JP2003316069A - Polymerization toner and method for manufacturing same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing polymerization toner in a suspension polymerization method for obtaining polymer fine particles suitable for the manufacture of toner so as to narrow the size distribution of the obtained polymer fine particles and to obtain high production efficiency. <P>SOLUTION: In the polymerization toner containing suspension polymerized fine particles obtained by suspension polymerization of a polymerizable monomer composition containing at least a polymerizable monomer and a coloring agent in an aqueous dispersion medium, the suspension polymerized fine particles are obtained by preliminarily dispersing the polymerizable monomer composition by a batch method in the aqueous dispersion medium to prepare a pre-dispersion liquid, introducing the liquid into a device which continuously adds shear force to prepare a dispersion liquid of the polymerizable monomer composition having a desired liquid drop diameter, and successively subjecting the liquid to a polymerization process to complete the polymerization. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerization toner used in electrophotography, electrostatic recording, magnetic recording and the like, and a method for producing the same.

[0002]

2. Description of the Related Art A toner used in an electrophotographic method has excellent fluidity and stable triboelectric charging property, does not cause fog on the photoreceptor and a decrease in image density for a long time, and has a high quality. It is required that printing is possible. If the fluidity of the toner is poor, the supply of the developer will be inadequate, and the image will be blurred or the image density will be reduced. In addition, cleaning failure occurs, the developer remains on the photosensitive member, fog occurs, and filming by toner occurs. When the toner film is formed on the photoreceptor, white spots and black stains occur on the image, and the image quality deteriorates.

In order for the toner to exhibit excellent fluidity and form a high quality image, it is desirable that the toner has a spherical shape and a sharp particle size distribution.

Conventionally, toners used for these purposes are generally toners having a desired particle size by a fine pulverizer and a classifier after melt-mixing a colorant consisting of dyes and pigments in a thermoplastic resin and uniformly dispersing them. Has been manufactured as.

While this method of manufacture can produce fairly good toners, it does have certain limitations, ie, the choice of toner materials. For example, the material must have sufficient brittleness to be comminuted in economically sound manufacturing equipment. However, when the material is made brittle in order to meet such requirements, the particle size distribution of the particles formed when the material is actually finely pulverized at a high speed tends to be broad, and particularly the ratio of the formed fine particles is large. The problem arises. In order for the toner to exhibit satisfactory developing characteristics, its particle size distribution must be narrow to some extent. Therefore, it is necessary to classify the particles obtained by pulverization to remove coarse particles and fine particles. Therefore, generally, the pulverization method has a poor yield and a low toner yield.

Further, such a material having high brittleness is liable to be further pulverized or pulverized when it is used for development in a copying machine or the like, which adversely affects the developability.

Further, according to this method, it is difficult to completely and uniformly disperse solid fine particles such as a colorant in the resin.
Depending on the degree of dispersion, fog may increase, image density may decrease, and color mixture and transparency may be poor. Therefore, sufficient attention should be paid to the dispersion of the colorant. Also,
Exposure of the colorant to the fracture surface of the crushed particles may cause fluctuations in developing characteristics.

Further, in the pulverization method, a spherical toner having a uniform surface cannot be produced, and it is difficult to obtain a toner having satisfactory fluidity and triboelectric chargeability.

In the toners obtained by the pulverization method, there is a limitation in adding a releasing agent such as wax. That is, in order to obtain a sufficient level of dispersibility of the release agent,
At the kneading temperature with the resin, it is necessary to maintain a certain degree of viscosity, and the content of the release agent is set to about 5% by mass or less. Due to such restrictions, there is a limit to the fixability and releasability of the toner by the pulverization method.

In order to overcome the problems of the toner due to the pulverization method, Japanese Patent Publications No. 36-10231 and 43-1.
Various polymerization method toners and methods for producing the same have been proposed, including suspension polymerization method toners described in JP-A No. 0799 and 51-14895. For example, in a suspension polymerization toner, a polymerizable monomer, a colorant, a release agent, a polymerization initiator, and if necessary, a crosslinking agent, a charge control agent, and other additives are uniformly dissolved or dispersed. After forming a monomer composition, this monomer composition is dispersed in a continuous phase containing a dispersion stabilizer, for example, in water using a suitable stirrer, and at the same time, a polymerization reaction is performed to obtain a desired particle size. To obtain toner particles. Since this method does not include a crushing step at all, the toner does not need to be brittle, a soft material can be used as the resin, and the colorant is not exposed on the surface of the particles, resulting in a uniform surface. There is an advantage that it has a triboelectric charging property.
Further, since the obtained toner has a relatively sharp particle size distribution, the toner can be obtained in a high yield even when the classification step is required. Furthermore, according to this method, in addition to the restrictions imposed on the above-mentioned pulverized toner, a release agent such as wax can be surely included, and good fixability and offset resistance can be obtained. . Since the polymerized toner obtained by this method is spherical and has a uniform surface,
It is characterized by good transferability, good development characteristics even after continuous development a number of times, less stress on the toner, and less filming on the photoreceptor.

[0011]

As described above, the toner produced by the suspension polymerization method has some advantages as compared with the toner produced by the pulverization method, but even when the suspension polymerization method is used, Generation of fine particles and coarse particles of some undesired particle size is inevitable. If the amount of fine particles or coarse particles is large, it is not preferable in terms of toner properties and production efficiency as described above, so it is necessary to narrow the particle size distribution during suspension polymerization as much as possible.

For the above-mentioned purpose, for example, Japanese Patent Laid-Open No. 1-22
JP-A-23470, JP-A-6-27717, JP-A-6-124000 and the like disclose a method of using a suspension stabilizer such as a surfactant in addition to a suspension stabilizer which is usually used. There is. However, in these methods, it is necessary to consider the effect of the suspension stabilizing auxiliary agent on the toner properties, and if the suspension stabilizing auxiliary agent needs to be removed, a removal step must be added, so that productivity is increased. Is not preferable from the viewpoint of. Further, JP-A-3-95564, JP-A-7-281480, and JP-A-10-18.
Japanese Patent No. 6719 discloses a method that does not rely on stirrers having a high shearing force that are generally used in the granulation step. According to these methods, a toner having a considerably good particle size distribution can be obtained, but it is considered that it is difficult to expand to an industrial scale from the viewpoints of productivity and maintainability, and therefore, the production efficiency is higher. A method is desired.

