JP2749234B2 - Polymerized toner and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerized toner and a method for producing the same. Specifically, the present invention
The present invention relates to a polymerized toner for developing an electrostatic latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and a method for producing the same.

[0002]

2. Description of the Related Art In electrophotography, as a method for permanently fixing a toner image formed on an image receiving sheet onto a sheet, a heating roller fixing method is widely used. According to this method, since the surface of the heating roller and the image surface of the sheet to be fixed come into pressure contact with each other, the toner image is excellent in heat efficiency when heat-welding the sheet to the sheet to be fixed, and quick fixing can be performed. Very suitable. However, although this method has the advantages described above, it has a serious problem that an offset phenomenon occurs. This is a phenomenon in which a part of the toner that forms an image at the time of fixing adheres to the surface of the heat roller and transfers to the next sheet to be fixed, thereby soiling the image.

As a countermeasure to prevent the offset phenomenon,
In addition to selecting the material of the roller, apply silicone oil or the like as a release agent to the heat roller, or include a low softening point wax in the toner as a release agent,
In order to increase the cohesion between the fused toners, measures such as broadening the molecular weight distribution have been taken.

As a method for producing such a toner, conventionally, a wax is added to a fixing resin medium together with a charge control agent and other toner components, melt-kneaded, and the resulting mass is finely pulverized. However, in this method, since the compatibility between the fixing resin and the wax is poor, the mixing ratio of the wax differs, the particle diameter of the wax increases, and the wax is liberated on the surface of the toner particles. Therefore, it is extremely difficult to give a toner in which the wax is uniformly dispersed, since it adversely affects the fixing property and the blocking resistance of the toner.

Therefore, in order to solve the above problems, Japanese Patent Application Laid-Open Nos.
38,845 proposes a method for producing a toner by a so-called polymerization method, in which a wax is mixed with a polymerizable monomer and the polymerizable monomer is polymerized to obtain a toner. However, even in this polymerization, the wax component in the polymerizable monomer is in an agglomerated state, and the amount of the wax component in each generated toner varies, or the wax is aggregated in the central portion of the toner. No toner has been obtained which satisfies the charging characteristics, fixability, fluidity and blocking resistance of each toner.

When the toner particles are to be produced by the suspension polymerization method, the wax component is generally lipophilic and strongly hydrophobic, so that the wax component is buried in the oil droplets of the polymerizable composition during suspension. In order to solve the problem that when a toner particle is formed, the wax component does not exist in the vicinity of the surface and the effect as a release agent is not exhibited, Japanese Patent Publication No. 3-2390
In 3 and JP fair 3-23906 discloses an average diameter ratio of the average diameter D ₁ of the wax for D ₂ of toner particles (D ₁ / D ₂₎ relatively large as 0.4 to 2.0 It is proposed to carry out suspension polymerization to produce a toner having a high content of wax component, i.e., a toner in which a mixture of toner particles containing no wax component and particles containing a rather large wax particle. I have. However, in such a toner, although the offset resistance is certainly improved to some extent due to the presence of toner particles having a high wax component content, the toner content of each toner particle is greatly different, so the toner charge A major problem remains in properties, fixability, fluidity and blocking resistance.

Further, in Japanese Patent Application Laid-Open No. 62-295,073, a wax is once dissolved in a polymerizable composition and then precipitated to precipitate the wax in the polymerizable composition in fine particles. It has been proposed to perform turbid granulation to obtain oil droplet particles and polymerize them.

However, in this method, it is possible to reduce the dispersed particle diameter of the wax to 5 μm or less. However, since the interfacial energy between the wax particles precipitated in fine particles and the polymerizable monomer is high, the compatibility is poor. In the granulation step after cooling, the wax particles reaggregate, the amount of wax component in each oil droplet particle generated by suspension still varies, and the toner obtained after polymerization has the wax particles as a core. A mixture containing defective particles composed of aggregates obtained is obtained, which also adversely affects the charging characteristics. Further, since the wax component of each toner is not uniform, a satisfactory prevention effect cannot be obtained, and a toner having excellent offset resistance, blocking resistance and fixing property has not yet been obtained.

It has also been proposed to externally add wax fine particles obtained by a mechanical pulverization method or a melt cooling method to the surface of the toner particles obtained by suspension polymerization. It is considered to exhibit good offset resistance, but the wax fine particles are exposed on the surface of the toner particles, so the fluidity of the toner is poor, and the rising of charging is also poor, which causes the problem of toner scattering. Met.

Conventionally, low molecular weight polypropylene, low molecular weight polyethylene, paraffin wax and the like have been used as wax contained in toner particles. Among them, low-molecular-weight polyethylenes of low density and relatively low crystallinity are used. Therefore, when particles of polyethylene wax are obtained by a melt cooling method, the shape of the particles becomes a spindle shape.
When such wax fine particles are contained in the toner particles, when the size of the wax particles is considerably smaller than the toner particle diameter, the wax fine particles located near the center of the toner particles are released during fixing. It does not substantially function as an agent. Therefore, without sufficiently increasing the particle diameter of the wax particles or increasing the content of the wax more than necessary, in order to sufficiently exhibit the releasing effect of the wax, the wax particles should be placed near the outer surface of the toner particles. The technique of localizing without exposing is required, but as described above, the wax component generally has a strong lipophilicity and a high hydrophobicity, and thus tends to be buried in the polymerizable composition oil droplets when suspended. Therefore, it was difficult to establish a technique for localizing the wax particles without exposing them near the outer surface of the toner particles.

[0011]

Accordingly, an object of the present invention is to provide an improved polymerized toner and a method for producing the same. Another object of the present invention is to provide a polymerized toner having excellent offset resistance, blocking resistance and fixability, and a method for producing the same.

[0012]

SUMMARY OF THE INVENTION The above objects are as follows.
A polymerized toner containing at least a binder resin, a colorant and / or magnetic powder, and a wax component, wherein the wax component is a polyethylene wax having a crystallinity of more than 80%, and the wax is short in toner particles. This is achieved by a polymerized toner characterized by being dispersed as a fibrous body. Here, the crystallinity of the wax is a value measured by an X-ray diffraction method.

In the polymerized toner of the present invention, the polyethylene wax has a softening point of 120 ° C. or more and a molecular weight of 1,000.
Preferably, the average particle diameter of the toner is 2 to 20 μm, and the average length of the short fibrous body of wax is 0.5 to 20 μm.

Another object of the present invention is to provide a method for producing a polymerized toner containing at least a binder resin, a colorant and / or a magnetic powder, and a wax component, wherein the polymerizable monomer has a crystallinity of 80%. The polyethylene wax is heated and melted and then cooled and then cooled, whereby the polyethylene wax is dispersed in the form of short fibers in the polymerizable monomer in advance, and the polymerizable monomer is mixed with the polymerizable monomer in the presence of the short fibrous body of the polyethylene wax. The present invention is also achieved by a method for producing a polymerized toner, wherein a polymerizable composition containing a colorant and / or a magnetic powder is subjected to suspension polymerization in an aqueous medium.

In the method for producing a polymerized toner of the present invention,
Polyethylene wax has a softening point of 120 ° C or higher and a molecular weight of 1
2,000 to 20,000, and the average length of the short fibrous body of polyethylene wax is 0.5 to 20 μm.
m, and the average particle diameter of the oil droplet particles of the polymerizable composition during suspension polymerization is desirably adjusted to 2 to 20 μm.

Further, in the method for producing a polymerized toner of the present invention, the step of dispersing the polyethylene wax into short fibers in the polymerizable monomer is performed in a continuous process apparatus having a heating zone and a cooling zone. The mixture of the monomer and the wax is supplied to a heating zone having a heating device having a heat transfer area of 0.3 cm ² or more per 1 cc of heating capacity to heat and melt the wax, and then a high-speed shear mixer, an ultrasonic wave In a cooling zone provided with one of a stirrer consisting of a homogenizer and an in-pipe mixer, a heating mixture derived from the heating zone, and a polymerizable material as a cooling liquid supplied through a separate flow path from the heating mixture The monomer and the monomer are simultaneously supplied to the vicinity of the stirring region of the stirring device and cooled to precipitate wax. It is preferable to carry out by taking out the wax dispersion obtained by dispersing the box.

