JP3919529B2 - Method for producing polymerized toner - Google Patents

Description

【０１２８】
【発明の効果】
本発明においては、微粒状着色剤を液状単量体混合物へ微細に均一に、かつ効率良く分散できるので、着色力に優れ、粒度分布のよりシャープな電子写真特性に優れる重合トナーを製造し得るものである。
【図面の簡単な説明】
【図１】メデイア粒子撹拌湿式分散機と冷却手段とホールディングタンクと循環ポンプを使用した分散工程の説明図である。
【図２】分散機の側面図である。
【図３】図１及び２中のＡ−Ａ’線に沿うケーシング内の断面図である。
【図４】本発明の他のロータを設置した図１及び２中のＡ−Ａ’線に沿うケーシング内の断面図である。
【図５】図２中のＢ−Ｂ’線に沿うケーシング内の断面図である。
【図６】回転ロータの斜視図である。
【図７】本発明の他の回転ロータの斜視図である。
【図８】セパレータの斜視図である。
【図９】本発明の重合トナーの製造方法に関するフローチャートの一例を示す。
【図１０】トナー粒子の断面を示す模式的説明図である。
【図１１】従来の分散工程の一例を示す説明図である。
【図１２】従来の分散工程の一例を示す説明図である。
【符号の説明】
１ メディア型分散機
２、２１、３１ ケーシング（容器部）
３、３’ ロータ
４ セパレータ
５ メディア粒子
６ 液体供給口
７ 液体排出口
８ ホールディングタンク
１０ 循環ポンプ
１１ 冷却手段
１２ 温度計
１８ ジャケット
１９ バルブ
２０ 三方バルブ
２１ 駆動軸
２２ 内室
２３ 外室[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a polymerized toner having excellent electrophotographic characteristics in which fine particulate colorants are finely and uniformly dispersed.
[0002]
[Prior art]
As described in U.S. Pat. No. 2,297,691, etc., a number of methods are known for electrophotography. Generally, a photoconductive material is used on a photoreceptor by various means. An electric latent image is formed, and then the latent image is developed using toner, and the toner image is transferred to a transfer material such as paper as necessary, and then fixed by heating, pressure, solvent vapor, or the like. Get. Various methods have been proposed in the past as a method for developing with toner or a method for fixing a toner image, and a method suitable for each image forming process is employed.
[0003]
Conventionally, toners used for these purposes are generally produced by melt-mixing a colorant composed of a dye / pigment in a thermoplastic resin and uniformly dispersing it, and then producing a toner having a desired particle size using a fine pulverizer and a classifier. I have done it.
[0004]
While this method of manufacture can produce fairly good toners, it has certain limitations, i.e., limited choice of toner materials. For example, the resin colorant dispersion must be sufficiently brittle and capable of being finely pulverized with economically possible production equipment. However, if the resin colorant dispersion is made brittle to meet these requirements, the particle size range of the particles formed when the powder is actually pulverized at high speed is likely to be widened. The problem of being included arises. Further, such a highly brittle material is likely to be further pulverized or powdered when used for development in a copying machine or the like. Also, with this method, it is difficult to completely disperse solid fine particles such as a colorant in the resin, and depending on the degree of dispersion, the increase in fog, the decrease in image density, and the color mixing / transparency may be difficult. Care must be taken to disperse as it will cause defects. Further, exposure of the colorant to the fracture surface may cause a change in development characteristics.
[0005]
On the other hand, in order to overcome the problems of the toner by the pulverization method, various polymerization method toners including the toner by the suspension polymerization method are disclosed in Japanese Patent Publication Nos. 36-10231, 43-10799, and 51-14895. And manufacturing methods thereof. For example, in the suspension polymerization method, a monomer composition is obtained by uniformly dissolving or dispersing a polymerizable monomer, a colorant, a polymerization initiator and, if necessary, a crosslinking agent, a charge control agent, and other additives. After that, the monomer composition is dispersed in a continuous phase containing a dispersion stabilizer, for example, an aqueous phase using a suitable stirrer, and at the same time, a polymerization reaction is performed to obtain toner particles having a desired particle size. obtain.
[0006]
Since this method does not include any pulverization step, the toner does not need to be brittle, and a soft material can be used as the resin, and there is no exposure of the colorant to the particle surface and uniform friction. There is an advantage that a toner having chargeability can be obtained. Further, since the particle size distribution of the obtained toner is relatively sharp, the classification step can be omitted, or the toner can be obtained in a high yield even if the classification is performed. Further, since a large amount of a low softening point substance can be encapsulated in the toner as a release agent, there is an advantage that the obtained toner has excellent offset resistance.
[0007]
Conventionally, in obtaining the above-mentioned fine colorant-containing monomer mixture, DYNOMILL commercialized by Shinmaru Enterprises Co., Ltd. described in JP-A-6-11900 and JP-A-6-6 It was common to use a Coball mill manufactured by Shinko Pantech Co., Ltd. described in Japanese Patent Publication No. -75429.
[0008]
FIG. 11 shows a sectional view of the dyno mill main body and a system diagram incorporating the main body. 121 is a main body casing, 122 is a raw material inlet, 123 is an outlet, 124 is an agitator shaft, 125 is a medium, 126 is a circulation pump, 127 is a holding tank, and 128 is an agitator disk. The liquid to be dispersed introduced into the holding tank 127 is supplied from the raw material introduction port 122 through the circulation pump 126, and is dispersed through the layer of the medium 125 that repeats the movement by the rotational force of the agitator disk 128. After the separation, the circulation is performed by repeating the circulation of being discharged from the discharge port 122 and returning to the holding tank 127 again.
[0009]
FIG. 12 shows a cross-sectional view of the coball mill main body and a system diagram incorporating the main body. Reference numeral 231 denotes a main body casing, 232 a raw material input port, 233 a discharge port, 234 a media separator, 235 a media layer, 236 a circulation pump, 237 a holding tank, and 238 a rotor. The liquid to be dispersed charged into the holding tank 237 is supplied from the raw material inlet 232 via the circulation pump 236, and is dispersed through the narrow media layer 235 that repeats the movement by the rotational force of the rotor 238. After separation from the media by the media separator 234, dispersion is performed by repeating the circulation of being discharged from the discharge port 233 and returning to the holding tank 237 again.
[0010]
However, in order to obtain the fine particle colorant-containing monomer mixture, if the conventional media type dispersers such as these are used, the flow direction of the monomer system and the centrifugal force direction do not coincide with each other. When the force is superior to the flow of the monomer system, the packing phenomenon in which the media is pressed outward by the centrifugal force of the rotor becomes remarkable, and the media filling layer in the apparatus becomes non-uniform. As a result, there is a problem that the flow of the monomer system tends to pass through the thinned portion of the media layer with less resistance, and the efficiency of dispersion is greatly reduced.
[0011]
If the centrifugal force of the rotor is inferior to that of the monomer system, the media will be pushed near the discharge port by the monomer system flow, and a media blocking phenomenon will occur near the discharge port, making the device stable. It was difficult to drive. Thus, it has been difficult to stably produce the fine colorant-containing monomer mixture by balancing the centrifugal force due to the rotation of the rotor and the flow of the monomer system.
