JP4194486B2 - Toner manufacturing method and apparatus - Google Patents

Description

  The present invention relates to a method for producing toner used in an image forming apparatus such as an electrophotographic method, an electrostatic recording method, and electrostatic printing, and an apparatus therefor.

  Generally, the toner production method includes a pulverization method and a polymerization method. The toner produced by the pulverization method has an advantage that the production cost is lower than that of the polymerization method at present, and is widely used in copiers, printers and the like at present. When the toner is manufactured by the pulverization method, a predetermined amount of a binder resin, a colorant and the like are first mixed, melt-kneaded, cooled, pulverized, classified, and then a fluidity improver is added to manufacture the toner. .

  In recent years, copying machines and the like have been demanded to improve image quality, save energy, and cope with the environment. On the other hand, the technical concept of toner has shifted to the spheroidization in order to achieve high transfer efficiency and reduce waste toner. In order to achieve such a technical concept by the pulverization method, a method using a mechanical pulverization method (for example, refer to Patent Document 1), a method using hot air (for example, refer to Patent Document 2), and the like can be mentioned. However, the mechanical impact force method cannot achieve sufficient spheroidization, and the hot air method controls the toner particle surface properties by starting the melting of the wax when the wax is contained in the toner. It becomes difficult to do so, and problems remain from the viewpoint of quality stability. On the other hand, an apparatus capable of simultaneously performing high-performance surface treatment and fine powder removal has been proposed (see Patent Document 3). This apparatus is a batch-type apparatus, and the operation for each batch is continuously performed in production. When increasing the productivity of this apparatus, the amount of one batch will increase, but in that case, the discharge performance for each batch will decrease, and the temperature inside the apparatus will tend to decrease, and the fine powder removal efficiency will decrease. It is desired to solve this problem.

Japanese Patent Laid-Open No. 9-85741 JP 2000-29241 A JP 2002-233787 A

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner method and apparatus characterized in that the batch-type apparatus that simultaneously performs surface modification and fine powder removal has good discharge performance for each batch.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner manufacturing method and apparatus characterized in that a temperature increase inside the apparatus can be suppressed in a batch type apparatus that simultaneously performs surface modification and fine powder removal.

  SUMMARY OF THE INVENTION An object of the present invention is to provide a toner manufacturing method and apparatus capable of removing ultrafine powder and suppressing generation of fog in a batch-type apparatus that simultaneously performs surface modification and fine powder removal. .

  As a result of intensive studies, the inventors have improved the internal configuration of the surface reforming apparatus that performs classification and surface modification processing at the same time, thereby improving the batch dischargeability of the apparatus, suppressing exhaust temperature rise, and removing ultrafine powder. We have found that this can be achieved, and have completed the present invention.

That is, a step of melt-kneading a mixture containing at least a binder resin and a colorant, cooling and solidifying the obtained kneaded product, pulverizing the cooled and solidified solidified product to obtain a finely pulverized product, and the obtained fine pulverization In a method for producing a toner having a step of subjecting a product to surface modification and classification simultaneously,
The step of simultaneously processing the surface modification and classification is performed using a cylindrical batch type surface modification device, and the batch type surface modification device includes a cylindrical main body casing and the finely pulverized product. A charging unit that is charged into the main body casing, and a classification that rotates in a predetermined direction for continuously removing fine particles having a predetermined particle diameter or less from the finely pulverized material charged into the main body casing to obtain treated particles. Means for discharging the fine powder removed by the classification means to the outside of the main casing, and for subjecting the particles to be treated from which the fine powder has been removed to surface modification treatment using a mechanical impact force. Surface modification means that rotates in the same direction as the rotation direction, and first and second spaces provided between the classification means and the surface treatment means, wherein the particles to be treated are introduced into the classification means. First space for and said treated Fine powder having a predetermined particle size or less is removed by the second space for introducing the child into the surface modifying means, the guide means for partitioning the first space and the second space, and the classifying means, and the surface A discharge unit that discharges the particles to be treated, which have been surface-modified by the reforming means, to the outside of the main casing as surface-modified particles. It is introduced into one space, the fine particles having a predetermined particle diameter or less are removed by the classifying means, and continuously discharged out of the apparatus through the second space, and introduced into the surface modifying means for surface modification. The treatment is repeated, and the classification and the surface modification treatment are repeated by circulating again to the first space, thereby obtaining the surface modified particles from which fine powder having a predetermined particle size or less is removed,
The guide means has at least a concentric cylindrical partition member, and the concentric cylindrical partition member is fixed to the main body directly or indirectly by a connecting member, and at least the connection in the short axis direction portion of the connecting member. In the vertical cross-sectional shape in the short axis direction of the member, the ratio A / B of the long side A and the short side B of the rectangle that circumscribes the cross-sectional shape and has the minimum area is 1.0 to 2.0. have a cross sectional shape such as, for producing a toner, wherein at least 50% of the area of the connecting member is the cross-sectional shape a / B is a circular or approximate circular 1.1 1.0 .