According to Japanese Examined Patent Publication No. 6-102681 and the like, as a method for achieving a narrow particle size distribution and high productivity, as shown in FIG. 5, a polymerizable monomer composition and an aqueous dispersion medium are used. A dispersion liquid for the polymerizable monomer composition is prepared by suspension in each of the tanks 41 and 42, which are separately supplied to the high-shearing agitator 44 simultaneously and continuously through independent paths from the respective tanks. A method of doing is disclosed. According to these methods, particles having a fairly narrow particle size distribution can be produced, but the polymerizable monomer composition and the aqueous dispersion medium are independently supplied to a high shearing force agitator, and for the first time, both liquids are mixed / mixed. Since the particles are dispersed, the density distribution in the high-shearing agitator becomes non-uniform, and the throwing energy per unit flow rate varies.Therefore, the particle size distribution of the resulting polymer fine particles must be slightly broad. I can't.

Therefore, an object of the present invention is to narrow the particle size distribution of the obtained polymer fine particles and to produce the polymer fine particles in the suspension polymerization method for obtaining the polymer fine particles suitable for the production of the toner particularly used in the electrophotographic method. An object of the present invention is to provide a method for producing a polymerized toner having high efficiency.

Another object of the present invention is to have a narrow particle size distribution,
An object of the present invention is to provide a polymerized toner that can obtain a good image when used in an electrophotographic method and does not cause filming on a photoreceptor or the like.

[0016]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found the following method.

That is, according to the present invention, a heavy polymer having suspension polymer fine particles obtained by suspension polymerization of a polymerizable monomer composition containing at least a polymerizable monomer and a colorant in an aqueous dispersion medium. In the case of a legal toner, the polymerizable monomer composition is preliminarily dispersed in an aqueous dispersion medium by a batch method to obtain a preliminary dispersion liquid, which is then introduced into an apparatus for continuously applying a shearing force to a desired liquid. There is provided a polymerization method toner having suspension polymer fine particles obtained by forming a polymerizable monomer composition dispersion having a droplet size and subsequently completing the polymerization in a polymerization step.

Furthermore, according to the present invention, a heavy polymer having suspension polymer fine particles obtained by suspension polymerization of a polymerizable monomer composition containing at least a polymerizable monomer and a colorant in an aqueous dispersion medium. In the method for producing a legal toner, the polymerizable monomer composition is predispersed in an aqueous dispersion medium by a batch method to obtain a predispersion liquid, which is then introduced into a device for continuously applying a shearing force. To form a polymerizable monomer composition dispersion having a desired droplet size, and subsequently to complete the polymerization in a polymerization step to obtain suspension polymer fine particles. It

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below in detail with reference to the drawings, but the present invention is not limited to these drawings. In addition, each of the tanks described below has an appropriate temperature adjusting means and an appropriate stirring means.

FIG. 1 is an example of an apparatus used to carry out the present invention. In the figure, reference numeral 1 is a polymerizable monomer composition tank, reference numeral 2 is an aqueous dispersion medium tank, reference numeral 3 is a preliminary dispersion tank, reference numeral 4 is a metering pump, reference numeral 5 is a device for applying a shearing force, reference numeral 6 is a polymerization tank. Are shown respectively. In the polymerizable monomer composition tank 1, the polymerizable monomer and additives such as a colorant, a release agent, a charge control agent, a cross-linking agent and a polymerization initiator are uniformly dispersed by a stirring device or a dispersing device that is usually used. To be a polymerizable monomer composition. On the other hand, an aqueous dispersion medium containing a dispersion stabilizer is prepared in the aqueous dispersion medium tank 2.
Both are put into the pre-dispersion tank 3 and preliminarily dispersed by a batch method by means such as stirring to obtain a pre-dispersion liquid. The polymerizable monomer composition dispersion is obtained by supplying the preliminary dispersion to the device 5 that continuously applies a shearing force using the metering pump 4. The polymerizable monomer composition dispersion is introduced into the polymerization tank 6, and if necessary, the polymerization is completed with stirring to obtain polymer fine particles having a narrow particle size distribution. Preliminary dispersion is performed batchwise to obtain a preliminarily dispersed liquid having a uniform dispersion density of the polymerizable monomer composition in the aqueous dispersion medium, so that this is continuously supplied to the device for applying the shearing force in the subsequent stage. In such a case, the throwing energy per unit flow rate becomes uniform, so that it is considered that a polymerizable monomer composition dispersion liquid having a more uniform droplet diameter can be obtained.

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

Another example of the apparatus used to carry out the present invention will be described with reference to FIG. In the figure, reference numeral 11 is a polymerizable monomer composition tank, reference numeral 12 is an aqueous dispersion medium tank, reference numeral 13 is a preliminary dispersion tank, reference numeral 14 is a metering pump, reference numeral 15 is a polymerization initiator tank, and reference numeral 16 is shearing force. The apparatus, which is designated by reference numeral 17, is a polymerization tank. In the polymerizable monomer composition tank 11, the polymerizable monomer and additives such as a colorant, a release agent, a charge control agent and a cross-linking agent are uniformly dissolved or dispersed by a commonly used stirring device or dispersion device. A sessile polymerizable monomer composition. On the other hand, an aqueous dispersion medium containing a dispersion stabilizer is prepared in the aqueous dispersion medium tank 12. Both are put into the preliminary dispersion tank 13 and preliminarily dispersed in a batch manner by means such as stirring to obtain a preliminary dispersion liquid. The preliminary dispersion liquid is supplied to a device 16 for continuously applying a shearing force by using a metering pump 14. At the same time, by supplying the polymerization initiator or the polymerization initiator solution or the suspension of the polymerization initiator held in the polymerization initiator tank 15 to the device 16 for continuously applying the shearing force using the metering pump 14, A polymerizable monomer composition dispersion is obtained. Retaining or predispersing the polymerizable monomer composition in the polymerizable monomer composition tank 11 by supplying the polymerization initiator from the independent tank without adding it to the polymerizable monomer composition. Even if the liquid is held in the pre-dispersion tank 13 for a long time, the polymerization reaction is not promoted by the polymerization initiator, so that the physical properties of each liquid do not change during the manufacturing process. Further, the risk of the polymerization reaction running away is reduced, so that the safety is excellent. Further, since the adhesion of the polymer does not occur in the polymerizable monomer composition tank 11 and the preliminary dispersion tank 13, these are removed. This is advantageous in terms of productivity because toner can be repeatedly manufactured without steps. The polymerizable monomer composition dispersion is introduced into the polymerization tank 17, and if necessary, the polymerization is completed with stirring to obtain polymer fine particles having a narrow particle size distribution.