[0012]
Further, when image evaluation is performed with a toner obtained by using a monomer mixture containing fine particulate colorant that is insufficiently dispersed in a toner property imparting agent such as a colorant and a charge control agent, the image density decreases. If granulation is carried out under the presence of a dispersion stabilizer using a fine colorant-containing monomer mixture that is insufficiently dispersed, there is a problem that the granulation property tends to be lowered. Therefore, in order to obtain a well-dispersed fine colorant-containing monomer mixture using a media-type disperser, it is necessary to improve the media efficiency. In order to improve the media efficiency, the media efficiency is remarkably improved by using a medium having a small diameter, specifically, a medium of 2 mm or less. However, when a medium of 2 mm or less is used, the filling rate is increased, so that the packing phenomenon and the blocking phenomenon are more likely to occur, the stable apparatus cannot be operated, and the particulate colorant-containing monomer is stably used. It was difficult to produce a mixture.
[0013]
Furthermore, in order to obtain a well-dispersed polymerizable monomer composition using a conventional media-type disperser while alleviating the packing phenomenon and blocking phenomenon, beads larger than 2 mm, preferably beads larger than 3 mm are used. However, it took a long time to obtain a predetermined dispersion.
[0014]
[Problems to be solved by the invention]
An object of the present invention is to provide a toner manufacturing method that solves the above-described problems.
[0015]
Specifically, it is an object of the present invention to provide a production method for efficiently and stably producing a toner having a more uniform colorant dispersion and a good image density in the production of a toner by a polymerization method.
[0016]
It is another object of the present invention to provide a production method for efficiently and stably producing a toner having a more uniform and sharp particle size distribution in which a colorant and the like are dispersed in the production of a toner by a polymerization method.
[0017]
[Means for Solving the Problems]
The present invention provides a polymerized toner having at least a dispersion step of dispersing a fine colorant in a liquid monomer mixture containing at least a liquid polymerizable monomer to obtain a fine colorant-dispersed liquid monomer mixture. Is the way
In the dispersion step, an inner chamber and an outer chamber are formed by a cylindrical separator having a slit inside a cylindrical container portion having a first wall surface having a liquid supply port and a second wall surface having a liquid discharge port. A rotating rotor is installed in the inner chamber so that it can be rotated by rotation of the drive shaft, and a plurality of spherical media particles are built in the inner chamber, the rotating rotor diameter A, the rotating rotor, and the cylinder Relationship with the distance B formed by the separator
3 <A / B <16
Is a media particle agitation type wet disperser And a plurality of uneven portions on the protrusion of the rotary rotor. A method for producing a polymerized toner.
[0018]
As a result of diligent research by the present inventors, a media-type disperser in which the direction in which the monomer flows and the centrifugal force generated by the rotation of the rotating rotor coincide with each other, the rotating rotor diameter A, the rotating rotor, and the cylindrical shape are used. The relationship with the distance B formed by the separator is
3 <A / B <16
As a result, it was found that when the colorant was dispersed in the monomer system, it could be stably dispersed in a short time, and the present invention was completed.
[0019]
Furthermore, the present invention provides a dispersion step of dispersing a fine colorant in a liquid monomer mixture containing at least a liquid polymerizable monomer to obtain a fine colorant-dispersed liquid monomer mixture, and the resulting fine particles A granulating step of dispersing a colorant-dispersed liquid monomer mixture in an aqueous dispersion to produce particles of a polymerizable monomer composition; and
A method for producing a polymerized toner having at least a polymerization step of polymerizing a polymerizable monomer in particles of a polymerizable monomer composition in an aqueous dispersion medium to produce toner particles,
(A) In the dispersing step, an inner chamber is formed by a cylindrical separator having a slit inside a cylindrical container portion having a first wall surface having a liquid supply port and a second wall surface having a liquid discharge port. An outer chamber, a rotating rotor is installed in the inner chamber so as to be rotatable by rotation of the drive shaft, a plurality of spherical media particles are built in the inner chamber, the rotating rotor diameter A and the rotating rotor And the distance B formed by the cylindrical separator is
3 <A / B <16
A media particle agitation type wet disperser is used as a dispersing means,
(B) (1) While rotating the rotary shaft by rotating the drive shaft, the fine colorant is introduced into the center of the inner chamber together with the liquid monomer mixture from the liquid supply port,
(2) While dispersing the fine colorant in the liquid monomer mixture by the centrifugal force and media particles generated by the rotation of the rotary rotor, the liquid monomer mixture and the fine colorant are dispersed by the centrifugal force generated by the rotation of the rotary rotor. Transport from the inner chamber to the outer chamber through the slit of the separator,
(3) A method for producing a polymerized toner, wherein a liquid monomer mixture in which a fine colorant is dispersed is discharged from the outer chamber through a liquid discharge port to obtain a fine colorant-containing monomer mixture. About.
[0020]
As a result of diligent research by the present inventors, a media-type disperser in which the direction in which the monomer flows and the centrifugal force generated by the rotation of the rotating rotor coincide with each other, the rotating rotor diameter A, the rotating rotor, and the cylindrical shape are used. The relationship with the distance B formed by the separator is
3 <A / B <16
As a result, it was found that when the colorant was dispersed in the monomer system, it could be stably dispersed in a short time, and the present invention was completed.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
As an example of the media particle agitation type wet disperser used in the present invention, the dispersers shown in FIGS. 1 to 5 are preferably used. FIG. 1 shows an example of a dispersion system incorporating a media particle agitation type wet disperser used in the present invention, FIG. 2 shows a side view of the disperser body used in the present invention, and FIGS. 3 and 4 show A in FIG. -A 'sectional view, FIG. 5 is a BB' sectional view in FIG. Further, perspective views of the rotary rotors 3 and 3 ′ are shown in FIGS. 6 and 7, and a perspective view of the separator 4 is shown in FIG.
[0022]
A disperser 1 shown in FIG. 1 to FIG. 5 includes a rotary rotor 3 and 3 ′ for stirring media particles in a casing 2, and a slit 4a for separating the media particles 5 and the liquid monomer mixture on the outer periphery thereof. There is a separator 4 having. When the rotating rotors 3 and 3 ′ are rotated, a centrifugal force is generated, and the centrifugal force causes the media particles 5 to form a layer on the outer separator 4 and to rotate by the rotating force of the rotating rotors 3 and 3 ′. Therefore, a strong shearing force is generated and the fine colorant is dispersed.
[0023]
In this media particle agitation type wet disperser, there is a relationship between the rotary rotor diameter A shown in FIG. 5 and the distance B formed by the rotary rotor and the cylindrical separator.
