JP4850635B2 - Toner production method - Google Patents

Description

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

  As a method for producing toner particles used in electrophotography, there has been proposed a method for producing polymerized toner particles in which a polymerizable monomer is dispersed in the form of droplets and polymerization is performed to directly obtain toner particles. For example, in the method for producing toner particles by suspension polymerization, a polymerizable monomer, a colorant, a release agent, a polymerization initiator, and a cross-linking agent, a charge control agent and other additives are uniformly added as necessary. After dissolving or dispersing to obtain a polymerizable monomer composition, this is dispersed in an aqueous medium containing a dispersion stabilizer using an appropriate stirrer, and a polymerization reaction is performed to obtain a desired particle size. A suspension of polymerized toner particles is obtained. If necessary, the suspension of the polymerized toner particles is treated with an acid or an alkali to remove the dispersion stabilizer, and then the aqueous medium is separated in a solid-liquid separation step to obtain toner particles.

  Polymerized toner particles obtained by such a method have a spherical or nearly spherical shape and a uniform surface, so that fluidity and transferability are good, and good development characteristics are exhibited even after many continuous developments. . Further, the toner particles are characterized by little stress on the toner particles and little filming on the photoreceptor. Further, since the method does not include a pulverization step, the toner particles obtained can be obtained in a high yield even when a classification step is required because the particle size distribution of the obtained toner particles is sharp.

  Further, in order to improve the toner fixing property and the toner offset resistance when transferring as a toner image from a photoreceptor onto a transfer material such as paper, a release agent such as wax is added to the toner particles. Polymerized toner particles obtained by the polymerization method can be blended in a large amount, and can be encapsulated in the polymerized toner particles, so that good fixing properties and offset resistance can be obtained.

  If a wax having a low melting point is used as a release agent, the plasticity of the toner is increased even at low temperature fixing, and the fixing property in the low temperature region is improved. On the other hand, when a wax having a high melting point is used, the releasability of the toner from the fixing member at a high temperature increases, and the fixing property at a high temperature region is improved. Further, two or more kinds of waxes having different melting points can be added in order to have both characteristics in the same toner.

  When a release agent is added to the polymerized toner particles, if the melting point of the release agent is lower than the temperature during the polymerization step, it may be mixed as it is with the raw material composition, but the melting point of the release agent is that during the polymerization step. When it is higher than the temperature, the release agent is kept in a solid state. For this reason, a coarse release agent lump is generated, and it may be difficult to completely and uniformly enclose the toner particles.

  If the added release agent is not encapsulated in the toner particles and part of the release agent is released as a lump from the toner particles, the fluidity of the entire toner may be lowered. Alternatively, it may cause toner aggregation with a release agent lump as a core, thereby causing deterioration in image quality when a toner image is formed.

  Further, even if the release agent is completely encapsulated in the toner particles, if the distribution state is not uniform, the content of the release agent is different for each toner particle, and the toner particles exhibit different properties. When the image is formed, the image quality may be deteriorated.

  In order to uniformly enclose a release agent having a melting point higher than the polymerization temperature in the toner particles, it has been proposed to use a release agent having a high melting point which is finely powdered or finely dispersed in a liquid medium.

  As a method for producing a fine dispersion of a high melting point release agent, a high melting point release agent is stirred and dispersed in an organic solvent at a temperature equal to or higher than the melting point of the release agent, and then rapidly cooled. A method for producing a fine dispersion has been proposed (see, for example, Patent Document 1).

  In another method, a fine dispersion of a release agent is obtained by ejecting a liquid mixture of a release agent having a high melting point and an organic solvent from a nozzle at high pressure and colliding with a wall surface (for example, Patent Document 2). reference).

  In still another method, a fine dispersion of a release agent is obtained by wet-pulverizing a release agent having a high melting point in a polymerizable monomer using a pulverizer using a medium (for example, Patent Document 3). 4).

  However, the above-mentioned high melting point release agent is dissolved in an organic solvent, the high melting point release agent is stirred and dispersed at a temperature higher than the melting point, and then rapidly cooled, and the mixture of the high melting point release agent and the organic solvent is subjected to high pressure. In the method of ejecting from the nozzle and colliding with the wall surface, there is a problem that the release agent cannot be finely dispersed to a particle size small enough to be uniformly encapsulated in the toner particles, even if fine dispersion is possible There were problems such as too long. Further, there is a problem that developability is deteriorated due to a coarse release agent and an aggregate of release agents which are released without being included in the toner.

  In addition, when wet pulverization is performed using a medium, the pulverization efficiency is good, but a fine release agent generated by over-pulverization may aggregate in a later step, and the aggregate is included in the toner. However, the problem arises that the resin is liberated and the developability is lowered. Further, the deterioration of the particle size distribution of the toner particles due to the aggregates has been a problem.

  Furthermore, when the mold release agent is wet pulverized using a medium, a great deal of labor is required for maintenance.

JP-A-6-130723 (page 4) Japanese Patent Laid-Open No. 10-207116 (page 7, FIG. 2, FIG. 3) Japanese Patent No. 3298443 Japanese Patent Laid-Open No. 11-38676

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

  Another object of the present invention is to provide a new method for producing toner which is finely and uniformly contained in toner particles in a method for producing toner particles including a step of dispersing a release agent in a liquid medium. It is in.

  Another object of the present invention is to provide a new method for producing toner particles having excellent image characteristics and fixability.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the release agent in the liquid medium is sufficiently small and has a uniform particle size and a small amount of aggregation according to the following method. It has been found that the release agent is uniformly encapsulated in the toner particles by being finely dispersed. That is, the present invention has the following features:
(1) A release agent dispersion step for obtaining a release agent dispersion by finely dispersing at least a release agent in a liquid medium; mixing the release agent dispersion, a polymerizable monomer and a colorant; A preparation step for preparing a monomer composition, a granulation step for granulating the polymerizable monomer composition in an aqueous medium, and a polymerization of the polymerizable monomer in the polymerizable monomer composition A toner production method including a polymerization step of producing toner particles , wherein the release agent dispersion step mechanically pulverizes the release agent in a liquid using a pulverizer and releases the release agent dispersion liquid. The pulverizing apparatus includes a rotating main shaft at the center of a cylindrical container, supports a plurality of sub shafts around the main shaft at intervals, and a plurality of the sub shafts. The ring-shaped member of the ring is rotatable, and a gap is provided between the sub shaft and the ring. Loosely fitted, and method for producing a toner, wherein the outer peripheral surface of the ring-shaped member is one that is in contact with the inner peripheral surface of the container.
(2) In the release agent dispersion step, when the concentration of the release agent in the release agent dispersion is A (%) and the viscosity of the release agent dispersion is B (cps),
30A ≦ B ≦ 300A
The toner production method as described in (1) above, wherein
(3) The method for producing a toner according to (1) or (2), wherein the releasing agent dispersing step is performed within a range of 5 ° C. or higher and 80 ° C. or lower.
(4) The method for producing a toner according to any one of (1) to (3), wherein an average particle diameter of the release agent processed using the pulverizer is 5 μm or more and 200 μm or less.