Another example of the apparatus used to carry out the present invention will be described with reference to FIG. In the figure, reference numeral 21 is a polymerizable monomer composition tank, reference numeral 22 is an aqueous dispersion medium tank, reference numeral 23 is a preliminary dispersion tank, reference numeral 24 is a preliminary dispersion liquid storage tank, reference numeral 25 is a metering pump, reference numeral 26 is a polymerization initiator tank. Reference numeral 27 indicates a device for applying a shearing force, and reference numeral 28 indicates a polymerization tank. In the polymerizable monomer composition tank 21, the polymerizable monomer and additives such as a colorant, a release agent, a charge control agent and a cross-linking agent are uniformly dissolved or dispersed by a commonly used stirring device or dispersion device. A sessile polymerizable monomer composition. On the other hand, an aqueous dispersion medium containing a dispersion stabilizer is prepared in the aqueous dispersion medium tank 22. Both are put into the preliminary dispersion tank 23 and preliminarily dispersed by a batch method by means such as stirring to obtain a preliminary dispersion liquid. After transferring the preliminary dispersion liquid to the preliminary dispersion liquid storage tank 24, the preliminary dispersion liquid is supplied from the preliminary dispersion liquid storage tank 24 to a device 27 for continuously applying a shearing force using a metering pump 25. At the same time, by supplying the polymerization initiator or the polymerization initiator solution or the suspension of the polymerization initiator held in the polymerization initiator tank 26 to the device 27 for continuously applying the shearing force using the metering pump 25, A polymerizable monomer composition dispersion is obtained. On the other hand, during this period, the preliminary dispersion process is performed again in the preliminary dispersion tank 23, and the obtained preliminary dispersion liquid is stored in the preliminary dispersion liquid storage tank 2
Before all the pre-dispersion liquid in 4 is introduced into the shear-applying device 27, the pre-dispersion liquid is transferred to the pre-dispersion liquid storage tank, so that the pre-dispersion liquid is continuously supplied to the shearing force-applying device 27. To be done. The polymerizable monomer composition dispersion liquid obtained by passing the preliminary dispersion liquid through a device 27 for applying a shearing force is introduced into a polymerization tank 28 and narrowed by completing the polymerization with stirring if necessary. Polymer fine particles having a particle size distribution can be obtained.

Another example of the apparatus used to carry out the present invention will be described with reference to FIG. In the figure, reference numeral 31 is a polymerizable monomer composition tank, reference numeral 32 is an aqueous dispersion medium tank, reference numeral 33 is a preliminary dispersion tank, reference numeral 34 is a preliminary dispersion liquid storage tank, reference numeral 35 is a metering pump, and reference numeral 36 is a polymerization initiator tank. Reference numeral 37 indicates a static mixer, reference numeral 38 indicates a device for applying a shearing force, and reference numeral 39 indicates a polymerization tank. In the polymerizable monomer composition tank 31, the polymerizable monomer and additives such as a colorant, a release agent, a charge control agent and a cross-linking agent are uniformly dissolved or dispersed by a commonly used stirring device or dispersion device. A sessile polymerizable monomer composition. On the other hand, an aqueous dispersion medium containing a dispersion stabilizer is prepared in the aqueous dispersion medium tank 32. Both are put into the preliminary dispersion tank 33 and preliminarily dispersed in a batch manner by means such as stirring to obtain a preliminary dispersion liquid. After the preliminary dispersion liquid is transferred to the preliminary dispersion liquid storage tank 34, the preliminary dispersion liquid is transferred from the preliminary dispersion liquid storage tank 34 to the static mixer 37 using a metering pump 35.
Supply to. Simultaneously with this, the polymerization initiator or the polymerization initiator solution or the suspension of the polymerization initiator held in the polymerization initiator tank 36 is continuously supplied to the static mixer 37 using the metering pump 35 so that the preliminary dispersion is performed. Since the liquid and the polymerization initiator are supplied to the device 38 for applying a shearing force in a sufficiently mixed state, the throwing energy per unit flow rate becomes constant, and a more uniform polymerizable monomer composition dispersion liquid is obtained. can get. On the other hand, during this period, the preliminary dispersion process is performed again in the preliminary dispersion tank 34, and the obtained preliminary dispersion liquid is re-prepared in the preliminary dispersion liquid storage tank 34 before all the preliminary dispersion liquid in the preliminary dispersion liquid storage tank 34 is introduced into the static mixer 37. By transferring to the static mixer, the preliminary dispersion liquid is supplied to the static mixer 37 without interruption.
The polymerizable monomer composition dispersion obtained by passing the pre-dispersion through the device 38 for applying a shearing force is the polymerization tank 3
The polymer fine particles having a narrow particle size distribution can be obtained by introducing the compound into the polymer No. 9 and completing the polymerization with stirring if necessary.

As the polymerizable monomer used in the toner of the present invention, a vinyl-based polymerizable monomer capable of radical polymerization is used. As the vinyl-based polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Monofunctional polymerizable monomers include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene and pn-butylstyrene. , P-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p- Styrene derivatives such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-
Propyl acrylate, n-butyl acrylate, is
o-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate Acrylic polymerizable monomers such as ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl Methacrylate, tert
-Butyl methacrylate, n-amyl methacrylate,
Methacrylic polymerizable monomers such as n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid ester, Vinyl acetates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone, vinyl isopropyl ketone Such vinyl ketones are listed.

As the polyfunctional polymerizable monomer, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy)
Phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate,
1,3-butylene glycol dimethacrylate, 1,6
-Hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxydiethoxy) phenyl) propane, 2,2'-bis (4- (methacryloxypolyethoxy) ) Phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether and the like.

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

Examples of the colorant used in the present invention include carbon black, iron black, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Mordant Red 30, C.I. I. Direct Blue 1,
C. I. Direct Blue 2, C.I. I. Acid Blue 9, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Mordant Blue 7, C.I. I. Direct Green 6, C.I.
I. Basic Green 4, C.I. I. Dyes such as Basic Green 6, Yellow Lead, Cadmium Yellow, Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NC
G, tartrazine lake, molybdenum orange, permanent orange GTR, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt, brilliant carmine 3B, fast violet B, methyl violet lake, navy blue,
Pigments such as cobalt blue, alkali blue lake, Victoria blue lake, quinacridone, rhodamine lake, phthalocyanine blue, fast sky blue, pigment green B, malachite green lake, and final yellow green G are listed.

In selecting the colorant, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the colorant, and it is preferable to carry out surface modification, for example, hydrophobic treatment with a substance that does not inhibit polymerization. It's better to leave. In particular, since many dyes and carbon black have a polymerization inhibitory property, caution is required when using them. A preferred method of surface-treating a dye system is a method of polymerizing a polymerizable monomer in the presence of these dyes in advance, and the obtained colored polymer is added to the polymerizable monomer composition. Further, the carbon black may be subjected to a treatment similar to that of the above dye, or a graft treatment with a substance that reacts with the surface functional group of the carbon black, for example, polyorganosiloxane.