3 <A / B <16
In order to stably disperse the finely divided colorant in the polymerizable monomer in a short time,
5 <A / B <11
It is preferable that
[0024]
When A / B ≧ 16, the centrifugal force generated by the rotating rotor becomes excessive, and it becomes difficult to stably disperse the fine colorant in the polymerizable monomer in a short time. In particular, when the centrifugal force generated by the rotating rotor is excessive, the friction between the media particles in the disperser is dominant, which is not preferable. That is, when the wear of the media particles increases, the rotor rotational power resulting from the friction becomes excessively necessary, and there is a tendency to consume a large amount of power. Further, due to the increase of the friction, contamination to the fine colorant-containing monomer mixture is generated and the product quality is impaired. Furthermore, since the wear of the media particles is severe, it is not preferable because the exchange period of the media particles is shortened and the production cost is increased.
[0025]
In order to prevent friction between the media, the rotor may be operated at a reduced rotational speed. However, if the rotor is operated at a reduced rotational speed, the dispersion capacity per unit time is lowered, and the dispersion time for obtaining a desired dispersion is undesirably increased.
[0026]
In addition, when A / B ≦ 3, in order to disperse the fine colorant in the polymerizable monomer, the rotating rotor is operated at a high speed, specifically, 17 m / s to 20 m / s. However, the media in the apparatus cannot be moved efficiently by generating an appropriate centrifugal force. Further, in order to operate the rotating rotor at a high speed, it is not preferable to operate at more than 20 m / s because the durability of the rotor bearing portion and the shaft seal portion is remarkably shortened. As a result, it was impossible to efficiently and stably disperse the fine colorant in the polymerizable monomer.
[0027]
The liquid monomer mixture charged into the holding tank 8 in the system including the media particle agitation type wet disperser described above is supplied from the raw material charging port 6 through the circulation pump 10 and is subjected to centrifugal force by the rotation of the rotary rotor 3. It passes through the media layer formed on the outer periphery of the rotor and is surely finely dispersed. Thereafter, the liquid monomer mixture is separated from the media particles 5 by the separator 4, discharged from the discharge port 7, and returns to the holding tank 8 via the cooling means 11. The monomer mixture in the holding tank 8 is uniformly and efficiently dispersed into the polymerizable monomer while repeating the cycle circulation between the disperser 1 and the holding tank 8. It is.
[0028]
At this time, a polymerizable monomer, a colorant, a charge control agent, and the like may be put into the holding tank 8 as they are, but they may be put into the holding tank 8 after being mixed in advance.
[0029]
The rotating rotor diameter A is
50mm <A ≦ 1000mm
Preferably, the diameter of the rotating rotor A is
100mm <A ≦ 600mm
It is preferable that
[0030]
If the rotor diameter A is A ≧ 1000 mm, the centrifugal force generated by the rotation of the rotor increases in proportion to the rotor diameter, which is not preferable because excessive centrifugal force is generated and the above-mentioned media friction is increased.
[0031]
Further, when the rotor diameter A is 50 mm> A, a small-capacity casing is required to obtain an optimum shearing force for processing, and as a result, the processing amount of the media particle agitation type wet disperser itself is reduced. Since this can only be produced in a small amount, it is not preferable because it causes an increase in production cost when a large amount of toner is manufactured.
[0032]
Further, since heat generation occurs during dispersion and the monomer composition is likely to be affected, a heat exchanger may be installed as a cooling means in the circulation system line to perform operation while performing heat exchange. At that time, the liquid temperature is preferably adjusted to 10 to 40 ° C. (more preferably 15 to 35 ° C.).
[0033]
Further, in the disperser as shown in FIGS. 1 to 5, it is preferable to use the diameter of the media in the range of 0.1 mm to 1 mm from the viewpoint of dispersibility of the colorant and the like.
[0034]
Further, in terms of dispersibility of colorants, media wear, and stable operation of the apparatus itself, the total volume C of media particles in the disperser, and between the rotors 3 and 3 ′ and the separator 4 The relationship of space volume D is
0.7 <C / D <1.3
It is preferable that it is the range of these. The total volume C of the media particles is E, where the bulk density of the media particles is E, and F is the charged mass of the media particles into the device.
C = F / E
The media particles obtained by accurately weighing the charged mass F are put into a measuring cylinder and the total volume C of the media particles is accurately measured.
[0035]
The space volume D between the rotors 3 and 3 ′ and the separator 4 is the total volume of the portion shown in FIGS.
[0036]
Further, as shown in FIGS. 4 and 7, it is preferable that the protrusions of the rotor have a plurality of irregularities. As described above, when the friction between the media particles in the disperser becomes dominant, the dispersion time of the fine colorant to the polymerizable monomer is extended, the dispersion efficiency is lowered, the media is contaminated by the wear and the durability of the media. Is significantly reduced. In order to prevent these, a rotor shape that can move freely so that the media in the apparatus does not cause packing is preferable, but the protrusion shape shown in FIGS. 4 and 7 can prevent friction between media particles. preferable.
[0037]
Moreover, it is preferable to use the peripheral speed of the tip of the rotating rotor in the range of 5 m / s to 20 m / s in terms of dispersibility of colorants and the like, wear of media particles, and stable operation of the apparatus itself, More preferably, it is used in the range of 7 m / s to 17 m / s.
[0038]
In order to disperse the inside of the disperser while applying pressure, it is preferable to provide a valve 19 on the downstream side of the discharge port 7 in order to improve the dispersion efficiency of the colorant and prevent a short pass. When the circulation operation is performed, the dispersion processing time is 10 to 300 minutes, more preferably 20 to 180 minutes.
[0039]
Examples of the material of the media particles used in the disperser include glass, steel, chromium alloy, alumina, zirconia, zircon, and titania. Among the above-mentioned media materials, zirconia and titania are more preferable from the viewpoint of wear resistance.
[0041]
In the present invention, as a method for producing polymerized toner particles, the suspension polymerization method described in JP-B-36-10231, JP-A-59-53856, and JP-A-59-61842 is used. Thus, it is possible to manufacture toner using a method for directly generating toner.
[0042]
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. An example of the manufacturing flow is shown in FIG.
[0043]
In the present invention, it is necessary to encapsulate the low softening point substance in the outer shell resin inevitably because of the necessity of including a large amount of low softening point substance in the toner from the viewpoint of fixing properties. As a specific method for embedding the low softening point substance, the polarity of the material in the aqueous medium is set to be smaller for the low softening point substance than the main monomer, and a small amount of a resin or monomer having a large polarity. Is added to obtain a toner having a so-called core-shell structure in which a low softening point substance is coated with an outer shell resin. Toner particle size distribution control and particle size control can be done by changing the type and amount of a poorly water-soluble inorganic salt or protective colloid acting and the amount of mechanical equipment, such as rotor peripheral speed, number of passes, and stirring. A predetermined toner of the present invention can be obtained by controlling stirring conditions such as blade shape, container shape, solid content concentration in an aqueous solution, and the like.