  According to the present invention, the release agent is finely dispersed with a sufficiently small and uniform particle size, and the release agent can be uniformly encapsulated in the toner particles.

  Further, toner particles having an excellent particle size distribution can be produced by reducing aggregates of fine release agents during the coarse WAX / toner production process. Furthermore, toner particles having improved fixability and image characteristics in a high temperature region can be produced in a short time and with a simple operation.

≪Releasing agent dispersion process≫
FIG. 1 shows a release agent dispersion process system including a pulverizer preferably used in the present invention, FIG. 2 shows a top view of a rotating body, and FIG. 3 shows a side view of a sub-shaft equipped with a ring-shaped member so as to be rotatable. This will be described with reference to the drawings.

  However, the disperser used in the present invention is not limited to this.

  Hereinafter, FIG. 1, FIG. 2 and FIG. 3 will be described in detail.

  The release agent dispersion charged in the holding tank 1 is sufficiently stirred by the stirring blade 12 in the tank and then flows into the apparatus by the pump 2. On the other hand, when the main shaft 3 is rotated at a high speed via the motor 15, the subshaft 4 is also rotated at a high speed, and the plurality of ring-shaped members 5 loosely fitted to the subshaft 4 along with the rotation of the subshaft 4 are The outer peripheral edge of the ring-shaped member slides on the inner wall surface of the cylindrical container 7 at a high speed. The introduced release agent mixed liquid is sent to the inner wall surface side of the apparatus by the centrifugal force of the rotating body 6 that rotates at a high speed, and shearing force is generated by sliding between the outer peripheral edge of the ring-shaped member 5 and the inner wall surface of the cylindrical container 7. And the release agent in the liquid is pulverized. Next, the release agent dispersion liquid discharged from the apparatus passes through the heat exchanger 8 (use of the heat exchanger is optional) and is returned to the holding tank 1 to repeat the circulation. Milled to particle size.

  Further, the cooling water is supplied from the cooling water supply line 10 into the heat exchanger 8, and the cooling water in the heat exchanger 8 is discharged from the cooling water drain line 11, so that the liquid generated in the cylindrical container 7 is discharged. Heat generation is suppressed. Furthermore, it is possible to further cool the liquid by providing a jacket 9 to the holding tank 1 and flowing cooling water.

  Further, by adjusting the valve 13 provided in the middle of the path for returning the release agent dispersion from the cylindrical container to the holding tank 1, back pressure is applied to suppress foaming of the release agent dispersion in the cylindrical container. In addition, it is possible to increase the pulverization efficiency of the release agent.

The back pressure can be measured by the pressure gauge 14, and the treatment is preferably performed within the range of 0.05 to 7 kg / cm ² .

  As the above-mentioned disperser, for example, Micros (manufactured by Nara Machinery Co., Ltd.) can be preferably used, but this is not a limitation.

In the present invention, in the release agent dispersion step, when the concentration of the release agent in the polymerizable monomer is A (%) and the viscosity of the obtained release agent dispersion is B (cps),
30A ≦ B ≦ 300A
It is preferable to grind so that it may become in this range.

  In the case of B <30A, which deviates from this range, since the viscosity is low, the shearing force applied by sliding between the outer peripheral edge of the annular body and the inner wall surface of the cylindrical container is reduced, and the grinding efficiency is preferably reduced. Absent.

  In the case of B> 300A, since the viscosity is too high, an excessive shearing force is imparted, resulting in overgrinding, which may cause aggregation of the release agent in a later step.

  In addition, if the release agent is pulverized by the apparatus used in the present invention, the increase in viscosity is moderately suppressed compared to the case of using a disperser using spherical media, and thus relatively soft pulverization becomes possible. Over-pulverization can be suppressed.

  Moreover, in this invention, it is preferable that the temperature of the mold release agent dispersion liquid in a mold release agent dispersion | distribution process exists in the range of 5 to 80 degreeC.

  When the temperature of the release agent dispersion that deviates from the above range is less than 5 ° C., it is not preferable because the cooling equipment is loaded.

  In addition, when the temperature of the release agent dispersion is higher than 80 ° C., it is not preferable because the pulverization efficiency is decreased due to the decrease in viscosity. Further, it is not preferable because a rapid increase in viscosity and aggregation of the release agent start due to dissolution of low molecular weight components.

  In the present invention, it is preferable to use a release agent having a volume-based median diameter in the range of 5 μm or more and 200 μm or less in the release agent dispersion step. More preferably, a release agent having a volume-based median diameter in the range of 5 μm to 100 μm is used.

  The release agent in the above particle size range is preferably generated by coarsely pulverizing in advance in the liquid. If the release agent is in the above range, it can be generated with a simple pulverizer. .

  When the volume-based median diameter deviating from the above range is less than 5 μm, it is not preferable because rough pulverization is an area that cannot be achieved by simple pulverization. Furthermore, when the volume-based median diameter is larger than 200 μm, the release agent does not efficiently flow between the outer peripheral edge of the annular body and the inner wall surface of the cylindrical container, and the pulverization efficiency may be reduced. . Furthermore, when processing by a circulation system, homogeneous transport becomes difficult, and accordingly, uniform pulverization may not be achieved.

  Preliminary coarse pulverization includes a turbine blade, an edged turbine blade and the like having a high shearing force among ordinary stirring blades, Ultra Turrax (manufactured by IKA), T.C. K. Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) K. Dispersing machines such as Fillmix (made by Special Machine Engineering Co., Ltd.) and Claremix (made by M Technique Co., Ltd.) can be used. A continuous disperser such as Ebara Milder (Ebara Seisakusho) or Cavitron (Eurotech) may also be used. These can be used in one pass, or can be used by passing a plurality of times through a circulation line.

  In addition, the centrifugal effect of the rotating body including the main shaft, the sub shaft, and the ring-shaped member in the present invention is preferably in the range of 15 to 350.

  When the centrifugal effect deviating from the above range is less than 15, sufficient shearing force cannot be applied, and the pulverization efficiency is lowered. On the other hand, when the centrifugal effect is greater than 350, the surface of the release agent may be altered, and sufficient fixability may not be obtained. Moreover, there exists a possibility of inducing | aggregating aggregation of a mold release agent in a later process by overgrinding. Furthermore, since the temperature rise of the release agent dispersion becomes intense, a large load is required for cooling, which is not preferable.

  Stainless steel, carbide, carbon steel, alumina, ceramic, zirconia, and polyacetal are preferably used as the material for covering the inner wall surface of the device for mechanically crushing the release agent and the material of the ring-shaped member from the viewpoint of strength. It is done. Moreover, it is more preferable to use zirconia from the viewpoint of grindability.

≪Toner manufacturing process≫
In the present invention, polymerization in a polymerizable monomer composition containing a dispersion of a release agent finely dispersed in a liquid medium (hereinafter also referred to as “release agent dispersion”) and a polymerizable monomer. The toner particles can be produced by polymerizing the polymerizable monomer.

