KR960005188B1 - Toner for electrophotography - Google Patents

Abstract

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Description

Electrophotographic toner

1 is an electron micrograph of block-like particles obtained by the heat treatment step of the method of the present invention.

2 is an electron micrograph of colored fine particles obtained by the method of the present invention.

The present invention relates to a method for producing colored fine particles and an electrophotographic toner made by using the colored fine particles thus obtained. More specifically, the method of producing colored fine particles and colored fine particles that can be used in colorants such as toners, paints, inks, resin moldings, and the like, by uniformly dispersing the colorant in the particles and modifying the surface of the particles. The present invention relates to an electrophotographic toner, which can be formed by use of a toner in a printer device such as a laser printer or a liquid crystal printer.

Moreover, this invention relates to the recovery method of the spherical microparticles | fine-particles which consist mainly of resin from suspension. More specifically, the present invention relates to a method for efficiently collecting extremely small spherical fine particles obtained by, for example, suspension polymerization in suspension.

The electrophotographic method forms an electric latent image on a photoconductor made of a photoconductor material such as selenium, zinc oxide, cadmium sulfide, etc., develops it into a powder phosphor, transfers it onto paper, and fixes it.

Conventionally, toners used in the development of electrophotographic are generally melt mixed with colorants and other additives (charge control agents, anti-offset agents, lubricants, etc.) and dispersed in thermoplastic resins, and then finely divided and classified solids. It was manufactured from colored fine particles of a desired particle size.

However, various drawbacks exist in the method for producing toner by the pulverization. First, many processes such as manufacturing a resin, mixing a resin with a colorant or other additives, crushing a solid, and classifying the pulverized product to obtain colored fine particles having a desired particle size, and various kinds of apparatuses accompanying them, It is necessary, and the toner produced by this method is inevitably expensive. In particular, the process of classifying in order to obtain a toner having an optimum particle size range for forming a clear and low blurring image is an essential requirement, and there are problems in productivity and yield. Second, in the mixing process, it is extremely difficult for the colorant or other additives to be uniformly dispersed in the resin. Therefore, the toner produced by this method has different triboelectric charge characteristics of the particles due to the poor dispersion of the colorant and the charge control agent. This leads to a decrease in resolution. This problem becomes more prominent with the particle size hardening of the toner, which is an essential condition for the future improvement of the image quality. That is, current mills have limitations in obtaining a small particle size toner, and even if a small particle size toner is obtained, scattering with a larger charge amount occurs due to poor dispersion of a colorant and a charge control agent.

In order to improve various defects seen in toners by these grinding methods, a method of producing toners by emulsion polymerization method or suspension polymerization method has been proposed (JP-A-36-10,231). , Commando 43-10, 799, Commando 47-518, 305, Commando 51-14, 895, etc.). Such a method is a method for synthesizing toner containing a colorant material by emulsifying or suspending polymerizing a colorant material such as carbon black and other additives in a polymerizable monomer. This method can significantly improve the disadvantages of the conventional grinding method. That is, since the grinding process is not included at all, the weakness of the conventional grinding method is not necessary. Since the shape is spherical and the fluidity is excellent, the triboelectric charging property is uniform. However, there is also a problem in the toner production method by the polymerization method.

First, since hydrophilic substances such as dispersants and surfactants used during polymerization cannot be completely removed even by the washing process, they remain on the surface of the toner, and thus the chargeability is easily affected by the environment. Second, the toner obtained by the polymerization method is spherical in shape and extremely smooth in surface, making it difficult to remove the toner adhered to the photosensitive member, resulting in poor cleaning.

In order to solve these problems, various methods have been suggested by Japanese Patent Application Laid-Open No. 61-255, 354, Japanese Patent Application No. 53-17, 736, Japanese Patent Application No. 63-17, 460, Japanese Patent Application No. 61-167, 956, etc. The effect is incomplete or unusable due to cost increases.