[0044]
In the present invention, as a specific method for measuring the tomographic plane of the toner, a cured product obtained by sufficiently dispersing the toner in an ordinary temperature curable epoxy resin and then curing it in an atmosphere at a temperature of 40 ° C. After staining with ruthenium oxide and, if necessary, osmium tetroxide, a flaky sample was cut out using a microtome equipped with diamond teeth, and the tomographic morphology of the toner was measured using a transmission electron microscope (TEM). In the present invention, it is preferable to use a ruthenium tetroxide dyeing method in order to provide contrast between materials by utilizing a slight difference in crystallinity between the low softening point substance used and the resin constituting the outer shell. A typical example is shown in FIG. In the toner particles obtained in the examples, it was clearly observed that the low softening point substance was encapsulated in the outer shell resin.
[0045]
Examples of the polymerizable monomer that can be used in the polymerized toner include styrene monomers such as styrene, o (m-, p-)-methylstyrene, m (p-)-ethylstyrene; methyl (meth) acrylate. , Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, (Meth) acrylic acid ester monomers such as (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid dimethylaminoethyl, (meth) acrylic acid diethylaminoethyl; butadiene, isoprene, cyclohexene, (meth) acrylonitrile, acrylic Vinyl monomers such as acid amides are preferably used. These may be used alone or generally as appropriate so that the theoretical glass temperature (Tg) described in the publication Polymer Handbook 2nd edition III-P139-192 (John Wiley & Sons) is 40-75 ° C. Used by mixing. When the theoretical glass transition temperature is less than 40 ° C., there are problems in terms of storage stability of the toner and durability of the developer. On the other hand, when it exceeds 75 ° C., the fixing point is increased. In some cases, the color toners are not sufficiently mixed, resulting in poor color reproducibility. Further, the transparency of the OHP image is remarkably lowered, which is not preferable from the viewpoint of high image quality.
[0046]
The low softening point substance used in the present invention is preferably a compound having a main maximum peak value measured in accordance with ASTM D3418-8 of 40 to 90 ° C. When the maximum peak is less than 40 ° C., the self-aggregation force of the low softening point substance becomes weak, and as a result, the high temperature offset resistance becomes weak, which is not preferable for a full color image forming toner. On the other hand, if the maximum peak exceeds 90 ° C., the fixing temperature becomes high, and it becomes difficult to appropriately smooth the surface of the fixed image, which is not preferable from the viewpoint of color mixing. Furthermore, when toner is obtained by direct polymerization, granulation and polymerization are carried out in an aqueous system, so if the temperature at the maximum peak value is high, a low softening point substance mainly precipitates during granulation and inhibits the suspension system. Therefore, it is not preferable.
[0047]
For the measurement of the temperature of the maximum peak value of the present invention, for example, DSC-7 manufactured by Perkin Elmer is used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. For the sample, an aluminum pan was used and an empty pan was set for control. Measure with.
[0048]
Specifically, paraffin wax, polyolefin wax, Fischer tropish wax, amide wax, higher fatty acid, ester wax and derivatives thereof, or graft / block compounds thereof can be used as the low melting point substance. The low softening point substance is preferably added to the toner in an amount of 5 to 30% by mass. If the addition is less than 5% by mass, sufficient toner fixability cannot be obtained. If it exceeds 30% by mass, toner particles tend to coalesce during the granulation step, and a toner having a wide particle size distribution is likely to be produced. It was unsuitable for the present invention.
[0049]
In the present invention, it is particularly preferable to add a polar resin in addition to the outer shell resin in order to encapsulate the low softening point substance in the outer shell resin. As the polar resin used in the present invention, a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a saturated polyester resin, and an epoxy resin are preferably used. The polar resin is particularly preferably one containing no unsaturated group capable of reacting with the outer shell resin or the monomer. In the case of containing a polar resin having an unsaturated group, a cross-linking reaction occurs with the monomer forming the outer shell resin layer, and as a full color toner, it becomes extremely high molecular weight, which is disadvantageous for the color mixture of four color toners, which is not preferable .
[0050]
As the colorant used in the present invention, carbon black and a magnetic material are used as a black colorant, and the following yellow / magenta / cyan colorants are used for color.
[0051]
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.
[0052]
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.
[0053]
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.
[0054]
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.
[0055]
When a magnetic material is used as the black colorant, it is preferably used by adding 40 to 150 parts by mass with respect to 100 parts by mass of the resin, and the surface of the magnetic material is hydrophobized, unlike other colorants. .
[0056]
As the charge control agent used in the present invention, known ones can be used. However, a charge control agent that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable. Further, when the direct polymerization method is used in the present invention, a charge control agent having no polymerization inhibition and no solubilized product in an aqueous system is particularly preferable. Specific examples of the negative compounds include salicylic acid, naphthoic acid, dicarboxylic acid metal compounds, sulfonic acid, polymer compounds having carboxylic acid in the side chain, boron compounds, urea compounds, silicon compounds, calixarene, and the like. As a positive system, a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, an imidazole compound, and the like are preferably used. The charge control agent is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the resin. However, in the present invention, it is not essential to add a charge control agent. When a two-component development method is used, frictional charging with a carrier is used, and even when a non-magnetic one-component blade coating development method is used, the blade It is not always necessary to include a charge control agent in the toner by actively utilizing frictional charging with the member or the sleeve member.
[0057]
Examples of the polymerization initiator that can be used in the polymerized toner according to the present invention include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1 ′. -Azo or diazo polymerization initiators such as azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide; Peroxide polymerization initiators such as methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butylperoxyl diethylhexanate are used. The addition amount of the polymerization initiator varies depending on the target degree of polymerization, but generally 0.5 to 20% by mass is added to the monomer. The kind of the polymerization initiator varies slightly depending on the polymerization method, but can be used alone or in combination with reference to the 10-hour half-life temperature.
[0058]
In order to control the degree of polymerization, a known crosslinking agent, chain transfer agent, polymerization inhibitor and the like can be further added and used.
[0059]
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.
[0060]
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.
[0061]
Moreover, you may use 0.001-0.1 mass part surfactant for fine dispersion | distribution of these stabilizers. This is to promote the intended action of the dispersion stabilizer, and specific examples include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, lauric acid. Examples thereof include sodium, potassium stearate, calcium oleate and the like.
[0062]
【Example】
The toner production method of the present invention will be described more specifically.
[0063]
At least a colorant and a charge control agent are added to the polymerizable monomer, and the relationship between the diameter A of the rotary rotor and the distance B formed by the rotary rotor and the cylindrical separator is as described above.
3 <A / B <16
After the dispersion with a media-type disperser in which the direction of flow of the monomer system and the direction of the centrifugal force coincide with each other, a release agent composed of a low softening point substance and other additives are added, and a dispersion stabilizer is contained. Disperse uniformly in the aqueous phase with a normal stirrer, clear mixer, homogenizer, homomixer, ultrasonic disperser or the like. Preferably, granulation is performed by adjusting the stirring speed and time so that the monomer droplets have a desired toner size. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersion stabilizer. The polymerization initiator may be added at any point after being dispersed by the media type disperser, specifically, immediately before being dispersed in the aqueous phase containing the dispersion stabilizer, or while being dispersed in the aqueous phase, and Any of them after completion of dispersion in the aqueous phase may be used. 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 washed, filtered and dried to produce toner particles.
