JPH1020551A - Electrophotographic toner and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide production method of an electrophotographic toner uniform in grain size distribution and high in resolving property by using resin particles containing a colorant component as seed particles. SOLUTION: The resin particles containing the colorant component is used as the seed particles. Here, various types colored resin particles may be used as the colored resin particles which is the resin particles containing the colorant component and used as the seed particles, but either colored resin particles in which the resin particles are formed by polymerizing a polymerizable monomer or its mixture, the colorant component incorporated in the resin particles is a pigment and the resin particles are formed by adding an aq. dispersion of this pigment at the polymerizing stage of the resin particles formable monomer or its mixture are preferable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electrophotographic copying machine,
The present invention relates to a method for producing an electrophotographic toner having a uniform particle size distribution and a high resolution, particularly a colored electrophotographic toner, which can be advantageously used as a developer in an electrophotographic device such as an electrophotographic printer and an electrostatic printer. . The present invention also relates to a method for producing a resin particle containing a colorant component, which can be advantageously used in the production of such a colored toner and other uses.

[0002]

2. Description of the Related Art Conventionally, electrophotography widely used in copiers, printers, printing presses, and the like generally employs a uniform static electricity on a photoconductive insulator such as a photosensitive drum. Providing a charge and irradiating the photoconductive insulator with a light image by various means to partially erase the electrostatic charge on the insulator to form an electrostatic latent image, and the remaining electrostatic charge A fine powder of developer (toner) is attached to the latent image portion to visualize the latent image. The toner image obtained in this way is transferred to a recording medium such as paper in order to form a printed matter,
And it is fixed.

[0003] Toners conventionally used in electrophotography generally disperse a colorant such as a dye or carbon black, a charge controlling agent, and other additives in a binder resin composed of a natural or synthetic polymer substance. Then, this is pulverized and classified to obtain a fine powder having a particle size of about 1 to 30 μm. The fine powder of the toner is usually mixed with a carrier material (carrier) such as iron powder or ferrite powder to form a developer, and is subjected to the above-described development process.

In recent years, as the demand for higher resolution in electrophotography has increased, a polymerization method, which is a simple method for producing a small particle size toner that is advantageous for higher resolution, has been actively studied.
For example, Japanese Unexamined Patent Publication Nos.
JP-A-7-53756 discloses a toner production method by a suspension polymerization method.
JP-A-3-205665 discloses a method for producing a toner by an emulsion polymerization method, JP-A-3-229268 discloses a toner production method by a dispersion-polymerization method, and JP-A-60-258203 discloses a method for producing a toner. Particles (seed particles)
A method for producing a toner by absorbing a monomer and polymerizing the monomer in seed particles, that is, a toner production method by a seed polymerization method (two-stage swelling polymerization method) has been proposed.

[0005] Among the seed polymerization methods, the two-stage swelling polymerization method uses seed particles having a uniform particle size distribution as a starting material, and swells the seed particles using a lipophilic solvent in a first step. By absorbing the polymerizable monomer to increase the number of particles, many advantages can be obtained. Than when the polymerizable monomer is directly absorbed by the seed particles,
By swelling the seed particles with a solvent at the previous stage, the absorption efficiency of the polymerizable monomer can be significantly improved, and the particle size distribution is relatively large in a micron to several tens of microns. A uniform polymer particle can be produced. Since the obtained toner has a narrow particle size distribution, when the toner is used in an electrophotographic process, the charge amount distribution becomes sharp, and the selective development of the toner can be prevented. It can fully cope with resolution. However, this two-step swelling polymerization method remains problematic in the production of colored toners. Because, usually, the pigment is electrostatically adsorbed on the surface of the seed particles composed of the resin particles that have absorbed the monomer, thereby coloring the resin particles. Has not been put to practical use because of its poor dispersibility. Further, in such a toner, the problem caused by the lipophilic solvent added for the preparation cannot be overlooked. That is, since the lipophilic solvent added to improve the absorption efficiency of the polymerizable monomer finally remains in the toner, the apparent glass transition temperature of the toner decreases, and during storage, the apparent There is a problem that blocking tends to occur during stirring.

In order to produce a toner having a uniform particle size distribution by the two-stage swelling polymerization method, the more uniform the particle size distribution of the seed particles as a starting material, the more satisfactory a toner can be obtained. A method for producing resin particles containing a colorant and having a relatively uniform particle size distribution is already known. Specifically, for example, JP-A-5-222109, JP-A-5-262809, JP-A-5-271213, and JP-A-5-303231 disclose uniform coloring with a uniform particle size distribution by a seed polymerization method. A method for making particles is disclosed. On the other hand, JP-A-63-205665 and JP-A-6-239907 disclose a method for producing colored particles having a uniform particle size distribution by an emulsion polymerization method / a precipitation polymerization method.

However, the colored particles obtained by the above-mentioned polymerization method have a small particle size and a large particle size of about 3 μm, and cannot be used as a toner as it is. In order to solve the problem of the small particle size of the colored particles, the above-mentioned publication proposes that a plurality of colored particles be aggregated and fused for the purpose of growing the colored particles to a desired particle size level. However, as a result of this additional processing, the uniformity of the particle size distribution, which is an important toner characteristic, is impaired. JP-A-63-20 referred to above
Taking the disclosure of Japanese Patent No. 5665 as an example, the toner finally obtained has a particle size distribution in the range of 2 to 50 μm, and it is desirable to make the particle size distribution uniform. That is, as can be understood from the above description, although it has been already studied to grow colored particles having a relatively small particle size and a relatively uniform particle size distribution into a toner particle size by agglomeration and fusion, a two-step process is described. There has not yet been studied a method of producing colored particles having a uniform particle size distribution by a swelling polymerization method and growing the particle size while maintaining the uniformity of the particle size distribution.

Further, resin particles themselves, which are used as seed particles in the above-described two-stage swelling polymerization method, particularly, are colored by a coloring agent are also important. As is well known, resin particles containing a colorant and having a particle size of about several μm are:
It can be used as an electrophotographic toner, a cosmetic additive, a paint additive, a liquid crystal gap adjusting material, and the like, and has been actively studied. Furthermore, if such a colored resin particle has a uniform particle size distribution, when used as an electrophotographic toner, as described above, the charge amount distribution becomes sharp, and selective development of the toner does not occur. For example, it is possible to cope with higher resolution of electrophotography, and development is being promoted.

Meanwhile, the production of resin particles is mainly performed by a suspension polymerization method, an emulsion polymerization method, a dispersion polymerization method, or the like. Among such polymerization methods, the emulsion polymerization method and the dispersion polymerization method are effective in obtaining resin particles having a uniform particle size distribution, but it is difficult to contain a colorant component in principle. After the formation of the resin particles, a separate step for forming a composite with the colorant component is generally required. For example, JP-A-1-44456, JP-A-2-44
In Japanese Patent No. 302761 and JP-A-5-222109, resin particles produced by an emulsion polymerization method are further grown by seed polymerization, and a colorant component is added in the process. As described above, including a colorant component in resin particles obtained by an emulsion polymerization method or a dispersion polymerization method, however, means a problem that a manufacturing process becomes complicated and a manufacturing cost increases.

On the other hand, in the suspension polymerization method, it is relatively easy to prepare resin particles containing a colorant component. . The particles obtained also have the problem of a broad particle size distribution in addition to the problem of such a large particle size. In fact, it is currently considered impossible to obtain uniform particles having a narrow particle size distribution by a suspension polymerization method.

Further, Japanese Patent Application Laid-Open No. Hei 6-239907 discloses a method for producing submicron colored resin particles by aqueous precipitation polymerization. In this method, 1
In a simple polymerization step, colored resin particles having a uniform particle size distribution can be obtained. However, even with this method, it is difficult to provide colored resin particles having a particle size of about several μm.

As can be understood from the above description, colored resin particles having a particle size of about several μm,
Direct production of colored particles having a relatively uniform particle size distribution from a polymerizable monomer or a mixture thereof by a one-stage polymerization operation has not yet been performed. Referring again to the method for producing the toner. The two-stage swelling polymerization method described in detail above, the suspension polymerization method, the emulsion polymerization method briefly mentioned above,
The dispersion polymerization method is superior to the conventional pulverization method in which the mainstream is to pulverize and classify resin masses containing various additives in terms of reducing the particle size of the toner and controlling the particle size distribution. ing. The suspension polymerization method comprises vigorously stirring and shearing a water-insoluble polymerizable monomer in an aqueous medium to form an emulsion, and then polymerizing and solidifying the emulsion. Although the suspension polymerization method is the simplest process and is being actively developed, it has a disadvantage that the obtained toner has a slightly broad particle size distribution. However, as a method for overcoming the disadvantage of the particle size distribution, for example, JP-A-3-95564 and JP-A-6-118636 disclose a method for producing a toner using porous glass. The porous glass, for example, after cooling the _{CaO-Al 2 O 3 -B 2} O 3 -SiO 2 based glass melt by heating for several tens of hours from ten hours at 600 to 700 ° C., silicate It is obtained by separating the phases into a salt-rich glass phase and a borate-rich glass phase, and eluting the latter by acid treatment. According to the method described in the above publication, for example, a monomer composition containing a polymerizable monomer, passing through a porous glass having pores, containing a dispersion stabilizer and the polymerizable monomer Is dispersed and suspended in a liquid dispersion medium which is substantially incompatible with the above, and is directly granulated. Then, the toner is obtained by subjecting the granulated monomer composition (liquid particles) to suspension polymerization. Can be manufactured. In such a polymerization method, therefore, the particle size and the particle size distribution of the liquid particles, and therefore the particle size and the particle size distribution of the toner, are greatly influenced by the pore size of the porous glass used and its uniformity. However, the pore size of the porous glass can be arbitrarily controlled by the glass composition, heat treatment conditions, and acid treatment conditions, and the pore size distribution can be uniformly controlled at a high level. A narrow emulsion can be obtained.

However, if solid fine particles are present in the monomer composition, the pores of the glass are closed by the solid fine particles at the stage of passing the composition through the porous glass, and the emulsion is formed. There is a high possibility that the problem that the production efficiency is reduced will occur. This is due to the fact that the pores of the porous glass have an open cell structure in which the pores are intertwined three-dimensionally, and the aggregation of pigment particles. Therefore,
When coloring the toner, a substance soluble in the polymerizable monomer, for example, a dye, must be usually used as a coloring agent, and the printed image is insufficient in light resistance, weather resistance, and storage stability. Can only get.

Furthermore, in addition to the fact that the toner has a small particle size and a uniform particle size distribution as described above, it is also important what shape the toner has. For example, the two-stage swelling polymerization method described above is suitable for obtaining a monodisperse toner having a small particle diameter, but since the obtained toner is a spherical toner, the residual toner on the photosensitive drum is cleaned. At the time, it is easy to slip through the cleaning blade,
A problem arises in cleaning performance.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to solve various problems of the prior art as described above. An object of the present invention is to provide a method for producing an electrophotographic toner having a uniform particle size distribution and high resolution.

Another object of the present invention is to provide a method for producing a toner which does not cause blocking when stored and stirred in a developing device. Another object of the present invention is to provide a resin particle containing a colorant component, which has a particle size of about several μm and a relatively uniform particle size distribution, by using a polymerizable monomer or It is an object of the present invention to provide a method for producing colored resin particles, which can be directly produced from the mixture by one-stage polymerization operation.

Still another object of the present invention is to provide:
An object of the present invention is to provide a method for producing a toner having a small particle diameter and a monodispersed toner and having excellent cleaning properties. The above and other objects of the present invention will be easily understood from the following detailed description of the present invention.

[0018]

According to one aspect of the present invention, there is provided a method for producing a toner by a two-stage swelling polymerization method using a seed particle, a lipophilic solvent and a polymerizable monomer or a mixture thereof as starting materials. A method for producing an electrophotographic toner, wherein resin particles containing a colorant component are used as the seed particles.

The present invention further provides a method for producing the above-mentioned electrophotographic toner, wherein the polymerization is carried out in the presence of an organic silane compound. In another aspect of the present invention, in producing resin particles colored with a colorant component, the water-insoluble colorant component is dispersed in a hydrophilic resin in an aqueous dispersion, and the resin particles are formed. For producing colored resin particles, characterized in that a polymerizable monomer or a mixture thereof is polymerized with a water-soluble polymerization initiator.

In another aspect of the present invention, in producing a toner by a suspension polymerization method using a polymerizable monomer or a mixture thereof as a starting material, the monomer or a mixture thereof is added to an aqueous medium. The polymerization is performed after preparing an emulsion for polymerization by suspending and dispersing in
At that time, a monomer composition is prepared by combining the monomer or a mixture thereof with a polymerization inert solvent, and the monomer composition is passed through a porous sieving member having a hydrophilic surface to form the aqueous composition. A method for producing an electrophotographic toner comprising suspending and dispersing in a medium to obtain the emulsion, and removing the solvent from the emulsion during and / or after polymerization.