  Further, the method of the present invention can be constituted by a step of producing toner particles by aggregating polymer particles in the presence of a release agent finely dispersed in a liquid medium.

  In the present invention, toner particles are obtained by granulating in an aqueous medium in the presence of a fine dispersion and a polymerizable monomer, and polymerizing the polymerizable monomer in the generated polymerizable monomer composition. It can comprise by the process of manufacturing.

  Further, the method of the present invention comprises a step of preparing a polymerizable monomer composition containing a release agent dispersion and a polymerizable monomer, and granulating the polymerizable monomer composition in an aqueous medium. And a step of producing toner particles by polymerizing a polymerizable monomer in a polymerizable monomer composition dispersed in an aqueous medium.

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

  The toner of the present invention is a fine polymer particle obtained by emulsion polymerization of monomers in various polymerization methods such as dispersion polymerization, emulsion polymerization, suspension polymerization, etc., and a liquid to which an emulsion of necessary additives is added. And thereafter, an organic solvent, a flocculant and the like are added, and the product is associated with the release agent in the release agent fine dispersion. A method of preparing by mixing with a dispersion liquid of a coloring agent necessary for the constitution of the toner at the time of association, or a polymerizable monomer containing a release agent fine dispersion liquid, a polymerizable monomer and a colorant. And a method of emulsion polymerization of the monomer composition. Here, the association means that a plurality of resin particles and colorant particles are fused.

  In addition, the aqueous medium as used in the field of this invention shows what contained 50 mass% or more of water at least.

  The production method of the suspension polymerization method is not particularly limited, but the toner can be produced specifically by the following production method.

  In the release agent dispersion step, the release agent is pulverized in the polymerizable monomer to prepare a release agent dispersion, and in the subsequent preparation step, the colorant, charge control agent, Add a polymerization initiator and other additives, and dissolve or disperse them uniformly using a homogenizer, ultrasonic disperser, etc. (charge control agent, colorant, polymerization initiator, etc. are introduced into the release agent dispersion step, Dispersion may be performed, that is, the preparation step may be omitted). The monomer system prepared in the above preparation step is dispersed in an aqueous phase containing a dispersion stabilizer by a normal stirrer, CLEARMIX, homomixer, homogenizer or the like. Preferably, granulation is performed by adjusting the stirring speed and time so that the monomer droplets have a desired toner particle size. Here, the dispersion state of the colorant and the concentration of the dispersion aid can contribute to the influence on the granulation property.

  In the release agent dispersion step, the monomer composition in which the release agent is finely and uniformly ground without agglomeration shows a good particle size distribution in the granulation step through the following preparation step. On the other hand, when the release agent is poorly pulverized and coarse release agent particles are present, or when aggregates of the release agent are formed by over-pulverization, the granulation property is deteriorated. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. The polymerization is preferably carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. In addition, the temperature may be raised in the latter half of the polymerization reaction, and in order to remove unreacted polymerizable monomers and by-products that cause odor during toner fixing, the latter half of the reaction, or the completion of the reaction. A part of the aqueous medium may be distilled off later. After completion of the reaction, the produced toner particles are recovered by washing and filtration and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by mass of water as a dispersion medium with respect to 100 parts by mass of the monomer system.

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

Further, as a method for producing the toner of the present invention, a method of adjusting by fusing resin particles in an aqueous medium can also be mentioned. This method is not particularly limited, and examples thereof include the following methods. That is, constituent materials such as resin particles or resin particles generated in the liquid, a colorant refined in the liquid, and a release agent crushed in the liquid using the stirring device including the ring-shaped member described above A method of associating a plurality of fine particles composed of various material particles or resin, release agent, colorant and the like;
In particular, after dispersing these in an aqueous medium using an emulsifier, a coagulant having a critical coagulation concentration or higher is added for salting out, and at the same time, heat fusion is performed at or above the glass transition temperature of the formed polymer itself. The toner of the present invention can be formed by filtering and drying the toner particles. Here, an organic solvent that is infinitely soluble in water may be added simultaneously with the flocculant.

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

  As the polymerizable monomer suitably used in 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.

≪Materials used≫
As the polymerizable monomer suitably used in 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.

Examples of the monofunctional polymerizable monomer include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, and 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, styrene derivatives such as p-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, n-octyl acrylate Acrylic polymerizable monomers such as n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate Methacrylic polymerizable monomers such as n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate;
Vinyl esters such as methylene aliphatic monocarboxylic acid esters, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate;
Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether;
And vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

  Examples of the polyfunctional polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tripropylene. Glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, tri Ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethyleneglycol Rudimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxydiethoxy) phenyl) propane 2,2′-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene and divinyl ether.

  In the present invention, the above-mentioned monofunctional polymerizable monomers are used alone or in combination of two or more, or the above-mentioned monofunctional polymerizable monomers and polyfunctional polymerizable monomers are combined, Or a polyfunctional polymerizable monomer is used individually or in combination of 2 or more types. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in combination, or in combination with other monomers from the viewpoints of development characteristics and durability of the toner.

  In the present invention, in the case of a polymerization method using an aqueous medium such as suspension polymerization, the inclusion of a release agent can be promoted by adding a polar resin to the polymerizable monomer composition. it can. When a polar resin is present in a polymerizable monomer composition suspended in an aqueous medium, the polar resin moves to the vicinity of the interface between the aqueous medium and the polymerizable monomer composition due to the difference in affinity for water. Therefore, the polar resin is unevenly distributed on the surface of the toner particles. As a result, the toner particles have a core-shell structure, and the inclusion property of the release agent is improved even when a large amount of the release agent is contained.

  In addition, if a resin with a high melting temperature is selected as the polar resin used for the shell, even if the binder resin is designed to be melted at a lower temperature for the purpose of fixing at low temperature, it may cause problems such as blocking during storage. Can be suppressed.

  As such a polar resin, since the fluidity of the polar resin itself can be expected when the shell is formed unevenly distributed on the surface of the toner particles, a saturated or unsaturated polyester resin is particularly preferable.

  As said polyester-type resin, what carried out the condensation polymerization of the acid component monomer and alcohol component monomer which are mentioned below can be used. Acid monomers 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, sebacic acid, camphor Examples include acids, cyclohexanedicarboxylic acid, and trimellitic acid.

Examples of the alcohol component monomer include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxy Alkylene glycols such as methyl) cyclohexane and polyalkylene glycols,
Examples thereof include bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane, and pentaerythritol.

  In the production method of the present invention, an external additive can be used for the purpose of imparting various properties to the toner. The external additive preferably has a particle size of 1/10 or less of the average particle size of the toner particles from the viewpoint of durability when added to the toner. Examples of the external additive include aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide and other metal oxides, nitrides such as silicon nitride, carbides such as silicon carbide, Inorganic metal salts such as calcium sulfate, barium sulfate and calcium carbonate, fatty acid metal salts such as zinc stearate and calcium stearate, carbon black and silica are used.