[0064]
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.
[0065]
The particle size distribution of the toner can be measured by various methods. In the present invention, the particle size distribution was performed using a Coulter counter.
[0066]
A Coulter Counter Multisizer (manufactured by Coulter Inc.) was used as a measuring device, and an electrolyte (1) was connected by connecting an interface (manufactured by Nikka) and a PC9801-1 personal computer (manufactured by NEC) that output number average distribution and volume average distribution. Prepare 1% NaCl aqueous solution using grade sodium chloride.
[0067]
As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolyte solution in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the particle size distribution of particles of 2 to 40 μm on the basis of the number using the 100 μm aperture as the aperture by the Coulter counter multisizer. And then determine various values.
[0068]
In the present invention, since the fine colorant is finely and uniformly dispersed in the monomer mixture, the weight average diameter is 4 to 10 μm (more preferably 4 to 9 μm), and the coefficient of variation in the number distribution A small particle toner having a sharp particle size distribution of 35% or less (more preferably 30% or less) can be produced efficiently and with a high yield.
[0069]
The coefficient of variation in the number distribution is calculated from the following equation.
[0070]
Coefficient of variation (%) = [S / D1] × 100
[In the formula, S represents a standard deviation in the number distribution of toner particles, and D1 represents a number average diameter (μm) of toner particles. ]
[0071]
( reference Example 1)
The dispersion process was performed using the dispersion system shown in FIG. The rotor shape at this time was as shown in FIG. In the dispersion system, 170 parts by mass of a styrene monomer, 10 parts by mass of a fine magenta colorant (CI Pigment Red 122, number average diameter 0.05 μm or less) and a negative charge control agent (dialkyl) are contained in a holding tank 8. 3 parts by mass of a metal compound of salicylic acid) was introduced, and the stirring blade was rotated by the stirring motor 13 to prepare a styrene monomer mixture containing a fine magenta colorant. At that time, the cooling water was introduced into the jacket 18 from the inlet 16 and discharged from the outlet 17 to adjust the liquid temperature of the styrene monomer mixture to about 20 ° C. Spherical media particles 24 (zirconia spherical particles having a diameter of 0.3 mm) are converted to 1.6 × 10 6 by the circulation pump 10 using the prepared styrene monomer mixture. ^-3 m ^Three (About 1.4 × 10 ⁸ The particles were introduced into the filled media particle agitation type wet disperser 1.
[0072]
At this time, the relationship between the rotary rotor diameter A and the distance B formed by the rotary rotor and the cylindrical separator was A / B = 8.2. The ratio (C / D) of the volume C of media particles to the space volume D of the disperser 1 was 1.2.
[0073]
As shown in FIGS. 1, 2, 3, and 5, the media particle agitation type wet disperser 1 has a rotating rotor 3 in a casing 2 (rotating rotor diameter A = 196 mm) and is driven by a motor included in the disperser. The styrene monomer mixture was introduced from the first wall surface having the liquid supply port 6 at the center while rotating the rotary rotor 3 at a rotational speed of 16.7 rps (circumferential speed 10.3 m / s) by the drive roller 21. The amount of styrene monomer mixture introduced into the casing 2 is 0.9 m. ^Three It adjusted with the circulation pump 10 so that it might become / h. At that time, the internal pressure in the casing was 196.1 kPa. The styrene monomer mixture introduced from the liquid supply port 6 is conveyed from the central portion of the inner chamber 22 toward the separator 4 by the centrifugal force generated by the rotation of the rotating roller 3 from the central portion of the inner chamber. , The shear force of the media particles 24 and the passage of the styrene monomer mixture containing the particulate colorant between the layers of the fluidized media particles 24 on the separator 4. Was refined and dispersed in a styrene monomer mixture. Then, the styrene monomer mixture having the fine particulate colorant dispersed is conveyed to the outer chamber 23 through the slit 4a, and the styrene monomer is supplied from the liquid discharge port 7 provided on the side wall (second wall surface). The body mixture was discharged and introduced into the holding tank 8 via the valve 19 and the thermometer 12 and the cooling means 11.
[0074]
The styrene monomer mixture discharged from the liquid discharge port 7 has a temperature of 30 ° C. as measured by the thermometer 12, so that cooling water is introduced from the introduction port 14 and discharged by the cooling means 11 discharged from the discharge port 15. The monomer mixture was adjusted to a temperature of 20 ° C. The fine colorant was dispersed in the styrene monomer mixture for 60 minutes in the dispersion step. The styrene monomer mixture passed through the disperser at about 36 times / hour. The styrene monomer mixture in which the fine colorant was finely and uniformly dispersed was conveyed to the preparation process by operating the three-way valve 20.
[0075]
Further, the dispersion state of the fine colorant in the dispersion was measured by measuring the gloss (glossiness) of the dispersion. The gloss of the dispersion was measured after the dispersion was uniformly applied to art paper and sufficiently dried. That is, when the fine colorant is well dispersed, smoothness and gloss are generated on the coated surface and the gloss value is increased. On the contrary, when the dispersion of the fine colorant is poor, the unevenness remains on the coating surface, and the gloss value becomes low because it becomes dull. For measurement of gloss (glossiness), a VG-10 glossiness meter manufactured by Nippon Denshoku Co., Ltd. was used. For measurement, first set it to 6V with a constant voltage device, then adjust the light projection angle and light reception angle to 60 °, use the zero point adjustment and the standard plate, and after the standard setting, three blank sheets on the sample stage The measurement was performed by placing the coated sample on top of it, and the numerical value shown on the marking portion was read in units of%. The results are shown in Table 1. As an evaluation standard, when the gloss value is 40% or more, good dispersibility is shown. When the gloss value is 35% or more and less than 40%, there is a problem in the image, but there is no problem in practical use. Dispersibility which is quite severe and is undesirable on the product.
[0076]
In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0077]
In the preparation step, a styrene monomer mixture having 170 parts by mass of a styrene monomer, 30 parts by mass of a fine colorant and 3 parts by mass of a negative charge control agent is added to 30 parts by mass of an n-butyl acrylate monomer. Part, polar resin (saturated polyester resin = polyester resin obtained by condensation polymerization of terephthalic acid and propylene oxide-modified bisphenol A, acid value 13 mgKOH / g, main peak molecular weight 7000) and 20 parts by mass of ester wax are added, and temperature is added. The mixture was mixed at 60 ° C., and further 10 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator to prepare a polymerizable monomer composition.
[0078]
On the other hand, in a four-necked vessel equipped with a high-speed stirring device TK-homomixer, 710 parts by mass of ion-exchanged water was added with 0.1 mol / liter-Na. _Three PO _Four 450 parts by mass of the aqueous solution was added, and the mixture was heated to 60 ° C. while rotating the TK-homomixer at 200 rps. Here 1.0 mol / liter CaCl ₂ Adds 68 parts by weight of aqueous solution to form a slightly water-soluble dispersant Ca _Three (PO _Four ) ₂ A dispersion medium system containing was prepared.