In another aspect, the present invention provides a method for producing an electrophotographic toner comprising polymerized core particles and projecting polymerized fine particles adhered and fixed to the surface of the core particles. Seed particles are prepared from a forming monomer or a mixture thereof, and the obtained seed particles are swelled with a poorly water-soluble substance to increase the particle size. The seed particles grown by absorbing and growing the mixture, taking in the post-added monomer or the mixture thereof, and the post-added monomer or the post-added monomer located outside the particle without being absorbed by the seed particles Mixed with the droplets of the mixture, the post-added monomer or a mixture thereof is polymerized under predetermined conditions,
The polymerized core particles are formed from the seed particles, and the fine particles having a smaller particle size than the core particles are simultaneously formed from the droplets, and a predetermined salt is added to the product obtained in the above step to form the core. A method for producing an electrophotographic toner, characterized in that the fine particles are adhered and fixed to the surface of the particles.

[0022]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention can be advantageously implemented in various forms, as described in detail below.
In the following description, "monomer or a mixture thereof" may be referred to as "monomer" for simplicity of description, and the term "polymer" is used in a broad sense. And copolymers obtained when a monomer mixture is used as a starting material (two-component, three-component copolymers, etc.).

The present invention provides, in one preferred form thereof,
In producing a toner by a two-step swelling polymerization method using a seed particle, a lipophilic monomer and a polymerizable monomer or a mixture thereof as a starting material, resin particles containing a colorant component are used as the seed particles. is there. Here, resin particles containing a colorant component to be used as seed particles (hereinafter also referred to as “colored resin particles”)
Can include various types of colored resin particles, but preferably are not limited to those described below, but (1) the resin particles may be polymerized monomers or mixtures thereof. The colorant component contained in the resin particles is a pigment, and an aqueous dispersion of the pigment is added during the polymerization process of the resin particle-forming monomer or a mixture thereof. (2) The resin particles are formed by polymerization of a polymerizable monomer or a mixture thereof, the colorant component contained in the resin particles is a pigment, and a surfactant is used. What was formed by performing emulsion polymerization or precipitation polymerization of the resin particle-forming monomer or a mixture thereof in water in which the pigment was dispersed,
(3) those in which the resin particles are formed by emulsion polymerization or soap-free emulsion polymerization of a polymerizable monomer or a mixture thereof, and after the resin particles are formed, dyeing with the colorant component is performed; And (4) the resin particles are formed by polymerization of a polymerizable monomer or a mixture thereof, the colorant component contained in the resin particles is a water-insoluble pigment, and the pigment is hydrophilic. One formed by polymerizing the above-mentioned resin particle-forming monomer or a mixture thereof with a water-soluble polymerization initiator in an aqueous dispersion liquid dispersed with a water-soluble resin. These colored resin particles may be used alone,
Otherwise, two or more kinds of particles may be mixed and used. In the colored resin particles (4), the hydrophilic resin used for dispersing the pigment is preferably compatible with the resin particle-forming monomer or a mixture thereof. Further, at least one of the monomer units constituting the hydrophilic resin and at least one of the monomer units constituting the resin particle-forming monomer or a mixture thereof have the same structure. preferable. In addition,
In the specification of the present application, although a pigment is mentioned as a preferred example of the colorant, the term “pigment” also includes a dye, unless otherwise specified, as will be clear from the following description.

In the method for producing a toner according to the present invention,
The above-described two-stage swelling polymerization method using the colored resin particles (seed particles) and the polymerizable monomer or a mixture thereof as starting materials can be performed according to various conventional procedures. After the oily solvent is absorbed, the polymerizable monomer or a mixture thereof is further absorbed by the seed particles, and then the polymerization is carried out. As the lipophilic solvent, one member selected from the group consisting of alkyl halides, phenylalkyl, phthalic esters, fatty acid esters, phosphoric esters and mixtures thereof can be advantageously used.

The absorption of the lipophilic solvent, the polymerizable monomer or a mixture thereof into the seed particles can be advantageously performed in an aqueous medium. Further, it is preferable that after the seed particles are suspended and dispersed in an aqueous medium, an aqueous emulsion of the lipophilic solvent and the polymerizable monomer or a mixture thereof is added to an aqueous dispersion of the seed particles. The polymerization of the polymerizable monomer or a mixture thereof for producing the toner is preferably performed in the presence of a poorly water-soluble polymerization initiator.

In the method of the present invention, as described above, after the lipophilic solvent is absorbed by the seed particles containing the colorant, the polymerizable monomer mixture is absorbed, and the colorant and the polymerizable monomer are uniformly dispersed. Is formed, and then the monomer oil droplets are polymerized to form toner particles. According to this method, a problem arises in a method of electrostatically adsorbing a colorant on the surface of an oil droplet after forming a monomer oil droplet, which is generally performed in the production of a toner by a conventional two-stage swelling polymerization method. Further, localization of the colorant can be prevented.

Further, by producing the seed particles containing the colorant in accordance with the above-described method, the uniformity of the particle size distribution of the obtained toner can be improved. This is because, according to the method of the present invention, since seed particles having a relatively sharp particle size distribution can be produced, the particle size distribution of the toner on which the seed particles are grown becomes sharp.

In more detail, the electrophotographic toner according to the present invention can be advantageously manufactured using suitable materials and procedures as described below. First,
Seed particles, that is, colored resin particles are prepared. Colored resin particles may be made of a suitable monomer or a mixture thereof (hereinafter, referred to as
This may be prepared according to a known method (for example, a method described in JP-A-5-27112) starting from “seed-forming monomer”), or may be colored as described above. Aqueous dispersion of the agent is added during the polymerization process of the resin particle-forming monomer or its mixture, and emulsification of the resin particle-forming monomer or its mixture in water in which a colorant is dispersed using a surfactant. It may be prepared by conducting polymerization or precipitation polymerization, forming resin particles by emulsion polymerization or soap-free emulsion polymerization of a polymerizable monomer or a mixture thereof, and then dyeing with a colorant. Otherwise, as specifically described below, in accordance with a technique first found by the present inventors, in an aqueous dispersion in which a coloring agent is dispersed with a hydrophilic resin, a resin particle-forming monomer or a resin particle-forming monomer thereof is used. It may be prepared by polymerizing the mixture with a water-soluble polymerization initiator.

The polymerizable monomer or a mixture thereof, which can be advantageously used for the preparation of the colored resin particles, ie, the seed-forming monomer, may be any of those commonly used in this technical field for the same purpose. It can be used as it is or modified, and preferably, the same or similar one as the toner-forming monomer described below can be used. Examples of suitable seed-forming monomers include, but are not limited to, those described below, for example, styrene and its derivatives, acrylate-based monomers, methacrylate-based monomers, and the like.

The coloring agent to be dispersed and contained in the obtained resin particles includes many known pigments and dyes, and can be arbitrarily selected and used. Suitable pigments and dyes include, for example, various types of black carbon black (channel black, furnace black, etc.)
And black dye nigrosine-based compounds, and color pigments,
For example, benzidine-based yellow pigments, quinacdrine-based, rhodamine-based magenta pigments, and phthalocyanine-based cyan pigments can be exemplified. These pigments and dyes may be used alone or may be mixed and used to obtain a desired toner color.
Further, a charge control agent may be added for the purpose of enhancing the environmental stability of the charge characteristics of the toner.

In the method for producing a toner according to the present invention, preferably, after preparing colored resin particles as seed particles, the resin particles are made to absorb a lipophilic solvent.
The toner-forming polymerizable monomer or a mixture thereof is absorbed, and finally the desired polymerization is carried out. The lipophilic solvent to be absorbed by the colored resin particles prior to the toner-forming monomer or the mixture thereof has two functions. That is, the lipophilic solvent can have a function of improving the production process by assisting the absorption of the monomer and a function as a plasticizer and / or a release agent in the obtained toner. Such lipophilic solvents are:
Basically, any solvent may be used as long as it has a relatively low molecular weight and is substantially insoluble in water, and the type of the solvent is not particularly limited. However, it is particularly desirable to use a solvent having excellent compatibility with the toner-forming monomer or a mixture thereof as the lipophilic solvent.

Suitable lipophilic solvents for use are not limited to those listed below, but include
Examples include alkyl halides such as chlorododecane, phenyl alkyls, phthalic esters such as dibutyl phthalate, fatty acid esters such as dioctyl adipate, phosphoric esters such as tricresyl phosphate, silicone oil, and the like. Usually, these lipophilic solvents are preferably used in an amount of 0.1 to 10 times by weight of the colored resin particles, and more preferably in an amount of 0.5 to 3 times by weight. Here, when the amount of the lipophilic solvent used is smaller than 0.1 times by weight of that of the colored resin particles, the polymerizable monomer in the subsequent step cannot be sufficiently absorbed by the colored resin particles. On the other hand, if the amount is more than 10 times by weight, the absorption of the lipophilic solvent will take an extremely long time.

After the lipophilic solvent as described above is absorbed by the colored resin particles, a polymerizable monomer or a mixture thereof (hereinafter, also referred to as "toner-forming monomer") for forming a toner is absorbed. . The toner-forming monomer used here is not particularly limited as long as the desired toner can be provided after the completion of the polymerization. Suitable toner-forming monomers are preferably those having at least one ethylenically unsaturated bond in the molecule of the monomer, and are not limited to those listed below. Styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-ethyl styrene, p-methoxy styrene, p-phenyl styrene, p
-Chlorostyrene, 3,4-dichlorostyrene, 2,4
-Dimethylstyrene, pn-butylstyrene, pt
tert-butylstyrene, pn-nonylstyrene, p
-N-octylstyrene, pn-hexylstyrene,
Styrene and its derivatives such as pn-dodecylstyrene, unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; vinyl chlorides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate , Vinyl esters such as vinyl propionate, vinyl butyrate, and vinylbenzoyl, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, Acrylic acid-2
Acrylates such as -ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-methacrylate -Methacrylates such as octyl, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, vinyl methyl ether, vinyl ethyl ether , Vinyl ethers such as vinyl isobutyl ether, vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, N-vinyl Roll, N- vinylcarbazole,
N such as N-vinylindole and N-vinylpyrrolidone
-Acrylic acid or methacrylic acid derivatives such as vinyl compounds, vinyl naphthalenes, acrylonitrile, methacrylonitrile, acrylamide, and the like. These monomers may be used alone or otherwise,
Two or more monomers may be used in combination.

These toner-forming monomers can be used in any amount depending on various factors such as the composition of the colored resin particles to be used, the polymerization conditions to be applied, and the desired toner composition. Although it can be used, it is usually good to use the colored resin particles in an amount of 3 to 1000 times by weight, preferably 20 to 500 times by weight, more preferably 50 to 150 times by weight. is there. If the amount of the monomer used is less than 3 times by weight of the colored resin particles, disadvantages such as a decrease in storage stability of the toner occur. Conversely, if the amount is more than 1000 times by weight, Problems such as the inability to obtain the effect of the colored resin particles will occur.

The toner-forming monomers as described above include:
For the purpose of controlling the molecular weight distribution of the obtained polymer, a crosslinking agent, a chain transfer agent and the like may be added to the monomer. Suitable crosslinking agents include, but are not limited to, those compounds having two or more unsaturated double bonds in one molecule of the crosslinking agent compound, for example, divinylbenzene, divinylnaphthalene. And derivatives thereof, ethylenically unsaturated carboxylic esters such as ethylene glycol dimethacrylate and diethylene glycol dimethacrylate, divinyl compounds such as divinyl ether and N, N-divinylaniline, and the like. Suitable chain transfer agents include t-
Dodecyl mercaptan, t-decyl mercaptan, t-
Mercaptan compounds such as tetradecyl mercaptan, t-hexadecyl mercaptan, disulfide compounds such as diisopropylzantogen disulfide, chloroform, chloromethane tribromide, carbon tetrachloride, halogen compounds such as carbon tetrabromide, diazothioether compounds Compounds and others. Each of these crosslinking agents and chain transfer agents may be used alone, or two or more of them may be used as a mixture.

Further, a polymerization initiator is used to induce the polymerization of the toner-forming monomer as described above. In the practice of the present invention, it is possible to form monomer oil droplets using any of a water-soluble initiator and an oil-soluble initiator, but in terms of suppressing the generation of by-product particles in water. Preferably, an oil-soluble initiator is used. Suitable oil-soluble polymerization initiators include, but are not limited to, those listed below, benzoyl peroxide (BPO), methyl ethyl ketone peroxide, isopropyl peroxycarbonate, cumene hydroperoxide,
Peroxides such as dioctanoyl peroxide and lauroyl peroxide, and various azo compounds such as 2,2-azobis (isobutyronitrile) (AIBN), for example, V-70, V-68, V-65, V-59, V-40
And V-601 (both manufactured by Wako Pure Chemical Industries), and others. Usually, the amount of the polymerization initiator used is about 0.01 to 10% by weight of the monomer, and more preferably 0.05 to 7% by weight.