In order to solve this problem, for example, the polymerizable monomer, the colorant and / or the magnetic component and the polymerization initiator are emulsified and dispersed in the presence of an emulsifier to prepare the main resin component, and the resulting polymer solution The electrophotographic toner having a desired particle size is solidified by solidifying at a temperature below the glass transition point of the resin component and further heating the particles obtained after solidification to a temperature above the glass transition point of the main resin component to classify the obtained particles. A manufacturing method is disclosed (Japanese Patent Laid-Open Nos. 61-167, 955, 61-167, 956, 61-167, 957 and 61-72, 258).

However, since the polymerization is mainly carried out by emulsion polymerization, the particle size of the polymer particles to be obtained becomes submicron, and colorants such as carbon black are not included in the polymer particles and exist outside the particles. It is impossible to disperse | distribute uniformly even if it contains in larger particle | grains in a process and a heat-melting process. This results in nonuniformity of the colorant, which, in the case of use, for example, as an electrophotographic toner, causes nonuniformity of charging or causes toner scattering and causes blurring and drum contamination. In addition, since the particle system of the polymer obtained by polymerization is small, it is necessary to increase the particle size and to control the particle size by solidifying at a temperature below the glass transition point in the solidification step. In this case, an inorganic acid, an organic acid, or the like may be used as a coagulant. There is a need. This coagulant cannot be completely removed even if the toner obtained is washed, and there is a problem that the remaining coagulant causes environmental dependency and insufficient electrical characteristics.

It is therefore an object of the present invention to provide a method for producing new colored fine particles and an electrophotographic toner made of the colored fine particles obtained thereby.

Another object of the present invention is to provide a method for producing colored fine particles in which the colorant is uniformly dispersed in the particles and the surface of the particles is modified.

Still another object of the present invention is to provide a method for producing colored fine particles that can be used in colorants such as toners, paints, inks and resin moldings.

Still another object of the present invention is to provide an electrophotographic toner capable of forming a clear image by use in toners of printer devices such as laser printers and liquid crystal printers.

It is still another object of the present invention to provide a new method for recovering spherical fine particles, mainly composed of resin from suspension.

It is still another object of the present invention to provide a method for efficiently recovering very small spherical fine particles obtained by, for example, suspension polymerization in suspension.

MEANS TO SOLVE THE PROBLEM As a result of earnest research in view of the said phenomenon, the colored fine particle obtained by processing the colored spherical microparticles obtained by suspension polymerization in a specific order has solved all the said problems, In addition, the electrophotographic toner, which is preferably used in colorants such as paints, inks, resin moldings, and the like, is used in printer devices such as laser printers and liquid crystal printers, and thus has no problems with the prior art. Discovering the point that can form a clear image came to complete this invention.

The various objects are suspended in a suspension medium in the presence of a colorant and / or a magnetic component to carry out suspension polymerization, and colored spherical fine particles having an average particle diameter of 3 to 50 µm are obtained by water at 50 to 130 ° C. as a medium. And heat treatment to melt these particles to form a block, and then the block-shaped particles are pulverized substantially to the average particle diameter of the colored spherical fine particles before fusion. Is achieved by.

In the method for producing colored fine particles of the present invention, the heat treatment may be performed in a state where colored spherical fine particles are present in a suspension medium that is water after suspension polymerization. Alternatively, the heat treatment may be performed on a cake of colored spherical fine particles extracted from the suspension medium.

In a preferred embodiment of the method for producing colored fine particles of the present invention, a colored spherical polymer having a mean particle size of 3 to 50 µm is obtained by suspending polymerization by suspending the polymerizable monomer in a suspension medium in the presence of a colorant and / or a magnetic component. The suspension of the fine particles is heated at a temperature of 50-98 ° C. to carry out polymerization aging, and the particles are fused together to form a block, and then the block-like particles are substantially ground to an average particle diameter of the colored spherical fine particles before fusion. .

In another embodiment of the method for producing colored fine particles of the present invention, the polymerization is carried out by suspending the polymerizable monomer in a suspending medium in the presence of a colorant and / or a magnetic component, thereby obtaining a coloring having an average particle diameter in the range of 3 to 50 µm. In the suspension when the polymerization rate of the spherical fine particles reached 90% or more

1) After adding water-insoluble particles

2) Heat treatment at 50 ~ 98 ℃

At the same time as polymerization aging, the colored spherical fine particles are fused together to form a block, and then the block-shaped particles are pulverized substantially to the average particle diameter of the colored spherical fine particles before fusion.