  Furthermore, in order to suitably solve the problems of the present invention, it is preferable that the guide means is composed of a concentric cylindrical partition member and a connecting member.

  Further, in order to suitably solve the problem of the present invention, the guide means is composed of a concentric cylindrical fixing member, a concentric cylindrical partition member, and a connecting member for connecting the fixing member and the partition member. Preferably it is.

Further, the present invention is obtained by melt-kneading a mixture containing at least a binder resin and a colorant, cooling and solidifying the obtained kneaded product, and finely pulverizing the cooled and solidified product to obtain a finely pulverized product. A batch-type surface modification device used for the production of toner, wherein the finely pulverized product is classified and surface-modified at the same time.
Cylindrical main body casing, input portion for supplying the finely pulverized material into the main body casing, fine powder having a predetermined particle size or less is continuously removed from the finely pulverized material charged into the main body casing to be processed. Classifying means that rotates in a predetermined direction for obtaining particles, fine powder discharging unit that discharges fine powder removed by the classification means to the outside of the main body casing, surface to be treated from which the fine powder is removed using mechanical impact force A surface modification means for rotating in the same direction as the rotation direction of the classification means, and first and second spaces provided between the classification means and the surface treatment means for the modification treatment, A first space for introducing the particles to be treated into the classification means, a second space for introducing the particles to be treated into the surface modification means, and the first space and the second space are partitioned. Guiding means and the classifier And a discharge part for discharging the particles to be treated, which have been subjected to the surface modification treatment by the surface modification means, to the outside of the main body casing as surface modified particles. The finely pulverized material introduced into the main body casing from the section is introduced into the first space, the fine particles having a predetermined particle diameter or less are removed by the classification means, and continuously discharged out of the apparatus via the second space. The surface is introduced into the surface modification means, subjected to the surface modification treatment, and recirculated to the first space to repeat the classification and the surface modification treatment, thereby removing the fine particles having a predetermined particle size or less. The guide means has at least a concentric cylindrical partition member, and the concentric cylindrical partition member is directly or indirectly fixed to the main body by a connecting member, and at least the connecting member. In the minor axis direction The ratio A / B of the long side A and the short side B of the rectangle in which the cross-sectional shape circumscribes the cross-sectional shape and has the minimum area is 1.0 to 2 have a .0 become such cross-sectional shape, characterized in that at least 50% of the area of the connecting member is the cross-sectional shape a / B is a circular or approximate circular 1.1 1.0 surface The present invention relates to a reformer.

  According to the present invention, in the production of high value-added toner, it is possible to improve the batch dischargeability of the surface reforming device, suppress the increase in exhaust temperature, and further suppress the generation of ultrafine powder.

  First, an overview of the surface modification apparatus used in the production method of the present invention will be given.

  The surface modification device of the present invention is a batch-type device that performs classification and surface modification treatment at the same time, and has a cylindrical main body casing, a charging unit for charging the finely pulverized material into the main body casing, and the main body casing. A classifying means that rotates in a predetermined direction for continuously removing fine powder having a predetermined particle size or less from the finely pulverized product to the outside of the apparatus to obtain treated particles, and the fine powder removed by the classifying means is removed from the main body casing. A fine powder discharge section for discharging the particles, a surface modification means for rotating the treated particles from which the fine powder has been removed using a mechanical impact force in the same direction as the rotation direction of the classification means, First and second spaces provided between the classification means and the surface treatment means, the first space for introducing the particles to be treated into the classification means and the surface treatment particles. To introduce to quality means Fine powder having a predetermined particle size or less was removed by the second space, the guide means for partitioning the first space and the second space, and the classification means, and the surface modification treatment was performed by the surface modification means. A discharge section for discharging the particles to be processed out of the main casing as surface-modified particles;

  FIG. 1 is a schematic cross-sectional view showing a preferred example of a surface modifying apparatus used in the present invention. 2 and 3 are an external view, a side view, and a top view of the guide means for suitably achieving the object of the present invention. FIG. 4 is an external view, a side view, a top view, and a sectional view showing the form of the connecting member of the guide means used in the present invention. FIG. 5 is a schematic diagram of the behavior of the distributed rotor drive motor load current value during continuous operation.

  The detailed configuration of the apparatus configuration will be further described below.