As the release agent, a wax in a solid state at room temperature is preferable, and a solid wax having a melting point of 40 to 100 ° C. is particularly preferable in terms of toner blocking resistance, multi-sheet durability, low-temperature fixing property and offset resistance.

As the wax, paraffin wax, polyolefin wax, microcrystalline wax, polymethylene wax such as Fischer-Tropsch wax, amide wax, higher fatty acid, long chain alcohol, ester wax and graft compounds thereof,
Examples thereof include derivatives such as block compounds, and those having a sharp maximum endothermic peak of the DSC endothermic curve from which low molecular weight components have been removed are preferable.

Examples of waxes preferably used include linear alkyl alcohols having 15 to 100 carbon atoms, linear fatty acids, linear acid amides, linear esters and montan derivatives. Those in which impurities such as liquid fatty acid have been previously removed from these waxes are more preferable.

In order to improve the translucency of the fixed image, a solid ester wax is particularly preferable, and a solid ester wax having a melting point of 40 to 100 ° C. is preferably used.

The release agent is contained in an amount of 1 to 40 parts by weight, preferably 4 to 30 parts by weight, based on 100 parts by weight of the polymerizable monomer.

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

Known charge control agents can be used. For example, organometallic compounds and chelate compounds are effective for controlling the toner to be negatively charged. Monoazo dye metal compounds, acetylacetone metal compounds, Examples thereof include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. Further, urea derivatives, salicylic acid-containing compounds, quaternary ammonium salts, calixarene, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene-acrylic-sulfonic acid copolymers, non-metals Examples thereof include carboxylic acid compounds.

To control the toner to be positively charged, a modified product of nigrosine and a fatty acid metal salt, a quaternary compound such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, etc. Ammonium salts, onium salts such as phosphonium salts which are analogs thereof, lake pigments thereof, triphenylmethane dyes and lake pigments thereof (as a laker, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid) , Tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids,
Dibutyltin oxide, dioctyltin oxide,
There are diorgano tin oxides such as dicyclohexyl tin oxide, dibutyl tin borate, dioctyl tin borate, and diorgano tin borates such as dicyclohexyl tin borate, and these can be used alone or in combination of two or more kinds. Of these, a charge control agent such as a nigrosine type quaternary ammonium salt is particularly preferably used.

These charge control agents are polymerizable monomers 100
It is preferable to use 0.01 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to parts by mass.

As the polymerization initiator which can be used in the present invention, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'- Azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,
Azo-based polymerization initiators such as 4-dimethylvaleronitrile and azobismethylbutyronitrile; benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis (benzoylper) (Oxy) hexane, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclododecane, t-butylperoxymaleic acid, bis (t-butylperoxy)
Isophthalate, methyl ethyl ketone peroxide,
Organic peroxide type polymerization initiators such as tert-butylperoxy-2-ethylhexanoate, diisopropylperoxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide; hydrogen peroxide, persulfate ( Inorganic peroxides such as sodium salts, potassium salts, ammonium salts, etc.), oxidizing substances such as oxidizing metal salts such as tetravalent cerium salts, divalent iron salts, monovalent copper salts, trivalent chromium Reducing metal salts such as salt, ammonia,
Lower amine (C1 such as methylamine, ethylamine etc.
To about 6 amines), amino compounds such as hydroxylamine, reducing sulfur compounds such as sodium thiosulfate, sodium hydrosulfite, sodium hydrogen sulfite, sodium sulfite, sodium formaldehyde sulfoxylate, lower alcohols (having 1 to 6 carbon atoms). Degree), ascorbic acid or a salt thereof, and a redox type initiator composed of a combination with a reducing substance such as a lower aldehyde (having about 1 to 6 carbon atoms). The initiator is selected with reference to the 10-hour half-life temperature and used alone or in combination. The amount of the polymerization initiator added varies depending on the desired degree of polymerization, but generally 0.5 to 20 parts by mass is added to 100 parts by mass of the polymerizable monomer and used.

Examples of the cross-linking agent include divinylbenzene, 4,4'-divinylbiphenyl, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, glycidyl (meth) acrylate, trimethylolpropane tri (meth) acrylate. And other polyfunctional compounds.

As a dispersion stabilizer for favorably dispersing the polymerizable monomer composition in an aqueous dispersion medium, for example, inorganic oxides such as tricalcium phosphate and magnesium phosphate,
Examples thereof include aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina and titania. Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like. The dispersion stabilizer is preferably used in an amount of 0.2 to 10.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

Commercially available dispersion stabilizers may be used as they are, but in order to obtain finely dispersed particles having a uniform particle size, the inorganic compound may be formed in a dispersion medium with stirring. For example, in the case of tricalcium phosphate,
A dispersant suitable for the suspension polymerization method can be obtained by adding and mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution into water with stirring.

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

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

As the polyester resin, those obtained by condensation polymerization of the following acid component monomers and alcohol component monomers can be used. Acid component monomers include terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid,
Pimelic acid, suberic acid, azelaic acid, sebacic acid,
Examples include camphoric acid, cyclohexanedicarboxylic acid, trimellitic acid and the like. As the alcohol component monomer, ethylene glycol, diethylene glycol,
Alkylene glycols and polyalkylene glycols such as triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane and the like, Examples thereof include bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin, trimethylolpropane and pentaerythritol.

In using the toner produced by the present invention, an external additive may be used for the purpose of imparting various characteristics. The external additive preferably has a particle diameter of 1/10 or less of the average particle diameter of the toner particles from the viewpoint of durability when added to the toner. The particle size of the additive means the average particle size obtained by observation with an electron microscope. Examples of the external additive include metal oxides (aluminum oxide, titanium oxide, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), inorganic substances. Metal salts (calcium sulfate, barium sulfate, calcium carbonate, etc.),
Fatty acid metal salts (zinc stearate, calcium stearate, etc.), carbon black, silica and the like are used.

These external additives are used in an amount of 0.01 to 10 parts by mass, preferably 0.
05-5 parts by mass are used. The external additives may be used alone or in combination of two or more, but those subjected to a hydrophobic treatment are more preferable.

Further, the toner produced by the present invention is
It can also be used as a magnetic toner by containing a magnetic material. In this case, the magnetic material can also serve as a coloring agent. In the present invention, as the magnetic material contained in the magnetic toner, magnetite, hematite, iron oxide such as ferrite, iron, cobalt, metals such as nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, Examples thereof include alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.