In another embodiment of the method for producing red fine particles of the present invention, the polymerizable monomer is suspended in a suspension medium in the presence of a colorant and / or a magnetic component to polymerize, and the colored spherical fine particles having an average particle size in the range of 3 to 50 µm is obtained. The agglomerates obtained by separating the fine particles from the suspension of the particles are fused together to form blocks by heating at a high temperature at a temperature of 50 to 130 ° C. and a relative temperature of 70 to 100%, thereby forming a block shape. It grind | pulverizes to the average particle diameter of previous colored spherical microparticles | fine-particles.

In another embodiment of the colored fine particles of the present invention, a suspension of colored spherical fine particles having an average particle size in the range of 3 to 50 µm is obtained by performing polymerization by suspending the polymerizable monomer in a suspension medium in the presence of a colorant and / or a magnetic component. The fine particles are separated from each other, and the resulting lump is fused with each other by hot water heating at a temperature of 50 to 130 ° C. to form a block, and then the block-like particles are substantially ground to an average particle diameter of the colored spherical fine particles before fusion.

The present invention is also an electrophotographic toner containing colored fine particles obtained by the above production method.

In the present invention, a polymerizable monomer is suspended in a suspension medium to carry out suspension polymerization, non-aqueous particles are added to a suspension of the obtained spherical fine particles, the spherical fine particles are aggregated, and the spherical fine particles are aggregated by filtration to separate them in a suspension medium. A method for recovering suspended fine particles from a suspending medium.

According to the production method of the present invention, the particle size is uniform, the surface of the particles is irregular, and the surfactant and dispersant used in the suspension polymerization are remarkably reduced, and the coloration in which the variation in physical properties accompanying temperature change is almost eliminated. Fine particles can be obtained. Therefore, the colored fine particles of the present invention can be used as a colorant or modifier of other paints, inks and resin compositions as well as being able to form a clear image and being suitably used as an electrophotographic toner having excellent fluidity and cleaning properties. have. In particular, the electrophotographic toner according to the present invention using such colored fine particles is formed by using the colored fine particles, and is capable of forming an image without blur due to temperature at all times in a high quality environment under various environments. It can be used for the device.

In addition, the method for recovering the spherical fine particles from the suspension medium according to the present invention makes it possible to facilitate solid-liquid separation using a general filtration apparatus even if the particle size of the spherical fine particles obtained by suspension polymerization becomes small. In the production of the colored fine particles as described above, the productivity can be improved.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail based on an Example.

In the method for producing colored fine particles of the present invention, polymerization is first carried out by suspending the polymerizable monomer in a suspension medium in the presence of a colorant and / or a magnetic component. The colored spherical fine particles obtained by the suspension polymerization are particle sizes in the range of 3 to 50 µm, preferably 5 to 20 µm, and the size of the particles is very important for obtaining the colored fine particles of the present invention through the heat treatment and grinding steps described below. It has meaning. The average particle diameter of the spherical polymer by polymerization method other than suspension polymerization, for example, emulsion polymerization method, is usually about 0.1 μm, and the fine particles obtained by heat treatment and pulverization of the spherical polymers are compared with the colored fine particles obtained by the production method of the present invention. The shape and particle size distribution are remarkably different, and even if this is used as a toner, an image of satisfactory image quality cannot be obtained.

The suspension polymerization is preferably carried out after the particle size is regulated or while the particle size is regulated. Particularly, the suspension polymerization is preferably performed after the particle size is regulated. For example, the particle size is regulated once in a line mixer such as T. K homomixer (manufactured by Special Vaporization Co., Ltd.) or Ebara Milder (manufacturer's product). To several times.

The suspension polymerization reaction is usually carried out at a temperature of 40 to 130 ° C., preferably at 50 to 90 ° C. for 0.5 to 30 hours, preferably 2 to 10 hours.