[0079]
268 parts by mass of the polymerizable monomer composition heated to 60 ° C. was put into a medium system heated to 60 ° C., and granulated for 13 minutes while rotating the TK-homomixer at 200 rpm. Thereafter, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, and the mixture was reacted at 60 ° C. for 5 hours.
[0080]
After completion of the polymerization, a part of the slurry was sampled, further washed and dried, and the physical properties of the obtained magenta toner were measured. The weight average diameter of the magenta toner measured using a Coulter counter was 6.5 μm, and the number variation coefficient was 22%.
[0081]
About the granulation property in a granulation process, it investigated by the number variation coefficient measured with the above-mentioned Coulter counter. That is, if the number variation coefficient is less than 35%, good granulation properties are exhibited. If it is 35% or more and less than 40%, there is a slight problem with the image, but there is no problem in practical use. Is quite intense and exhibits undesirable granulation properties on the product. The results are shown in Table 1.
[0082]
As a result of TEM observation, a structure in which an ester wax, which is a low softening point substance, is covered with an outer shell resin as shown in FIG.
[0083]
The specific surface area by the BET method is 200 m with respect to 100 parts by mass of the obtained toner. ² A magenta toner was prepared by externally adding 0.7 parts by mass of hydrophobic silica having a / g content. 93 parts by mass of an acrylic coated magnetic ferrite carrier was mixed with 7 parts by mass of magenta toner to obtain a two-component developer.
[0084]
Using this developer and magenta toner, the development contrast was set to 300 V with a commercially available plain paper color copier (Color Laser Copier 500, manufactured by Canon Inc.), and the image was printed at 23 ° C./65%. . The obtained image was Macbeth RD918 type, and reflection density measurement was performed using an SPI filter (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. In this case, the image density is extremely unfavorable for the product because the influence on the image is so severe.
[0085]
( reference Example 2)
0.8mm diameter media particles (material zirconia) 1.6 × 10 ^-3 m ^Three (About 7.2 × 10 ⁶ The same operation as in Example 1 was carried out except that the product was used. The obtained toner had a weight average diameter of 6.7 μm and a number variation coefficient of 29%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0086]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0087]
( reference Example 3)
Except that the rotor speed was 20.8 rps (circumferential speed 12.8 m / s), reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 6.5 μm and a number variation coefficient of 20%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0088]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0089]
( reference Example 4)
0.3mm diameter media particles (material zirconia) 1.3x10 ^-3 m ^Three (About 1.1 × 10 ⁸ ) And (C / D = 1.0) was used, reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 6.7 μm and a number variation coefficient of 24%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0090]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0091]
( reference Example 5)
reference The dispersion process was performed using the mixture used in Example 1 and the dispersion system shown in FIG. Media particles (material zirconia) with a diameter of 0.3 mm in a media particle agitation type wet disperser (rotating rotor diameter 400 mm, A / B = 8.0) shown in FIGS. ^-2 m ^Three (About 8.7 × 10 ⁸ (C / D = 1.0) and dispersed at a rotational speed of 8.3 rps (circumferential speed 10.5 m / s) for 60 minutes to obtain a liquid monomer mixture. The rotor shape at this time was as shown in FIG. At this time, the flow rate of the mixture is set to 3.6 m using a circulation pump. ^Three It adjusted so that it might become the circulation frequency 32 times / h by / h, and the mill internal pressure was 245.2kPa. After that reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 6.7 μm and a number variation coefficient of 23%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0092]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0093]
( reference Example 6)
reference The dispersion process was performed using the mixture used in Example 1 and the dispersion system shown in FIG. Media particles (material zirconia) with a diameter of 0.3 mm were added to a media particle agitation type wet disperser (rotating rotor diameter 390 mm, A / B = 7.2) shown in FIGS. ^-2 m ^Three (About 9.3 × 10 ⁸ (C / D = 1.0) and dispersed at a rotational speed of 8.3 rps (circumferential speed 10.2 m / s) for 60 minutes to obtain a liquid monomer mixture. The rotor shape at this time was as shown in FIG. At this time, the flow rate of the mixture is set to 3.6 m using a circulation pump. ^Three It adjusted so that it might become the circulation frequency 32 times / h by / h, and the mill internal pressure was 245.2kPa. After that reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 6.8 μm and a number variation coefficient of 23%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0094]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0095]
( reference Example 7)
reference The dispersion process was performed using the mixture used in Example 1 and the dispersion system shown in FIG. Media particles (material zirconia) having a diameter of 0.3 mm were added to a media particle agitation type wet disperser (rotor rotor diameter: 330 mm, A / B = 4.1) shown in FIGS. ^-2 m ^Three (About 1.3 × 10 ⁹ (C / D = 1.0) and dispersed at a rotational speed of 8.3 rps (peripheral speed 8.6 m / s) for 60 minutes to obtain a liquid monomer mixture. The rotor shape at this time was as shown in FIG. At this time, the flow rate of the mixture is set to 3.6 m using a circulation pump. ^Three It adjusted so that it might become the circulation frequency 32 times / h by / h, and the mill internal pressure was 245.2kPa. After that reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 6.8 μm and a number variation coefficient of 27%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0096]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0097]
( reference Example 8)
Except for the rotor speed of 5 rps (circumferential speed 3.1 m / s), reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 6.5 μm and a number variation coefficient of 37%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0098]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0099]
( reference Example 9)
reference The dispersion process was performed using the mixture used in Example 1 and the dispersion system shown in FIG. Media particles (material zirconia) with a diameter of 0.3 mm in a media particle agitation type wet disperser (rotating rotor diameter 196 mm, A / B = 8.2) shown in FIGS. ^-Four m ^Three (About 6.8 × 10 ⁷ (C / D = 0.6) and dispersed at a rotational speed of 16.7 rps (circumferential speed 10.3 m / s) for 60 minutes to obtain a liquid monomer mixture. The rotor shape at this time was as shown in FIG. At this time, the flow rate of the mixture is 0.9 m with a circulation pump. ^Three It adjusted so that it might become the circulation frequency 36 times / hour by / h, and the mill internal pressure was 196.1 kPa. After that reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 6.5 μm and a number variation coefficient of 30%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0100]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0101]
(Example 1 )
Except for changing the rotor shape to that shown in FIGS. 4 and 7, reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 6.5 μm and a number variation coefficient of 19%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0102]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0103]
(Reference example 10 )
reference The dispersion process was performed using the mixture used in Example 1 and the dispersion system shown in FIG. Media particles with a diameter of 0.3 mm (material zirconia) 9.1 × 10 in a media particle agitation type wet disperser (rotating rotor diameter 220 mm, A / B = 16.9) shown in FIGS. ^-Four m ^Three (About 7.8 × 10 ⁷ (C / D = 1.2) and dispersed at a rotational speed of 16.7 rps (circumferential speed 11.5 m / s) for 60 minutes to obtain a liquid monomer mixture. At this time, the flow rate of the mixture is 0.9 m with a circulation pump. ^Three It adjusted so that it might become the circulation frequency 36 times / hour by / h, and the mill internal pressure was 196.1 kPa. After that reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 6.7 μm and a number variation coefficient of 27%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0104]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0105]
