable rotor and media particles,
A media particle separation separator for separating the media particles and the monomer mixture is a disperser provided at the center of the rotary rotor, and the monomer mixture is fed to the media type disperser to form fine particles The method for producing toner particles according to claim 1, wherein a colorant-dispersed liquid monomer mixture is obtained.   In the dispersion step, the colorant is dispersed while applying pressure for a certain time from the liquid discharge port of the media-type disperser toward the liquid introduction port to remove clogging between the slits of the media particle separation separator. The method for producing toner particles according to any one of claims 1 to 3, wherein:   The method for producing toner particles according to any one of claims 1 to 4, wherein the synergist is zinc phthalocyanine or a zinc phthalocyanine derivative.

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