Examples of the polymerizable monomer used for the polymerizable monomer component of the suspension polymerization include the following, and these may be used alone or in combination of two or more thereof.

Styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, p-methoxy styrene, p-tert-butyl styrene, p-phenyl styrene, o-chloro styrene, m-chloro styrene, styrene monomers such as p-chloro styrene; Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate Acrylic acid or methacrylic acid monomers such as isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate; Ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile.

The workability at the time of grinding | pulverization becomes favorable by heat-processing the colored spherical microparticles | fine-particles obtained by suspension-polymerizing the said polymerizable monomer on condition as mentioned later. In the heat treatment, if the fusion of the particles proceeds too much, the efficiency at the time of later grinding decreases, and if the fusion is insufficient, sufficient treatment effect on the surface of the particles can be obtained. In order to avoid excessive fusion, a crosslinking agent may be used during suspension polymerization.

As a crosslinking agent, For example, aromatic divinyl compounds, such as divinylbenzene, divinyl naphthalene, these derivatives, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethyl propane tri Diethylenically unsaturated carboxylic acid esters such as acrylate, allyl methacrylate, t-butylaminoethyl methacrylate, tetra ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, N, N-divinyl Aniline, divinyl ether divinyl sulfide, all the divinyl compounds of divinyl sulfonic acid, and the compound which has 3 or more vinyl groups are mentioned.

Moreover, polybutene, polyisoprene, unsaturated polyester, chloro sulfonated polyolefin, etc. are also effective.

The coloring agent used for obtaining colored spherical microparticles | fine-particles is dyes, pigments, etc. which are well known to a person skilled in the art, and are both organic and inorganic. Specific examples thereof include, for example, carbon black, nigrosine dye, aniline blue, chaco oil blue, chrome yellow, ultramarine blue, Dupont oil red, quinoline yellow, methylene blue chloride, phthalocyanine blue, malachite green oxalate, lamp black , Oil black, azo oil black, rose bangal, and the like, and two or more of these may be used in combination if necessary.

Examples of the magnetic material, that is, powders of ferromagnetic metals such as iron, cobalt, and nickel, powders of metal compounds such as magnetite, hematite, and ferrite, and the like, may be mentioned. These magnetic components can be used alone or in combination with the colorant.

Although these coloring agents and / or magnetic components may be used as they are, using the coloring agent and / or magnetic component which surface-treated by an appropriate method, the colored fine particle which this colorant and / or magnetic component disperse | distributed uniformly can be obtained, for example, For example, when used in toner, a high quality image is formed. For example, when carbon black is used as a coloring agent, the carbon black graft polymer of Unexamined-Japanese-Patent No. 63-270, 767 and 63-265, 913 is preferable.

Moreover, also when the coloring agent other than carbon black is used, the surface-treated coloring agent obtained by the method of Unexamined-Japanese-Patent No. 1-118, 573 is preferable. These are added here because they are relevant.

Although it can be set as a wide range according to the kind of coloring agent and / or magnetic component which use the addition amount of the said coloring agent and / or the said magnetic component, and the colored fine particle obtained, Preferably it is 1- with respect to 100 weight part of polymerizable monomers. 200 parts by weight, more preferably 1 to 100 parts by weight.

To obtain colored spherical fine particles using a colorant and / or a magnetic component, it is usually convenient to suspend-polymerize a polymerizable monomer obtained by dissolving or dispersing the colorant and / or magnetic component. It is also possible to use a method of absorbing a colorant and / or a magnetic component into a spherical polymer particle polymerized without using a suitable solvent.

As a stabilizer used for suspension polymerization, water-soluble polymers, such as polyvinyl alcohol, starch, methyl cellulose, carboxymethyl cellulose, hydroxy ethyl cellulose, sodium polyacrylate, sodium polymethacrylate; There are surfactants such as anionic surfactants, cationic surfactants, zwitterionic surfactants and nonionic surfactants. Others include barium sulfate, calcium sulfate, barium carbonate, magnesium carbonate, calcium phosphate, talc, clay, silicon Earth, metal oxide powder, etc. are used.