(Reference example 11 )
Reference example except that the rotor speed was 20.8 rps (circumferential speed 14.4 m / s) 10 The same operation was performed. The obtained toner had a weight average diameter of 6.6 μm and a number variation coefficient of 28%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0106]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0107]
(Reference example 12 )
Reference example except that the rotor speed was 5 rps (circumferential speed 3.5 m / s) 10 The same operation was performed. The obtained toner had a weight average diameter of 9.8 μm and a number variation coefficient of 38%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0108]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0109]
(Reference example 13 )
reference The dispersion process was performed using the mixture used in Example 1 and the dispersion system shown in FIG. Media particles (material zirconia) with a diameter of 0.3 mm in a media particle agitation type wet disperser (rotating rotor diameter 220 mm, A / B = 16.9) shown in FIGS. ^-Four m ^Three (About 3.9 × 10 ⁷ (C / D = 0.6) and dispersed at a rotational speed of 16.7 rps (circumferential speed 11.5 m / s) for 60 minutes to obtain a liquid monomer mixture. At this time, the flow rate of the mixture is 0.9 m with a circulation pump. ^Three It adjusted so that it might become the circulation frequency 36 times / hour by / h, and the mill internal pressure was 196.1 kPa. After that reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 8.0 μm and a number variation coefficient of 35%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0110]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0111]
(Reference example 14 )
reference The dispersion process was performed using the mixture used in Example 1 and the dispersion system shown in FIG. Media particles (material zirconia) having a diameter of 0.3 mm were added to a media particle agitation type wet disperser (rotating rotor diameter 220 mm, A / B = 16.9) shown in FIGS. ^-3 m ^Three (About 9.8 × 10 ⁷ (C / D = 1.5) and started operation at a rotational speed of 16.7 rps (circumferential speed 11.5 m / s). When the rotational speed reaches the specified rotational speed, Since the temperature of the circulating mixture rose to 70 ° C., it was cooled to 35 ° C. by a cooling means. This abnormal temperature rise is thought to be caused by frictional heat between the media particles as a result of the media particles in the apparatus becoming abnormally dense, and it seems that the rotor and media particles were in a kind of co-rotation state. Operation is a reference example 10 The operation was continued for 60 minutes in the same manner as above, but steady operation was very difficult due to the temperature rise. After that reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 9.8 μm and a number variation coefficient of 40%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0112]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0113]
(Reference example 15 )
reference The dispersion process was performed using the mixture used in Example 1 and the dispersion system shown in FIG. Media particles with a diameter of 0.3 mm (material zirconia) 5.8 × 10 in a media particle agitation type wet disperser (rotating rotor diameter 450 mm, A / B = 16.6) shown in FIGS. ^-3 m ^Three (About 4.9 × 10 ⁸ (C / D = 1.0) and dispersed at a rotational speed of 8.3 rps (circumferential speed 11.8 m / s) for 60 minutes to obtain a liquid monomer mixture. At this time, the flow rate of the mixture is set to 3.6 m using a circulation pump. ^Three It adjusted so that it might become the circulation frequency 32 times / h by / h, and the mill internal pressure was 245.2kPa. After that reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 6.9 μm and a number variation coefficient of 28%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0114]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0115]
(Reference example 16 )
reference The dispersion process was performed using the mixture used in Example 1 and the dispersion system shown in FIG. Media particle agitating wet disperser (rotating rotor diameter 210 mm, A / B = 1.5) shown in FIGS. ^-2 m ^Three (About 8.8 × 10 ⁷ (C / D = 1.0) and dispersed at a rotational speed of 8.3 rps (circumferential speed 5.5 m / s) for 60 minutes to obtain a liquid monomer mixture. The rotor shape at this time was as shown in FIG. At this time, the flow rate of the mixture is set to 3.6 m using a circulation pump. ^Three It adjusted so that it might become the circulation frequency 32 times / h by / h, and the mill internal pressure was 245.2kPa. After that reference The same operation as in Example 1 was performed. The obtained toner had a weight average diameter of 9.7 μm and a number variation coefficient of 38%. Using this developer and externally added toner, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0116]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1. In addition, after the dispersion process was completed, the dispersion was recovered from the disperser, but the recoverability of the dispersion was also good. Further, a visual inspection was performed on the media after the dispersion was completed, but abnormal media was found. There wasn't.
[0117]
[Comparative Example 1]
reference An aqueous medium was obtained in the same manner as in Example 1.
[0118]
reference A polymerizable monomer mixture having the same composition as in Example 1 was placed in a media-type disperser as shown in FIG. 10 with media particles having a diameter of 1 mm (material zirconia) 1.23 × 10. ^-2 m ^Three 1m through a pump ^Three At a supply rate of 14 times / h. Dispersed in a circulating manner at a rotor peripheral speed of 13 m / s for 60 minutes to prepare a dispersion. After the dispersion process, the operation is reference In the same manner as in Example 1, a polymerized toner was obtained.
[0119]
The obtained toner had a weight average diameter of 12.1 μm and a number variation coefficient of 48%. Using this toner, developer reference Prepared as in Example 1, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0120]
Also, evaluate the dispersibility of the dispersion and the granulation properties in the granulation process. reference Evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
[0121]
[Comparative Example 2]
reference An aqueous medium was obtained in the same manner as in Example 1.
[0122]
reference A polymerizable monomer mixture having the same composition as in Example 1 was placed in a media-type disperser as shown in FIG. 11 with media particles (material zirconia) having a diameter of 0.8 mm of 7.5 × 10. ^-Four m ^Three And 2.25x10 via pump ^-3 m ^Three At a supply rate of 3.6 times / hour. Dispersed in a circulating manner at a rotor peripheral speed of 13 m / s for 60 minutes to prepare a dispersion. After the dispersion process, the operation is reference In the same manner as in Example 1, a polymerized toner was obtained.
[0123]
The obtained toner had a weight average diameter of 11.3 μm and a number variation coefficient of 43%. Using this toner, developer reference Prepared as in Example 1, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0124]
[Comparative Example 3]
reference An aqueous medium was obtained in the same manner as in Example 1.
[0125]
reference A polymerizable monomer mixture having the same composition as in Example 1 is heated to 60 ° C. and circulated at a supply rate of 180 kg / h through a pump to a medialess disperser Ebara Milder (manufactured by Ebara Corporation). It was supplied at a frequency of about 60 times / h. A dispersion was prepared by dispersing the rotor at a rotational speed of 5000 rpm (circumferential speed: 15 m / s) for 60 minutes in a circulating manner. After the dispersion process, the operation is reference In the same manner as in Example 1, a polymerized toner was obtained.
[0126]
The obtained toner had a weight average diameter of 16.3 μm and a number variation coefficient of 52%. Using this toner, developer reference Prepared as in Example 1, reference Image density measurement was performed under the same conditions as in Example 1. The results are shown in Table 1.