[0017]

The polymerized toner of the present invention uses polyethylene wax having a crystallinity of more than 80% as a wax component blended in the toner, and the wax is contained as short fibers in the toner particles. . When the wax component is contained as a short fibrous body having a sufficient size compared to the diameter of the toner particles, as shown in FIG. And a short fibrous body 32 near the outer surface of the toner particles 31.
Will be located. Therefore, at the same time as the binder resin component in the vicinity of the outer surface of the toner particles is melted during the heat fixing, the wax melt is discharged from the portion near the outer surface of the toner particles of the short fibrous body of the wax present in the toner particles. , A good offset resistance is exhibited. Further, in the polymerized toner of the present invention, since the wax component is widely dispersed and contained in the width direction of the toner particles as a short fibrous body, the wax component exposed on the outer surface of the toner is very little, if any. It is difficult to cause the problem of blocking at the time of storage or transportation.In addition, in order to include the wax component as a short fibrous body, it is necessary to arrange the wax component near the outer surface of the toner more than necessary. There is no need to increase the content of the components, and the fixing property and the stability of the toner particles are improved.

Hereinafter, the present invention will be described in more detail based on embodiments. Examples of the polymerizable monomer used in the method for producing the polymerized toner of the present invention include α, β-ethylenically unsaturated monomers, and examples thereof include styrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene. Methylstyrene, α-
Styrene monomers such as methylstyrene, p-methoxystyrene, p-tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene; acrylic acid, methyl acrylate, ethyl acrylate N-butyl acrylate, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, Acrylic or methacrylic monomers such as dodecyl methacrylate, stearyl methacrylate, 2-ethylhexyl methacrylate; ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile, acrylamide, Examples thereof include methacrylamide and N-vinylpyrrolidone, and one or more of these are used. Among these, a styrene- (meth) acrylate mixture containing 50% by weight or more of styrene is most preferable from the viewpoint of the thermal characteristics of the toner as a final product.

The wax component used in the present invention is a polyethylene wax having a crystallinity of more than 80%, preferably more than 85%, and desirably has a softening point of 120 ° C. or more, more preferably Is 12
It is desired that the temperature is 5 to 140 ° C. and the molecular weight is 1,000 to 20,000, more preferably about 2,000 to 10,000. The reason why the crystallinity of the polyethylene wax used in the present invention is limited to more than 80% is that if the crystallinity is 80% or less, sufficient hot offset resistance cannot be obtained. It is. As such polyethylene wax, specifically, Mitsui High Wax 100P, 200P, 400P, 800P,
1100P (all manufactured by Mitsui Petrochemical Industries, Ltd.).

In the method for producing a polymerized toner of the present invention,
The amount of the polyethylene wax having a crystallinity exceeding 80% is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of the total amount of the polymerizable monomer.
Most preferably, it is 1 to 5 parts by weight. That is, 0.
If the amount is less than 5 parts by weight, it is difficult to prevent the offset phenomenon. On the other hand, if the amount exceeds 20 parts by weight, the fluidity and charging characteristics of the toner deteriorate. In addition, the total amount of the polymerizable monomer which is a reference here means not only the polymerizable monomer to be initially blended at the time of melt precipitation of the polyethylene wax, but also to be later blended and suspended as necessary. It also includes the amount of the polymerizable monomer used for the polymerization.

In the method for producing a polymerized toner according to the present invention,
In order to improve the dispersion stability of the short fibrous material of the wax precipitated in the polymerizable monomer and to improve the uniformity of the amount of wax contained in each obtained toner particle, if necessary, a graft-modified polyethylene wax is used. You may mix. This graft-modified polyethylene wax is obtained by graft-polymerizing the polymerizable monomer to polyethylene wax. In this case, the obtained graft-modified polyethylene wax may have a functional group, but if it does not, a better effect is obtained. The compounding amount of the graft-modified polyethylene wax is 1 to 100% by weight, preferably 1 to 2% by weight based on the unmodified polyethylene wax.
0% by weight, most preferably 3 to 15% by weight. The graft ratio is such that the polymerizable monomer to be grafted per 100 parts by weight of unmodified polyethylene wax is 5 to 200.
0 parts by weight, preferably 20 to 400 parts by weight, more preferably 20 to 60 parts by weight. That is, if the ratio is out of this range, the particle size of the unmodified polyethylene wax becomes too large, and the unmodified polyethylene wax is discharged during the polymerization.

As such graft-modified polyethylene wax, Mitsui High Wax 1120H, 1140
H, 1160H, 2235H (Styrene-modified wax manufactured by Mitsui Petrochemical Industry Co., Ltd.), Mitsui High Wax 3010R (Styrene manufactured by Mitsui Petrochemical Industry Co., Ltd.)
Acrylic-modified wax).

In this case, it is desirable that the polymerizable monomer to be grafted is the same as the polymerizable monomer used in the suspension polymerization. Therefore, for example, when styrene is used as an essential component of the polymerizable monomer, it is desirable to use a graft-modified polyethylene wax with styrene.

In the method for producing a polymerized toner according to the present invention, first, a blend of the polymerizable monomer and the polyethylene wax is heated to melt the polyethylene wax in the polymerizable monomer, and thereafter, Upon cooling, the polyethylene wax is precipitated as short fibrous particles. As a temperature condition in the step of dispersing the polyethylene wax into the short fibrous body in the polymerizable monomer, first, the cloud point of the polymerizable composition of the polymerizable monomer and the polyethylene wax is higher by 1 ° C. or more than the cloud point. And a temperature lower than the melting point of the polyethylene wax, preferably 2 ° C. or more above the cloud point and 5 ° C. or more lower than the melting point of the polyethylene wax,
Most preferably, the polyethylene wax is dissolved by heating to a temperature of at least 2 ° C. above the cloud point and at least 10 ° C. below the melting point of the polyethylene wax, and then at least 3 ° C., preferably 5 ° C., above the cloud point of the polymerizable composition. As described above, it is most preferable to rapidly cool to a temperature lower by 10 ° C. or more. If the heating temperature is lower than the cloud point by less than 1 ° C., the dissolution of the polyethylene wax is insufficient, and the size of the wax particles in the dispersion obtained after cooling may vary. If the cooling temperature is lower than the cloud point by less than 3 ° C., there is a possibility that the particle size of the precipitated polyethylene wax becomes large.

The measurement of the cloud point shown above is based on JIS
K 2266-1965 "Petroleum product cloud point test method". The measurement of the melting point is performed by a differential scanning calorimetry (DSC method).

The process of dispersing the polyethylene wax into short fibers in the polymerizable monomer can be carried out by a batch method. However, there is little danger of ignition, explosion, etc., and productivity and energy efficiency are reduced. Therefore, it is desirable to carry out the treatment by a continuous process method because the method is good, the apparatus is small, and the cost is low. Such a continuous process uses a heating device with a very large heat transfer area in the heating zone and generally a small processing volume; and / or
Alternatively, in the cooling zone, using a stirring device selected from the group consisting of a high-speed shearing mixer, an ultrasonic homogenizer, and an in-pipe mixer, the heating mixture further derived from the heating zone, and another heating mixture. This can be more preferably performed by simultaneously supplying the polymerizable monomer as the cooling liquid supplied through the flow path to the vicinity of the stirring region of the stirring device.