  The batch type surface reforming apparatus shown in FIG. 1 includes a cylindrical main body casing 30; a top plate 43 installed so as to be openable and closable at the upper part of the main body casing; a fine powder discharge casing 44 as a fine powder discharge section; Cooling jacket 31 capable of water; a plurality of square discs 33 on the upper surface, which are attached to the central rotating shaft in the main body casing 30 as surface modification means (even number is preferable in consideration of rotational balance) And a dispersion rotor 32 that is a disk-like rotating body that rotates at a high speed in a predetermined direction (counterclockwise as viewed from the upper surface of the apparatus); fixedly arranged around the dispersion rotor 32 at a constant interval; Liner 34 as a fixed body having a number of grooves on the surface (there is no need to have grooves on the liner surface); the surface-modified raw material particles are classified to a predetermined particle size. A classification rotor 35 as a classifying means that rotates in the same direction as the rotation direction of the dispersion rotor 32 for continuously removing fine powder having a predetermined particle size or less; fine powder removed by the classification rotor 35 is outside the apparatus (that is, the main body casing 30). A fine powder discharge port 45 as a fine powder discharge part formed on the side surface of the main body casing 30 for discharging to the outside); and a cold air inlet 46 for introducing cold air into the main body casing 30; for introducing raw material particles A raw material charging port 37 and a raw material supply port 39 as input portions formed on the side surface of the main body casing 30; for discharging the surface-modified powder (that is, surface-modified particles) out of the main body casing 30. Product discharge port 40 and product extraction port 42 as a discharge part; Furthermore, it is provided between the raw material input port 37 and the raw material supply port 39 so that the surface modification time can be adjusted freely. Having a product discharge valve 41 installed between the open material feed valve 38 and product discharge port 40 and the product extracting hole 42, which is.

The surface modification apparatus further includes a guide ring 36 as a cylindrical guide means having an axis perpendicular to the top plate 43 in the main body casing 30. The upper end of the guide ring 36 is provided at a predetermined distance from the top plate, and is installed in a state where at least a part of the classification rotor 35 is covered with the cylinder. Further, the lower end of the guide ring 36 is provided at a predetermined distance from the disk portion of the dispersion rotor 32 or the square disk 33. By this guide ring 36, the space between the classification rotor 35 and the dispersion rotor 32-liner 34 in the apparatus is divided into a first space 47 outside the cylinder and a second space 48 inside the cylinder. . Here, the first space 47 is a space for introducing the particles to be processed into the classification rotor 35, and the second space is a space for introducing the particles to be processed into the dispersion rotor. Further, a gap between the plurality of rectangular disks 33 installed on the dispersion rotor 32 and the liner 34 is the surface modification zone 49, and the classification rotor 35 and the peripheral portion of the rotor are the classification zone 50.

  The finely pulverized product supplied into the apparatus from the raw material supply port 39 is outside the guide ring by the swirl flow formed by the suction air volume by the blower (not shown), the rotation of the dispersion rotor 32, and the rotation of the classification rotor 35. , While reaching the classification zone 50 in the vicinity of the classification rotor 35, the classification process is performed. Here, since the direction of the swirl flow formed in the apparatus is the same as the rotation direction of the dispersion rotor 32 and the classification rotor 35, in this embodiment, it is counterclockwise as viewed from the upper surface of the apparatus.

  The fine powder to be removed by the classifying means is sucked through a slit (not shown) of the classification rotor 35 and removed through the fine powder discharge port 45. The particles to be treated after the fine powder removal reaches the surface modification zone 49 in the vicinity of the dispersion rotor 32 via the second space 48, and the surface is modified by the hammer provided in the dispersion rotor 32 and the liner 34 provided in the main body casing. Quality processing is performed. The particles to be treated that have undergone surface modification reach the classification rotor 35 again while turning along the guide ring 36 described above, and the same processing is repeated. After performing the treatment for a predetermined time, the discharge valve 41 is opened, and the surface-modified particles from which fine powder having a predetermined particle diameter or less is removed can be obtained.

  In the apparatus in which raw material charging and discharging are continuously performed, such as the batch processing apparatus of the present apparatus, the present inventors have confirmed that the processed powder remains in the tank during the discharging operation. It has been found that it adversely affects operation, exhaust temperature control, and the like.

  The present inventors pay attention to the structure of the guide means constituting the surface reforming apparatus, and if it has a certain shape defined in the present invention, the one-batch discharge performance is improved, the exhaust temperature is suppressed, and the superfine powder It has been found that it is possible to remove this. That is, the shape of the connecting member constituting the guide means (guide ring) which is a constituent member of the surface modification apparatus according to the present invention has an important influence.

  Specifically, in the vertical cross-sectional shape of the connecting member in the short-axis direction at least in the short-axis direction portion of the connecting member, the long side A of the rectangle that circumscribes the cross-sectional shape and has a minimum area If the cross-sectional shape is such that the ratio A / B of the short side B is 1.0 to 2.0, the object of the present invention can be suitably achieved.