In addition to the polymerization initiator, a water-soluble polymerization inhibitor such as hydroquinone may be added to the monomer oil droplets in order to more effectively suppress the generation of by-product particles in water. It may be added to water during the polymerization.
Furthermore, when polymerizing monomer oil droplets, a suspension stabilizer can be used for the purpose of increasing the stability of the oil droplets.
Suitable suspension stabilizers include, for example, polyvinyl alcohol, gelatin, hydrophilic polymers such as methylcellulose, water-insoluble inorganic powders such as tricalcium phosphate, barium sulfate, aluminum hydroxide and silica, cationic, anionic or Nonionic surfactants and others can be mentioned.

Although the various components that can be included in the electrophotographic toner of the present invention have been described above, the toner of the present invention may further have other additives. For example, the toner of the present invention may have a charge control agent commonly used in this technical field for the purpose of enhancing environmental safety of toner charging characteristics. Further, the toner may have a conventional external additive for modifying the surface of the toner, improving the fluidity of the toner, and for other purposes.

The electrophotographic toner according to the present invention can be prepared according to various procedures using the above-mentioned components. For example, the electrophotographic toner of the present invention can be prepared according to the following suitable procedure. Absorption of lipophilic solvent into seed particles (colored resin particles): First, a lipophilic solvent is added to water in which a surfactant is dissolved,
Thorough mixing by high-speed stirring or the like. For this high-speed stirring, for example, a rotor-stator homogenizer, a knife homogenizer, an ultrasonic homogenizer, a pressure homogenizer, or the like can be advantageously used. An aqueous medium (aqueous emulsion) in which a lipophilic solvent is finely dispersed is obtained. Here, in order to reduce the stability of the oil droplets of the lipophilic solvent, it is preferable to form oil droplets having the smallest possible particle size.

Next, an aqueous suspension in which the colored resin particles are suspended in water is added to the aqueous emulsion prepared as described above. The lipophilic solvent in the aqueous emulsion is absorbed into the colored resin particles. At this time, it is preferable to add a water-soluble organic solvent such as acetone in order to elute the lipophilic solvent into water. Further, together with the lipophilic solvent, a polymerization initiator may be absorbed in the colored resin particles.
Thus, an aqueous dispersion of the colored resin particles having absorbed the lipophilic solvent (hereinafter, referred to as “dispersion I”) is obtained. Absorption of the polymerizable monomer into the colored resin particles that have absorbed the lipophilic solvent: Subsequently, the colored resin particles that have absorbed the lipophilic solvent further absorb the polymerizable monomer for forming the toner. This monomer absorption step can be advantageously performed by adding the dispersion I obtained in the previous step to an aqueous emulsion of monomers. At this time, if desired, the polymerization initiator may be simultaneously absorbed by the colored resin particles. In this manner, the colorant, the lipophilic solvent, the polymerizable monomer, and the aqueous dispersion in which the polymerization initiator is uniformly dispersed (corresponding to the monomer oil droplet described above; hereinafter, “dispersion II "
) Is obtained. Polymerization of monomer oil droplets: dispersion II prepared as described above
After the addition of a suspension stabilizer, a water-soluble polymerization inhibitor, and the like, if necessary, the monomer oil droplets are heated and polymerized according to a conventional method.
This polymerization is carried out, for example, at a temperature of about 60-100 ° C. for about 2-10
It can be advantageously carried out by heating for 0 hours. In this way, polymer particles having a uniform particle size distribution and a uniformly dispersed colorant are obtained.

After the colored polymer particles are prepared as described above, if necessary, inorganic particles such as silica and titanium oxide and / or resin particles are externally added. A toner having the desired composition and characteristics can be obtained. The present invention
In another preferred embodiment, in producing an electrophotographic toner by polymerizing a polymerizable monomer or a mixture thereof, the polymerization is performed in the presence of an organic silane compound. Although the production of the toner from the polymerizable monomer or a mixture thereof can be carried out according to various polymerization methods, it is preferable to use the seed particles, particularly the colored seed particles, and the polymer particles, as specifically described above. Can be carried out according to a two-stage swelling polymerization method using a reactive monomer or a mixture thereof as a starting material. The organic silane compound used at the time of polymerization includes various compounds, but as described in detail below, an organic silane compound having a radically reactive carbon-carbon double bond in the molecule is used. Is preferred. Further, the organic silane compound is preferably used in an aqueous medium.

According to the present invention, after the lipophilic solvent is absorbed by the seed particles (colored resin particles) in the aqueous medium, the polymerizable monomer or a mixture thereof is absorbed to form monomer oil droplets. Further, while polymerizing the monomer oil droplets to produce toner particles, and dissolving the organic silane compound in an aqueous medium and performing a polymerization reaction, the organic silane compound adheres to and binds to the toner particles, It is possible to obtain toner particles whose surface is coated with a compound having a high glass transition temperature. By this method, it is possible to prevent blocking of toner particles caused by the remaining lipophilic solvent, which could not be avoided in the prior art. Further, according to this method, as described above, a toner having a small particle size, a uniform particle size distribution, and excellent resolution can be obtained.

Colored resin particles which can be advantageously used as seed particles in the method for producing a toner according to the present invention, a method for producing the same, and a lipophilic polymerization inert solvent and a polymerizable monomer used in combination with the colored seed particles Alternatively, the mixture thereof and the other components have already been described in detail in the production method according to the first preferred embodiment, respectively, and thus description thereof will be omitted here to avoid duplication.

Since the electrophotographic toner produced by the method of the present invention has a silicon-containing compound which is preferably formed continuously in the form of a thin film on the surface layer of the toner particles of the polymerized toner, the toner is stored during development. It is possible to significantly prevent fusion (blocking) between particles at the time of stirring in the apparatus or the like. Usually, when used as an electrophotographic toner,
It has been practiced to attach fine powder such as silica to the outside of the toner particles in order to improve the charging characteristics and fluidity. However, in the toner of the present invention, the silicon-containing compound which is present in the surface layer of the toner particles is The thin film is clearly distinguished from the fine powder such as silica, which is discontinuously distributed in the surface layer of the toner particles, in terms of constitution and function. The thin film of the silicon-containing compound formed on the surface layer of the toner particles is formed by bonding or adhering the radical-reactive organic silane compound present during the formation of the polymerized toner to the surface of the toner particles.

The organic silane compound used in the practice of the present invention by being added to an aqueous medium is generally called a silane coupling agent, and can be represented by the following formula (I).

[0046]

Embedded image

In the above formula, R, X, Y and Z are each composed of a hydrophobic organic group and a hydrophilic hydrolyzable group, and have a functional group such as an alkyl group, a vinyl group, an epoxy group, and an acrylic group. , Amino groups and the like. In the present invention, in particular, a radically reactive organic silane compound having one or more organic groups having an unsaturated carbon bond such as a carbon-carbon double bond is used. Such an organic silane compound is combined with a polymerizable monomer or a mixture thereof serving as a core of the toner particles by radical polymerization to form a thin film, or the toner particles are coated with a polymer of the organic silane compound. The thin film or coating formed by chemically bonding with the polymer of the toner is made of a silicon-containing compound having a high glass transition temperature, and can enhance the effect of suppressing blocking.

Suitable organic silane compounds are not limited to those listed below, but include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane. Examples thereof include silane, allyltrimethylsilane, and methacryloxymethyltrimethoxysilane. These organosilane compounds are usually hydrophobic and have low solubility in water at pH = 7.
Therefore, when using such an organic silane compound, it is necessary to adjust the pH according to each type and hydrolyze a hydrolyzable group contained in the molecule to a silanol group to perform a water-solubilizing treatment, thereby performing a water-solubilizing treatment on the toner surface. It is preferable for homogeneity. Generally, pH = 3 with hydrochloric acid, formic acid, acetic acid, etc.
It is optimally set to ５5. When the pH is high or low, the reactivity of the silanol group increases, and a water-insoluble siloxane oligomer is generated by the condensation reaction, and when added to the suspension system, aggregation of particles is caused. May reduce suspension stability. If necessary, a small amount of a solvent such as alcohol, acetone, and toluene may be added to improve the solubility of the organic silane compound.

The amount of the organic silane compound to be added may be all at once, or may be gradually added little by little. The total amount of the organic silane compound is preferably 5% by weight or less based on the polymerizable monomer or a mixture thereof. If the amount added is too large, it will polymerize and precipitate in an aqueous medium, or toner particles will aggregate during polymerization,
Manufacturing problems such as fusion may occur. Although the lower limit of the amount of the organic silane compound is not particularly limited, it is generally preferable that the lower limit is about 0.1% by weight based on the polymerizable monomer.

The aqueous medium to which the organosilane compound is to be added usually contains, in addition to water as a main component, a dispersion stabilizer for preventing coalescence of droplets of a polymerizable monomer or a mixture thereof. Preferably, it is configured. The dispersion stabilizer used here can be the same as the suspension stabilizer already described in the production method according to the first preferred embodiment, and specifically, for example, sodium dodecylbenzenesulfonate, dodecyl Sodium sulfonate, sodium dodecyl sulfate, sodium decyl sulfate,
Water-soluble surfactants such as dodecylviridonium bromide, dodecyltrimethylammonium bromide, decyltrimethylammonium bromide, tetradodecylammonium chloride, sodium tetradecylsulfonate and sodium tetradecyl sulfate can be exemplified.

The production of an electrophotographic toner involving a polymerization step in the presence of an organic silane compound can be carried out according to various procedures using the above-mentioned constituent components. For example, the electrophotographic toner of the present invention can be prepared according to the following suitable procedure by changing the procedure of the first embodiment described above. Absorption of lipophilic solvent into seed particles (colored resin particles): A lipophilic solvent is added to water in which a surfactant is dissolved, and the mixture is carefully mixed by high-speed stirring or the like. An aqueous medium (aqueous emulsion) in which a lipophilic solvent is finely dispersed is obtained. Here, in order to reduce the stability of the oil droplets of the lipophilic solvent, it is preferable to form oil droplets having the smallest possible particle size.

Next, an aqueous suspension in which the colored resin particles are suspended in water is added to the aqueous emulsion prepared as described above. The lipophilic solvent in the aqueous emulsion is absorbed into the colored resin particles. At this time, it is preferable to add a water-soluble organic solvent such as acetone in order to elute the lipophilic solvent into water. Further, together with the lipophilic solvent, a polymerization initiator may be absorbed in the colored resin particles.
Thus, an aqueous dispersion of the colored resin particles having absorbed the lipophilic solvent (hereinafter, referred to as “dispersion I”) is obtained. Absorption of the polymerizable monomer into the colored resin particles that have absorbed the lipophilic solvent: The colored resin particles that have absorbed the lipophilic solvent further absorb the polymerizable monomer for forming the toner. This monomer absorption step can be advantageously performed by adding the dispersion I obtained in the previous step to an aqueous emulsion of monomers. At this time, if desired, the polymerization initiator may be simultaneously absorbed by the colored resin particles. In this manner, an aqueous dispersion (equivalent to the monomer oil droplets described above) in which the colorant, the lipophilic solvent, the polymerizable monomer, and the polymerization initiator are uniformly dispersed; "). Polymerization of monomer oil droplets: dispersion II prepared as described above
After the addition of a suspension stabilizer, a water-soluble polymerization inhibitor, and the like, if necessary, the monomer oil droplets are heated and polymerized according to a conventional method.
The polymerization is carried out, for example, at a temperature of about
It can be performed by heating for 00 hours. The organic silane compound may be added to the dispersion II before the polymerization, or may be added during the polymerization. Organic silane compounds are usually hydrophobic and have a pH =
7 has low solubility in water, for example, hydrochloric acid, formic acid,
It is preferable to dissolve in an acidic aqueous solution adjusted to pH = 3 to 7 by adding an acid such as acetic acid, and then to add it to the dispersion II.

After the completion of the polymerization, the suspension stabilizer, surfactant and the like adhering to the particle surface are removed using an acid or water. Colored polymer particles having a narrow particle size distribution are obtained. After the colored polymer particles are prepared as described above, if necessary, inorganic particles such as silica and titanium oxide and / or resin particles are externally added. A toner having the desired composition and characteristics can be obtained.

The present invention also provides, in another preferred form thereof, a colorant component which, as set forth in the preceding description, can be used advantageously as seed particles, especially in the manufacture of electrophotographic toners. Colored resin particles, i.e., in the method for producing colored resin particles, and in an aqueous dispersion in which a water-insoluble colorant component is dispersed in water with a hydrophilic resin, polymerizable for forming the resin particles. It is characterized in that a monomer or a mixture thereof (hereinafter also referred to as “seed-forming monomer”) is polymerized with a water-soluble polymerization initiator. Here, the hydrophilic resin is preferably compatible with the seed-forming monomer. Preferably, at least one of the monomer units constituting the hydrophilic resin and at least one of the monomer units constituting the seed-forming monomer have the same composition.