  As the release agent used in the present invention, a wax in a solid state at room temperature may be used in terms of toner blocking resistance, durability of a large number of sheets, low-temperature fixability, and offset resistance.

  Examples of the wax include polymethylene wax such as paraffin wax, polyolefin wax, microcrystalline wax and Fischer-Tropsch wax, amide wax, higher fatty acid, long chain alcohol, ester wax and derivatives thereof such as graft compounds and block compounds. These are preferably removed from the low molecular weight component and have a sharp maximum endothermic peak in the endothermic curve obtained by a differential scanning calorimeter.

  Among these, the wax preferably used in the releasing agent dispersion step has a melting point represented by a maximum endothermic peak obtained by a differential scanning calorimeter of 80 ° C. or higher and 170 ° C. or lower. In the case of a wax having a melting point of less than 80 ° C., the wax once finely dispersed causes thermal aggregation depending on the polymerization temperature during the polymerization process, and the particle size of the release agent particles dispersed in the toner particles may increase. This is not preferable. The melting point is a measurement temperature range of 30 to 200 ° C., a temperature increase rate of 10 ° C./min, and a DSC curve in a temperature range of 30 to 200 ° C. is obtained by a second temperature increase process in a normal temperature and humidity environment. The temperature of the endothermic main peak of the obtained DSC curve can be measured using, for example, MDSC-2920 (manufactured by TA Instruments) which is a differential scanning calorimeter (DSC).

  Moreover, it is preferable that the mold release agent used for this invention is a thing with a penetration of 10 or less at 25 degreeC when measured according to the test method prescribed | regulated to JISK2235 (1991). More preferably, a mold release agent having a penetration of 5 or less at 25 ° C. is used. In the case of a mold release agent having a penetration of greater than 10 at 25 ° C., the brittleness is insufficient, so that in the coarse dispersion step, sufficient dispersion can be achieved with a simple dispersion device such as the above-described stirring device having high shearing force. This is not preferable because it cannot be performed, and it is necessary to use a large-scale apparatus such as a high-pressure disperser or a complicated operation such as an operation of heating and melting and then cooling.

  To the toner particles produced according to the present invention, a second release agent having a melting point lower than 80 ° C. can be used in combination in order to increase the plasticity of the toner particles and improve the fixability in the low temperature region. The melting point of the second release agent is also represented by the melting point represented by the maximum endothermic peak obtained by the differential scanning calorimeter.

  As the second release agent, a linear alkyl alcohol having 15 to 100 carbon atoms, a linear fatty acid, a linear acid amide, a linear ester, or a montan derivative wax is preferably used. It is more preferable that impurities such as liquid fatty acid have been previously removed from these waxes.

  In order to improve the translucency of the image fixed on the OHP, a linear ester wax is particularly preferably used as the second release agent.

  The linear ester wax is preferably contained in an amount of 1 to 40 parts by mass, more preferably 4 to 30 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

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

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

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

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

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

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

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

  In order to polymerize the polymerizable monomer, a polymerization initiator can be used. Examples of the polymerization initiator that can be used in the present invention include azo polymerization initiators. As the azo polymerization initiator, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) ), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobismethylbutyronitrile.

  An organic peroxide initiator can also be used. Organic peroxide initiators include benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, bis (4-t-butyl) (Cyclohexyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclododecane, t-butylperoxymaleic acid, bis (t-butylperoxy) isophthalate, methyl ethyl ketone peroxide, tert-butylperoxy Examples include 2-ethylhexanoate, diisopropyl peroxycarbonate, cumene hydroperoxide, and 2,4-dichlorobenzoyl peroxide.

  A redox initiator in which an oxidizing substance and a reducing substance are combined can also be used. Examples of the oxidizing substance include inorganic peroxides such as hydrogen peroxide and persulfates (sodium salts, potassium salts, ammonium salts, etc.), and oxidizing metal salts such as tetravalent cerium salts. Reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts, trivalent chromium salts, etc.), ammonia, lower amines (amines having about 1 to 6 carbon atoms such as methylamine and ethylamine). , Amino compounds such as hydroxylamine, sodium thiosulfate, sodium hydrosulfite, sodium hydrogen sulfite, sodium sulfite, sodium formaldehyde sulfoxylate and other reducing sulfur compounds, lower alcohols (about 1 to 6 carbon atoms), ascorbic acid or Examples thereof include salts and lower aldehydes (about 1 to 6 carbon atoms).

  The polymerization initiator is selected with reference to a 10-hour half-life temperature, and is used alone or in combination. Although the addition amount of the said polymerization initiator changes with the target degree of polymerization, generally 0.5-20 mass parts is added with respect to 100 mass parts of polymerizable monomers.

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

  In the present invention, for example, when a polymerizable monomer is polymerized, various crosslinking agents can be used. Examples of the crosslinking agent include divinylbenzene, 4,4′-divinylbiphenyl, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, and trimethylolpropane tri (meth) acrylate. Examples include functional compounds.

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

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

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

  In the production method of the present invention, an external additive can be used for the purpose of imparting various properties to the toner. The external additive preferably has a particle size of 1/10 or less of the average particle size of the toner particles from the viewpoint of durability when added to the toner. Examples of the external additive include aluminum oxide, titanium oxide, strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide and other metal oxides, nitrides such as silicon nitride, carbides such as silicon carbide, Inorganic metal salts such as calcium sulfate, barium sulfate and calcium carbonate, fatty acid metal salts such as zinc stearate and calcium stearate, carbon black and silica 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 toner particles. The external additives may be used alone or in combination of two or more, but it is more preferable to use a hydrophobized one.

  The toner produced according to the present invention can be used for both a one-component developer and a two-component developer. The toner produced in the present invention is used for image formation by an appropriate method according to the type. For example, in the case of a magnetic toner containing a magnetic material in a toner particle as a one-component developer, the magnetic toner is conveyed using a magnet built in the developing sleeve when an image is formed using the magnetic toner. A method of charging is used. When non-magnetic toner containing no magnetic material is used, during image formation using this non-magnetic toner, for example, a blade and a fur brush are used to forcibly frictionally charge the developing sleeve, and the toner is placed on the sleeve. The method of conveying by attaching is used.

  On the other hand, when the toner obtained by the production method of the present invention is used as a commonly used two-component developer, it is used as a developer using a carrier together with the toner. The carrier used in the present invention is not particularly limited, but particles containing single or composite ferrite mainly composed of iron, copper, zinc, nickel, cobalt, manganese and chromium elements are used.

  The carrier shape is also important because the saturation magnetization and electric resistance can be controlled over a wide range. For example, it is preferable to select the shape of the carrier from spherical, flat, indeterminate, etc., and to control the fine structure of the surface of the carrier, for example, the surface irregularity.

  As the carrier, generally, a resin-coated carrier obtained by firing and granulating the above metal compound to produce carrier core particles and coating the resin thereon. From the viewpoint of reducing the load on the toner of the carrier, a low-density dispersion carrier obtained by kneading a magnetic material and a resin, then pulverizing and classifying, or a kneaded product of a metal compound and a monomer directly in an aqueous medium. Polymer carriers obtained by suspension polymerization and dispersion in a true sphere can also be used as the carrier. The carrier core particles can be used for the carrier.