[0127]
[Table 1]

[0128]
【The invention's effect】
In the present invention, a finely divided colorant can be dispersed finely, uniformly and efficiently in a liquid monomer mixture, so that it is possible to produce a polymerized toner having excellent coloring power and excellent electrophotographic characteristics with a sharper particle size distribution. Is.
[Brief description of the drawings]
FIG. 1 is an explanatory view of a dispersion process using a media particle agitating wet disperser, a cooling means, a holding tank, and a circulation pump.
FIG. 2 is a side view of a disperser.
FIG. 3 is a cross-sectional view inside the casing along the line AA ′ in FIGS. 1 and 2;
4 is a cross-sectional view inside the casing along the line AA ′ in FIGS. 1 and 2 in which another rotor of the present invention is installed. FIG.
FIG. 5 is a cross-sectional view inside the casing along the line BB ′ in FIG. 2;
FIG. 6 is a perspective view of a rotating rotor.
FIG. 7 is a perspective view of another rotating rotor of the present invention.
FIG. 8 is a perspective view of a separator.
FIG. 9 shows an example of a flowchart relating to a method for producing a polymerized toner of the present invention.
FIG. 10 is a schematic explanatory view showing a cross section of toner particles.
FIG. 11 is an explanatory diagram showing an example of a conventional dispersion process.
FIG. 12 is an explanatory diagram showing an example of a conventional dispersion process.
[Explanation of symbols]
1 Media type disperser
2, 21, 31 Casing (container part)
3, 3 'rotor
4 Separator
5 Media particles
6 Liquid supply port
7 Liquid outlet
8 Holding tank
10 Circulation pump
11 Cooling means
12 Thermometer
18 jacket
19 Valve
20 Three-way valve
21 Drive shaft
22 Interior
23 Outside room

Claims (17)

A method for producing a polymerized toner having at least a dispersion step of dispersing a fine colorant in a liquid monomer mixture containing at least a liquid polymerizable monomer to obtain a fine colorant-dispersed liquid monomer mixture,
In the dispersion step, an inner chamber and an outer chamber are formed by a cylindrical separator having a slit inside a cylindrical container portion having a first wall surface having a liquid supply port and a second wall surface having a liquid discharge port. A rotating rotor is installed in the inner chamber so that it can be rotated by rotation of the drive shaft, and a plurality of spherical media particles are built in the inner chamber, the rotating rotor diameter A, the rotating rotor, and the cylinder The relation with the distance B formed by the separator is 3 <A / B <16
Media using particle agitation type wet-dispersion machine, a manufacturing method of polymerized toner, which comprises have a plurality of uneven portions protruding portion of the rotating rotor is. A granulating step for producing particles of a polymerizable monomer composition by dispersing the fine colorant-dispersed liquid monomer mixture obtained in the dispersing step in an aqueous dispersion; and
The method for producing a polymerized toner according to claim 1, further comprising a polymerization step of polymerizing a polymerizable monomer in particles of the polymerizable monomer composition in an aqueous dispersion medium to produce toner particles. (A) In the dispersing step, an inner chamber is formed by a cylindrical separator having a slit inside a cylindrical container portion having a first wall surface having a liquid supply port and a second wall surface having a liquid discharge port. An outer chamber, a rotating rotor is installed in the inner chamber so as to be rotatable by rotation of the drive shaft, a plurality of spherical media particles are built in the inner chamber, the rotating rotor diameter A and the rotating rotor And the distance B formed by the cylindrical separator is 3 <A / B <16
A media particle agitation type wet disperser is used as a dispersing means,
(B) 1) While rotating the rotating shaft by rotating the drive shaft, the fine colorant is introduced into the center of the inner chamber from the liquid supply port together with the liquid monomer mixture,
2) While dispersing the fine colorant in the liquid monomer mixture by the centrifugal force and media particles generated by the rotation of the rotary rotor, the liquid monomer mixture and the fine colorant are contained by the centrifugal force generated by the rotation of the rotary rotor. Conveyed from the chamber to the outer chamber through the slit of the separator,
3) The liquid monomer mixture in which the fine colorant is dispersed is discharged from the outer chamber through the liquid discharge port to obtain the fine particle colorant-containing monomer mixture. A method for producing the polymerized toner according to claim. The relationship between the rotary rotor diameter A and the distance B formed by the rotary rotor and the cylindrical separator is 5 <A / B <11.
The method for producing a polymerized toner according to any one of claims 1 to 3, wherein: The rotating rotor diameter A is 50 mm <A ≦ 1000 mm
The method for producing a polymerized toner according to claim 1, wherein: The rotating rotor diameter A is 100 mm <A ≦ 600 mm
The method for producing a polymerized toner according to claim 1, wherein: The total volume C of media particles in the media particle stirring type wet disperser and the space volume D between the rotor and the separator are 0.7 <C / D <1.3.
The method for producing a polymerized toner according to any one of claims 1 to 6, wherein the method is a range of The liquid monomer mixture in which the fine colorant is dispersed is again introduced into the center of the inner chamber from the liquid supply port of the media particle agitation type wet disperser to disperse the fine colorant in the liquid monomer mixture. method for producing a polymerized toner according to any one of claims 1 to 7. Introducing the liquid monomer mixture to the media particles agitation type wet-dispersion machine - is circulated repeatedly discharged, of claims 1 to 8 micronized form colorant performs a predetermined time dispersion is dispersed in a liquid monomer mixture A method for producing a polymerized toner according to any one of the above. The method for producing a polymerized toner according to any one of claims 1 to 9 , wherein the media diameter of the media particle agitation type wet disperser is in a range of 0.1 mm to 1 mm. The method for producing a polymerized toner according to any one of claims 1 to 10 , wherein the peripheral speed of the rotary rotor tip of the media particle agitation type wet disperser is in the range of 5 m / s to 20 m / s. The method for producing a polymerized toner according to any one of claims 1 to 11 , wherein the liquid temperature of the liquid monomer mixture dispersed by a stirring type wet disperser of media particles is adjusted to 10 to 40 ° C. The method for producing a polymerized toner according to any one of claims 1 to 11 , wherein the liquid temperature of the liquid monomer mixture dispersed in the agitation type wet disperser of media particles is adjusted to 15 to 35 ° C. The production of the polymerized toner according to any one of claims 1 to 13 , further comprising a preparation step of adding an additional liquid polymerizable monomer, a polymer, and a wax to the fine colorant-containing monomer mixture via the dispersion step. Method. The method for producing a polymerized toner according to any one of claims 1 to 14 , wherein a polymerization initiator is added after completion of the dispersion step or after the preparation step, during the granulation step, or during the polymerization step. The method for producing a polymerized toner according to any one of claims 1 to 15 , wherein a treatment time of the dispersing step is 10 to 300 minutes. The method for producing a polymerized toner according to any one of claims 1 to 15 , wherein a treatment time of the dispersing step is 20 to 180 minutes.

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