According to the present invention, resin particles containing a colorant component and having a particle size of about several μm and having a relatively uniform particle size distribution can be obtained. Although the reason has not been clarified yet, according to the present inventors' consideration, the following inference can be made: The method of preparing the resin particles of the present invention is based on the fact that the water-insoluble colorant component contains a water-soluble resin. This is similar to the soap-free emulsion polymerization particle production method, except that it is previously dispersed in an aqueous medium via a solvent. In normal emulsion polymerization and soap-free polymerization, polymerization nuclei are formed by aggregation of fine resin particles at the beginning of the polymerization stage. It is conceivable that it is aggregated with the fine resin particles to form a polymerization nucleus because it is covered with the resin.

Further, a method of producing a toner by absorbing a lipophilic solvent into the colored resin particles and then absorbing and polymerizing a polymerizable monomer, as described in detail above, employs a two-stage swelling weight. It is called legal and is adapted to the production of toner. The present invention not only makes it possible to make the particle size distribution of the finally obtained toner uniform, but also makes it easy to grow the colored resin particles up to the target toner particle size. This eliminates the need for multiple particle growth operations and fine adjustment of the amount of surfactant. Further, there is an advantage that the toner particle size can be easily controlled by the charged monomer amount.

However, in the preparation of a toner using the conventional two-step swelling polymerization method, it is difficult to disperse the colorant component in the resin particles, and the pigment is electrostatically adsorbed on the particle surface. There is a problem that the dispersibility of is poor. According to the present invention, since the colorant component is dispersed in the seed particles in advance, the dispersibility of the colorant is improved. The method for producing colored resin particles according to the present invention is directed to a method for producing a polymerizable monomer or a mixture thereof (seed-forming monomer) with a water-soluble polymerization initiator in an aqueous solvent in which a water-insoluble colorant component is dispersed by a hydrophilic resin. Polymerizing the monomer). Materials suitable for producing such colored resin particles are, for example, those described below. It is for dispersing the hydrophilic resin colorant component in the aqueous solvent, is hydrophilic, has compatibility with the seed-forming monomer,
Any resin may be used as long as it is capable of dispersing the poorly water-soluble component in the aqueous solvent. For example, when a styrene-acrylic monomer is used as a seed-forming monomer in the production of an electrophotographic toner, a styrene-acrylic resin may be advantageously used as the hydrophilic resin. it can. Colorant components As water-insoluble colorant components, the colorants already described in the production process according to the first preferred embodiment can likewise be used advantageously. Similarly, a charge control agent may be added for the purpose of enhancing the environmental stability of the charge characteristics of the toner.

A colorant dispersion obtained by dispersing such a colorant component in an aqueous solvent using a hydrophilic resin is, for example, H
I micron K MAGENTA, HI micron K BL
UE, HI micron K YELLOW, HI micron K
BLACK and the like are commercially available from Okuni Shikisha. Seed-forming monomer As the seed-forming monomer , the monomers already described in the production method according to the first preferred embodiment can likewise be used advantageously. Similarly, a crosslinking agent and a chain transfer agent may be added for the purpose of controlling the molecular weight distribution. As the water-soluble polymerization initiator for polymerizing the seed-forming monomer, if it is a water-soluble polymerization initiator that can be generally used for soap-free emulsion polymerization, its type is particularly limited. Nor. Potassium peroxodisulfide and the like are preferred.

The production of the colored resin particles can be carried out according to various procedures using the above-mentioned components. The colored resin particles of the present invention can be prepared, for example, according to the following suitable procedure. First,
The water-insoluble colorant component is suspended and dispersed in an aqueous solvent using a hydrophilic resin. This operation may be performed using a dispersing machine such as a ball mill or an attritor. Otherwise, instead of preparing the dispersion, an aqueous dispersion of the above-described commercially available colorant may be used as it is.

Next, the seed-forming monomer is added to the aqueous solvent in which the colorant component is dispersed, and the nitrogen is replaced sufficiently to remove the dissolved oxygen in the solvent. The system is heated to the polymerization temperature, generally at a temperature of about 60-100 ° C, and the polymerization initiator is added while stirring. The system is maintained at the polymerization temperature for 6 to 24 hours with gentle stirring to polymerize the monomers. The desired colored resin particles are obtained.

The method for producing an electrophotographic toner according to the present invention is advantageous in that after the lipophilic solvent is absorbed in the colored resin particles prepared as described above, the toner-forming monomer is absorbed and polymerized. Can be implemented. Materials suitable for the production of such a toner, such as a lipophilic solvent, a toner-forming monomer, and a suspension stabilizer, have already been described in the production method according to the first preferred embodiment. The description in is omitted.

In another preferred embodiment of the present invention, in producing a toner by a suspension polymerization method using a polymerizable monomer or a mixture thereof as a starting material, the monomer or a mixture thereof (toner formation) is used. ) Is prepared by suspending and dispersing a monomer in an aqueous medium to prepare an emulsion for polymerization, and then polymerizing the toner, and combining the toner-forming monomer with a polymerization-inactive solvent. A composition is prepared, the monomer composition is suspended and dispersed in the aqueous medium through a porous sieving member having a hydrophilic surface to obtain the emulsion, and during and / or after polymerization. A method for producing an electrophotographic toner, comprising removing the solvent from the emulsion.

In carrying out the method of the present invention, the monomer composition as described above may further have a hydrophobic surface, or a colorant fine particle whose surface has been subjected to a hydrophobic treatment, or a hydrophobic surface. Alternatively, it is preferable to include at least one additive selected from the group consisting of charge control agent fine particles having a hydrophobic surface and a release agent fine particle having a hydrophobic surface or having a hydrophobic surface. . Further, the polymerization-inactive solvent used in combination with the toner-forming monomer in the method of the present invention is preferably a solvent exhibiting poor water solubility. Further, the aqueous medium used for suspending and dispersing the toner-forming monomer further comprises at least one additive selected from the group consisting of a poorly water-soluble inorganic powder, a water-soluble polymer and a surfactant. It is preferred to include.

As the porous sieving member for allowing the monomer composition to pass in the method of the present invention, any material can be used as long as the desired separation effect is obtained and there is no adverse effect such as clogging. May be. According to the findings of the present inventors, however, porous glass can be advantageously used, and will be described below with reference to porous glass. Here, the “porous glass” is a material mainly composed of silicic acid, boric acid, alumina, or the like, as is well known in the art, and for example, a glass raw material containing such a component is used. Heated at high temperature and separated into a phase consisting of components that are easily dissolved in acid and other phases,
It can then be prepared by eluting the former from the glass with an acid. Such porous glass is commercially available, for example, as microporous glass (MPG), shirasu porous glass (SPG), and the like. The porous glass can preferably be used in the form of a pipe inside a membrane module arranged in an emulsifying and dispersing device.

As described above, when an emulsion is formed using porous glass and the emulsion is further polymerized, polymer particles having a narrow particle size distribution can be easily obtained. In this case, the particle size of the emulsion formed by passing through the pores of the porous glass is approximately several times the pore size of the pores of the glass. Therefore, for example, when it is desired to produce a toner having a particle diameter of 2 to 10 μm, it is necessary to control the diameter of the pores of the porous glass used to about 0.5 to 5 μm. However, when a monomer composition containing a toner-forming monomer and additive fine particles such as a colorant, a release agent, and a charge control agent is introduced into an aqueous medium through porous glass, the toner-forming monomer In some cases, only the liquid phase portion selectively passes through the pores of the glass or the pores are blocked by the fine particles of the additive. Therefore, as a result of intensive research aimed at stably producing a toner using porous glass, the present inventors have found that, as described above, at least, a toner-forming monomer, a polymerization-inactive solvent, and A polymerizable monomer mixture composed of an additive that cannot be dissolved in the toner-forming monomer is introduced into an aqueous medium through a porous glass having a hydrophilic surface and suspended therein. A method for producing a toner has been found which comprises polymerizing a suspension and removing the solvent during and / or after the polymerization. In the method of the present invention, since the polymerizable monomer mixture contains a polymerization-inactive solvent, the amount of the solvent is smaller than that in the case of using a monomer mixture containing no such solvent. The monomer composition can be granulated using a porous glass having a large pore size, and therefore, the influence of the internally added additive fine particles can be reduced, and the productivity of the particles can be improved. The particle size of the toner can be controlled by the pore size of the porous glass and the ratio of the toner-forming monomer to the polymerization-inactive solvent. Although the particle size distribution of the toner depends on the uniformity of the pore size of the porous glass, the pore size distribution of the porous glass is fairly uniform, so that the production efficiency is much higher than when manufacturing by classification after grinding. Excellent, a toner having a narrow particle size distribution can be obtained as compared with the ordinary suspension polymerization method.

The toner of the present invention is, specifically, a toner-forming monomer, a polymerization-inert solvent, an additive that cannot be dissolved in the toner-forming monomer, and a toner necessary for preparing the toner of the present invention. Other additives are manufactured by dispersing and mixing by a known method using a ball mill, an attritor, a homogenizer, or the like. Next, the obtained mixture is introduced into an aqueous medium through a porous glass to form an emulsion. Here, it is preferable that the surface of the porous glass is sufficiently wetted with water by, for example, placing the glass in water and irradiating ultrasonic waves in advance. If the surface of the glass is hydrophobic,
In other words, if the affinity with the toner-forming monomer, solvent, additive, etc. is high, when extruded from the pores of the glass into the aqueous medium, it is difficult to separate those components from the glass surface, and the No.

Subsequently, the emulsion of the polymerizable monomer mixture prepared using the porous glass is heated and polymerized in the same manner as in a conventional polymerization method using suspension polymerization. The solvent may be removed during the polymerization reaction, after the polymerization reaction or from the polymerization reaction to after the polymerization reaction, by distilling off by heating or the like, or may be performed by spray-drying the suspension or the like. .

The obtained particles are subjected to acid washing and water washing as necessary, then subjected to solid-liquid separation and dried. Finally,
When a polar functional group is introduced into the surface or the surface is modified with an external additive such as silica powder, a target toner is obtained.
Materials suitable for the production of toner as described above include, for example,
It is as described below. In addition, since many of the materials are the same as those already described in the manufacturing method according to the first preferred embodiment, refer to the above description for such materials. Toner-forming monomer As the toner-forming monomer , the monomers already described in the production method according to the first preferred embodiment can likewise be advantageously used. It is also the same that a crosslinking agent and a chain transfer agent may be added to the monomer for the purpose of controlling the molecular weight of the obtained polymerized toner. Polymerization initiator As the polymerization initiator, the monomers already described in the production method according to the first preferred embodiment can likewise be used advantageously. The amount used is the same. Polymerization-inactive solvent As the polymerization-inactive solvent, a solvent having compatibility with the toner-forming monomer and being substantially insoluble in water can be used. Examples of such a solvent include toluene, benzene, chlorobenzene, xylene, dichloroethane, chloroform, carbon tetrachloride, methyl acetate, ethyl acetate, methyl ethyl ketone, diethyl ketone, cyclohexane, hexane, n-octane, diethyl ether, and the like. it can. Additives that cannot be dissolved in the toner-forming monomer The additives that cannot be dissolved in the toner-forming monomer include fine particles such as a colorant, a charge control agent, and a release agent. Need to be hydrophobic. This is because, if these fine particles are hydrophilic, not only are the dispersibility in the toner-forming monomer inferior, but also the colorant adheres to the hydrophilic surface of the porous glass, and the toner-forming unit is not easily dispersed. This is because only the liquid phase portion of the monomer and the solvent passes through the pores of the glass to form droplets in water, and the toner-forming monomer and the colorant are separated. In addition, the coloring agent can adhere to the inner wall of the pores of the glass and cause the pores to be blocked.

The colorant is not particularly limited, so that known organic pigment particles or inorganic pigment particles can be used. Examples of suitable organic pigments include known colorants such as benzidine-based yellow pigments, quinacridone-based or rhodamine-based magenta pigments, and phthalocyanine-based cyan pigments. Examples of suitable inorganic pigments include various carbon blacks such as channel black and furnace black, magnetite,
Magnetic materials such as ferrite and the like can be mentioned.
These organic and inorganic pigments may be used alone,
Alternatively, two or more pigments may be used as a mixture.

Since the surface of the inorganic pigment particles is usually hydrophilic, it is preferable to use the inorganic pigment particles after performing a hydrophobic treatment. Preferred surface treatment agents for hydrophobization include, for example, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methylphenyldimethoxysila, diphenyldimethoxysilane, γ-methacryloxypropyltrimethoxy Silane, γ-glycidoxypropyltrimethoxysilane, N- (2-aminoethyl) -3
Silane compounds such as aminopropyltrimethoxysilane, octadecyltrimethoxysilane, octadecylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, titanium compounds such as isopropyltriisostearoyl titanate, isopropyltridecylbenzenesulfonyl titanate, acetoalkoxy aluminum diamine Aluminum compounds such as isopropylate,
Others can be mentioned. In addition to these compounds, various dyes soluble in the toner-forming monomer, such as a nigrosine compound and an azo compound, may be used as a colorant.