These ferromagnetic materials have an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm.
The amount contained in the toner is about 20 to 200 parts by mass, preferably 40 to 150 parts by mass, based on 100 parts by mass of the polymerizable monomer.

Further, the magnetic characteristics under application of 800 kA / m are coercive force (Hc) of 1.6 to 24 kA / m and saturation magnetization (σ
s) 50 to ²⁰⁰ Am ² / kg, remanent magnetization (σr) 2
It is preferably ²⁰ Am ² / kg.

In order to improve the dispersibility of these magnetic materials in the toner particles, it is also preferable to make the surface hydrophobic. Coupling agents such as a silane coupling agent and a titanium coupling agent are used for the hydrophobic treatment, and among them, the silane coupling agent is preferably used. As the silane coupling agent, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, dimethyl. Examples thereof include diethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane and n-octadecyltrimethoxysilane.

The toner produced by the present invention can be used as a one-component or two-component developer in any developing method. For example, in the case of a magnetic toner in which a magnetic material is contained in the toner as a one-component developer, there is a method of transporting and charging the magnetic toner by using a magnet incorporated in the developing sleeve. When a non-magnetic toner containing no magnetic substance is used, there is a method in which a blade and a fur brush are forcibly triboelectrically charged by a developing sleeve and the toner is adhered onto the sleeve to carry the toner.

On the other hand, when used as a commonly used two-component type developer, a carrier is used together with the toner obtained by the present invention and used as a developer. The carrier used in the present invention is not particularly limited, but mainly iron, copper, zinc, nickel, cobalt,
It is composed of a single or composite ferrite state composed of manganese and chromium elements. The carrier shape is also important in that saturation magnetization and electric resistance can be controlled over a wide range, and it is preferable to select, for example, a spherical shape, a flat shape, or an indeterminate shape, and also to control the fine structure of the carrier surface state such as surface irregularity. Generally, a method of forming carrier core particles in advance by firing and granulating the oxide of the above metal and then coating with a resin is used, but from the viewpoint of reducing the load on the toner of the carrier. The method of kneading the metal oxide and the resin, pulverizing and classifying the resin to obtain a low-density dispersed carrier, and further directly kneading the metal oxide and the monomer in suspension in an aqueous medium to form a true spherical shape. It is also possible to use a method of obtaining a polymerized carrier for obtaining a dispersion carrier.

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

The substance adhered to the surface of the carrier varies depending on the toner material. For example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, metal compound of di-tert-butylsalicylic acid, Styrene resin, acrylic resin, polyamide, polyvinyl butyral, nigrosine, amino acrylate resin, basic dye and its lake, silica fine powder, alumina fine powder and the like are suitable, but it is not always necessary to use them. Not restricted.

The total amount of the above compounds treated is generally 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the carrier.

The average particle size of these carriers is 10 to 100.
It is desirable that the thickness is μm, more preferably 20 to 50 μm.

As a particularly preferred embodiment of the carrier,
Cu-Zn-Fe ternary ferrite, the surface of which is a combination of resins such as fluorine resin and styrene resin, for example, polyvinylidene fluoride and styrene-methyl methacrylate resin, polytetrafluoroethylene and styrene-methyl methacrylate. 0.01 to 5% by mass, preferably a mixture of a resin, a fluorine-based copolymer and a styrene-based copolymer in a ratio of 90:10 to 20:80, preferably 70:30 to 30:70. A coating having 0.1 to 1% by mass of coating and passing through a sieve having an opening of 63 μm and sieving, 70% by mass or more of carrier particles remaining on the sieve having an opening of 37 μm, and having the above-mentioned average particle size. Examples include those that are ferrite carriers.
As the fluorine-based copolymer, vinylidene fluoride-tetrafluoroethylene copolymer (10:90 to 90:10)
Examples of the styrene-based copolymer include styrene-2-ethylhexyl acrylate (20:80 to 80: 2).
0), styrene-2-ethylhexyl acrylate-methyl methacrylate (20 to 60: 5 to 30:10 to 50)
Is exemplified.

The above-mentioned coated ferrite carrier has a sharp particle size distribution, and it is possible to obtain a preferable triboelectrification property for the toner of the present invention and to improve electrophotographic characteristics.

When a two-component developer is prepared by mixing with the toner of the present invention, the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass as the toner concentration in the developer.
A good result is usually obtained. If the toner concentration is less than 2% by mass, the image density is too low to be practical, and if it exceeds 15% by mass, fog and scattering in the machine are increased and the useful life of the developer is shortened.

Further, the magnetic properties of the carrier are as follows. Intensity of magnetization at 80 kA / m after magnetically saturated is required to be 30~300Am ² / kg. To achieve higher image quality, it is preferably 35 to 250 Am ² / kg. 300
If it is larger than Am ² / kg, it becomes difficult to obtain a high-quality toner image. If it is less than 30 Am ² / kg, the magnetic binding force is reduced and carrier adhesion is likely to occur.

[0062]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these.

In the examples, the following measuring methods were used.

(1) Measurement of particle size distribution and volume average particle size In 100 to 150 ml of a 1 mass% sodium chloride aqueous solution, an alkylbenzene sulfonate as a surfactant was added in an amount of 0.
1 to 5 ml was added, and 0.5 to 50 mg of the measurement sample was further added. This solution was subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and then, with a Coulter Multisizer (manufactured by Coulter Co.), a dispersion of 2 to 4 using a 100 μm aperture.
The particle size distribution of 0 μm particles was measured to obtain the volume average particle size.

(2) Calculation of coefficient of variation The narrowness of the particle size distribution was evaluated by the coefficient of number variation calculated by the following formula. Coefficient of variation (%) = number standard deviation / number average particle size × 100

(3) Image quality evaluation of image quality of color two-component color developer To the obtained toner particles, a hydrophobic silica fine powder having a specific surface area of 200 m ² / g measured by the BET method was added.
External addition was carried out so that the content would be 7% by mass. A ferrite carrier coated with an acrylic resin was mixed so that the externally added toner was 8% by mass to obtain a color two-component developer. Under the environment where this developer does not fluctuate, a full-color copying machine CLC700 manufactured by Canon Inc. was used to perform an image output durability test by continuous paper feeding, and visually evaluated fluctuations in image density and unevenness.

Evaluation of Image Quality of Monochrome Mono-Component Developer For the obtained toner particles, 1. a hydrophobic silica fine powder having a specific surface area of 250 m ² / g measured by BET method was prepared.
External addition was carried out so as to be 2% by mass to obtain a monochrome one-component developer. Under the environment where this developer did not fluctuate, an image output durability test by continuous paper feeding was performed using a laser printer LBP-1760 manufactured by Canon, and the fluctuation and unevenness of the image density were visually evaluated.