As shown in FIG. 1, for example, an apparatus used in such a continuous process includes a mixing zone 1 for mixing a polymerizable monomer and a polyethylene wax, and a polymerizable zone derived from the mixing zone 1. It has a heating zone 2 for heating a mixture of a monomer and a polyethylene wax, and a cooling zone 3 for cooling a heating mixture derived from the heating zone 2, and a liquid outlet of the mixing zone 1 and a heating zone. The liquid inlet of the heating zone 2 and the liquid inlet of the cooling zone 3 are connected to each other by a line 6 such as a pipe. The liquid inlet of the cooling zone 3 is provided with a line 8 for supplying an organic solvent and / or a polymerizable monomer as a cooling liquid.
Preferably, the cooling zone 3 has two liquid inlets, one of which is connected to the line 7.
And another inlet is connected to line 8. Further, the liquid outlet of the cooling zone 3 is connected to a line 9 extending outside the system. In the apparatus shown in FIG.
Liquid pumps 4 and 5 are provided in the middle of the line 8 and a thermometer 10 for measuring the temperature of the fluid flowing in the line 7 is provided in the middle of the line 7.

The mixing zone 1 for mixing the polymerizable monomer and the polyethylene wax can be constituted by, for example, a bottomed mixing tank provided with various stirrers.

The heating zone 2 for heating the mixed solution of the polymerizable monomer and the polyethylene wax to dissolve the polyethylene wax has a danger of explosion due to heating a large amount of the polymerizable monomer and the polymerizable monomer. In order to prevent the problem of polymer formation due to long-lasting heating, it is necessary that a relatively small amount of the mixture can be efficiently and continuously heated in a short period of time. Desirably, it is 0.3 cm ² or more, more preferably 0.5 cm ² or more. Specifically, for example, a multi-tube heat exchanger, a coil heat exchanger, a double-tube heat exchanger, a spiral heat exchanger, a cascade heat exchanger, etc., further have a heat exchange efficiency and a dissolution rate of polyethylene wax. Static mixer (manufactured by Noritake Co., Ltd.) having a structure in which a baffle plate or the like is provided in the pipe for the purpose of improving the quality, etc .; ) Can be used alone or in combination of two or more. Of course, the heat transfer area is not limited to those exemplified above, and the heat transfer area is equal to the heating capacity 1c.
Any type of heating device can be suitably used as long as it has a heating device of 0.3 cm ² or more per c.

On the other hand, the cooling zone 3, in which the heating mixture containing the polyethylene wax heated and melted in the heating zone 2 is cooled to precipitate the polyethylene wax as a short fibrous body, is instantaneously stirred under high stirring. It is important to cool. For this purpose, a high-speed shear mixer, an ultrasonic homogenizer, and a stirrer selected from the group consisting of in-pipe mixers are used, and more preferably, the heated mixture derived from the heating zone 2 and the heated mixture The polymerizable monomer as a cooling liquid supplied through another flow path is simultaneously supplied to the vicinity of the stirring area of the stirring device, and the heated mixture and the cooling liquid are instantaneously and uniformly mixed.
Ideally, the mixing is macroscopically uniform and microscopically uniform.

As the high-speed shear mixer used in the cooling zone 3, a homogenizer Polytron (trade name)
Central Scientific Trading), Homogenizer Histron (Nichion Medical Science Instruments Co., Ltd.), Biomixer (Nippon Seiki Co., Ltd.), Turbo Stirrer (Kodaira Co., Ltd.), Ultra Dispers (Asada Steel Corp.) ),
Ebara Milser (EBARA CORPORATION), TK homomixer, TK lab disperser, TK pipeline mixer, TK homomic line mill, TK homojetter,
TK Unimixer, TK Homomic Line Flow, TK
A homodisper (above, Tokushu Kika Kogyo Co., Ltd.) and the like. Examples of the ultrasonic homogenizer include an ultrasonic homogenizer (Nippon Seiki Seisakusho). Examples of the in-pipe mixer include a static mixer (Noritake Co., Ltd.), a Sulzer mixer (Sumitomo Heavy Industries, Ltd.), a stationary in-pipe mixer (Toray Co., Ltd.), and a skaya mixer (Sakura Seisakusho) And TK-ROSS LPD mixer (Special Kika Kogyo Co., Ltd.). These stirrers are mainly used alone, but depending on the case, two or more kinds may be used in combination. In particular, the ultrasonic homogenizer is desirably used in combination with a stirrer capable of macroscopically uniform mixing.

As described above, in a preferred embodiment,
The heating mixture of the polyethylene wax and the polymerizable monomer sent from the heating zone 2 through the line 7 and the polymerizable monomer as the cooling solution sent through another line 8 are mixed in the cooling zone 3. Since it is necessary to simultaneously supply the liquid to the vicinity of the stirring area of the stirring device described above, among the commercially available products as described above, in the case of having a stirring container body and having a liquid supply portion having only one liquid inlet, It is desired that the liquid supply unit be improved to have two liquid inlets without directly using the liquid supply unit.

FIG. 2 shows an example of a more specific configuration of the heating zone and the cooling zone of the apparatus used in the continuous process as described above. In the configuration example shown in FIG. 2, the heating zone 2 is constituted by a spiral heat exchanger 12 using steam as a heating medium, and a polyethylene wax and a polymerizable monomer are mixed from a mixing zone 1 (not shown). A line 6 for feeding the mixture with the above is connected to a heated fluid inlet of the heat exchanger 12, and a line 7 is connected to a heated fluid outlet of the heat exchanger 12. On the other hand, the cooling zone 3 has a mixing vessel 1 having two liquid inlets at the bottom and a liquid outlet at the upper side.
4, a line 7 extending from the heat exchanger 12 is connected to one of the two liquid inlets at the bottom of the mixing vessel 14, A line 8 for feeding a polymerizable monomer as a cooling liquid is connected to another liquid inlet at the bottom of the mixing vessel 14. Therefore, the heated mixture and the cooling liquid introduced into the mixing container 14 from the bottom of the mixing container 14 are placed under the stirring area of the high-speed shear mixer 13 at the same time as the introduction.

FIG. 3 schematically shows the structure of an apparatus used in still another embodiment. The apparatus shown in FIG. 3 comprises a mixing and heating zone 21 for mixing and heating the polymerizable monomer and the polyethylene wax simultaneously,
It has a cooling zone 23 for cooling a heated mixture of the polymerizable monomer derived from the mixing and heating zone 21 and the polyethylene wax, and a liquid outlet of the mixing and heating zone 21 and a liquid in the cooling zone 23. The inlet is connected by a line 27. The cooling zone 23
Apart from the liquid inlet connected to the line 27 from the mixing and heating zone 21, it has another liquid inlet, which is provided with a polymerizable monomer as a cooling liquid. It is connected to the supply line 28. In the apparatus shown in FIG. 3, liquid feed pumps 24 and 25 are provided in the middle of the line 27 and the line 28, respectively.

Mixing and heating zone 1 in FIG.
Can be constituted by, for example, a stirrer, a thermometer, a bottomed jacket-added heating pot equipped with a reflux cooling pipe, and the like. The cooling zone 23 is provided with a stirring device similar to that used in the cooling zone 3 shown in FIGS. In the embodiment using the apparatus configuration shown in FIG. 3, the heating efficiency when heating the polymerizable monomer and the polyethylene wax is compared with the embodiment using the apparatus configuration shown in FIGS. However, if the polymerizable monomer used is relatively stable against heating to the temperature required for dissolving the polyethylene wax, an apparatus having such a configuration is used. Is used, a polyethylene wax dispersion having a uniform particle size distribution can be continuously obtained.

When a mixing zone is provided before the heating zone when the melt deposition of polyethylene wax is performed in a continuous process, the polyethylene wax is mixed with the above-mentioned polymerizable monomer in the mixing zone 1 with stirring.
A mixture having a uniform composition is obtained. The stirring and mixing in this mixing zone is performed at ambient temperature without applying heat.
The temperature is maintained, for example, while maintaining a liquid temperature of about 5 to 40 ° C.