For controlling the chargeability of the toner, a conventional charge control agent may be added. In some cases, the above-mentioned coloring agent acts as the charge control agent. The release agent is used for preventing the offset phenomenon in which the molten toner adheres to the heat roller in the heat fixing toner. As such a release agent, for example, low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, carnauba wax,
Known release agent compounds such as higher fatty acids such as beeswax, stearic acid, and palmitic acid and metal salts thereof, and others can be used. These compounds may be used alone or as a mixture of two or more compounds. Aqueous Medium In the aqueous medium, a suspension stabilizer can be used for the purpose of enhancing the stability of the emulsion of the toner-forming composition. Suitable suspension stabilizers include, for example, known anionic, nonionic or cationic surfactants, polyvinyl alcohol, gelatin, hydrophilic polymer compounds such as methyl cellulose, tricalcium phosphate, barium sulfate, aluminum hydroxide, silica And other water-insoluble inorganic powders.

For the purpose of suppressing the generation of by-product particles in water, a water-soluble polymerization inhibitor such as hydroquinone may be added to water when polymerizing monomer droplets. In the method for producing a toner as described above, the step of preparing a polymerization emulsion by passing a monomer composition containing a toner-forming monomer and the like through a hydrophilic surface-containing porous glass involves the use of apparatuses having various configurations. It can be implemented using An example of such an apparatus is an emulsifying and dispersing apparatus as shown in the form of a flow sheet in FIG. The illustrated emulsifying and dispersing apparatus has a separated phase container 1 in which the monomer composition is charged. The separated phase container 1 has a pressure gauge 6. The monomer composition in the container 1 is pressurized by the nitrogen gas in the nitrogen cylinder 7 and pressed into the inside (the aqueous medium side) of the porous glass pipe 4 from the outside through the membrane module 3. . On the other hand, the continuous-phase vessel 2 is charged with an aqueous medium, for example, a mixture of ion-exchanged water, tricalcium phosphate and dodecylbenzene sulfonic acid.
Circulate through the inside of the porous glass pipe 4.
The monomer composition is suspended and dispersed in the circulating aqueous medium, and the emulsion for polymerization can be collected in the continuous phase container 2.

The present invention still further provides, in another preferred embodiment thereof, an electron beam for developing an electrostatic image, comprising polymerized core particles and projecting polymerized fine particles adhered and fixed to the surface of the core particles. A method for producing a photographic toner. In the toner production method of the present invention, seed particles are prepared from a seed particle-forming monomer or a mixture thereof, and the obtained seed particles are swelled with a poorly water-soluble substance to increase the particle size, thereby allowing swelling. The seed particles grown by absorbing the post-addition monomer or the mixture thereof into the seed particles, the seed particles grown by incorporating the post-addition monomer or the mixture thereof, and the seed particles without being absorbed by the seed particles. The post-addition monomer or a mixture of the droplets located outside is mixed, and the post-addition monomer or the mixture thereof is polymerized under predetermined conditions, and the polymerized core particles are formed from the seed particles. ,
And simultaneously generating microparticles having a smaller particle size than the core particles from the droplets, and adding a predetermined salt to the product of the above step to adhere and fix the microparticles on the surface of the core particles. It is characterized by being confused.

In the method of the present invention, a monomer or a mixture thereof (hereinafter also referred to as “monomer” for simplicity) used for forming the core particles and the projecting fine particles is:
It may be the same as that specifically described in the manufacturing method according to the first preferred embodiment above, and may therefore be the same or different from each other. These seed particles and post-added monomer may be used, if necessary,
Preferably, it can be used in combination with a colorant component for the production of a colored toner. The combination of the monomer and the colorant component can be performed according to various methods. For example, when performed according to the method used for forming the colorant-containing seed particles described above, a colorant is introduced when preparing the seed particles from the seed particle-forming monomer, and the colorant-containing seed particles are prepared. can do. If necessary, the colorant may be absorbed by the droplets of the post-addition monomer mixed outside the particles without being absorbed by the seed particles.
Examples of suitable colorants are also listed above under the manufacturing method according to the first preferred embodiment.

The toner for developing an electrostatic charge image produced by the method of the present invention is composed of monodisperse non-spherical polymer particles, and each of the polymer particles is composed of the polymer core particles and the core particles as described above. And polymer particles in the form of protrusions adhered and fixed to the surface by a wet method. here,
"Monodisperse" means that the particle size and form of the polymer particles constituting the toner are substantially equal and the particle size distribution is narrow.

The average particle size of the produced monodispersed toner is preferably in the range of about 5 to 10 μm. Also, as described below, soap-free emulsion polymerization is preferred as a method for producing such a toner,
In order to finally obtain a monodispersed toner having an average particle size of about 5 to 10 μm, the ratio of the monomer, water and initiator is adjusted from the stage of seed particle production to obtain a monodispersed and somewhat large particle size. It is necessary to have

Further, the average particle size of the projection-like fine particles adhered to the core particles of the toner is generally about 0.1 to 3
μm range. If the average particle size of the fine particles is 0.1
If it is smaller than μm, the resulting toner has too small projections on its surface and becomes almost spherical, which does not lead to improvement in triboelectric charging characteristics and cleaning properties. Conversely, if the average particle size of the fine particles is larger than 3 μm, the particle size distribution of the whole toner becomes broad.

FIG. 2 is a schematic view for explaining the structure of the polymerized toner particles obtained by the method of the present invention.
Although simplified for clarity,
The polymer core particles 10 constituting the main component of the toner have a plurality of integrally-projected fine particles 11 adhered and fixed to the surface thereof. The size of the fine particles can be varied in a wide range as long as the desired effect is not adversely affected, and this is reflected in the drawing. Polymerized core particles 10 and projecting fine particles 11
May be spherical or nearly spherical, or non-spherical.

The method for producing a toner according to the present invention can be preferably carried out according to the following procedure. First, a seed particle is formed by polymerizing a seed particle-forming monomer. This polymerization step can be carried out using various polymerization methods using various monomers as starting materials, but can be preferably carried out in the absence of a surfactant. That is, a suitable polymerization method is a soap-free emulsion polymerization method. Since this polymerization method does not require the use of a surfactant, it is useful in that adverse effects on environmental characteristics can be avoided. It is particularly advantageous that the polymer seed particles obtained by this polymerization step have a volume average particle size of 0.5 to 1.3 μm. The volume average particle size of the polymer seed particles is 0.5
The reason why it is preferable that the particle size is smaller than 0.5 μm is that if the particle size is smaller than 0.5 μm, even if the conditions of the intermediate steps are changed, the finally desired particle size (5 to 1 μm) is obtained.
(About 0 μm) cannot be obtained, and if an attempt is made to increase the particle diameter to more than 1.3 μm,
This is because the seed particles are likely to agglomerate and monodisperse grown particles cannot be obtained in a later step.

The polymerization step as described above can be carried out using a conventional polymerization method, including a soap-free emulsion polymerization method, which is a preferred polymerization method. The polymerization conditions can be appropriately selected according to various factors such as the type of the polymer seed particles to be formed. As an example, in the soap-free emulsion polymerization method, a seed particle-forming monomer and, if necessary, a crosslinkable monomer and a polymerization initiator and other optional additives are charged into a polymerization vessel, and water is added. By carefully stirring at a temperature of about 60-90 ° C. for about 4-24 hours in the presence of

The monomers which can be advantageously used in this polymerization step can be those described for the production method according to the first preferred embodiment. These monomers may be used alone or may be used in combination of two or more monomers. Further, the crosslinkable monomer which can be advantageously used in combination with these monomers is not limited to those listed below, but may be a crosslinkable monomer having two or more carbon unsaturated bonds. Monomers, such as divinylbenzene, divinylnaphthalene, divinylether, trimethylolpropane methacrylate, and the like.

Further, the polymerization initiator which can be advantageously used for inducing the polymerization of the monomer as described above is not limited to those listed below, but may be benzoyl peroxide, peroxide, or the like. Peroxides such as lauroyl oxide, potassium peroxodisulfate (hereinafter referred to as KPS), persulfates such as sodium persulfate and ammonium persulfate, 2,2′-azobis (2,4-dimethylvaleronitrile), 2, 2-azobis (isobutyronitrile)
And various azo compounds such as VA-545, VA
-546, VA-548, VA-500, VA-55
2, VA-553, VA-558, VA-041, VA
-044, VA-054, VA-058, VA-05
9, VA-060, VA-080, VA-086, etc. (all manufactured by Wako Pure Chemical Industries), and others. Further, in addition to the polymerization initiator, if necessary, a polymerization regulator such as tert-dodecanethiol may be added.

Optional additives that can be used in combination with the above-mentioned monomers, polymerization initiators and the like are, for example, charge control agents, coloring agents, waxes and the like. These additives may be added in the polymerization step described above, or may be added in other steps of the toner production process of the present invention. The colorant may be added during or after preparation of the seed particles, or otherwise, as described below, may be absorbed by the swollen seed particles after the polymer seed particles have been swollen, Alternatively, if necessary, the particles may be colored by applying to the polymer particles obtained after the completion of the polymerization step of the post-addition monomer.

Next, the polymer seed particles obtained in the previous step are swelled to increase the particle size. The role of the seed particle swelling step in the toner production process of the present invention is, in particular, in that the seed particles easily absorb the post-added monomer. The swelling step of the polymer seed particles can be performed by using a poorly water-soluble substance. More specifically, the desired swelling can be achieved, for example, by adding a poorly water-soluble substance in the form of an aqueous emulsion to the polymer seed particles. That is, a poorly water-soluble substance is emulsified and dispersed in water using a small amount of a surfactant. Next, the obtained aqueous emulsion alone or, preferably, a poorly water-soluble substance is transferred into the seed particles via the aqueous phase, and a water-soluble organic solvent having a function of accelerating absorption thereof is added to the aqueous emulsion. After being added to the emulsion, it is added to the polymer seed particles. Suitable poorly water-soluble substances for swelling of such seed particles include, for example, alkanes having about 8 to 20 carbon atoms or derivatives thereof. In alkanes, if the number of carbon atoms contained in the molecule is 7 or less, the absorption of the poorly water-soluble substance into the seed particles proceeds rapidly, so that the seed particles are difficult to swell uniformly. . Conversely,
When the number of carbon atoms in the alkane exceeds 20, it becomes difficult to absorb the poorly water-soluble substance. Alkanes or derivatives thereof suitable as such poorly water-soluble substances are specifically hexadecane, tetradecane, lauryl chloride (1-chlorododecane), dioctyl adipate, dioctanoyl peroxide, lauroyl peroxide, and others. . The ratio of the poorly water-soluble substance to the seed particles is usually 0.25 to
It is preferably 0.75 (volume ratio). Surfactants used in a small amount for preparing an aqueous emulsion include sodium dodecyl sulfate (hereinafter, referred to as SDS),
And sodium dodecylbenzenesulfonate. In general, the amount of the surfactant added is preferably 0.25 to 1% based on water. Further, examples of the water-soluble organic solvent suitable for promoting the swelling of the seed particles include acetone and lower alcohols such as methanol and ethanol. The swollen polymer seed particles obtained after the completion of this swelling step generally have an average particle size of about 0.7 to 1.5 μm.

Subsequently, the post-addition monomer is incorporated into the swollen seed particles obtained as described above. In the monomer incorporation step, preferably, a post-addition monomer which is a new monomer and an oil-soluble polymerization initiator for the polymerization thereof are subjected to the same emulsification and dispersion treatment as in the above-described seed particle swelling step, That is, it can be advantageously carried out by emulsifying in water in the same manner and absorbing and growing the polymer seed particles. Here, in the ordinary two-stage swelling polymerization method, stirring is performed for about 2 to 5 hours so that the entire monomer composition is absorbed by the seed particles, and then the final polymerization is started. However, in the method of the present invention,
Although the majority of the monomer composition is absorbed by the swelling seed particles as described above, a part of the monomer composition remains unabsorbed and has a diameter of 0.1 to 3 mm.
It remains in the form of droplets of about μm, mixed with grown particles. Such a droplet remaining state can be achieved by making the absorption time shorter than usual, preferably 10 minutes to 1 hour.

The post-added monomer which can be advantageously used in the monomer absorption step includes the same as the seed particle-forming monomer described above, and further includes the seed particle-forming monomer. May be used alone, or two or more monomers may be used in combination. The oil-soluble polymerization initiator that can be used together with the subsequently added monomer is specifically described in the above description. Again, suitable oil-soluble polymerization initiators are not limited to those listed below, but include benzoyl peroxide, methyl ethyl ketone peroxide, isopropyl peroxycarbonate, cumene hydroperoxide, dioctanoyl peroxide, Peroxides such as lauroyl peroxide, and 2,2-
Azobis (isobutyronitrile) and V-70, V
-68, V-65, V-59, V-40 and V-601
(All manufactured by Wako Pure Chemical Industries) and others.