  The effects of the present invention are considered as follows. In the conventional guide ring, since the connecting member is plate-shaped, the powder that has been wound on the swirling flow formed by the dispersed rotor collides with the swirling flow by colliding at an angle close to perpendicular to the plate surface. I think that the flow of powder tends to rise rapidly. Accordingly, since the laminar flow state is disturbed in the vicinity of the discharge port, it is considered difficult to flow into the discharge port side when the discharge valve is open. In such a situation, by making the connecting member into the shape defined in the present invention, the collision between the powder and the connecting member is alleviated, so that the swing without disturbance is maintained. Therefore, it is considered that even when the discharge valve is opened, the powder in the layer can smoothly flow out of the discharge port when the discharge valve is opened by maintaining the swing without disturbance in the vicinity of the discharge port.

  More preferably, in order to achieve the object of the present invention, the cross-sectional shape A / B is 1.0 to 1.1 in a region of 50% or more of the connecting member, and is preferably substantially circular. If the amount is less than 50%, the above-mentioned turning disturbance is likely to occur, leading to deterioration of discharge performance and a reduction in ultrafine powder removal efficiency. In the case where the cross-sectional shape A / B of the connecting member is 1.0 to 2.0 and the shape is almost circular, the impact of the powder and the powder on the connecting member can be suitably suppressed, and the object of the present invention is preferably achieved. be able to.

  As an example of the configuration of the guiding means, as shown in FIG. 2, a cylindrical partition member, a connecting member and a cylindrical fixing member formed in an integrated state are preferably used. This surface modification apparatus is used in a state where the guide means is mounted on the main body and the guide means is fixed.

  For example, as shown in FIG. 3, the guide means can also be preferably used when a cylindrical partition member and a connecting member are integrally formed.

  Further, there can be exemplified a case where the main body and the connecting member are integrally provided, and the guide means is composed of only a cylindrical partition member and is mounted on the main body. Here, “integral” refers to a state in which they are directly connected by welding, bolts, or the like.

Further, the position of the connecting member is not particularly limited to the illustrated position.
An example of the structure of the connecting member is shown in FIG. The shape is not particularly limited to these, and for example, the cross-sectional shape is a polygon such as a rhombus, a pentagon, a hexagon, etc., and the A / B is in the range of 1.0 to 2.0. It is preferably used.

  However, the A / B of the cross-sectional shape of a part of the connecting member does not have to satisfy 1.0 to 2.0, but a certain range of the central part of the connecting part (the horizontal length of the side view of the connecting member) On the other hand, it is preferable that at least 50% or more from the midpoint is 50% or more. This is because if the amount is less than 50%, the turbulent flow is likely to be disturbed as described above.

  “Surface modification” in the present invention means smoothing the unevenness of the particle surface, and means that the appearance of the particle approaches a spherical shape. As an indication of the degree of surface modification of the surface modified particles of the present invention, average circularity can be used as an index in the present invention.

The average circularity in the present invention is used as a simple method for quantitatively expressing the particle shape. In the present invention, the flow type particle image analyzer FPIA-2100 manufactured by Sysmex Corporation is used at 23 ° C. and 60%. Measurement is performed under the environment of RH, and particles within a circle equivalent diameter of 0.60 μm to 400 μm are measured. The circularity of the measured particle is obtained by the following equation (1), and further, the circle equivalent diameter is 3 μm to 400 μm. In the following particles, the value obtained by dividing the total circularity by the total number of particles is defined as the average circularity.
Circularity a = L ₀ / L (1)
[In the formula, L ₀ represents the perimeter of a circle having the same projection area as the particle image, and L represents the particle projection when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm). Indicates the perimeter of the image. ]

  The circularity used in the present invention is an index of the degree of unevenness of the toner particles, and indicates 1.00 when the toner is a perfect sphere. The more complicated the surface shape, the smaller the circularity. In addition, “FPIA-2100”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity by calculating the circularity of each particle. A calculation method is used in which 1.0 is divided into 61 classes and the average circularity is calculated using the center value and frequency of the division points. However, the error of the average circularity calculated by the calculation formula using the average circularity value calculated by this calculation method and the total circularity of each particle is very small and can be substantially ignored. In the present invention, for the reason of handling data such as shortening the calculation time and simplifying the calculation operation formula, the concept of the calculation formula using the sum of the circularity of each particle is used and partly changed. Such a calculation method may be used. Furthermore, the measurement device used in the present invention, “FPIA-2100”, has a thinner sheath flow (7 μm → 4 μm) than “FPIA1000” which has been used to calculate the shape of the toner. ) And the magnification of the processed particle image, and further the processing resolution of the captured image (256 × 256 → 512 × 512), the accuracy of toner shape measurement has been improved, thereby making sure the fine particles are more reliable. A device that has achieved capture. Therefore, when it is necessary to measure the shape and particle size distribution more accurately as in the present invention, the FPIA 2100 that can obtain information on the shape and particle size distribution more accurately is more useful.