The mixture of the polymerizable monomer and the polyethylene wax obtained in the mixing zone 1 is pumped to the heating zone 2 through the line 6 by the action of the pump 4. While passing through the heating zone 2, the mixture of the polymerizable monomer and the polyethylene wax is heated to the above-mentioned temperature condition in a short time, for example, about 3 to 40 seconds, and the polyethylene wax contained in the mixture is heated. The components dissolve.

After passing through the heating zone 2, the heated mixture of the polymerizable monomer having the polyethylene wax component in a dissolved state and the polyethylene wax is subsequently pumped through the line 7 to the cooling zone 3. On the other hand, at the same time, the liquid temperature as a cooling liquid -10 to -4 through another line 8 to the cooling zone 3.
A polymerizable monomer at 0 ° C, more preferably about -10 to 30 ° C, is pumped. At this time, the flow ratio between the heated mixture and the cooling liquid depends on the temperature and the like of both liquids, but it is desirable that the heating mixture: cooling liquid = 1: 0.5 to 1:10 by weight. The heating mixture and the cooling liquid introduced into the cooling zone 3 from the two liquid inlets of the cooling zone 3 in this manner are introduced into the cooling zone 3 and at the same time, the stirring device of the stirring device constituting the cooling zone 3 Put under the stirring area,
The heated mixture and the cooling liquid are instantaneously and uniformly mixed. The heating mixture of the polymerizable monomer and the polyethylene wax by being mixed with the cooling liquid, the above-mentioned temperature conditions for a short time,
For example, it is cooled for 0.1 to 10 seconds, and the polyethylene wax component is a short fibrous body having a uniform size, for example, having an average length of 0.5 to 20 μm, preferably 0.5 to 10 μm, more preferably 0.5 to 10 μm. It precipitates as a short fibrous body of about 5 μm, and the polyethylene wax short fibrous body is uniformly dispersed in the polymerizable monomer. At a temperature at which the cooling temperature is lower than the cloud point by less than 3 ° C., there is a possibility that the particle size of the precipitated polyethylene wax becomes large. The polyethylene wax dispersion thus obtained in the cooling zone 3 is:
From the liquid outlet of the cooling zone 3, the liquid is transferred to the next polymerization step through the line 9.

In the production method of the present invention, the suspension polymerization comprises:
The polymerizable monomer composition obtained by precipitating and dispersing the short fibrous body of polyethylene wax as described above is suspended in an aqueous medium, and further blended, if necessary, in the presence of a colorant and / or a magnetic powder. Together with a polymerizable monomer such as 5
It is carried out at a temperature of 0 to 90C, preferably 60 to 80C. As the polymerizable monomer to be further added, those described above are used. When the polymerizable monomer is added, the polyethylene wax is dissolved in the polymerizable monomer composition, and then the short fibrous body of the polyethylene wax is precipitated in the polymerizable monomer composition. Any time before the monomer composition is suspended in the aqueous medium.

In the suspension polymerization, it is preferable to carry out the reaction after regulating the particle diameter of the suspended particles or while regulating the particle diameter. Particularly, it is preferable to carry out the reaction after regulating the particle diameter. Is preferred. The regulation of the particle size is, for example, as follows: K. Stir with a homomixer. Alternatively, it is carried out by passing once or several times through a high-speed stirrer such as a line mixer (for example, Ebara Milder). By performing such a regulation of the particle size, the average particle size of the suspended particles during suspension polymerization is 2 to 20 μm,
Preferably, it is about 3.5 to 15 μm.

The coloring agent and / or the magnetic powder may be added together with the polymerizable monomer at the same time or at a different time as in the additional period of the polymerizable monomer.
It is preferably added after the precipitation of short fibrous bodies of polyethylene wax.

The colorant used to obtain the toner is a dye or pigment well known to those skilled in the art, and may be any of organic and inorganic. Specific examples thereof include, for example, carbon black, nigrosine dye, aniline blue, calco oil blue, chrome yellow, ultramarine blue,
Dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachide greenoxalate, lamp black, oil black, azo oil black, rose bengal, and the like. If necessary, use two or more of these in combination. Is also good.

A substance having magnetism, that is, a magnetic substance can also be used as a coloring agent. As a magnetic material, for example,
Examples include powders of ferromagnetic metals such as iron, cobalt, and nickel, and powders of metal compounds such as magnetite, hematite, and ferrite. These magnetic materials can be used alone or in combination with the dyes and pigments as a coloring agent.

Although these coloring agents may be used as they are,
It is preferable to use a colorant whose surface has been treated by an appropriate method since a toner in which the colorant is uniformly dispersed is obtained and a high-quality image is formed. For example, when carbon black is used as a coloring agent, carbon black bluff polymers described in JP-A-63-270767 and JP-A-63-265913 are suitable. Further, when a coloring agent other than carbon black is used, the method disclosed in
A surface-treated colorant obtained by the method described in JP-A-573-573 is suitable.

The amount of the colorant added can be in a wide range depending on the type of the colorant used and the toner to be obtained, but is preferably 1 to 100 parts by weight per 100 parts by weight of the polymerizable monomer.
It is 200 parts by weight, more preferably 1 to 100 parts by weight.

In the suspension polymerization, a dispersion stabilizer can be added to stabilize the suspended particles. As dispersion stabilizers, polyvinyl alcohol, gelatin,
Water soluble polymers such as tragacanth, starch, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, sodium polyacrylate, sodium polymethacrylate, sodium dodecylbenzenesulfonate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, allyl-alkyl- Sodium polyethersulfonate, sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate, potassium stearate, calcium oleate, 3,3 '
Sodium disulfonediphenylurea-4,4'-diazo-bis-amino-8-naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2 ', 5,5'-tetramethyl-tri Phenylmethane-1,1'-diazo-bis-β-naphthol-
Surfactants such as sodium disulfonate, other alginates, zein, casein, barium sulfate, calcium sulfate, barium carbonate, magnesium carbonate, calcium phosphate, talc, clay, diatomaceous earth, bentonite, titanium hydroxide, thorium hydroxide, metal oxide Substance powder or the like is used.

The composition and amount of these dispersion stabilizers are appropriately adjusted so that the particle size of the resulting polymerized toner particles is a predetermined size, for example, 2 to 20 μm, preferably 3.5 to 15 μm. It is to be used. For example, when a water-soluble polymer is used, it is preferably 0.01 to 20% by weight, preferably 0.1 to 10% by weight, based on the polymerizable monomer component. is there. In the case of a surfactant, it is suitably from 0.01 to 10% by weight, preferably from 0.1 to 5% by weight, based on the polymerizable monomer.

As the polymerization initiator used for the polymerization, oil-soluble peroxide-based or azo-based initiators usually used for suspension polymerization can be used. By way of example, for example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxybenzoyl peroxide, methyl ethyl ketone peroxide,
Peroxide initiators such as diisopropylperoxydicarbonate, cumene hydroperoxide, cyclohexanone peroxide, t-butyl hydroperoxide, diisopropylbenzene hydroperoxide, 2,2′-azobisisobutyronitrile, 2 '
Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (2,3-dimethylbutyronitrile),
2,2′-azobis (2-methylbutyronitrile),
2,2'-azobis (2,3,3-trimethylbutyronitrile), 2,2'-azobis (2-isopropylbutyronitrile), 1,1'-azobis (cyclohexane-
1-carbonitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile, 4,4'-azobis (4-cyanovaleric acid), Dimethyl-2,2'-azobisisobutyrate and the like. The polymerization initiator is used in an amount of 0.01 to 20% by weight, especially 0.1 to 20% by weight, based on the polymerizable monomer.
It is preferred to use 1 to 10% by weight.

When the polymerizable monomer component is thus subjected to suspension polymerization to obtain a polymerized toner, another polymer such as a polyester may be present in the monomer component. Known additives such as a chain transfer agent for adjusting the degree may be appropriately blended. At the time of suspension polymerization, a crosslinking agent may be used.