  The average particle size of these carriers is 10 to 100 μm, more preferably 20 to 50 μm.

  When the two-component developer is prepared, the mixing ratio of the carrier and the toner produced in the present invention is usually 2-15% by mass, preferably 4-13% by mass as the toner concentration in the developer. Is obtained. When the toner concentration is less than 2% by mass, the image density is low and practical use is difficult. When the toner concentration exceeds 15% by mass, fogging and scattering in the apparatus increase, and image deterioration and developer consumption may occur.

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

  First, in the present invention, 1. 1. Evaluation method of dispersibility of release agent dispersion liquid 2. Toner granulating evaluation method 3. Method for measuring viscosity of release agent dispersion; 4. Image density evaluation method for toner; The fixing property evaluation method will be described below.

1. Method for evaluating dispersibility of release agent dispersion:
The dispersibility of the release agent dispersion is evaluated by determining the ratio of particles having a particle size of 2 μm or less from the volume-based particle size distribution using a laser diffraction / scattering particle size distribution analyzer LA-720 (manufactured by Horiba, Ltd.). went. The measurement method will be described below.

  The dispersion medium at the time of measurement was adjusted by using a batch type cell and adding a polymerizable monomer to an extent that satisfies 70 to 90% of the cell. The cell is agitated by a stirrer.

  Here, a measurement sample subjected to ultrasonic irradiation for 3 min was added so that the concentration of the colorant in the dispersion medium was 70 to 95%, and measurement was performed under the condition of a relative refractive index of 0.94. Moreover, the average particle diameter of the release agent in the present invention indicates a 50% diameter of the particle size distribution on a volume basis.

When the proportion of particles of 2 μm or less exceeds 85%, good dispersibility is exhibited. When the ratio is 75% or more and less than 85%, there is a slight problem in image characteristics and fixability, but there is no problem in practical use. Dispersibility that is unfavorable on the product is very severe on the image.
Dispersibility (2 μm or less): Over 85% .... A Good
: 75% or more, less than 85% ・ ・ B slightly inferior (no problem in practical use)
: Less than 75% ・ ・ ・ ・ C Evil

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

  Coulter Multisizer (manufactured by Coulter Co.) is connected to an interface (manufactured by Nikka) and a PC9801 personal computer (manufactured by NEC) that outputs number average distribution and volume average distribution, and the electrolyte is 1% using first grade sodium chloride. An aqueous NaCl solution is prepared.

  As a measurement method, 1.5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 130 ml of the electrolytic aqueous solution, and 10 mg of a measurement sample is further added. The electrolyte solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 2 minutes, and the particle size distribution of 2 to 40 μm particles based on the number is measured by the Coulter Multisizer using a 100 μm aperture as the aperture. Then, various values are obtained.

The coefficient of variation in the number distribution is calculated from the following equation.
Coefficient of variation (%) = [S / D1] × 100
[In the formula, S represents the standard deviation in the number distribution of toner particles, and D1 represents the number average particle diameter (μm) of the toner particles. ]
Number variation coefficient: Less than 35% ・ ・ ・ ・ A Good
: 35% or more and less than 40% ··· B slightly inferior (no product problems)
： 40% or more ・ ・ ・ ・ C Poor

3. Method for measuring viscosity of release agent dispersion:
Specifically, the release agent dispersion whose liquid temperature was adjusted to 30 ± 1 ° C. was measured under the following conditions using a Viscocoater VT550 (manufactured by HAAKE).

Sensor: MV-DIN
Shear rate: 1.075 (1 / s) <1 min> → 1.29 (1 / s) <1 min>
→ 4.3 (1 / s)
<1 min> → 12.9 (1 / s) <1 min> → 21.5 (1 / s) <1 min>
In addition, the measured value when 1 min passed at a shear rate of 12.9 (1 / s) was taken as the representative viscosity.

4). Toner image density evaluation method:
To 100 parts by mass of the toner obtained after drying, 2.0 parts by mass of hydrophobic silica having a specific surface area by the BET method of 200 m ² / g was externally added to obtain a toner. Using this developer, images were printed in an environment of 30 ° C./80% RH using LBP-2160 (manufactured by Canon).

  The obtained image was subjected to reflection density measurement using an SPI filter of Macbeth RD918 type (the same is true for the subsequent image density measurement methods). The results are shown in Table 1. As an evaluation standard, when the Macbeth density value is 1.2 or more, a good image density is shown. When the Macbeth density value is 1.0 or more and less than 1.2, there is a slight problem in the image, but there is no practical problem. If it is less than 1, the influence on the image is considerably severe, and an image density unfavorable on the product is exhibited.

Concentration value: 1.2 or more ・ ・ ・ ・ A Good
: 1.0 or more and less than 1.2 ··· B slightly inferior (no product problem)
: Less than 1.0 ・ ・ ・ ・ C Poor

5). Fixability evaluation method:
Toner is generated by the same method as the image density evaluation method, and an unfixed image with a toner loading amount of 0.55 mg / cm ² on paper is output using a modified iRC3220N (Canon) machine. Fixing was performed using a fixing device under conditions of paper feed speed: 100 mm / s and roller load: 294N.

The evaluation was performed by visually checking the state of offset when the unfixed image was fixed by swinging nine points in the range of 140 ° C. to 220 ° C. every 10 ° C. For evaluation, plain paper of 64 g / m ² was used.

Fixing temperature region where no offset occurs <140 to 220 ° C./all 9 points>: 4 points or more ..... A Good
: 2-3 points ・ ・ ・ ・ B Slightly inferior
(No problem in practical use)
: 1 point or less ・ ・ ・ ・ C Evil

  Next, production examples of the release agent dispersion are described below.

[Production Example of Release Agent Dispersion 1]
As preliminary pulverization, the following components were charged in a temperature-controllable container, and the temperature was constantly kept at 50 ° C. or lower using an Ultra Turrax T-50 (manufactured by IKA) and stirred for 40 minutes at 10000 rpm and averaged. A crude release agent dispersion having a particle size of 32 μm was obtained.
Styrene 24 parts by mass Mitsui High Wax 200P (Mitsui Chemicals) 6 parts by mass

  Next, the mold release agent was pulverized using the dispersing apparatus shown in FIGS.

  5 kg of the release agent coarse dispersion is put into the holding tank described in FIG. 1 (cooling water at 10 ° C. passes through the jacket), and the release agent is crushed under the following conditions to disperse the release agent. Liquid 1 was obtained.

Ring-shaped member material: Zirconia Circulating flow rate: 2kg / min
Total volume in container: 3.1L
Rotating body rotation speed: 1200rpm
Centrifugal effect of rotating body: 235
Dispersion time: 180 min

  Under the present circumstances, the temperature rising of the mold release agent dispersion liquid was suppressed by flowing a 10 degreeC cooling water through a jacket. The temperature of the release agent dispersion after the completion of dispersion was 33 ° C. The release agent dispersion had a viscosity of 3500 cps, and the ratio of the release agent in the release agent dispersion of 2 μm or less was 97%.