As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersing agent to 200 to 300 ml of water from which impurities in the container have been removed in advance, and a measurement sample is 0. Add about 1-0.5g. The suspension in which the sample is dispersed is dispersed with an ultrasonic oscillator for 2 minutes, and the circularity distribution of the particles is measured at a dispersion concentration of 0.2 to 1 million particles / μl. As the ultrasonic oscillator, for example, the following apparatus is used, and the following dispersion conditions are used.
UH-150 (manufactured by SMT Corporation)
OUTPUT level: 5
Constant mode

  The outline of the measurement is as follows.

  The sample dispersion is passed through a flow path (expanded along the flow direction) of a flat and flat flow cell (thickness: about 200 μm). The strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other so as to form an optical path that passes through the thickness of the flow cell. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell. Photographed as a two-dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter. The circularity of each particle is calculated from the projected area of the two-dimensional image of each particle and the perimeter of the projected image using the above circularity calculation formula.

  In the present invention, the toner particle ratio of 0.6 μm or more and less than 3 μm is 0% by number in the number-based particle size distribution of toner particles having an equivalent circle diameter of 0.6 μm or more and 400 μm or less measured by a flow type particle image measuring apparatus. It is preferable that the number is less than 18% by number, preferably 0% or more and less than 15%, more preferably 1% or more and less than 13%. Toner particles having a size of 0.6 μm or more and less than 3 μm have a great influence on the developability of the toner, particularly the fog characteristics. Such a fine particle toner has an excessively high chargeability, is easily developed excessively at the time of developing the toner, and appears as fog on the image. However, in the present invention, the fog can be reduced by the small proportion of the fine particle toner.

  The particle size distribution of the toner can be measured by various methods. In the present invention, the following measurement apparatus was used.

  That is, a Coulter Counter TA-II type or Coulter Multisizer II (manufactured by Coulter, Inc.) was used as a measuring device. A 100 μm aperture was used as the aperture, and the volume and number distribution of the toner were measured to calculate the volume distribution and the number distribution. Then, the weight-average weight average particle diameter obtained from the volume distribution according to the present invention was obtained.

  Next, the method for producing the toner of the present invention will be outlined. In the present invention, the toner can be produced by, for example, a binder resin, a pigment or dye as a colorant, a wax, a metal salt or a metal complex, a magnetic substance (when producing a magnetic toner), and a charge as necessary. Control agents, other additives, etc. are thoroughly mixed with a mixer such as a Henschel mixer or ball mill, and then melt-kneaded using a heat kneader such as a heating roll, kneader, or extruder to make the resins compatible with each other. A metal compound, pigment, dye, and magnetic substance are dispersed or dissolved therein to obtain a kneaded product. The obtained kneaded product is cooled and solidified, and the solidified product is roughly pulverized, and then finely pulverized by an air impact pulverizer such as an I mill or a mechanical impact pulverizer such as a turbo mill or a kryptron to obtain a finely pulverized product. . Thereafter, the finely pulverized product is classified and surface-treated at the same time by using the batch-type surface treatment device preferably used in the present invention to obtain toner particles having a desired particle size as surface-modified particles. Can do. The toner in the present invention may be composed only of the toner particles thus obtained, or may be obtained by mixing known external additives to the toner particles as necessary. Good.

  Next, the constituent material of the toner particles containing the binder resin, wax and colorant according to the present invention will be described. In the present invention, various conventionally known toner particle materials can be used without particular limitation.

  As the binder resin constituting the toner particles, any resin usually used for toner can be used, and examples thereof include the following.

  The binder resin used in the present invention includes, for example, a homopolymer of styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene, and a substituted polymer thereof; styrene-p-chlorostyrene copolymer, styrene. -Vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer Polymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Styrenic copolymers such as coalesced; Vinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl Butyral, terpene resin, coumarone indene resin and petroleum resin can be used. Cross-linked styrene resins are also preferred binder resins.

  Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid. Monocarboxylic acid having a double bond such as acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof; for example, maleic acid, butyl maleate, Dicarboxylic acids having a double bond such as methyl maleate and dimethyl maleate and substituted products thereof; for example, vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; Ethylenic olefins such as alkylene; for example, vinyl methyl ketone, vinyl ketones such as vinyl hexyl ketone; for example, vinyl methyl ether, vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether; and the like. These vinyl monomers are used alone or in combination of two or more.

  Here, as the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol diacrylate and ethylene glycol diacrylate. Carboxylic acid esters having two double bonds, such as methacrylate and 1,3-butanediol dimethacrylate; divinyl compounds of divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups; Can be used alone or as a mixture of two or more.