Subsequently, it is preferable that the swelled particles grown as described above further absorb a colorant. Although the absorption of the coloring agent in the swelling particles can be performed by various methods, it is preferable to add a uniform slurry of the coloring agent and water to the swelling particles and to color the swelling particles. The colorant that can be advantageously used as a component of the toner in the present invention includes many pigments and dyes as described above, and can be arbitrarily selected and used.

After the incorporation of the post-addition monomer and the colorant in the swollen polymer seed particles is completed, the final polymerization is carried out to polymerize the post-addition monomer in and on the surface of the polymer seed particles. This polymerization step can be carried out using a conventional polymerization method, similarly to the polymerization method for forming seed particles described above, and depends on various factors such as the type of monomer used. Thus, the polymerization conditions can be appropriately selected. As a preferred example, a polymerization vessel is charged with polymer seed particles with post-added monomers and other optional additives, and is thoroughly stirred at a temperature of about 60 to 90 ° C. for about 2 to 8 hours. Thereby, polymerization can be carried out. During the polymerization, salts are added to adhere and fix the projecting fine particles on the surface of the core particles.

After the last polymerization, if necessary, a coloring agent and other additives may be absorbed into the particles via water or a water-soluble organic solvent. Finally, the obtained integrated structure of seed particles / projection-like fine particles is filtered, washed with water and dried in a conventional manner. Monodispersed toner particles having a non-spherical shape and an average particle size of about 5 to 10 μm are obtained.

[0090]

The present invention will be described below in detail with reference to preferred examples and comparative examples. However, it should be understood that the invention is not limited to these examples. Further, “parts” and “%” in Examples are based on weight unless otherwise specified. Example 1 Preparation of seed particles (colored resin particles): JP-A-5-271
Colored resin particles were prepared from the monomers described and a red pigment (CI Pigment No. 122) according to the method described in JP-A No. 312. The average particle size of the obtained particles was 1.5 μm. Absorption of lipophilic solvent into colored resin particles: The following components were contained in a Hiscotron-type homogenizer (manufactured by Nichion Medical Science Instrument Co., Ltd.) in the amounts described, and stirred at 10,000 rpm for 30 minutes.

Lauryl chloride (manufactured by Wako Pure Chemical Industries) 20 parts Ion-exchanged water 250 parts Sodium lauryl sulfate (manufactured by Wako Pure Chemical Industries) 0.6 parts Acetone 30 parts The obtained homogeneous mixture is mixed with the colored resin previously prepared. An aqueous dispersion in which the particles were dispersed in water was added in an amount of 10 parts based on the solid content, followed by gentle stirring at room temperature for 24 hours. In the obtained aqueous dispersion (dispersion I), lauryl chloride was uniformly absorbed in the colored resin particles. Formation of monomer oil droplets: The following components were placed in a Hiscotron-type homogenizer (manufactured by Nichion Medical Science Instrument Co., Ltd.) in the amounts described, and stirred at 10,000 rpm for 30 minutes.

Styrene (Wako Pure Chemical Industries) 64 parts n-butyl acrylate (Wako Pure Chemical Industries) 11 parts Divinylbenzene (Wako Pure Chemical Industries) 0.4 parts Azonitrile compound: V-65 (Wako Pure Chemical Industries) 3 parts Ion-exchanged water 750 parts Sodium lauryl sulfate 1.5 parts Dispersion I prepared in the previous step was added to the obtained homogeneous mixture.
Was added in 15 parts and gently stirred at room temperature for 3 hours. The above monomer mixture was further absorbed by the colored resin particles that had absorbed lauryl chloride. In this way, an aqueous dispersion (monomer oil droplets, dispersion liquid II) in which the colorant, lauryl chloride, the monomer mixture, and the polymerization initiator were uniformly dispersed was obtained. Polymerization of monomer oil droplets and formation of toner: the resulting dispersion II
To 15 parts of polyvinyl alcohol (as suspension stabilizer)
Was added, the stirring conditions were returned to gentle conditions, and polymerization was carried out at 70 ° C. for 10 hours under nitrogen replacement. After completion of the polymerization, the obtained particles were washed with water and dried. Colored polymer particles in which the colorant was uniformly dispersed were obtained. The obtained particles have a volume average particle size of 8.0 μm and a number average particle size of 7.
9 μm, showing a fairly uniform particle size distribution. Finally, one part of hydrophobic silica (R-97) was added to 100 parts of the particles.
2D, manufactured by Nippon Aerosil Co., Ltd.) to complete the toner. Printing test: The toner particles prepared as described above were mixed with a magnetite carrier (KTS-1, manufactured by Hitachi Metals) to prepare a developer having a toner concentration of 10% by weight. The obtained developer is transferred to an electrophotographic printer (Print Partner 8).
000J, manufactured by Fujitsu) and a printing test was performed. The apparatus was stopped instantaneously, the developed toner image on the photosensitive drum was transferred to a transparent adhesive tape, and the developed toner image was observed. As a result, good fine line reproducibility with little dust was shown. Example 2 The procedure described in Example 1 above was repeated. However, in this example,
Blue pigment instead of red pigment (CI Pigment No. 15: 3)
It was used. As in the case of Example 1, good fine line reproducibility with less dust was confirmed. Example 3 Preparation of seed particles (colored resin particles): Polystyrene particles having a particle diameter of 0.8 µm were prepared by ordinary soap-free polymerization. After dispersing 25 parts of polystyrene particles in 150 parts of methanol, 1 part of a blue pigment (SOT BL
UE-1 manufactured by Hodogaya Chemical Co., Ltd.) in 50 parts of methanol was added to the dispersion, and the mixture was kept at 50 ° C. for 2 hours with gentle stirring to color the particles. The desired colored resin particles were obtained. Absorption of lipophilic solvent into colored resin particles: The procedure described in Example 1 was repeated. An aqueous dispersion (dispersion I) in which lauryl chloride was uniformly absorbed in the colored resin particles was obtained. Formation of monomer oil droplets: The procedure described in Example 1 was repeated. However, in this example, the addition amount of the dispersion liquid I prepared in the previous step was changed from 15 parts to 7.5 parts. An aqueous dispersion (monomer oil droplets, dispersion II) in which the colorant, lauryl chloride, monomer mixture, and polymerization initiator were uniformly dispersed was obtained. Polymerization of monomer oil droplets and formation of toner: The procedure described in Example 1 above was repeated. Colored polymer particles in which the colorant was uniformly dispersed were obtained. The obtained particles have a volume average particle size of 5.
The particle size was 5 μm and the number average particle size was 5.5 μm, showing a fairly uniform particle size distribution. Finally, hydrophobic silica was externally added to the particles in the same manner as in Example 1 to complete a toner. Printing test: The procedure described in Example 1 was repeated. The apparatus was stopped instantaneously, the developed toner image on the photosensitive drum was transferred to a transparent adhesive tape, and the developed toner image was observed. Comparative Example 1 Preparation of Toner: The procedure described in Example 3 was repeated. However, in this example, for comparison, a toner was prepared as follows.

The particle size is reduced to 0.1 by ordinary soap-free polymerization.
8 μm polystyrene particles were prepared. However, the polystyrene particles did not contain the blue pigment described in Example 3 above. The lipophilic solvent and the monomer mixture were absorbed in the obtained uncolored resin particles in the same manner as in Example 3. further,
On the surface of the obtained monomer oil droplets, JP-A-60-25820
According to the method described in JP-A No. 3 (Patent Document 3), a blue pigment (CI Pigment
No. 15: 3) was absorbed and polymerization was carried out. The obtained colored polymer particles had a volume average particle size of 5.6 μm and a number average particle size of 5.5 μm. Finally, hydrophobic silica was externally added to the particles to complete a toner. Printing test: Using the toner prepared as described above,
The procedure described in Example 3 was repeated. The apparatus was stopped instantaneously, the developed toner image on the photosensitive drum was transferred to a transparent adhesive tape, and the developed toner image was observed. As a result, significant fog occurred on the background portion of the print. Example 4 Preparation of seed particles (colored resin particles): JP-A-5-271
According to the method described in JP-A No. 312, a monomer, butyl acrylate and a colorant, a red pigment (CI Pigment No. 12)
Colored resin particles were prepared from 2). The average particle size of the obtained particles was 1.5 μm. Absorption of lipophilic solvent into colored resin particles: The following components were contained in a Hiscotron-type homogenizer (manufactured by Nichion Medical Science Instrument Co., Ltd.) in the amounts described, and stirred at 10,000 rpm for 30 minutes.

Lauryl chloride (manufactured by Wako Pure Chemical Industries) 20 parts Ion exchange water 250 parts Sodium lauryl sulfate (manufactured by Wako Pure Chemical Industries) 0.6 parts Acetone 30 parts An aqueous dispersion in which the particles were dispersed in water was added in an amount of 10 parts based on the solid content, followed by gentle stirring at room temperature for 24 hours. In the obtained aqueous dispersion (dispersion I), lauryl chloride was uniformly absorbed in the colored resin particles. Formation of monomer oil droplets: The following components were placed in a Hiscotron-type homogenizer (manufactured by Nichion Medical Science Instrument Co., Ltd.) in the amounts described, and stirred at 10,000 rpm for 30 minutes.

Styrene (Wako Pure Chemical Industries) 64 parts n-butyl acrylate (Wako Pure Chemical Industries) 11 parts Divinylbenzene (Wako Pure Chemical Industries) 0.4 parts Azonitrile compound: V-65 (Wako Pure Chemical Industries) 3 parts Ion-exchanged water 750 parts Sodium lauryl sulfate 1.5 parts Dispersion I prepared in the previous step was added to the obtained homogeneous mixture.
Was added in 15 parts and gently stirred at room temperature for 3 hours. The above monomer mixture was further absorbed by the colored resin particles that had absorbed lauryl chloride. In this way, an aqueous dispersion (monomer oil droplets, dispersion liquid II) in which the colorant, lauryl chloride, the monomer mixture, and the polymerization initiator were uniformly dispersed was obtained. Polymerization of monomer oil droplets and formation of toner: the resulting dispersion II
To 15 parts of polyvinyl alcohol (as suspension stabilizer)
After the addition of, the stirring conditions were returned to gentle conditions, and heating was started at 70 ° C. under nitrogen replacement. When heating for one hour was completed, 0.38 parts of γ-methacryloxypropyltrimethoxysilane (manufactured by Toshiba Silicone) was added to
After dissolving in 0 ml of 1% acetic acid aqueous solution, it was added. Subsequently, heat polymerization was performed at 70 ° C. for 9 hours. After completion of the polymerization, the obtained particles were washed with water and dried. Colored polymer particles in which the colorant was uniformly dispersed were obtained. The obtained particles have a volume average particle size of 8.0 μm and a number average particle size of 7.
9 μm, showing a fairly uniform particle size distribution. Finally, one part of hydrophobic silica (R-97) was added to 100 parts of the particles.
2D, manufactured by Nippon Aerosil Co., Ltd.) to complete the toner. Printing test: The toner particles prepared as described above were mixed with a magnetite carrier (KTS-1, manufactured by Hitachi Metals) to prepare a developer having a toner concentration of 10% by weight. The obtained developer is transferred to an electrophotographic printer (Print Partner 8).
000J, manufactured by Fujitsu) and a printing test was performed. The apparatus was stopped instantaneously, the developed toner image on the photosensitive drum was transferred to a transparent adhesive tape, and the developed toner image was observed. Further, the toner was left at a temperature of 50 ° C. for 12 hours, but no toner blocking occurred. Example 5 The procedure described in Example 4 above was repeated. However, in this example,
Blue pigment instead of red pigment (CI Pigment No. 15: 3)
It was used. As in the case of Example 1, good fine line reproducibility with little dust was confirmed, and no blocking occurred. Comparative Example 2 The procedure described in Example 4 was repeated. However, in this example,
For comparison, the addition of the organic silane compound, γ-methacryloxypropyltrimethoxysilane, was omitted. Example 4 above
When a printing test was performed in the same manner as described above, good fine line reproducibility was shown, but when left in an environment of 50 ° C., toner blocking occurred. Comparative Example 3 The following components were contained in a Hiscotron-type homogenizer (manufactured by Nichion Medical Science Instrument Co., Ltd.) in the amounts described, and 10,000 rpm
for 30 minutes.

Styrene (Wako Pure Chemical Industries) 64 parts n-butyl acrylate (Wako Pure Chemical Industries) 11 parts Divinylbenzene (Wako Pure Chemical Industries) 0.4 parts Azonitrile compound: V-65 (Wako Pure Chemical Industries) 3 parts Ion-exchanged water 750 parts Sodium lauryl sulfate 1.5 parts The obtained homogeneous mixture was mixed with the aqueous solution of the colored resin particles prepared in the step of “Preparation of seed particles (colored resin particles)” in Example 4 above. The dispersion was added in 15 parts and stirred gently at room temperature. Although an attempt was made to make the colored resin particles absorb the monomer mixture, even after 6 hours, the particle size of the resin particles grew only to 2.8 μm. Comparative Example 4 The following components were contained in a Hiscotron-type homogenizer (manufactured by Nichion Medical Science Instrument Co., Ltd.) in the amounts described, and 10,000 rpm
for 30 minutes.