  The evaluation results of the dispersibility of the release agent dispersion 1 are shown in Table 1.

[Production Example of Release Agent Dispersion 2]
Except having processed the following component, it processed on the conditions similar to the manufacture example of the mold release agent dispersion 1, and the mold release agent dispersion 2 was produced.
Styrene 26 parts by mass HNP-10 (Nippon Seiki Co., Ltd.) 4 parts by mass (average molecular weight: 592, melting point: 75 ° C., penetration: 6)

  The average particle diameter of the release agent in the release agent crude dispersion after the preliminary pulverization was 68 μm.

  Moreover, the temperature of the mold release agent dispersion liquid after using the dispersion apparatus of the aspect shown in FIGS. Further, the viscosity of the release agent dispersion was 400 cps, and the ratio of 2 μm or less of the release agent in the release agent dispersion was 84%.

  The evaluation results of the dispersibility of the release agent dispersion 2 are shown in Table 1.

[Production Example of Release Agent Dispersion 3]
Except having processed the following component, it processed on the conditions similar to the manufacture example of the mold release agent dispersion 1, and the mold release agent dispersion 3 was produced.
Styrene 22.5 parts by mass Mitsui High Wax 800P (Mitsui Chemicals) 7.5 parts by mass

  The average particle size of the release agent in the release agent coarse dispersion after the preliminary pulverization was 52 μm.

  Moreover, the temperature of the mold release agent dispersion liquid after using the dispersion apparatus of the aspect shown in FIGS. Further, the viscosity of the release agent dispersion was 7000 cps, and the ratio of 2 μm or less of the release agent in the release agent dispersion was 78%.

  The evaluation results of the dispersibility of the release agent dispersion 3 are shown in Table 1.

[Production Example of Release Agent Dispersion 4]
In the dispersion apparatus of the embodiment shown in FIGS. 1, 2, and 3, the release agent dispersion is performed except that 1.6 kg of the release agent dispersion liquid is charged into the container without processing the circulation path and the batch processing is performed. The treatment was performed for 180 min under the same components and apparatus operating conditions as in the liquid 1 production example.

  The average particle size of the release agent in the release agent coarse dispersion after the preliminary pulverization was 32 μm.

  Moreover, the temperature of the mold release agent dispersion liquid after using the dispersion apparatus of the aspect shown in FIGS. Moreover, the viscosity of the release agent dispersion was 3600 cps, and the ratio of 2 μm or less of the release agent in the release agent dispersion was 98%.

  The evaluation results of the dispersibility of the release agent dispersion 4 are shown in Table 1.

[Production Example of Release Agent Dispersion Liquid 5]
In the dispersion apparatus of the embodiment shown in FIGS. 1, 2, and 3, other than suppressing the temperature rise of the release agent dispersion liquid by mixing the antifreeze liquid into the refrigerant flowing through the jacket and holding tank and flowing the refrigerant at −10 ° C. Were processed under the same components and apparatus operating conditions as in the production example of the release agent dispersion 1.
The average particle size of the release agent in the release agent coarse dispersion after the preliminary pulverization was 32 μm.

  Moreover, the temperature of the mold release agent dispersion liquid after using the dispersion apparatus of the aspect shown in FIGS. The viscosity of the release agent dispersion was 3400 cps, and the ratio of the release agent in the release agent dispersion of 2 μm or less was 80%.

  In the release agent dispersion after the treatment, moisture was observed to be mixed due to condensation.

  The evaluation results of the dispersibility of the release agent dispersion 5 are shown in Table 1.

[Production Example of Release Agent Dispersion 6]
In the dispersing apparatus shown in FIGS. 1, 2, and 3, the components and operating conditions are the same as in the production example of the release agent dispersion 1 except that no cooling water is allowed to flow through the jacket, holding tank, and heat exchanger. Was processed.

  The average particle size of the release agent in the release agent coarse dispersion after the preliminary pulverization was 32 μm.

  Moreover, the temperature of the mold release agent dispersion liquid after using the dispersion apparatus of the aspect shown in FIGS. Further, the viscosity of the release agent dispersion was 6000 cps, and the ratio of 2 μm or less of the release agent in the release agent dispersion was 76%.

  The evaluation results of the dispersibility of the release agent dispersion 6 are shown in Table 1.

[Production Example of Release Agent Dispersion 7]
As preliminary pulverization, the following components were charged in a temperature-controllable container, and the temperature was constantly kept at 50 ° C. or lower using an Ultra Turrax T-50 (manufactured by IKA) and stirred for 40 minutes at 10000 rpm and averaged. A crude release agent dispersion having a particle size of 32 μm was obtained.
Styrene 24 parts by mass Mitsui High Wax 200P (Mitsui Chemicals) 6 parts by mass

  The obtained release agent crude dispersion was further used with Cavitron CD1010 (manufactured by Eurotech), back pressure of the disperser: 0.3 Mpa, peripheral speed of the rotor: 31 m / s, circulation flow rate: 8 L / The treatment was performed for 120 minutes under the condition of min to obtain a crude release agent dispersion having an average particle diameter of 4 μm.

  Next, the mold release agent was dispersed under the same conditions as in the production example of the mold release agent dispersion 1 using the dispersion apparatus shown in FIGS.

  The temperature of the release agent dispersion after the completion of dispersion was 33 ° C. The viscosity of the release agent dispersion was 3600 cps, and the ratio of the release agent in the release agent dispersion of 2 μm or less was 99%.

  Moreover, since it processed through 3 processes, the yield of the mold release agent dispersion liquid was about 80% compared with the manufacture example of the mold release agent dispersion liquid 1. FIG.

  The evaluation results of the dispersibility of the release agent dispersion liquid 7 are shown in Table 1.

[Production Example of Release Agent Dispersion 8]
The pre-grinding treatment was performed for 10 minutes, and the treatment was performed under the same components and conditions as in the production example of the release agent dispersion 1 except that a coarse release agent dispersion having an average particle size of 190 μm was obtained. Went.

  The temperature of the release agent dispersion after using the dispersing apparatus shown in FIGS. 1, 2, and 3 was 31 ° C. The viscosity of the release agent dispersion was 3000 cps, and the ratio of the release agent in the release agent dispersion of 2 μm or less was 83%.

  The evaluation results of the dispersibility of the release agent dispersion 8 are shown in Table 1.

[Production Example of Release Agent Dispersion 9]
Styrene 24 parts by mass Mitsui High Wax 200P (Mitsui Chemicals) 6 parts by mass

Without pre-grinding, the wax with an average particle diameter of 1 mm is mixed as it is, at the ratio shown above,
The mixed solution was processed using the dispersing apparatus shown in FIGS.

  5 kg of the release agent coarse dispersion is put into the holding tank described in FIG. 1 (cooling water at 10 ° C. passes through the jacket), and the release agent is crushed under the following conditions. 1 was obtained.