  Among the toner physical properties, those attributable to the binder resin include at least a region having a molecular weight of 2,000 to 50,000 in the molecular weight distribution measured by GPC (gel permeation chromatography) soluble in THF (tetrahydrofuran). It is more preferable that a component having one peak and having a molecular weight of 1,000 to 30,000 is present in an amount of 50 to 90%.

  In the present invention, the following waxes are used as the material for the toner particles from the viewpoint of improving releasability from the fixing member at the time of fixing and improving fixability. Examples of the wax include paraffin wax and derivatives thereof, microcrystalline wax and derivatives thereof, Fischer-Tropsch wax and derivatives thereof, polyolefin wax and derivatives thereof, carnauba wax and derivatives thereof, and the derivatives include oxides and vinyl monomers. Block copolymers and graft-modified products. In addition, alcohols, fatty acids, acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes, mineral waxes, petrolactams and the like can also be used.

  In the present invention, a charge control agent is preferably blended (internally added) into toner particles or mixed (externally added) with toner particles as a material for toner particles. The charge control agent makes it possible to control the optimum charge amount according to the development system, and in particular, it is possible to produce a toner with a more stable balance between the particle size distribution and the charge amount.

  As the negative charge control agent for controlling the toner to be negatively charged, for example, organometallic complexes and chelate compounds are effective, and monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acid metal complexes, and aromatic dicarboxylic acids. A metal complex is mentioned. Others include aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenols.

  Examples of the positive charge control agent for controlling the toner to be positively charged include modified products of nigrosine and fatty acid metal salts, etc .; tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate Quaternary ammonium salts such as: onium salts such as phosphonium salts and their lake pigments; triphenylmethane dyes and lake pigments thereof (as rake agents include phosphotungstic acid, phosphomolybdic acid, Phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibuty Suzuboreto, dioctyl tin borate, such as diorganotin tin borate such dicyclohexyl tin borate; is. These charge control agents can be used alone or in combination of two or more.

  The charge control agent described above is preferably used in the form of fine particles. In this case, the number average particle diameter of these charge control agents is more preferably 4 μm or less, and particularly preferably 3 μm or less. When these charge control agents are internally added to the toner particles, it is preferable to add 0.1 to 20 parts by weight, particularly 0.2 to 10 parts by weight, to 100 parts by weight of the binder resin.

  In the present invention, various conventionally known colorants can be used as the toner particle material. The colorant used in the present invention is adjusted to black by a chromatic colorant such as carbon black or a magnetic material, a yellow colorant, a magenta colorant, and a cyan colorant shown below as a black colorant. A combination or the like is used.

  As the yellow colorant, compounds represented 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, 97, 109, 110, 111, 120, 127, 128, 129, 147, 168, 174, 176, 180, 181 and 191 are preferably used.

  As the magenta colorant, a condensed azo compound, diketopyrrolopyrrole compound, anthraquinone, quinacridone compound, basic dye lake compound, naphthol compound, benzimidazolone compound, thioindigo compound, and perylene compound are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 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 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. In the present invention, the colorant is selected in consideration of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. These chromatic colorants are contained in the toner particles in a total amount of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  Furthermore, in order to improve fluidity, transferability, etc., a toner can be obtained by externally adding a known external additive such as inorganic fine powder to the toner particles and passing through a known sieving step.

  Hereinafter, the present invention will be specifically described with specific toner production methods, examples, and comparative examples.

<Example 1>
Binder resin (styrene / acrylic copolymer, Tg = 62 ° C., peak molecular weight 13500)
100 parts by mass, magnetic substance (Fe ₃ O ₄ , number average particle shape: 0.20 μm) 95 parts by mass, charge control agent (monoazo iron complex) 2 parts by mass, paraffin wax (melting point 76 ° C.) 4 parts by mass After mixing the materials in a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Kako Co., Ltd.), a biaxial kneader (PCM-30 type, manufactured by Ikekai Tekko Co., Ltd.) set at a temperature of 110 ° C. And kneaded. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized product for toner production.

From the obtained toner raw material coarsely pulverized product, a finely pulverized product obtained by a mechanical pulverizer Turbo Mill T250 (manufactured by Turbo Kogyo Co., Ltd.) was obtained. As for the particle size of the finely pulverized product, D4 was 6.7 μm, and the number of particles of 4.0 μm or less was 45%. The finely pulverized product is processed by a surface treatment / classification simultaneous processing machine equipped with the guiding means shown in FIG. 2 (the connecting member is S1 shown in FIG. 4 and A / B is 1.0 and cylindrical), and D4 (weight average) As a result, toner particles having a particle size of 7.0 μm and 4.0 μm or less were 18%. The inside casing tank inner diameter of this apparatus was 440 mm and the depth direction was 400 mm. Inlet temperature -20 ° C., throughput 65 kg / hr, classification rotor rotation speed 6500 rpm (classification rotor outer diameter 240 mm, tip peripheral speed 81 m / sec), dispersion rotor 5300 rpm (dispersion rotor outer diameter 400 mm, tip peripheral speed is 111 m / sec, motor Max power 37 kW), 1 cycle time 46 sec (input time: 8 sec, treatment time 30 sec, discharge time 8 sec), and 12 minutes operation at an air volume of 21 m ³ / min. The exhaust temperature at 12 minutes was 33 ° C., and the batch dischargeability was 65%. The batch discharge was defined as follows, and it was judged that the larger the value, the better.