Examples of the crosslinking agent include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and derivatives thereof, ethylene glycol dimethacrylate,
Diethylenically unsaturated carboxylic acid esters such as diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylolpropane triacrylate, allyl methacrylate, t-butylaminoethyl methacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, etc. , N, N-divinylaniline, divinyl ether,
Examples include all divinyl compounds of divinyl sulfide and divinyl sulfonic acid, and compounds having three or more vinyl groups. Further, polybutadiene, polyisoprene, unsaturated polyester, chlorosulfonated polyolefin and the like are also effective.

The polymerized toner thus obtained has an average particle size of 2 to 20 μm, preferably 3.5 to 15 μm, and a particle size distribution of 0 to 80%, preferably 1 to 50%, in terms of the coefficient of variation of the particle size. Has a controlled spherical shape,
As described above, the average length of the polyethylene wax in each toner particle is 0.5 to 20 μm, preferably 0.1 to 20 μm.
Short fibrous bodies of 5 to 10 μm, more preferably 0.5 to 5 μm, are uniformly dispersed and contained.

The polymerized toner of the present invention may optionally contain additives commonly used in ordinary toners, such as a charge control agent for adjusting the charge and a fluidizing agent. The method for incorporating the charge control agent is not particularly limited, and any conventionally known method can be employed. For example, a method in which a charge control agent is previously contained in a polymerizable monomer composition in which a colorant and / or a magnetic powder is dispersed, or a method in which the toner of the present invention is used as a charge control agent And a method of attaching a charge control agent to the toner surface by post-treatment.

[0053]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, "parts"
All by weight unless otherwise noted.

Synthesis Example 1 Based on the flow chart of the apparatus shown in FIG. 1, as a mixing zone 1, a 30 L mixing tank of a bottomed type equipped with a stirrer, a heating zone 2
Heating capacity 200 ml, heat transfer area 0.1256 m ²
With a thermometer at the outlet of the spiral heat exchanger of
Further, as a cooling zone 3, in a mixing vessel having a capacity of 150 ml having two inlets at the bottom and an outlet at the upper side,
Using a biomixer (manufactured by Nippon Seiki Seisakusho Co., Ltd.) equipped with a generator, a continuous wax dispersion device was prepared. Using this equipment, styrene 16954
Part, low molecular weight polyethylene (Mitsui High Wax 200P
(Crystallinity 87%, softening point 130 ° C, molecular weight 200
0), 2400 parts of Mitsui Petrochemical Industry Co., Ltd.) were mixed in the mixing zone 1, and a gauge pressure of 0.8 kg / g was supplied from the mixing zone 1 to a line 6 having a liquid feed pump 4 on the way.
The low-molecular-weight polyethylene / styrene mixture was sent at a flow rate of 30 kg / hr to the spiral heat exchanger in the heating zone 2 heated by the steam of cm ² , and the low-molecular-weight polyethylene in the mixture was heated and dissolved in the heating zone 2. . The residence time of the mixture in the heating zone 2 was 20 seconds and the outlet temperature was 110 ° C.

The heat-melted low molecular weight polyethylene / styrene mixture flows from the heating zone 2 through the line 7 through one of the two inlets at the bottom of the mixing vessel in the cooling zone 3 into the mixing vessel, and is sent halfway. 60 kg / h of styrene at 15 ° C. through a line 8 having a liquid pump 5
At a flow rate of r, the solution is fed into the mixing vessel from another inlet at the bottom of the mixing vessel in the cooling zone, and these two fluids are simultaneously circulated under the stirring of the biomixer, and rapidly cooled by instantaneous mixing. Then, low molecular weight polyethylene was precipitated to obtain a low molecular weight polyethylene / styrene dispersion liquid (1). Then, the low molecular weight polyethylene / styrene dispersion liquid (1) was discharged from the outlet of the mixing vessel in the cooling zone 3. The outflow temperature of the low molecular weight polyethylene / styrene dispersion liquid (1) was 43 ° C., and the flow rate was 90 kg / hr. The low molecular weight polyethylene / styrene dispersion (1) had a wax content of 4.0% and an average wax particle size of 0.92.
μm and was free of aggregates and coarse particles. Further, the shape of the wax particles in the low molecular weight polyethylene / styrene dispersion liquid (1) was a short fiber. Further, in the low molecular weight polyethylene / styrene dispersion liquid (1), no polymer was generated by thermal polymerization of styrene.

The amount of wax shown above was the amount of residue from Soxhlet extraction. Acetone was used as the solvent. The particle size of the wax is measured by Shimadzu laser diffraction particle size distribution analyzer SA.
It measured using LD-1000 (made by Shimadzu Corporation). The calculation of the average particle size in the
Measurement of the projected image of the particle
The average particle diameter is calculated assuming that
Is calculated as if the wax is in the form of short fibers
The average particle size is determined by the length and width of the short fibrous wax.
Of these, it appears as a size almost equivalent to the length. Sand
In other words, because of the short fiber shape, the width value is extremely small compared to the length value.
Since the value is small at the end, the calculated value is a short fiber
This is because the effect of the length of the wax is extremely large. Ma
The presence or absence and particle size of the wax aggregates and coarse particles, and the shape of the wax dispersed particles were observed with an optical microscope. Further, the formation of a polymer by thermal polymerization of the polymerizable monomer was observed by an increase in solid content and GPC.

Synthesis Example 2 Using the same apparatus as used in Synthesis Example 1, styrene 16
954 parts, low molecular weight polyethylene (Mitsui High Wax 2)
00P, manufactured by Mitsui Petrochemical Industries, Ltd.) 2400 parts, graft-modified wax (Mitsui High Wax HW1140H,
240 parts (Mitsui Petrochemical Industry Co., Ltd.) are mixed in a 30 L mixing tank of a bottomed type equipped with a stirrer, and a gauge pressure of 0.8 Kg is supplied from the mixing mixing tank 1 to a line 6 having a liquid feed pump 4 in the middle. A low-molecular-weight polyethylene / graft-modified wax / styrene mixture is fed at a flow rate of 30 kg / hr to a heating zone consisting of a spiral heat exchanger heated by steam of / cm ² , and the low-molecular weight in the mixture is heated in heating zone 2. The polyethylene and the graft-modified wax were dissolved by heating. The residence time of the mixture in the heating zone 2 is 2
At 0 seconds, the outlet temperature was 110 ° C.

The heated and melted mixture is supplied to heating zone 2
Through a line 7 into one of the two inlets at the bottom of the mixing vessel in the cooling zone 3 into the mixing vessel, while passing styrene at 16 ° C. at 60 kg / hr through a line 8 with a liquid feed pump 5 on the way. The liquid is fed into the mixing vessel from the other inlet of the mixing vessel in the cooling zone at a flow rate, and these two liquids are simultaneously circulated under the agitation of the homomixer. The graft-modified wax was precipitated to obtain a low molecular weight polyethylene / graft-modified wax / styrene dispersion (2). The dispersion (2) was discharged from the outlet of the mixing vessel in the cooling zone 3. The temperature at the time of the outflow of the dispersion liquid (2) was 45 ° C., and the flow rate was 90 kg / hr. The properties of this dispersion (2) were measured in the same manner as in Synthesis Example 1. Table 1 shows the obtained results. Further, the shape of the wax particles in this dispersion (2) was a short fibrous body.