(4) Measurement of fog The measurement of fog is conducted by the REFLECTOMETER MOD.
It was measured using EL TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.) and calculated from the following formula. The smaller the number, the less fog. Fog (reflectance) (%) = reflectance of standard paper (%)-reflectance of non-image part of sample (%)

Example 1 Using the apparatus shown in FIG. 1, a polymerization toner composed of polymer fine particles was manufactured by the following procedure.

(Preparation of Polymerizable Monomer Composition) Styrene monomer 61.8 parts by mass n-butyl acrylate monomer 14.8 parts by mass Quinacridone pigment 7.0 parts by mass Unsaturated polyester resin 4.4 Parts by mass Divinylbenzene 0.3 parts by mass Di-tert-butylsalicylic acid aluminum compound 0.9 parts by mass Ester wax 10.8 parts by mass Part of the above-mentioned components, some of the styrene monomers, quinacridone pigments, di-tert- Aluminum butylsalicylate compound was mixed and dispersed for 5 hours using a handy mill (manufactured by Mitsui Mining Co., Ltd.), and this, the rest of the styrene monomer and other compositions were added to the polymerizable monomer composition tank. Then, the mixture was heated to 60 ° C. and mixed until a sufficient compatibility was obtained to obtain a polymerizable monomer composition.

(Preparation of Aqueous Dispersion Medium) Water 98.4 parts by mass Na ₃ PO ₄ 1.0 parts by mass The above components were put into an aqueous dispersion medium tank and stirred until Na ₃ PO ₄ was completely dissolved.

Then, 0.6 part by mass of CaCl ₂ was added to T. K. Using homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), stirring was performed at 1500 rpm for 30 minutes and Ca was used.
An aqueous suspension of fine particles of ₃ (PO ₄ ) ₂ was obtained. Then, this was heated to 60 ° C. with gentle stirring to obtain an aqueous dispersion medium.

(Addition of Polymerization Initiator) 2.6 parts by weight of 2,2'-azobis- (2,4-dimethylvaleronitrile) was added as a polymerizable monomer to 100 parts by weight of the polymerizable monomer composition. The mixture was put into a body composition tank and mixed with stirring to prepare a polymerizable monomer composition containing a polymerization initiator.

(Preparation of Preliminary Dispersion) The polymerizable monomer composition and the aqueous dispersion medium were charged into a preliminary dispersion tank so that the mass ratio was 1: 4, and the T. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), stirring was carried out at a rotation speed of 3000 rpm for 5 minutes to prepare a preliminary dispersion liquid.

(Preparation of Polymerizable Monomer Composition Dispersion Liquid) The pre-dispersion liquid obtained in the above-mentioned step was added to CLEARMIX (M.
Continuously introduced into Technic Co., Ltd. and stirred at a rotation speed of 18,000 rpm to obtain a polymerizable monomer composition dispersion liquid.

(Polymerization Step) The polymerizable monomer composition dispersion obtained in the above step was continuously introduced into a polymerization tank capable of heating and stirring, and polymerization was carried out at a liquid temperature of 60 ° C. with stirring.
After 5 hours, the polymerization temperature was raised to 80 ° C. and heating and stirring were continued for another 4 hours to complete the polymerization to obtain a polymer fine particle dispersion. After the temperature of the polymer particle dispersion was lowered, diluted hydrochloric acid was added to the polymer particle dispersion discharged from the polymerization tank to dissolve Ca ₃ (PO ₄ ) ₂ covering the surface of the polymer particles, and after solid-liquid separation, By washing with water, filtering and drying, toner particles which are fine particles of the polymerizable monomer were obtained.

(Evaluation of Toner) The particle size distribution of the toner particles was measured. As a result, the volume average particle size was 7.2 μm, the coefficient of variation was 24%, and the particle size distribution was sharp.

Next, hydrophobic silica was externally added to the obtained toner particles, and a ferrite carrier coated with an acrylic resin was mixed to obtain a two-component developer. When an image output test of 20,000 sheets was conducted, fog was 0.8%, and the image density was not fluctuated from beginning to end and a clear image having excellent fixability was stably obtained.

Comparative Example 1 Using the apparatus shown in FIG. 5, the polymerizable monomer composition and the aqueous dispersion medium were mixed at a mass flow rate ratio of 1: 4 per unit time without the preliminary dispersion step, and the total volume was 160 ml. A polymerized toner was manufactured in the same manner as in Example 1 except that the toner was directly introduced into Clearmix at a flow rate of 1 / min. The obtained toner particles had a volume average particle size of 8.0 μm and a coefficient of variation of 31%, and the particle size distribution was much larger in both fine and coarse powders than in Example 1.

Next, when an image output test of 20,000 sheets was carried out in the same manner as in Example 1, fog was 2.4%, and white streaks and uneven density occurred from a relatively early stage.

Example 2 Using the apparatus shown in FIG. 1, a polymerization toner was manufactured by the following procedure.

(Preparation of Polymerizable Monomer Composition) Styrene monomer 38.4 parts by mass n-butyl acrylate monomer 10.8 parts by mass Silane coupling treated magnetic iron oxide particles 44.3 parts by mass Unsaturated Polyester resin 2.0 parts by weight Saturated polyester resin 0.5 parts by weight Resin charge control agent 0.5 parts by weight Ester wax 2.0 parts by weight Of the above components, other than the ester wax is added to the polymerizable monomer composition tank. Then, at room temperature, the T. K. After stirring for 15 minutes with a homodisper (Special Kika Kogyo Co., Ltd.) at a rotation speed of 3000 rpm, the temperature was raised to 60 ° C., ester wax was added, and stirring was continued for another 20 minutes for polymerization. It was made into a monomer composition.

(Preparation of Aqueous Dispersion Medium) Water 98.1 parts by mass Na ₃ PO ₄ 1.2 parts by mass The above components were put into an aqueous dispersion medium tank and stirred until Na ₃ PO ₄ was completely dissolved.

Then, 0.7 part by mass of CaCl ₂ was added to the T. K. Using homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), stirring was performed at 1500 rpm for 30 minutes and Ca was used.
An aqueous suspension of fine particles of ₃ (PO ₄ ) ₂ was obtained. Then, this was heated to 60 ° C. with gentle stirring to obtain an aqueous dispersion medium.

(Addition of Polymerization Initiator) 1.5 parts by mass of benzoyl peroxide was added to 100 parts by mass of the polymerizable monomer composition in a tank of the polymerizable monomer composition, and the mixture was stirred and mixed to carry out polymerization. A polymerizable monomer composition containing an initiator was prepared.