  Batch discharge property: The amount of powder remaining in the tank after the discharge operation after batch processing for a certain time is evaluated by paying attention to the load current value of the dispersion rotor. The current value of the dispersion rotor in the empty state is I0, the maximum load current value of the dispersion rotor during processing is I1, and the load current value of the dispersion rotor after discharging is I2. The batch dischargeability was determined from ((I1-I2) / (I1-I0)) × 100.

  Toner particles were obtained by externally adding 1.2 parts by weight of hydrophobic silica to 100 parts by weight of toner particles. Next, the prepared toner was used for evaluation by the following method. The evaluation results are shown in Table 2.

  The fog was evaluated using a laser beam printer Laser Jet 4300n manufactured by Hewlett-Packard.

Image printing test of 9000 sheets on plain paper for copying machines (A4 size: 75 g / m ² ) at a printing speed of 5/10% in a low-temperature and low-humidity environment (15 ° C, 10% RH), 2/10 printing speed. The test was performed for a total of 18000 sheets, leaving 9000 sheets for a day. The results are shown in Table 1.

  For the image density, a “Macbeth reflection densitometer” (manufactured by Macbeth) was used to measure a relative density with respect to a printout image of a white background portion having an original density of 0.00.

  The fog was calculated from a comparison between the whiteness of the transfer paper measured by a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper after printing solid white.

<Example 2>
A toner was prepared and evaluated in the same manner as in Example 1 except that the treatment amount in the surface treatment apparatus was 100 kg / hr. The results are shown in Table 1.

<Example 3>
A toner was prepared and evaluated in the same manner as in Example 1 except that the treatment amount in the surface treatment apparatus was changed to 130 kg / hr. The results are shown in Table 1.

<Example 4>
A toner was prepared and evaluated in the same manner as in Example 1 except that the connecting member of the guide means was of the S2 type shown in FIG. 4 (A / B = 1.0 and the cross-sectional shape was square). . The results are shown in Table 1.

<Example 5>
The toner was prepared and evaluated in the same manner as in Example 1 except that the connecting member of the guide means was of the S3 type (A / B = 2.0, the cross-sectional shape was oval) shown in FIG. . The results are shown in Table 1.

<Example 6>
The shape of the connecting member of the guide means is the S4 type shown in FIG. 4 (60% of the central portion of the connecting member is A / B = 1.0 to 2.0, and the cross-sectional shape is rectangular or square). Except for the above, a toner was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Comparative Example 1>
The toner was prepared and evaluated in the same manner as in Example 1 except that the connecting member of the guide means was of the S5 type (A / B = 5.0, the cross-sectional shape was rectangular) shown in FIG. . The results are shown in Table 1.

<Comparative example 2>
A toner was prepared and evaluated in the same manner as in Comparative Example 1 except that the treatment amount in the surface reforming apparatus was 100 kg / hr. The results are shown in Table 1.

It is a schematic sectional drawing of the surface modification apparatus used in the surface modification process of this invention. It is a block diagram of the guide means of the surface modification apparatus used in the surface modification process of this invention. It is a block diagram of the guide means of the surface modification apparatus used in the surface modification process of this invention. It is a form figure of the connection member of the guide means of the surface modification apparatus used in the surface modification process of this invention. It is the schematic of the behavior of the load current value of the dispersion | distribution rotor drive motor at the time of continuous operation in the surface modification apparatus used in the surface modification process of this invention.

Explanation of symbols

30 Main body casing 31 Cooling jacket 32 Dispersion rotor 33 Square disk 34 Liner 35 Classification rotor 36 Guide ring 37 Raw material inlet 38 Raw material supply valve 39 Raw material supply port 40 Product discharge port 41 Product discharge valve 42 Product extraction port 43 Top plate 44 Fine powder Discharge casing 45 Fine powder discharge port 46 Cold air inlet 47 First space 48 Second space 49 Surface modification zone 50 Classification zone 51 Sealing material

Claims (6)