Synthesis Example 3 The cooling zone 3 of Synthesis Example 1 was modified from the suction port of TK Homomic Line Flow (manufactured by Tokushu Kika Kogyo Co., Ltd.) to have a suction port with two inflow ports. Except for Synthesis Example 1
A continuous wax dispersion apparatus having the same configuration as that of the above was used. First, 6188 parts of styrene, n-acrylic acid
Butyl 1092 parts, low molecular weight polyethylene (Mitsui High Wax 400P (crystallinity 85%, softening point 136 ° C, molecular weight 4000), manufactured by Mitsui Petrochemical Industry Co., Ltd.) 1500
Part, graft-modified wax (Mitsui High Wax HW30
10R, 100 parts of Mitsui Petrochemical Industry Co., Ltd.) were mixed in the mixing zone 1, and a gauge pressure of 0.7 kg / cm was supplied from the mixing zone 1 to a line 6 having a liquid feed pump 4 on the way.
^A low molecular weight polyethylene / graft-modified wax / 45 kg / hr flow rate was applied to a heating zone consisting of a spiral heat exchanger heated by steam and a jacketed static mixer heated by a heating medium at 100 ° C.
A styrene / n-butyl acrylate mixture was fed, and in heating zone 2, the low molecular weight polyethylene and the graft-modified wax in the mixture were heated and dissolved. The residence time of the mixture in the heating zone 2 was 15 seconds and the outlet temperature was 100.
° C.

The heat-melted mixture is supplied to heating zone 2
From the inlet of the modified TK homomic line flow in the cooling zone 3 through one of the two inlets through the line 7 into the TK homomic line flow, while passing through the line 8 having the liquid feed pump 5 on the way. A mixture of styrene / n-butyl acrylate at a weight ratio of 85/15 at 20 ° C. is sent at a flow rate of 90 kg / hr from the other inlet of the TK homomic line flow in the cooling zone into the TK homomic line flow. Then, these two liquids are simultaneously passed under stirring with a homomixer, and rapidly cooled by instantaneous mixing to precipitate a low molecular weight polyethylene and a graft-modified wax to precipitate a low-molecular weight polyethylene / graft-modified wax / styrene / n-acrylic acid. A butyl dispersion (3) was obtained. Then, the dispersion (3) was allowed to flow out from the outlet of the TK homomic line flow in the cooling zone 3. The temperature at the time of the outflow of this dispersion liquid (3) is 47 ° C., and the flow rate is 135 kg /
hr. The properties of this dispersion (3) were measured in the same manner as in Synthesis Example 1. Table 1 shows the obtained results. Further, the shape of the wax particles in this dispersion liquid (3) was a short fibrous body.

Synthesis Example 4 The spiral heat exchanger used in heating zone 2 in Synthesis Example 1 was further provided with a heating capacity of 11 ml and a heat transfer area of 86.7 c.
using m ² static mixer jacketed those connecting the (Co. Noritake Company Ltd.) as a heating zone 2, also has a suction unit having two inlets a converted inlet as the cooling zone 3 Ebaramairu Synthesis Example 1 except for using a user (manufactured by EBARA CORPORATION)
7270 parts of styrene, 5500 parts of low molecular weight polypropylene (Viscol 660P (crystallinity: 60%) , manufactured by Sanyo Chemical Industries, Ltd.), and graft modified wax (Mitsui High 550 parts of wax HW1160H (manufactured by Mitsui Petrochemical Industry Co., Ltd.) are mixed in the mixing zone 1, and from the mixing zone 1, a line 6 having a liquid feed pump 4 in the middle
And a heating zone consisting of a spiral heat exchanger heated by steam at a gauge pressure of 1 kg / cm ² and a static mixer with a jacket heated by a heat medium at 115 ° C. at a flow rate of 43 kg / hr and a low molecular weight polypropylene. / Graft modified wax / Styrene mixture,
In the heating zone 2, the low molecular weight polypropylene and the graft-modified wax in the mixture were heated and dissolved. The residence time of the mixture in the heating zone 2 was 14 seconds, and the outlet temperature was 115 ° C.

The heat-melted low molecular weight polypropylene / graft-modified wax / styrene mixture is passed through line 7 from heating zone 2 to one of the two inlets of the suction port of the modified ebara mizar in cooling zone 3 into the ebara miruser. And styrene at 20 ° C. at a flow rate of 86 kg / hr through the line 8 having the liquid feed pump 5 on the way from the other inlet of the inlet of the modified Ebara Milzer in the cooling zone into the Ebara Milzer. These two liquids are simultaneously circulated under the stirring of an Ebara Milser stirrer and rapidly cooled by instantaneous mixing to precipitate low-molecular-weight polypropylene and graft-modified wax, and to precipitate low-molecular-weight polypropylene / graft-modified wax / styrene. A dispersion (4) was obtained. Then, the low molecular weight polypropylene /
The graft-modified wax / styrene dispersion (4) was drained. The temperature of the dispersion (4) at the time of outflow was 52 ° C., and the flow rate was 129 kg / hr. The properties of this dispersion (4) were measured in the same manner as in Synthesis Example 1. Table 1 shows the obtained results. Further, the shape of the wax particles in this dispersion (4) was spherical.

[0063]

[Table 1]

Synthesis Example 5 Polyvinyl alcohol (PVA-) was added to a flask equipped with a stirrer, an inert gas inlet tube, a reflux condenser, and a thermometer.
205 parts, manufactured by Kuraray Co., Ltd.) was charged with 200 parts of deionized water in which 0.1 part was dissolved. 97.5 parts of styrene and 2.5 parts of glycidyl methacrylate previously adjusted there.
Benzoyl peroxide 8
The mixture in which the parts were dissolved was charged and stirred at high speed to form a uniform suspension. Then, the mixture was heated to 80 ° C. while blowing in nitrogen gas, and the mixture was stirred at this temperature for 5 hours to carry out a polymerization reaction. Then, water was removed to obtain a polymer (1) having an epoxy group as a reactive group.

40 parts of a polymer (1) having an epoxy group as a reactive group, 15 parts of carbon black MA-100R (manufactured by Mitsubishi Kasei Kogyo KK), and a charge control agent (Aizen Spilon)
Black TRH, 2 parts of Hodogaya Chemical Industry Co., Ltd.) were kneaded using a Labo Plastomill at 160 ° C. and 1000 rpm for 20 minutes, reacted, cooled, pulverized and carbon black graft as a colorant Polymer (1) was obtained.

Synthesis Example 6 20 parts of the polymer (1) having an epoxy group as a reactive group obtained in Synthesis Example 5, 80 parts of a magnetic material MG-RF (manufactured by Mitsui Mining & Smelting Co., Ltd.) and a charge control agent ( Aizen SpilonBlack TR
H, 2 parts of Hodogaya Chemical Industry Co., Ltd.) were kneaded with a Labo Plastomill at 180 ° C. and 100 rpm for 30 minutes, surface-treated, then cooled and pulverized to give a surface treatment as a colorant. A magnetic material (2) was obtained.

Example 1 Low molecular weight polyethylene (high wax 200P) / styrene dispersion (1) 85 parts n-butyl acrylate 15 parts Divinylbenzene 0.2 parts Carbon black graft polymer (1) 50 parts Azobisisobutyro Nitrile 2 parts 2,2'-azobis (2,4-dimethylvaleronitrile) 3 parts A polymerizable composition in which the above components were mixed and dispersed was obtained.

This was mixed with 350 parts of deionized water in which 0.5 part of Hytenol N-08 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was previously dissolved.
Part, T. K. Homomixer (Special Kika Kogyo Co., Ltd.)
Was stirred at 7000 rpm for 5 minutes to form a uniform suspension. Thereafter, the suspension was heated at 75 ° C. for 5 hours to polymerize, thereby obtaining a suspension of colored spherical fine particles having an arithmetic mean diameter of 6.43 μm (Coulter Multisizer, aperture 50 μm).

Five parts of a 10% by weight methanol dispersion of Aerosil R972 (manufactured by Nippon Aerosil) was added to the obtained suspension of the colored spherical fine particles, and the mixture was heated at 65 ° C. for 30 minutes. The mixture was pulverized by a jet mill to obtain a polymerized toner having an average diameter of 6.29 μm. Using the polymerized toner of the present invention, a commercially available copying machine (U-box 1805M
R (manufactured by Konica Corporation), and 5000 images were obtained. As a result, a good image was obtained without occurrence of offset. Table 2 shows the results.