As the anionic surfactant, fatty acid salts such as sodium oleate and castor oil, alkyl sulfate ester salts such as sodium lauryl sulfate and ammonium lauryl sulfate, alkylbenzene sulfonates such as sodium dodecyl benzene sulfonate, alkyl naphthalene sulfonates and alkanes Sulfonate, dialkyl sulfonate, alkyl phosphate ester salt, naphthalene sulfonate formalin condensate, polyoxeethylene alkyl phenyl ether sulfate ester salt, polyoxyethylene alkyl sulfate ester salt and the like.

As a nonionic surfactant, Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxy sorbitan fatty acid ester, polyoxyethylene alkyl amine; Glycerin fatty acid esters, oxyethylene oxypropylene block polymers, and the like.

Cationic surfactants include alkylamine acids such as lauryl amine acetate and stearyl amine acetate, and quaternary ammonium oxides such as lauryl trimethyl ammonium chloride.

As an amphoteric ion surfactant, lauryl dimethyl amine oxide etc. are mentioned.

These stabilizers should be used by appropriately adjusting the composition and the amount of use so that the particle size of the colored spherical microparticles obtained is in the range of 3 to 50 µm, preferably 3.5 to 20 µm. For example, when using a water-soluble polymer as a stabilizer, it is preferable to set it as 0.01 to 20 weight% with respect to a polymerizable monomer component, Preferably it is 1 to 10 weight% of range. In the case of a surfactant, it is preferable to set it as 0.01 to 10 weight% with respect to a polymeric monomer component, Preferably it is 0.1 to 5 weight% of range.

As a polymerization initiator used for superposition | polymerization, a fat-soluble peroxide type or an azo type initiator normally used for suspension polymerization can be used. For example, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochloro benzoyl peroxide, orthomethoxy benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy dicarbonate, silicenyl hydroperoxide, cyclohexanone peroxide Peroxide initiators such as oxides, t-butyl hydroperoxide, diisopropyl benzene hydroperoxide, 2,2'-azobis isobutylonitrile, 2,2'-azobis- (2,4-dimethyl valero Nitrile), 2,2'-azobis-2,3-dimethylbutylonitrile, 2,2'-azobis- (2-methylbutylonitrile), 2,2'-azobis-2,3,3 -Trimethyl butyronitrile, 2,2'-azobis-2-isopropyl butyronitrile, 1,1'-azobis- (cyclohexane-1-carbonitrile), 2,2'-azo-bis- (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutylonitrile, 4,4'-azobis-4-cyanovaleric acid, dimethyl-2,2 Azobis isobutylate. It is preferable that the said polymerization initiator is used in 0.01-20 weight%, especially 0.1-10 weight% with respect to a polymerizable monomer.

In this way, when the polymerizable monomer component is suspended and polymerized to obtain colored spherical fine particles, another polymer such as polyester may be present in the monomer component, and in particular, a chain transfer agent for adjusting the degree of polymerization. You may mix | blend a well-known additive suitably. When the colored fine particles of the present invention are used in an electrophotographic toner, a wax or a charge control agent may be blended with the polymerizable monomer to obtain colored fine particles containing the wax or charge control agent. The colored spherical fine particles thus obtained have an average particle diameter of 3 to 50 µm, preferably 3.5 to 20 µm, with a particle size distribution of 0 to 80%, preferably 1 to 50%, as a coefficient of variation of the particle diameter. It is desirable to do. However, the variation coefficient of particle diameter here is a percentage of the value which the standard deviation divided by the average particle diameter.

In the manufacturing method of this invention, about the colored spherical microparticles | fine-particles which have an average particle diameter of 3-50 micrometers obtained by suspension polymerization in this way, it heat-processes the said particle | grains by heat-processing with water as a medium at 50-130 degreeC temperature once, It is in block.