Ring-shaped member material: Zirconia Circulating flow rate: 2kg / min
Total volume in container: 3.1L
Rotating body rotation speed: 1200rpm
Rotating body centrifugal effect: 235
Dispersion time: 180 min

  Under the present circumstances, the temperature rising of the mold release agent dispersion liquid was suppressed by flowing a 10 degreeC cooling water through a jacket. The temperature of the release agent dispersion after the completion of dispersion was 28 ° C. Further, the viscosity of the release agent dispersion was 2400 cps, and the ratio of 2 μm or less of the release agent in the release agent dispersion was 76%.

  The evaluation results of the dispersibility of the release agent dispersion 9 are shown in Table 1.

[Production Example of Release Agent Dispersion 10]
The processing was performed under the same components and conditions as in the production example of the release agent dispersion liquid 1 except that the rotational speed of the rotating body was 429 rpm and the centrifugal effect of the rotating body was 15.

  The average particle size of the release agent in the release agent coarse dispersion after the preliminary pulverization was 32 μm.

  Moreover, the temperature of the mold release agent dispersion liquid after using the dispersion apparatus of the aspect shown in FIGS. Moreover, the viscosity of the release agent dispersion was 2500 cps, and the ratio of the release agent in the release agent dispersion of 2 μm or less was 76%.

  The evaluation results of the dispersibility of the release agent dispersion 10 are shown in Table 1.

[Production Example of Release Agent Dispersion 11]
The treatment was performed under the same components and conditions as in the production example of the release agent dispersion liquid 1 except that the rotational speed of the rotating body was 2071 rpm and the centrifugal effect of the rotating body was 350.

  The average particle size of the release agent in the release agent coarse dispersion after the preliminary pulverization was 32 μm.

  Moreover, the temperature of the mold release agent dispersion liquid after using the dispersion apparatus of the aspect shown in FIGS. Moreover, the viscosity of the release agent dispersion was 4000 cps, and the ratio of the release agent in the release agent dispersion of 2 μm or less was 95%.

  The evaluation results of the dispersibility of the release agent dispersion 11 are shown in Table 1.

[Production Example of Release Agent Dispersion 12]
-Styrene 24 mass parts-C-105 (Schumann-Sazol) Except being 6 mass parts, it processed on the apparatus operating conditions similar to the manufacture example of the mold release agent dispersion 1.

  The average particle diameter of the release agent in the release agent crude dispersion after the preliminary pulverization was 30 μm.

  Moreover, the temperature of the mold release agent dispersion liquid after using the dispersion apparatus of the aspect shown in FIGS. Moreover, the viscosity of the release agent dispersion was 3900 cps, and the ratio of 2 μm or less of the release agent in the release agent dispersion was 98%.

  The evaluation results of the dispersibility of the release agent dispersion 12 are shown in Table 1.

[Production Example of Release Agent Dispersion 13]
As preliminary pulverization, the following components were charged in a temperature-controllable container, and the temperature was constantly kept at 50 ° C. or lower using an Ultra Turrax T-50 (manufactured by IKA) and stirred for 40 minutes at 10000 rpm and averaged. A crude release agent dispersion having a particle size of 32 μm was obtained.
-Styrene 24 parts by mass-Mitsui High Wax 200P (Mitsui Chemicals) 6 parts by mass

  Next, the mold release agent was pulverized using the dispersing apparatus shown in FIGS.

  After putting the release agent coarse dispersion into the holding tank described in FIG. 1 (cooling water at 10 ° C. passes through the jacket), the following components are added and the release agent is crushed under the following conditions: And a release agent dispersion 13 was obtained.

(component)
Carbon black: 8.8 parts by mass Styrene: 58 parts by mass Zinc phthalocyanine: 0.2 parts by mass E-84 (manufactured by Orient Chemical Industries): 1 part by mass

(conditions)
Ring-shaped member material: Zirconia Circulating flow rate: 2kg / min
Total volume in container: 3.1L
Rotating body rotation speed: 1200rpm
Centrifugal effect of rotating body: 235
Dispersion time: 180 min

  Under the present circumstances, the temperature rising of the mold release agent dispersion liquid was suppressed by flowing a 10 degreeC cooling water through a jacket. The temperature of the release agent dispersion after the completion of dispersion was 39 ° C. The viscosity of the release agent dispersion was 2000 cps.

  The evaluation results of the dispersibility of the release agent dispersion 13 are shown in Table 1.

[Production Example of Release Agent Dispersion 14]
As preliminary pulverization, the following components were charged in a temperature-controllable container, and the temperature was constantly kept at 50 ° C. or lower using an Ultra Turrax T-50 (manufactured by IKA) and stirred for 40 minutes at 10000 rpm and averaged. A crude release agent dispersion having a particle size of 32 μm was obtained.
-Styrene 24 parts by mass-Mitsui High Wax 200P (Mitsui Chemicals) 6 parts by mass

  Next, the release agent was pulverized using a handy mill (Mitsui Mining Co., Ltd.).

The release agent crude dispersion obtained by the preliminary pulverization was put into the apparatus and treated under the following conditions to produce a release agent dispersion 14.
Bead diameter: 1.5 mm, operation time: 10 hr, stirring rotation speed: 800 r. p. m

  Under the present circumstances, the temperature rising of the mold release agent dispersion liquid was suppressed by flowing 10 degreeC cooling water through the jacket of a handy mill main body.

  The temperature of the release agent dispersion after the completion of dispersion was 30 ° C. Further, the viscosity of the release agent dispersion was 3200 cps, and the ratio of the release agent in the release agent dispersion of 2 μm or less was 88%. Moreover, since it took time to pulverize the release agent, the production efficiency was very poor.

  The evaluation results of the dispersibility of the release agent dispersion 14 are shown in Table 1.

[Production Example of Release Agent Dispersion 15]
As preliminary pulverization, the following components are charged into a temperature-controllable container, and the temperature of the liquid is always kept at 50 ° C. or lower using Ultra Turrax T-50 (manufactured by IKA) and stirred for 40 minutes at 10,000 rpm and separated. A crude mold dispersion was obtained.
-Styrene 24 parts by mass-Mitsui High Wax 200P (Mitsui Chemicals) 6 parts by mass

  The volume average median diameter of the release agent in the obtained release agent crude dispersion was 32 μm.

Next, the obtained release agent crude dispersion was continuously dispersed at a pressure of 500 kg / cm ² using a high-pressure emulsifier (APV GAULIN HOMOGENIZER 15MR type) to obtain a release agent dispersion 15.

  The temperature of the release agent dispersion after the completion of dispersion was 55 ° C.

  Further, the viscosity of the release agent dispersion was 5500 cps, and the ratio of the release agent in the release agent dispersion of 2 μm or less was 53%.

  The evaluation results of the dispersibility of the release agent dispersion 15 are shown in Table 1.