Example 2 In Example 1, low molecular weight polyethylene (high wax 200P) / graft-modified wax (high wax 1) was used instead of low molecular weight polyethylene / styrene dispersion (1).
140H) / Styrene dispersion liquid (2) was used, and the same method as in Example 1 was repeated, to obtain a polymerized toner having a weight-calculated average diameter of 6.51 μm.

Using this polymerized toner, 5000 images were obtained with a commercially available copying machine (Type 4060, manufactured by Ricoh Co., Ltd.). As a result, good images were obtained without occurrence of offset. Table 2 shows the results.

Example 3 Low molecular weight polyethylene (high wax 400P) / graft-modified wax (high wax 3010R) / styrene / n-butyl acrylate dispersion (3) 83 parts Styrene 18 parts Trimethylolpropane triacrylate 0.2 part Surface-treated magnetic substance (2) 100 parts Azobisisobutyronitrile 4 parts A polymerizable composition in which the above components were mixed and dispersed was obtained.

This was mixed with 350 parts of deionized water previously dissolved in 0.5 part of Hytenol N-08 (Daiichi Kogyo Seiyaku Co., Ltd.).
In addition, the mixture was stirred at 7000 rpm for 5 minutes with a homogenizer Histron (manufactured by Nichion Medical Science Instruments Co., Ltd.) to form a uniform suspension. Thereafter, the suspension was heated at 75 ° C. for 5 hours to be polymerized, and the weighted arithmetic mean diameter was 7.38.
μm (Coulter Multisizer, aperture 50μm)
Was obtained.

5 parts of a 10% by weight methanol dispersion of Aerosil R972 (manufactured by Nippon Aerosil) was added to the obtained suspension of the colored spherical fine particles, and the mixture was heated at 65 ° C. for 30 minutes. The mixture was pulverized by a jet mill to obtain a polymerized toner having an average diameter of 7.88 μm. A commercially available copying machine (RICOPY FT4) is prepared using the polymerized toner of the present invention.
630 (manufactured by Ricoh Co., Ltd.), images were obtained, and good images were obtained without occurrence of offset. Table 2 shows the results.

Comparative Example 1 In Synthesis Example 2, in place of Mitsui High Wax 200P, Mitsui High Wax 210P (crystallinity 75%, softening point 120 ° C., molecular weight 2000) Mitsui Petrochemical Industry Co., Ltd.
The same method as in Synthesis Example 2 was repeated except that the above-mentioned method was used to obtain a low-molecular-weight polyethylene / graft-modified wax / styrene dispersion (5). The amount of wax in the low molecular weight polyethylene / graft-modified wax / styrene dispersion (5) was 4.8%, the average particle diameter of the wax was 0.91 μm, the shape of the wax particles was spindle-shaped, and aggregates and coarse particles were Did not. Further, in this dispersion liquid (5), the formation of a polymer by thermal polymerization of styrene was not observed.

Then, in Example 2, low molecular weight polyethylene / graft-modified wax / styrene dispersion (2)
The same procedure as in Example 2 was repeated, except that the low-molecular-weight polyethylene / graft-modified wax / styrene dispersion (5) was used in place of the above, to obtain a polymerized toner having a weight-average diameter of 6.18 μm. When an image was formed using a commercially available copying machine (Type 4060, manufactured by Ricoh Co., Ltd.) using this polymerized toner, offset occurred and a satisfactory image was not obtained. Table 2 shows the results.

Comparative Example 2 In Synthesis Example 2, Mitsui High Wax 320P (crystallinity 65%, softening point 114 ° C., molecular weight 3000) was used instead of Mitsui High Wax 200P.
The same method as in Synthesis Example 2 was repeated except that the above-mentioned method was used to obtain a low-molecular-weight polyethylene / graft-modified wax / styrene dispersion (6). The amount of wax in this low molecular weight polyethylene / graft-modified wax / styrene dispersion (6) was 4.3%, the average particle diameter of the wax was 1.11 μm, the shape of the wax particles was spindle-shaped, and aggregates and coarse particles were Did not. Further, in this dispersion liquid (6), the formation of a polymer by thermal polymerization of styrene was not observed.

Then, in Example 2, low molecular weight polyethylene / graft-modified wax / styrene dispersion (2)
The same procedure as in Example 2 was repeated, except that the low-molecular-weight polyethylene / graft-modified wax / styrene dispersion (6) was used instead of, to obtain a polymerized toner having a weight-average diameter of 7.02 μm. When an image was formed using a commercially available copying machine (Type 4060, manufactured by Ricoh Co., Ltd.) using this polymerized toner, offset occurred and a satisfactory image was not obtained. Table 2 shows the results.

Comparative Example 3 Low molecular weight polypropylene (Biscol 660P) / graft-modified wax (High Wax 1160H) / Styrene dispersion (4) 35 parts Styrene 55 parts N-butyl acrylate 15 parts Divinylbenzene 0.2 parts Carbon black graft Polymer (1) 50 parts Azobisisobutyronitrile 2 parts 2,2'-azobis (2,4-dimethylvaleronitrile) 3 parts A polymerizable composition in which the above components were mixed and dispersed was obtained.

This was mixed with 350 parts of deionized water previously dissolved in 0.5 part of Hytenol N-08 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).
Part, T. K. Homomixer (Special Kika Kogyo Co., Ltd.)
Was stirred at 7000 rpm for 5 minutes to form a uniform suspension. Thereafter, the suspension was heated at 75 ° C. for 5 hours to polymerize, thereby obtaining a suspension of colored spherical fine particles having an arithmetic mean diameter of 5.68 μm (Coulter Multisizer, aperture 50 μm).

5 parts of a 10% by weight methanol dispersion of Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) was added to the obtained suspension of colored spherical fine particles, and the mixture was heated at 65 ° C. for 30 minutes. The mixture was pulverized by a jet mill to obtain a polymerized toner having an average diameter of 5.52 μm. Using this polymerized toner, a commercially available copying machine (U-box 1805MR)
(Konica Corporation), an offset was generated and a satisfactory image could not be obtained. Table 2 shows the results.

Comparative Example 4 Low molecular weight polyethylene Mitsui Hi-Wax 200P (manufactured by Mitsui Petrochemical Industries, Ltd.) was previously pulverized with a jet mill to obtain a powder having a weight-average arithmetic mean diameter of 9.31 μm. The particle size distribution of the wax particles was wide and the shape was not fibrous.

Styrene 85 parts N-butyl acrylate 15 parts Divinylbenzene 0.2 parts Carbon black graft polymer (1) 50 parts Azoisobutyronitrile 2 parts 2,2′-azobis (2,4-dimethylvaleronitrile) 3 parts The above-mentioned ground wax was added to the polymerizable composition obtained by mixing and dispersing the above components, and the mixture was uniformly dispersed to obtain the polymerizable composition. This was obtained from Hytenol N-08 (Daiichi Kogyo Seiyaku Co., Ltd.).
8 parts to 350 parts of previously dissolved deionized water.
K. 70 with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.)
The mixture was stirred at 00 rpm for 5 minutes to form a uniform suspension. Thereafter, the suspension was heated at 75 ° C. for 5 hours to polymerize, thereby obtaining a suspension of colored spherical fine particles having an arithmetic mean diameter of 13.6 μm (Coulter Multisizer, aperture 100 μm).

To the obtained suspension of colored spherical fine particles, 5 parts of a 10% by weight methanol dispersion of Aerosil R972 (produced by Nippon Aerosil Co., Ltd.) was added, and the mixture was heated at 65 ° C. for 30 minutes. The mixture was crushed by a jet mill to obtain a polymerized toner having an average diameter of 12.1 μm. Using this polymerized toner, a commercially available copying machine (U-box 1805MR)
(Konica Corporation), an offset was generated and a satisfactory image could not be obtained. Table 2 shows the results.

Comparative Example 5 A low molecular weight polyethylene (high wax 200P) / styrene dispersion (1) was devolatilized by a vacuum dryer to obtain a fine dispersion of Mitsui High Wax 200P (manufactured by Mitsui Petrochemical Industries, Ltd.). Was. The weight arithmetic mean diameter was 1.69 μm.