(Preparation of Preliminary Dispersion Liquid) The polymerizable monomer composition and the aqueous dispersion medium were charged into a preliminary dispersion tank so that the mass ratio was 1: 2, and T. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), stirring was carried out at a rotation speed of 3000 rpm for 5 minutes to prepare a preliminary dispersion liquid.

(Preparation of Polymerizable Monomer Composition Dispersion) The pre-dispersion liquid obtained in the above-mentioned step was used at a flow rate of 160 ml / min with CLEARMIX (M.
(Manufactured by Technic Co., Ltd.) and continuously stirred at a rotational speed of 18,000 rpm to disperse the polymerizable monomer composition containing the polymerization initiator in the polymerizable monomer composition. A liquid was obtained.

(Polymerization Step) The polymerizable monomer composition dispersion obtained in the above step was continuously introduced into a polymerization tank capable of heating and stirring, and stirred at 80 ° C. for 6 hours to complete polymerization. A coalesced fine particle dispersion was obtained. After the temperature of the polymer fine particle dispersion was lowered, dilute hydrochloric acid was added to the polymer fine particle dispersion discharged from the polymerization tank to cover the surface of the polymer fine particles with Ca ₃ (PO ₄ ).
₂ was dissolved, and after solid-liquid separation, washing with water, filtration, and drying were performed to obtain toner particles as polymerizable monomer fine particles.

(Evaluation of Toner) When the particle size distribution of the toner particles was measured, the volume average particle size was 7.1 μm, the coefficient of variation was 26%, and the particle size distribution was also extremely sharp.

Next, hydrophobic silica was externally added to the obtained toner particles to obtain a one-component type developer. When an image output test was performed on 20000 sheets, the fog was 0.9%, and the image density was not fluctuated from beginning to end, and a clear image having excellent fixability was stably obtained.

Example 3 Using the apparatus shown in FIG. 2, a polymerization toner was manufactured by the following procedure.

(Preparation of Polymerizable Monomer Composition) Styrene monomer 38.4 parts by mass n-Butyl acrylate monomer 10.8 parts by mass Silane coupling-treated magnetic iron oxide particles 44.3 parts by mass Unsaturated Polyester resin 2.0 parts by weight Saturated polyester resin 0.5 parts by weight Resin charge control agent 0.5 parts by weight Ester wax 2.0 parts by weight Of the above components, other than the ester wax is added to the polymerizable monomer composition tank. Then, at room temperature, the T. K. After stirring for 15 minutes with a homodisper (Special Kika Kogyo Co., Ltd.) at a rotation speed of 3000 rpm, the temperature was raised to 60 ° C., ester wax was added, and stirring was continued for another 20 minutes for polymerization. It was made into a monomer composition.

(Preparation of Aqueous Dispersion Medium) Water 98.1 parts by mass Na ₃ PO ₄ 1.2 parts by mass The above components were put into an aqueous dispersion medium tank and stirred until Na ₃ PO ₄ was completely dissolved.

Then, 0.7 part by mass of CaCl ₂ was added to the T. K. Using homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), stirring was performed at 1500 rpm for 30 minutes and Ca was used.
An aqueous suspension of fine particles of ₃ (PO ₄ ) ₂ was obtained. Then, this was heated to 60 ° C. with gentle stirring to obtain an aqueous dispersion medium.

(Preparation of Polymerization Initiator Suspension) 1.5 parts by mass of benzoyl peroxide and 9.0 parts by mass of water were added to 100 parts by mass of the polymerizable monomer composition in a polymerization initiator tank. Throw in T. K. Stirring was performed for 10 minutes at a rotation speed of 1500 rotations / minute using a homodisper to prepare a polymerization initiator suspension.

(Preparation of Preliminary Dispersion Liquid) The polymerizable monomer composition and the aqueous dispersion medium were put into a preliminary dispersion tank so that the mass ratio was 1: 2, and T.I. K. Using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.), stirring was carried out at a rotation speed of 3000 rpm for 5 minutes to prepare a preliminary dispersion liquid.

(Preparation of Polymerizable Monomer Composition Dispersion) CLEARMIX (M.
It was continuously introduced into Technic Co., Ltd. and stirred at 18,000 rpm. Simultaneously with this, the above-mentioned polymerization initiator suspension is continuously supplied to CLEARMIX at a flow rate of 16.8 ml / min, whereby a polymerizable monomer containing a polymerization initiator in the polymerizable monomer composition is added. A body composition dispersion was obtained. After the completion of the process, no polymer deposits were found in the polymerizable monomer composition tank and the preliminary dispersion tank, and the toner could be manufactured again. Further, even if toner production was repeated without cleaning the inside of both tanks, generation of polymer deposits and the like was not confirmed.

(Polymerization Step) The polymerizable monomer composition dispersion liquid obtained in the above step was continuously introduced into a polymerization tank capable of heating and stirring, and stirred at 80 ° C. for 6 hours to complete the polymerization. A coalesced fine particle dispersion was obtained. After the temperature of the polymer fine particle dispersion was lowered, dilute hydrochloric acid was added to the polymer fine particle dispersion discharged from the polymerization tank to cover the surface of the polymer fine particles with Ca ₃ (PO ₄ ).
₂ was dissolved, and after solid-liquid separation, washing with water, filtration, and drying were performed to obtain toner particles as polymerizable monomer fine particles.

(Evaluation of Toner) When the particle size distribution of the toner particles was measured, the volume average particle size was 7.0 μm, the coefficient of variation was 27%, and the particle size distribution was also extremely sharp.

Next, an image output test of 20000 sheets was carried out in the same manner as in Example 2. As a result, the fog was 0.7%, and the image density was stable and stable from beginning to end. It was obtained.

Example 4 Using the apparatus shown in FIG. 3, the procedure similar to that of Example 3 was repeated until the step of preparing the preliminary dispersion liquid was completed, and then the preliminary dispersion liquid was transferred to the preliminary dispersion liquid storage tank. Then, it was continuously introduced into CLEARMIX (manufactured by M Technique Co., Ltd.) equipped with a batch continuous adapter at a flow rate of 160 ml / min, and
Stirring was performed at a rotational speed of 000 rpm. At the same time, by continuously supplying the above-mentioned polymerization initiator suspension to CLEARMIX at a flow rate of 16.8 ml / min, a polymerizable monomer containing the polymerization initiator in the polymerizable monomer composition is added. A body composition dispersion was obtained. At the same time, the steps from the preparation of the polymerizable monomer composition to the preparation of the pre-dispersion liquid are performed again in the same procedure, and the pre-dispersion liquid storage tank is used before all the pre-dispersion liquid in the pre-dispersion liquid storage tank is introduced into Clearmix. Continuous production was carried out for a long time by repeating the procedure of transferring to. A polymerization method toner was manufactured by obtaining the polymerizable monomer composition dispersion and performing the subsequent steps in the same manner as in Example 2.