Next, a method for preparing a colorant dispersion is described below.
Carbon black: 8.8 parts by mass Styrene: 58 parts by mass Zinc phthalocyanine: 0.2 parts by mass E-84 (manufactured by Orient Chemical Industries): 1 part by mass using an attritor (manufactured by Mitsui Miike Chemical) Dispersion was performed for 3 hours to obtain a colorant dispersion.

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

Example 1
After adding 140 parts by mass of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution to 225 parts by mass of ion-exchanged water and heating to 60 ° C., 3,500 revolutions / min using Claremix (M Technique Co., Ltd.) Stir in minutes. To this was added 25 parts by mass of a 1.0 mol / liter-CaCl ₂ aqueous solution to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .
Then, as a dispersoid system,
-N-butyl acrylate 24 parts by mass-Saturated polyester resin 7 parts by mass (polycondensate of bisphenol A and terephthalic acid, acid value 10, glass transition point 65 ° C)
-Release agent dispersion 1 30 parts by mass-Colorant dispersion 68 parts by mass The above formulation was heated to 60 ° C and dissolved and mixed for 30 minutes. In this, 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was put into the aqueous dispersion medium and granulated for 15 minutes while maintaining the rotation speed. Then, the stirrer was changed from the high-speed stirrer to the propeller stirring blade, the internal temperature was raised to 80 ° C., and the polymerization was continued for 10 hours at 50 rpm. After completion of the polymerization, the slurry was cooled, diluted hydrochloric acid was added, and Ca ₃ (PO ₄ ) ₂ was dissolved, followed by filtration, washing with water, crushing and drying to obtain toner particles. To 100 parts by mass of the obtained toner, 1.7 parts by mass of hydrophobic silica having a specific surface area by a BET method of 200 m ² / g was externally added to obtain a toner. The obtained toner was evaluated according to the evaluation method for the dispersibility of the release agent dispersion, toner granulation property, image density, and fixability described above. The results are shown in Table 1.

(Examples 2 to 12)
The same procedure as in Example 1 was performed except that the release agent dispersion was changed as shown in Table 1 in the dispersoid system formulation of Example 1 to obtain a toner. Table 1 shows the evaluation results of the dispersibility of the release agent dispersion, toner granulation properties, image density, and fixability.

(Example 13)
After adding 140 parts by mass of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution to 225 parts by mass of ion-exchanged water and heating to 60 ° C., 3,500 revolutions / min using Claremix (M Technique Co., Ltd.) Stir in minutes. To this was added 25 parts by mass of a 1.0 mol / liter-CaCl ₂ aqueous solution to obtain an aqueous medium containing Ca ₃ (PO ₄ ) ₂ .

Then, as a dispersoid system,
-N-butyl acrylate 24 parts by mass-Saturated polyester resin 7 parts by mass (polycondensate of bisphenol A and terephthalic acid, acid value 10, glass transition point 65 ° C)
Release agent dispersion 13 98 parts by mass The above formulation was heated to 60 ° C. and dissolved and mixed for 30 minutes. In this, 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was put into the aqueous dispersion medium and granulated for 15 minutes while maintaining the rotation speed. Then, the stirrer was changed from the high-speed stirrer to the propeller stirring blade, the internal temperature was raised to 80 ° C., and the polymerization was continued for 10 hours at 50 rpm. After completion of the polymerization, the slurry was cooled, diluted hydrochloric acid was added, and Ca ₃ (PO ₄ ) ₂ was dissolved, followed by filtration, washing with water, crushing and drying to obtain toner particles. To 100 parts by mass of the obtained toner, 1.7 parts by mass of hydrophobic silica having a specific surface area by a BET method of 200 m ² / g was externally added to obtain a toner. The obtained toner was evaluated according to the evaluation method for the dispersibility of the release agent dispersion, toner granulation property, image density, and fixability described above. The results are shown in Table 1.

(Example 14)
As a dispersoid system
-N-butyl acrylate 24 parts by mass-Saturated polyester resin 7 parts by mass (polycondensate of bisphenol A and terephthalic acid, acid value 10, glass transition point 65 ° C)
-Toner was obtained in the same manner as in Example 1 except that 30 parts by mass of the release agent dispersion 1-12 parts by mass of behenyl behenate-68 parts by mass of the colorant dispersion were used.

  The obtained toner was evaluated according to the evaluation method for the dispersibility of the release agent dispersion, toner granulation property, image density, and fixability described above. The results are shown in Table 1.

(Reference Example 1)
The same procedure as in Example 1 was performed except that the release agent dispersion was changed as shown in Table 1 in the dispersoid system formulation of Example 1 to obtain a toner.

  Evaluation was performed according to evaluation methods for dispersibility of the release agent dispersion, toner granulation property, image density, and fixability. The results are shown in Table 1.

(Comparative Example 1)
The same procedure as in Example 1 was performed except that the release agent dispersion was changed as shown in Table 1 in the dispersoid system formulation of Example 1 to obtain a toner.

  Evaluation was performed according to evaluation methods for dispersibility of the release agent dispersion, toner granulation property, image density, and fixability. The results are shown in Table 1.

It is a system diagram of a mold release agent dispersion process including a pulverizer preferably used in the present invention. It is a top view of a rotary body and a cylindrical container. It is a side view of the sub shaft which comprised the ring-shaped member rotatably.

Explanation of symbols

1. Holding tank2. Pump 3. Main shaft 4. 4. Sub shaft Ring member 6. Rotating body 7. Cylindrical container8. Heat exchanger 9. Jacket 10 10. Cooling water supply line Cooling water discharge line 12. Stirring blade 13. Valve 14. Pressure gauge 15. Motor 16. Sealing lid 17. Elevating mechanism

Claims (4)

At least a release agent is finely dispersed in a liquid medium to obtain a release agent dispersion , and a release agent dispersion step , the release agent dispersion, a polymerizable monomer and a colorant are mixed to obtain a polymerizable monomer A preparation step for preparing a composition, a granulation step for granulating the polymerizable monomer composition in an aqueous medium, and a toner obtained by polymerizing the polymerizable monomer in the polymerizable monomer composition A method for producing a toner including a polymerization step for producing particles ,
The release agent dispersion step is a step of mechanically pulverizing the release agent in the liquid using a pulverizer to obtain a release agent dispersion.
The pulverizer has a rotating main shaft at the center of a cylindrical container, supports a plurality of sub-shafts around the main shaft at intervals, and rotates a plurality of ring-shaped members on the sub-shafts. The ring-shaped member is freely and freely fitted with a gap between the sub-shaft and the ring, and the outer peripheral surface of the ring-shaped member is in contact with the inner peripheral surface of the container. Toner manufacturing method. In the release agent dispersion step, when the concentration of the release agent in the release agent dispersion is A (%) and the viscosity of the release agent dispersion is B (cps),
30A ≦ B ≦ 300A
The toner production method according to claim 1, wherein:   The toner production method according to claim 1, wherein the releasing agent dispersion step is performed within a range of 5 ° C. or more and 80 ° C. or less.   4. The toner production method according to claim 1, wherein an average particle diameter of the release agent processed using the pulverizer is 5 μm or more and 200 μm or less. 5.

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