Styrene 85 parts N-butyl acrylate 15 parts Divinylbenzene 0.2 parts Carbon black graft polymer (1) 50 parts Azoisobutyronitrile 2 parts 2,2′-azobis (2,4-dimethylvaleronitrile) 3 parts The polymerizable composition obtained by mixing and dispersing the above components was added to 350 parts of deionized water in which 0.8 part of Hytenol N-08 (Daiichi Kogyo Seiyaku Co., Ltd.) was previously dissolved. K. The mixture was stirred with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at 7000 rpm for 5 minutes to form a uniform suspension. Thereafter, the suspension was heated at 75 ° C. for 5 hours to polymerize, thereby obtaining a suspension of colored spherical fine particles having an arithmetic mean diameter of 5.09 μm (Coulter Multisizer, aperture 50 μm).

To the obtained suspension of colored spherical fine particles, 5 parts of a 10% by weight methanol dispersion of Aerosil R972 (produced by Nippon Aerosil Co., Ltd.) was added, heated at 65 ° C. for 30 minutes, and the solid content was filtered and dried. The mixture was pulverized by a jet mill to obtain a polymerized toner having an average diameter of 5.22 μm. Using this polymerized toner, a commercially available copying machine (U-box 1805MR)
When an image was produced by Konica Corporation, offset was generated, and furthermore, a jam occurred and it was not usable.

After 100 parts of this polymerized toner and 5 parts of the finely dispersed polyethylene wax were mixed,
By treating with HS-1 (manufactured by Nara Machinery Co., Ltd.) for 30 seconds, polyethylene wax was immobilized on the surface of the toner particles. Using this toner, a commercially available copying machine (U-bix
1805 MR (manufactured by Konica Corporation), an image with high resolution was obtained without offset up to 1500 sheets. However, when the image was obtained, fog and scattering increased, and the fluidity of the toner increased. It was found that the charge was deteriorated and the rising of the charge became worse. Table 2 shows the results.

[0089]

[Table 2]

[0090]

As described above, the present invention provides a binder resin,
In a method for producing a polymerized toner containing at least a colorant and / or a magnetic powder and a wax component, a polyethylene wax having a crystallinity of more than 80% is used as a wax component, and the polyethylene wax is first used in a polymerizable monomer. By cooling after heating and melting, the polyethylene wax is dispersed in a short fiber form in the polymerizable monomer, and then the polymerizable monomer and a coloring agent and / or in the presence of the short fibrous body of the polyethylene wax. Since the polymerizable composition containing the magnetic powder is subjected to suspension polymerization in an aqueous medium, the wax is dispersed and contained as a short fibrous material in the obtained polymerized toner particles. And a portion of the short fibrous body is also located near the outer surface of the polymerized toner particles. In addition, since the wax component is exposed on the surface of the toner particles and is uniformly dispersed without being contained only in specific toner particles, the wax component also has properties such as blocking resistance and fixing property. It will be excellent.

[Brief description of the drawings]

FIG. 1 is a schematic view showing an example of an apparatus configuration used in a wax dissolving and precipitating step in a method for producing a polymerized toner of the present invention,

FIG. 2 is a schematic diagram showing an example of a more specific configuration of a heating zone and a cooling zone of an apparatus used in a wax melting and precipitation step;

FIG. 3 is a schematic view showing another example of an apparatus configuration used in a wax dissolving and precipitation step in the method for producing a polymerized toner of the present invention;

FIG. 4 is a cross-sectional view schematically showing the structure of the polymerized toner of the present invention.

[Explanation of symbols]

1 ... mixing zone, 2 ... heating zone, 3 ... cooling zone, 1
2: Spiral heat exchanger, 13: High-speed shear mixer, 1
4: mixing container, 21: mixing and heating zone, 23: cooling zone, 31: polymerized toner, 32: short fibrous body of polyethylene wax.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-73770 (JP, A) JP-A-4-188156 (JP, A) JP-A-62-295073 (JP, A) JP-A-54-1979 115135 (JP, A) (58) Field surveyed (Int. Cl. ⁶ , DB name) G03G 9/08

Claims (9)

(57) [Claims] 1. A polymerized toner containing at least a binder resin, a colorant and / or a magnetic powder, and a wax component, wherein the wax component is a polyethylene wax having a crystallinity of more than 80%. Wherein the wax is dispersed as a short fibrous material. 2. The polyethylene wax has a softening point of 120 ° C.
The polymerized toner according to claim 1, having a molecular weight of 1,000 to 20,000. 3. An average particle size of the toner is 2 to 20 μm, and an average length of the short fibrous body of the wax is 0.5 to 20 μm.
The polymerized toner according to claim 1, wherein 4. A method for producing a polymerized toner containing at least a binder resin, a colorant and / or a magnetic powder, and a wax component, wherein the crystallinity of the polymerizable monomer is 8 or less.
By heating, melting and cooling the polyethylene wax exceeding 0%, the polyethylene wax is dispersed in the form of short fibers in the polymerizable monomer in advance, and the polymerizable monomer is dispersed in the presence of the short fibrous body of the polyethylene wax. A method for producing a polymerized toner, comprising subjecting a polymerizable composition containing a body, a colorant and / or a magnetic powder to suspension polymerization in an aqueous medium. 5. The polyethylene wax has a softening point of 120 ° C.
The method for producing a polymerized toner according to claim 4, wherein the molecular weight is from 1,000 to 20,000. 6. An average length of the short fibrous body of polyethylene wax is 0.5 to 20 μm, and an average particle diameter of suspended particles of the polymerizable composition during suspension polymerization is 2 to 20 μm.
The method for producing a polymerized toner according to claim 4, wherein the toner is adjusted to: 7. The step of dispersing the polyethylene wax into short fibers in the polymerizable monomer is performed by mixing a mixture of the polymerizable monomer and the wax with a heat transfer area of 0.3 mm / cc of heating capacity.
is supplied to a heating zone having a heating device having a size of ² cm or more to heat and melt the wax.Then, a heated mixture derived from the heating zone is supplied to a cooling zone. The method for producing a polymerized toner according to any one of claims 4 to 6, wherein the method is performed by a continuous process of precipitating and removing a wax dispersion in which the wax is dispersed in a polymerizable monomer from the cooling zone. 8. The step of dispersing the polyethylene wax into short fibers in the polymerizable monomer comprises: supplying a blend of the polymerizable monomer and the wax to a heating zone to heat and dissolve the wax; In a cooling zone equipped with any one of a high-speed shearing mixer, an ultrasonic homogenizer, and an agitator comprising a pipe mixer, a heating mixture derived from the heating zone and a different flow path from the heating mixture are supplied. The polymerizable monomer as a cooling liquid to be supplied is supplied simultaneously to the vicinity of the stirring region of the stirring device and cooled to precipitate wax, and the wax is dispersed from the cooling zone to the polymerizable monomer. The method for producing a polymerized toner according to any one of claims 4 to 6, wherein the method is performed by a continuous process of removing a dispersion. 9. The step of dispersing polyethylene wax into short fibers in the polymerizable monomer comprises the step of dispersing a blend of the polymerizable monomer and the wax with a heat transfer area of 0.3 mm / cc of heating capacity.
The heating zone having a heating device having a heating device of not less than ² cm2, the wax is heated and dissolved, and then, in a cooling zone provided with any stirring device consisting of a high-speed shearing mixer, an ultrasonic homogenizer and an in-pipe mixer, The heating mixture derived from the heating zone and the polymerizable monomer as a cooling liquid supplied by a separate flow path from the heating mixture are supplied simultaneously to the vicinity of the stirring area of the stirring device and cooled. 7. The method according to claim 4, wherein the wax is deposited and a wax dispersion obtained by dispersing the wax in a polymerizable monomer is taken out of the cooling zone.
The method for producing a polymerized toner according to any one of the above.