A step of melt-kneading a mixture containing at least a binder resin and a colorant, cooling and solidifying the obtained kneaded product, finely pulverizing the cooled and solidified solidified product to obtain a finely pulverized product, and an obtained finely pulverized product. In a toner manufacturing method including a step of simultaneously performing surface modification and classification,
The step of simultaneously processing the surface modification and classification is performed using a cylindrical batch type surface modification device, and the batch type surface modification device includes a cylindrical main body casing and the finely pulverized product. A charging unit that is charged into the main body casing, and a classification that rotates in a predetermined direction for continuously removing fine particles having a predetermined particle diameter or less from the finely pulverized material charged into the main body casing to obtain treated particles. Means for discharging the fine powder removed by the classification means to the outside of the main casing, and for subjecting the particles to be treated from which the fine powder has been removed to surface modification treatment using a mechanical impact force. Surface modification means that rotates in the same direction as the rotation direction, and first and second spaces provided between the classification means and the surface treatment means, wherein the particles to be treated are introduced into the classification means. First space for and said treated Fine powder having a predetermined particle size or less is removed by the second space for introducing the child into the surface modifying means, the guide means for partitioning the first space and the second space, and the classifying means, and the surface A discharge unit that discharges the particles to be treated, which have been surface-modified by the reforming means, to the outside of the main casing as surface-modified particles. It is introduced into one space, the fine particles having a predetermined particle diameter or less are removed by the classifying means, and continuously discharged out of the apparatus through the second space, and introduced into the surface modifying means for surface modification. The treatment is repeated, and the classification and the surface modification treatment are repeated by circulating again to the first space, thereby obtaining the surface modified particles from which fine powder having a predetermined particle size or less is removed,
The guide means has at least a concentric cylindrical partition member, and the concentric cylindrical partition member is fixed to the main body directly or indirectly by a connecting member, and at least the connection in the short axis direction portion of the connecting member. In the vertical cross-sectional shape in the short axis direction of the member, the ratio A / B of the long side A and the short side B of the rectangle that circumscribes the cross-sectional shape and has the minimum area is 1.0 to 2.0. have a cross sectional shape such as, method for producing a toner, wherein at least 50% of the area of the connecting member is the cross-sectional shape a / B is a circular or approximate circular 1.1 and 1.0.   2. The toner manufacturing method according to claim 1, wherein the guide means comprises a concentric cylindrical partition member and a connecting member.   2. The toner production according to claim 1, wherein the guide means includes a concentric cylindrical fixing member, a concentric cylindrical partition member, and a connecting member that connects the fixing member and the partition member. Method. A mixture containing at least a binder resin and a colorant is melt-kneaded, the obtained kneaded product is cooled and solidified, the cooled and solidified solidified product is finely pulverized to obtain a finely pulverized product, and the obtained finely pulverized product is classified. A batch-type surface modification device used for the production of toner, which simultaneously performs surface modification treatment with
Cylindrical main body casing, input portion for supplying the finely pulverized material into the main body casing, fine powder having a predetermined particle size or less is continuously removed from the finely pulverized material charged into the main body casing to be processed. Classifying means that rotates in a predetermined direction for obtaining particles, fine powder discharging unit that discharges fine powder removed by the classification means to the outside of the main body casing, surface to be treated from which the fine powder is removed using mechanical impact force A surface modification means for rotating in the same direction as the rotation direction of the classification means, and first and second spaces provided between the classification means and the surface treatment means for the modification treatment, A first space for introducing the particles to be treated into the classification means, a second space for introducing the particles to be treated into the surface modification means, and the first space and the second space are partitioned. Guiding means and the classifier And a discharge part for discharging the particles to be treated, which have been subjected to the surface modification treatment by the surface modification means, to the outside of the main body casing as surface modified particles. The finely pulverized product introduced into the main body casing from the section is introduced into the first space, the fine particles having a predetermined particle diameter or less are removed by the classification means, and continuously discharged out of the apparatus via the second space. The surface is subjected to surface modification treatment by introducing it into the surface modification means, and the classification and surface modification treatment are repeated by circulating again to the first space, thereby removing the fine powder having a predetermined particle size or less. The guide means has at least a concentric cylindrical partition member, and the concentric cylindrical partition member is directly or indirectly fixed to the main body by a connecting member, and at least the connecting member. In the minor axis direction The ratio A / B of the long side A and the short side B of the rectangle in which the cross-sectional shape circumscribes the cross-sectional shape and has the minimum area is 1.0 to 2 have a .0 become such cross-sectional shape, characterized in that at least 50% of the area of the connecting member is the cross-sectional shape a / B is a circular or approximate circular 1.1 1.0 surface Reformer. 5. The surface reforming apparatus according to claim 4 , wherein the guide means comprises a concentric cylindrical partition member and a connecting member. 5. The surface modification according to claim 4 , wherein the guide means comprises a concentric cylindrical fixing member, a concentric cylindrical partition member, and a connecting member that connects the fixing member and the partition member. apparatus.

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