Styrene (Wako Pure Chemical Industries) 64 parts n-butyl acrylate (Wako Pure Chemical Industries) 11 parts Divinylbenzene (Wako Pure Chemical Industries) 0.4 parts Azonitrile compound: V-65 (Wako Pure Chemical Industries) 3 parts The obtained homogeneous mixture was charged into an aqueous medium composed of the following components.

Ion exchanged water 750 parts Tricalcium phosphate 12 parts Sodium dodecylbenzenesulfonate 0.07 part
After stirring at 000 rpm for 15 minutes to form a suspension,
Heat polymerization was performed at 70 ° C. for 8 hours under nitrogen substitution. After completion of the polymerization, the obtained particles were washed with water and dried.
Although colored polymer particles were obtained, the volume average particle size of the resin particles was 8.0 μm, the number average particle size was 5.7 μm, and the particle size distribution was broad. Example 6 Preparation of seed particles (colored resin particles): The following components were thoroughly mixed in the amounts described.

Pigment dispersion, HI micron K BLUE (manufactured by Mikuni Dye) 5 parts Ion-exchanged water 250 parts Styrene (manufactured by Wako Pure Chemical Industries) 28 parts n-butyl acrylate (manufactured by Wako Pure Chemical Industries) 5 parts Obtained After the uniform mixture was purged with nitrogen for 30 minutes, the temperature was raised to 70 ° C. with gentle stirring.
To this system, 1.3 parts of potassium peroxodisulfide dissolved in 50 parts of ion-exchanged water was added, and the mixture was heated at 70 ° C. for 8 hours.
Slow stirring was continued over time to carry out the polymerization.
Colored particles having a relatively average particle size distribution of 2.0 μm in volume average particle size and 1.5 μm in number average particle size were obtained. Examples 7 to 9 The procedure described in Example 6 was repeated. However, in this example,
As the pigment dispersion, commercially available products shown in Table 1 below were used. The results obtained are shown in Table 1 below together with the results of Example 6.

[0100] Table 1 Example Pigment Dispersion volume average particle size number average particle diameter yield 6 HI microns K BLUE 2.0 1.5 about 90% 7 HI microns K MAGENTA 1.8 1.3 to about 80% 8 HI Micron K YELLOW 1.9 1.3 about 80% 9 HI micron K BLACK 1.9 1.3 about 70% Example 10 The procedure described in Example 6 was repeated. However, in this example,
The amount of styrene used was changed to 10 parts, and the amount of n-butyl acrylate was changed to 2 parts. Volume average particle size
Colored particles having a relatively uniform particle size distribution of 2 μm and a number average particle size of 1.0 μm were obtained. Comparative Examples 5 to 8 The procedure described in Example 6 was repeated. However, in this example,
For comparison, a suspension dispersion prepared by mixing the following components in the amounts described below was used as the pigment dispersion.

Copper phthalocyanine pigment (CI Pigment No. 15-3) 15 parts Dispersant (see Table 2) 3 parts Ion-exchanged water 100 parts The results obtained are shown in Table 2 below. Table 2 Comparative Example Dispersant resulting particles 5 Dode Shiruhe Bu Nze Nsuruhon particles 6 reactive surfactant Rateramu S180 (manufactured by Kao Corporation) of sodium submicron not observed complexed seven polyoxyethylene higher alcohol ether complexed is seen Emulken L-40 (manufactured by Kao) 8 Polycarbonic acid califone L-400 (manufactured by Sanyo Chemical Co., Ltd.) No complexation was observed. It was impossible to obtain colored resin particles having the same. In particular, from Comparative Examples 7 and 8, it is clear that even if a hydrophilic resin has a different structural unit from the monomer used for polymerization, no colored particles are produced. Example 11 An electrophotographic toner was produced using the colored resin particles prepared in Example 6 as a starting material. Absorption of lipophilic solvent into colored resin particles: The following components were contained in a Hiscotron-type homogenizer (manufactured by Nichion Medical Science Instrument Co., Ltd.) in the amounts described, and stirred at 10,000 rpm for 30 minutes.

Lauryl chloride (manufactured by Wako Pure Chemical Industries) 5 parts Ion-exchanged water 250 parts Sodium lauryl sulfate (manufactured by Wako Pure Chemical Industries) 0.5 parts Acetone 20 parts An aqueous dispersion in which the colored resin particles are dispersed in water has a solid content of 10%.
And stirred gently at room temperature for 24 hours. In the obtained aqueous dispersion (dispersion I), lauryl chloride was uniformly absorbed in the colored resin particles. Formation of monomer oil droplets: The following components were placed in a Hiscotron-type homogenizer (manufactured by Nichion Medical Science Instrument Co., Ltd.) in the amounts described, and stirred at 10,000 rpm for 30 minutes.

Styrene (Wako Pure Chemical Industries) 60 parts n-butyl acrylate (Wako Pure Chemical Industries) 15 parts Divinylbenzene (Wako Pure Chemical Industries) 0.4 parts Azonitrile compound: V-65 (Wako Pure Chemical Industries) 3 parts Ion-exchanged water 750 parts Sodium lauryl sulfate 1.5 parts Dispersion I prepared in the previous step was added to the obtained homogeneous mixture.
Was added in an amount of 55 parts and stirred gently at room temperature for 3 hours. The above monomer mixture was further absorbed by the colored resin particles that had absorbed lauryl chloride. In this way, an aqueous dispersion (monomer oil droplets, dispersion liquid II) in which the colorant, lauryl chloride, the monomer mixture, and the polymerization initiator were uniformly dispersed was obtained. Polymerization of monomer oil droplets and formation of toner: the resulting dispersion II
To 15 parts of polyvinyl alcohol (as suspension stabilizer)
Was added, the stirring conditions were returned to gentle conditions, and polymerization was carried out at 70 ° C. for 10 hours under nitrogen replacement. After completion of the polymerization, the obtained particles were washed with water and dried. Colored polymer particles in which the colorant was uniformly dispersed were obtained. The obtained particles have a volume average particle size of 6.0 μm and a number average particle size of 5.
8 μm, showing a fairly uniform particle size distribution. Finally, one part of hydrophobic silica (R-97) was added to 100 parts of the particles.
2D, manufactured by Nippon Aerosil Co., Ltd.) to complete the toner. Printing test: The toner particles prepared as described above were mixed with a magnetite carrier (KTS-1, manufactured by Hitachi Metals) to prepare a developer having a toner concentration of 10% by weight. The obtained developer is transferred to an electrophotographic printer (Print Partner 8).
000J, manufactured by Fujitsu) and a printing test was performed. The device was stopped instantaneously, the developed toner image on the photosensitive drum was transferred to a transparent adhesive tape, and the developed toner image was observed. As a result, good fine line reproducibility was exhibited. Example 12 Preparation of monomer composition (toner-forming composition): styrene (manufactured by Wako Pure Chemical Industries) 23.0 parts n-butyl acrylate (manufactured by Wako Pure Chemical Industries) 5.7 parts divinylbenzene (Wako Pure Chemical Industries, Ltd.) 0.2 parts 2,2'-azobis (2,4-dimethylvalero nitrile (manufactured by Wako Pure Chemical Industries) 1.1 parts Magnetite powder: BL-200 (manufactured by Titanium Industry) 20.0 parts [alkyl Silane: Surface-treated with AY43-210MC (manufactured by Dow Corning Toray Silicone)] Methyl acetate 300.0 parts The above components were contained in a Hiscotron-type homogenizer (manufactured by SMT Co.) in the amount described above, and 10% at 10,000 rpm.
Stirred for minutes. A uniform monomer composition was obtained. Preparation of emulsion for polymerization: An emulsion for polymerization was prepared using the emulsifying and dispersing apparatus (manufactured by Ise Chemical Co., Ltd.) of FIG.

The monomer composition prepared in the above step was charged into the separation phase container 1 of the emulsifying and dispersing apparatus. Further, the continuous phase vessel 2 was charged with an aqueous medium composed of 2,000 parts of ion-exchanged water, 40 parts of tricalcium phosphate, and 0.01 part of dodecylbenzenesulfonic acid. The aqueous medium in the continuous phase vessel 2 was circulated through a porous glass pipe (pore diameter 4.2 μm, diameter 10 mm, length 235 mm) 4 in the membrane module 3. Subsequently, the interior of the separated phase vessel 1 was pressurized with nitrogen gas from a nitrogen cylinder 7, and the monomer composition of the content was injected from the outside of the pipe 4 into an aqueous medium circulating inside the pipe. After the press-in of a predetermined amount of the monomer composition was completed, the emulsion for polymerization was recovered in the container 2. Polymerization of polymerization emulsion and formation of toner: The obtained polymerization emulsion is charged into a polymerization reaction vessel, and the polymerization is carried out at 70 ° C. for 12 hours under a nitrogen atmosphere while gently stirring to prevent precipitation of the emulsion. went.
During this heat polymerization, the ethyl acetate used in the monomer composition was also distilled off. After the completion of the polymerization, the obtained particles were sequentially washed with an acid and water and dried. The obtained particles were measured for particle diameter using a Coulter Multisizer (aperture diameter 30 μm) to find that the average particle diameter was 6.8 μm and the CV value was 18%. Finally, 1 part of hydrophobic silica (R-972D, manufactured by Nippon Aerosil) was externally added to 100 parts of the particles to complete a toner. Printing test: The toner particles prepared as described above were subjected to magnetite carrier (KTC-S1 / 4, manufactured by Hitachi Metals).
To prepare a developer having a toner concentration of 10% by weight.
The obtained developer was mounted on an electrophotographic printer (Print Partner 8000J, manufactured by Fujitsu) and a printing test was performed. The apparatus was stopped instantaneously, the developed toner image on the photosensitive drum was transferred to a transparent adhesive tape, and the developed toner image was observed. Example 13 The procedure described in Example 12 was repeated. However, in this example, in the preparation of the monomer composition, magnetite powder: B
Instead of L-200, 3 parts of a cyan pigment dispersion, MHI cyan (30% solid content, manufactured by Mikuni Dye) were used in a styrene monomer. The average particle diameter of the obtained particles was measured in the same manner as in Example 12, and it was found that the average particle diameter was 6.5 μm and the CV value was 16%. Further, when the obtained toner was subjected to a printing test in the same manner as in Example 12, good toner reproducibility with little dust was exhibited. Example 14 The procedure described in Example 12 above was repeated. However, in this example, in the preparation of the monomer composition, magnetite powder: B
Instead of L-200, toner yellow, GRY-
80 (made by Hoechst) was used after ultrasonic heating. The average particle diameter of the obtained particles was 5.5 μm, and the CV value was 1 in the same manner as in Example 12.
6%. Further, when the obtained toner was subjected to a printing test in the same manner as in Example 12, good toner reproducibility with little dust was exhibited. Comparative Example 9 The procedure described in Example 12 was repeated. However, in this example, methyl acetate was omitted from the monomer composition for comparison. An aqueous medium comprising 1000 parts of ion-exchanged water, 20 parts of tricalcium phosphate and 0.005 parts of dodecylbenzene sulfonic acid as described in Example 12 above, using 200 parts of the obtained monomer composition. Press-fit. The porous glass pipe in the membrane module 3 used in this example is
The pore diameter was 1.8 μm, the diameter was 10 mm, and the length was 235 mm. As the injection of the monomer composition into the aqueous medium was continued, the injection speed gradually decreased, and finally introduction into the aqueous medium became almost impossible. Comparative Example 10 Preparation of Monomer Composition (Toner-Forming Composition): Styrene (manufactured by Wako Pure Chemical Industries) 23.0 parts n-butyl acrylate (manufactured by Wako Pure Chemical Industries) 5.7 parts Divinylbenzene (sum) 0.2 parts 2,2'-azobis (2,4-dimethylvalero nitrile (manufactured by Wako Pure Chemical Industries) 1.1 parts Magnetite powder: BL-200 (manufactured by titanium industry) 20.0 parts [ Alkylsilane: Surface-treated with AY43-210MC (manufactured by Dow Corning Toray Silicone)] The above components are contained in a Hiscotron-type homogenizer (manufactured by SMT Co., Ltd.) in the amounts described above, and 10 parts at 10,000 rpm.
Stirred for minutes. A uniform monomer composition was obtained. Preparation of emulsion for polymerization: The monomer composition prepared in the above step was put into an aqueous medium composed of 600 parts of ion-exchanged water, 12 parts of tricalcium phosphate and 0.003 parts of dodecylbenzenesulfonic acid. 10,000 rpm using a Hiscotron type homogenizer (manufactured by SMT)
For 30 minutes. An emulsion for polymerization was obtained. Polymerization of polymerization emulsion and formation of toner: charging the obtained polymerization emulsion into a polymerization reaction vessel;
200 rpm to prevent emulsion settling and coalescence
The temperature was raised to 70 ° C. while stirring slowly at m, and the polymerization was carried out at that temperature for 8 hours. After the completion of the polymerization, the obtained particles were sequentially washed with an acid and water and dried. The average particle diameter of the obtained particles was 7.8 μm, and the CV value was 40%, as measured by using a Coulter Multisizer (aperture diameter: 30 μm). Finally, 1 part of hydrophobic silica (R-972D, manufactured by Nippon Aerosil) was externally added to 100 parts of the particles to complete a toner. Printing test: The toner particles prepared as described above were subjected to a printing test according to the method described in Example 12. Although a developed toner image was formed on the photosensitive drum, a slight background fog was observed. Example 15 Preparation of Seed Particles: The following components were prepared in the amounts indicated.