The volume average particle diameter of the obtained toner particles is 7.
At 0 μm, the coefficient of variation was 26% and the particle size distribution was extremely sharp.

Next, an image output test of 20000 sheets was carried out in the same manner as in Example 2. As a result, the fog was 0.7% and the image density was stable throughout the time, and a clear image having excellent fixing property was stable. It was obtained.

Further, the properties of these toners hardly changed from the initial stage to the end of production, and stable long-term continuous operation was possible.

Example 5 Using the apparatus shown in FIG. 4, exactly the same as in Example 4 except that the polymerizable monomer composition and the aqueous dispersion medium were premixed with a static mixer before being introduced into Clearmix. Polymerized toner was manufactured by the procedure.

The volume average particle diameter of the obtained toner particles is 7.
0 μm, coefficient of variation 25%, particle size distribution of Example 4
It was even sharper than.

Next, an image output test of 20,000 sheets was carried out in the same manner as in Example 2. As a result, the fog was 0.6% and the image density was stable throughout the time, and a clear and stable image having a good fixing property was obtained. It was obtained.

Further, the properties of these toners hardly changed from the initial stage to the end of production, and stable long-term continuous operation was possible.

[0109]

According to the present invention, since the particle size distribution is narrow,
It is possible to provide a polymerized toner in which a good image is obtained when used in an electrophotographic method, and filming on a photoconductor or the like does not occur. Further, according to the present invention, since a particle size distribution is narrow in producing a polymerized toner, there is almost no loss due to classification, and a production method excellent in productivity is provided.

[Brief description of drawings]

1 is an illustration of an apparatus used to carry out the present invention.

FIG. 2 is an illustration of an apparatus used to carry out the present invention.

FIG. 3 is an illustration of an apparatus used to carry out the present invention.

FIG. 4 is an illustration of a device used to carry out the present invention.

FIG. 5 is an explanatory diagram of an apparatus used to carry out a comparative example.

[Explanation of symbols]

1. Polymerizable monomer composition tank 2. Aqueous dispersion medium tank 3. Preliminary dispersion tank 4. Metering pump 5. Device for applying shearing force 6. Polymerization tank 11. Polymerizable monomer composition tank 12. Aqueous dispersion medium tank 13. Preliminary dispersion tank 14. Metering pump 15. Polymerization initiator tank 16. Device for applying shearing force 17. Polymerization tank 21. Polymerizable monomer composition tank 22. Aqueous dispersion medium tank 23. Preliminary dispersion tank 24. Pre-dispersion liquid storage tank 25. Metering pump 26. Polymerization initiator tank 27. Device for applying shearing force 28. Polymerization tank 31. Polymerizable monomer composition tank 32. Aqueous dispersion medium tank 33. Preliminary dispersion tank 34. Pre-dispersion liquid storage tank 35. Metering pump 36. Polymerization initiator tank 37. Static mixer 38. Device for applying shearing force 39. Polymerization tank 41. Polymerizable monomer composition tank 42. Aqueous dispersion medium tank 43. Metering pump 44. Device for applying shearing force 45. Polymerization tank

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kiyuki Kimura             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Yoshinori Tsuji             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2H005 AB06

Claims (8)

[Claims] 1. A polymerization method toner having suspension polymer fine particles obtained by suspension polymerization of a polymerizable monomer composition containing at least a polymerizable monomer and a colorant in an aqueous dispersion medium. The polymerizable monomer composition is pre-dispersed in an aqueous dispersion medium according to the formula to obtain a pre-dispersion liquid, which is then continuously introduced into a device for applying a shearing force to achieve polymerization having a desired droplet size. Polymerization toner having suspension polymer fine particles obtained by forming a polymerizable monomer composition dispersion and subsequently completing the polymerization in a polymerization step. 2. The batch-prepared predispersion liquid is introduced into an apparatus for continuously applying a shearing force, and at the same time, a polymerization initiator is passed through an independent path to the predispersion liquid at a predetermined ratio with respect to the shearing force. The polymerization toner according to claim 1, wherein the toner is continuously introduced into a device for applying a force. 3. A batch type preparatory dispersion liquid is transferred to a preparatory dispersion liquid storage tank and then introduced into a device for continuously applying a shearing force from the preparatory dispersion liquid storage tank, and at the same time, the predispersion liquid is again batchwise prepared. A liquid is prepared and is transferred to all the predispersion liquids in the predispersion liquid storage tank before being introduced into a device for applying a shearing force.
The toner by the polymerization method described in 1. 4. The pre-dispersion liquid prepared by the batch method and the polymerization initiator are mixed by a mixing means installed in front of a device for applying a shearing force, and then introduced into a device for applying a shearing force. The polymerization toner according to any one of claims 1 to 3. 5. A polymerization toner having suspension polymer fine particles obtained by suspension polymerization of a polymerizable monomer composition containing at least a polymerizable monomer and a colorant in an aqueous dispersion medium is produced. In the method, the polymerizable monomer composition is predispersed in an aqueous dispersion medium by a batch method to obtain a predispersion liquid, which is then introduced into a device for continuously applying a shearing force to obtain desired droplets. A method for producing a polymerized toner, which comprises forming a dispersion of a polymerizable monomer composition having a diameter and then completing the polymerization in a polymerization step to obtain fine particles of a suspension polymer. 6. The batch-prepared predispersion liquid is introduced into a device for continuously applying a shearing force, and at the same time, a polymerization initiator is passed through an independent path to the predispersion liquid at a predetermined ratio with respect to the shearing force. The method for producing a polymerized toner according to claim 5, wherein the toner is continuously introduced into a device for applying force. 7. A batch type preparatory dispersion liquid is transferred to a preparatory dispersion liquid storage tank, and then introduced into a device for continuously applying a shearing force from the preparatory dispersion liquid storage tank, and at the same time, the preparatory dispersion liquid is again batchwise prepared. 7. A liquid is prepared and is transferred to all the predispersion liquids in the predispersion liquid storage tank before being introduced into a device for applying a shearing force.
The method for producing a polymerized toner according to 1. 8. A predispersion prepared by a batch method and a polymerization initiator are mixed by a mixing means installed in front of an apparatus for applying a shearing force and then introduced into an apparatus for applying a shearing force. The method for producing a polymerization toner according to claim 5, wherein