Styrene (manufactured by Wako Pure Chemical Industries) 25 parts Potassium peroxodisulfate (KPS) (manufactured by Wako Pure Chemical Industries) 1 part Water 250 parts First, styrene and water are charged into a polymerization vessel, and the three-one motor is replaced with nitrogen. 80 ° C using (Yamato Scientific)
And stirring was started at 200 rpm. Subsequently, KPS
Was added to initiate polymerization. The polymerization is carried out at a temperature of 80 ° C. for 8 hours.
Performed over time. Polymer seed particles having a volume average particle size of 1.1 μm were obtained. Swelling of seed particles: The following components were prepared in the amounts described.

Seed particles (as solid content) 30 parts Lauryl chloride (Wako Pure Chemical Industries) 15 parts Acetone (Wako Pure Chemical Industries) 75 parts Sodium dodecyl sulfate (SDS) (Wako Pure Chemical Industries) 2 parts Water 780 Part Lauryl chloride, SDS, acetone and water were mixed using a Hiscotron type homogenizer (manufactured by Nichion Medical Science Instrument Co., Ltd.)
Stirred at 9500 rpm for 15 minutes. The seed particles prepared above were added to the obtained aqueous emulsion, and the mixture was stirred for 5 hours using a magnetic stirrer. An emulsion containing the seed particles swollen with lauryl chloride was obtained. The average particle size of the polymerization core particles was approximately 1.5 μm. Absorption and polymerization of post-added monomer: The following components were prepared in the amounts described.

Emulsion containing swollen seed particles 20 parts Styrene 85 parts N-butyl acrylate (manufactured by Wako Pure Chemical Industries) 15 parts V-65 (azo compound manufactured by Wako Pure Chemical Industries) 4 parts Sodium dodecyl sulfate (SDS) ) (Wako Pure Chemical Industries) 2 parts Water 900 parts Carbon black MA-100 (Mitsubishi Chemical) 5 parts Oil Black BY (Orient) 3 parts Calcium chloride (Wako Pure Chemical Industries) 1 part Styrene, acrylic acid n -Butyl, V-65, SDS and water were stirred for 15 minutes at 12,500 rpm using a Hiscotron-type homogenizer (manufactured by Nichion Medical Science Instrument Co., Ltd.). The emulsion containing swelling seed particles prepared above was added to the obtained aqueous emulsion, and three-one motor (manufactured by Yamato Scientific) was added.
And stirred at 300 rpm at 30 ° C.

On the other hand, sodium dodecyl sulfate (SDS)
The carbon black MA-100 was dispersed in 100 parts of water in the same manner as described above, and this aqueous dispersion was added to the aqueous emulsion 30 minutes after the start of stirring. Observation using a microscope revealed that particles (seed particles) grown to a particle size of about 5 μm and droplets of a diameter of 1 μm or less (part of the post-added monomer) adhering to the surface of the particles were mixed, It was confirmed that both were colored.

One hour after the start of stirring, the temperature of the contents in the reaction vessel was raised to 70 ° C. to initiate polymerization. Two hours after the start of stirring (one hour after the start of polymerization), calcium chloride was added to the reaction vessel, and the polymerization was further continued. The polymerization time was a total of 8 hours. Finally, the resulting polymerization product was filtered, washed with water and dried. The desired polymer particles (toner) have a yield of 90% and a volume average particle size of 5.5.
μm.

When the obtained toner was observed with a microscope, it was confirmed that the toner particles had a uniform particle size and were non-spherical particles as a whole. Each of these particles had a shape in which a large number of fine spherical particles having different particle diameters (about 0.1 to 1 μm) were fixed on the surfaces of spherical particles having a particle diameter of about 5 μm. Printing test: Toner particles 25 prepared as described above
Was mixed with 75 parts of a magnetite carrier (KBN-100, manufactured by Hitachi Metals) to prepare a developer having a toner concentration of 25% by weight. The obtained developer was used in an optical printer (RX-71).
00, manufactured by Fujitsu), and a printing test was performed. The obtained print was clear and stable, and no cleaning failure occurred even in repeated printing. Example 16 The procedure described in Example 15 above was repeated. However, in this example, the same amount of hexadecane (manufactured by Wako Pure Chemical Industries) was used instead of lauryl chloride when the polymer seed particles were swollen. The desired polymer particles (toner) were obtained with a yield of 85% and a volume average particle size of 5.2 μm.

Observation of the obtained toner with a microscope revealed that, as in the case of Example 15, the toner particles had a uniform particle size, were non-spherical, and had large spherical particles and a large number of particles fixed on the surface of the particles. It was confirmed that the particles consisted of fine spherical particles having different particle diameters. Printing test: When a printing test was performed in the same manner as in Example 15, the obtained print was clear and stable, and no cleaning failure occurred even in repeated printing. Comparative Example 11 The procedure described in Example 15 was repeated. However, in this example, the addition of calcium chloride during polymerization was omitted for comparison. The polymer particles (toner) finally obtained had a yield of 90% and a volume average particle size of 5.0 μm.

Observation of the obtained toner with a microscope revealed that, in addition to spherical particles having a particle size of about 5 μm,
It was confirmed that many fine particles of about 1 μm were released. Printing test: When a printing test was performed in the same manner as in Example 15, it was confirmed that the printing was inferior to the prints in Examples 15 and 16 in sharpness. Only prints with defective cleaning were obtained. Comparative Example 12 The procedure described in Example 15 was repeated. However, in this example, for comparison, the same amount of n-hexane (manufactured by Wako Pure Chemical Industries) was used instead of lauryl chloride at the time of swelling of the polymer seed particles. The polymer particles (toner) finally obtained had a yield of 80% and a volume average particle size of 5.5 μm.

When the obtained toner was observed with a microscope, it was found to be non-spherical as in the case of Example 15, but the particle size was remarkably varied. Printing test: When a printing test was performed in the same manner as in Example 15, no cleaning failure occurred even with repeated printing. However, the resulting print was inferior in sharpness to those of Examples 15 and 16.

[0114]

As will be understood from the above description, according to the present invention, an electrophotographic toner having a uniform particle size distribution and high resolution can be provided. Further, since the seed particles having a relatively sharp particle size distribution can be used, the particle size distribution of the obtained toner is sharp. Further, when preparing a colored toner, localization of the colorant in the obtained toner can be prevented.

In the case where polymerization for forming a toner is carried out in the presence of an organic silane compound, blocking between toners caused by the remaining of the polymerization-inactive lipophilic solvent used during the polymerization is prevented. it can. Further, according to the present invention, resin particles containing a colorant component in a well dispersed state in advance, having a particle size of about several μm,
In addition, particles having a relatively uniform particle size distribution can be obtained.
When the thus obtained colored resin particles are used for preparing a toner, not only can the obtained toner have a uniform particle size distribution, but also it is easy to grow the colored resin particles to a desired toner particle size. A plurality of particle growth operations and fine adjustment of the amount of surfactant, which are problems in the ordinary two-stage swelling polymerization method, are not required. Further, there is an advantage that the toner particle size can be easily controlled by the charged monomer amount.

Further, according to the present invention, when a monomer composition containing solid particles such as a colorant and a charge controlling agent is polymerized after passing through a sieving member such as porous glass, By adding a solvent to be removed in the post-process to the monomer composition, it is possible to temporarily increase the bulk and to use a sieving member having a large pore, which is a major problem in the conventional technology. Can effectively eliminate the clogging of the pores, thereby increasing the production efficiency of the emulsion used for polymerization, and making it easy to control the particle size and narrowing the particle size distribution, which is compatible with forming high-quality printed images. Can be provided.

Furthermore, according to the present invention, a non-spherical
It is possible to provide a toner having a uniform particle diameter of about 5 to 10 μm, and by using this toner, it is possible to obtain a clear print free from triboelectric charging and poor cleaning.

[Brief description of the drawings]

FIG. 1 is a flow sheet showing an example of an emulsifying and dispersing apparatus used for preparing an emulsion to be subjected to polymerization in the method of the present invention.

FIG. 2 is a schematic view showing an example of a non-spherical toner obtained by the method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Separation phase container 2 ... Continuous phase container 3 ... Membrane module 4 ... Porous glass pipe 5 ... Liquid sending pump 6 ... Pressure gauge 7 ... Nitrogen cylinder 10 ... Core particle 11 ... Projection-like fine particle

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Atsushi Minagawa, Inventor 4-1-1, Kamidadanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture Inside Fujitsu Limited (72) Tsuneo Watanuki 4-1-1, Kamiodanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture No. 1 Inside Fujitsu Limited

Claims (9)

[Claims] In producing a toner by a two-step swelling polymerization method using a seed particle, a lipophilic solvent and a polymerizable monomer or a mixture thereof as a starting material, a resin particle containing a colorant component is used as the seed particle. A method for producing an electrophotographic toner. 2. The resin particles containing the colorant component, wherein: (1) the resin particles are formed by polymerization of a polymerizable monomer or a mixture thereof, and the coloring contained in the resin particles; An agent component is a pigment, and formed by adding an aqueous dispersion of the pigment during the polymerization process of the resin particle-forming monomer or a mixture thereof; (2) the resin particles are polymerizable monomers The colorant component contained in the resin particles is a pigment, and the resin particle-forming property in water in which the pigment is dispersed using a surfactant. (3) an emulsion polymerization or soap-free emulsification of a polymerizable monomer or a mixture thereof, wherein the resin particles are formed by emulsion polymerization or precipitation polymerization of a monomer or a mixture thereof. Are those formed by coupling and method according to claim 1, characterized in that the one dyeing by the coloring agent component after formation of the resin particles is performed is either. 3. The resin particles containing the colorant component,
An aqueous system formed by polymerizing a polymerizable monomer or a mixture thereof, wherein the colorant component contained in the resin particles is a water-insoluble pigment, and the pigment is dispersed in a hydrophilic resin. 2. The method according to claim 1, wherein the resin particle-forming monomer or a mixture thereof is polymerized in a dispersion with a water-soluble polymerization initiator. 4. After the lipophilic solvent is absorbed by the seed particles, polymerization is performed by absorbing the polymerizable monomer or a mixture thereof, wherein an alkyl halide, phenylalkyl, The method according to any one of claims 1 to 3, wherein a member selected from the group consisting of phthalic acid esters, fatty acid esters, phosphoric acid esters and mixtures thereof is used. 5. The method according to claim 1, wherein the polymerization is carried out in the presence of an organic silane compound. 6. In producing a resin particle colored with a colorant component, a polymerizable monomer for forming the resin particle in an aqueous dispersion in which a water-insoluble colorant component is dispersed with a hydrophilic resin. A method for producing colored resin particles, comprising polymerizing a polymer or a mixture thereof with a water-soluble polymerization initiator. 7. In preparing a toner by a suspension polymerization method using a polymerizable monomer or a mixture thereof as a starting material, the monomer or a mixture thereof is suspended and dispersed in an aqueous medium to prepare a polymerization emulsion. After performing the polymerization, and, at that time, to prepare a monomer composition by combining the monomer or a mixture thereof with a polymerization inert solvent,
The monomer composition is suspended and dispersed in the aqueous medium through a porous sieving member having a hydrophilic surface to obtain the emulsion, and the solvent is removed from the emulsion during and / or after polymerization. A method for producing an electrophotographic toner, wherein the toner is removed. 8. In producing an electrophotographic toner including polymerized core particles and projecting polymerized fine particles adhered and fixed to the surface of the core particles, the seed particles are formed from a seed particle-forming monomer or a mixture thereof. Is prepared by swelling the obtained seed particles with a poorly water-soluble substance to increase the particle size thereof, and allowing the swollen seed particles to grow by absorbing a post-added monomer or a mixture thereof. The seed particles grown by taking in the added monomer or the mixture thereof, and the post-added monomer or the mixture of the droplets located outside the particle without being absorbed by the seed particles are mixed, and The post-added monomer or a mixture thereof is polymerized under predetermined conditions, and the polymerized core particles from the seed particles, and the fine particles having a smaller particle size than the core particles from the droplets, simultaneously. Generate and then Electrophotographic method for producing a toner, wherein the allowed to adhere fix the fine particles by adding a predetermined salts in the product on the surface of the core particles of the above step. 9. The method according to claim 8, wherein a colorant component is used in combination with the seed particle-forming and / or post-added monomer or a mixture thereof.