The heat treatment can be carried out in a state where colored spherical fine particles are present in a suspension medium of water after suspension polymerization. Alternatively, the heat treatment can be performed on agglomerates of colored spherical fine particles extracted from a suspension medium. It is also possible to combine some of these processes. As a heat treatment method for agglomerates of colored spherical fine particles extracted from a suspension medium, for example, a method in which the hot water of the predetermined temperature is dropped into a shower phase on the agglomerates placed on a suitable support, or the agglomerates are subjected to high temperature conditions. A method of maintaining the temperature at a predetermined temperature and the like is specifically considered. In addition, this heat processing can be performed under normal pressure, reduced pressure, or under pressure.

This heat treatment is a very important and necessary process for modifying the red spherical particulate surface. At this time, when the hot water temperature is less than 50 ° C., the fusion of the red spherical fine particles does not occur at all or it is insufficient even if they are fused, and there is no significant surface modification effect. On the contrary, even if it exceeds 130 degreeC, it will become excessive fusion | melting state, and not only the later grinding | pulverization process is difficult, but the colored fine particle obtained becomes very large particle size distribution.

In 1st Example which heat-processes especially the suspension of colored spherical microparticles | fine-particles, it is preferable to make heating temperature of a suspension into 50-98 degreeC, especially 60-95 degreeC. This is because when the heating temperature exceeds 98 ° C., the progress of fusion is so fast that the temporal control is difficult, especially when it exceeds 100 ° C., it is necessary to carry out under pressure.

And in this 1st Example, 90% or more of the polymerization rate of the colored spherical microparticles | fine-particles in this suspension polymer liquid at the time of heat-sealing the said colored spherical microparticles | fine-particles is preferable. Even if the polymerization rate is 100%, the method of the present invention can be applied. The higher the polymerization rate, the longer it takes to prepare the suspension polymer liquid, and the subsequent heating temperature is increased, so that it is difficult to heat at normal pressure. It is preferable to use a method in which it cannot be heated and it needs to be heated under pressure using an autoclave or the like, and some unreacted monomers remain.

Therefore, it is preferable that industrially the polymerization rate exists in 90 to 99.9% of range, and it is especially preferable to exist in 95 to 99.9% of range. On the other hand, if the polymerization rate is less than 90%, since the colored spherical fine particles are plasticized by the unreacted monomer, the interface between the particles disappears and fuses due to heating, so that the average particle diameter of the colored spherical fine particles before fusion is crushed later. This is because it becomes difficult to obtain. Thus, in the suspension of colored spherical microparticles | fine-particles, it heat-processes and performs polymerization aging, further polymerizes an unreacted monomer, and fuse | melts these red spherical microparticles | fine-particles together, and obtains the blocky particle lump.

In addition, in the second embodiment in which the heat treatment heats the lumps of red fine particles separated from the suspension under high temperature, the temperature of the high temperature gas used for the treatment is preferably in the range of 70 to 100 ° C. It is preferable to set it as the conditions of the relative temperature of 70-100% of range, More preferably, it is 80-100%. If the relative temperature is less than 70%, the moisture in the mass evaporates, so that the fusion becomes uneven or does not fuse in a short time. Thus, high temperature heat processing carries out polymerization aging, further polymerizes an unreacted monomer, and fuses the said colored spherical microparticles | fine-particles together, and obtains the block-like particle | grains. The high temperature heat treatment is usually carried out for 2-90 minutes, preferably for 5-60 minutes.

In addition, in the third embodiment in which the heat treatment is performed by pouring hot water into a mass of colored fine particles separated from the suspension, the hot water used for the treatment is preferably to have a temperature in the range of 70 to 100 ° C.

Thus, the hot water heat treatment is carried out for polymerization aging to further polymerize the unreacted monomer, and at the same time, the colored spherical fine particles are fused together to obtain a blocky mass. The hot water heating treatment is usually performed for 2 to 90 minutes, preferably for 5 to 60 minutes. In addition, the hot water heating treatment can be performed on an apparatus used for extracting colored spherical fine particles in a suspension, for example, on a solid-liquid separator such as a filter or a centrifugal separator. .

The colored spherical fine particles are fused by such a heat treatment, but the fusion state may be arbitrarily controlled in accordance with a desired treatment effect. However, it will be uniform particle size distribution in the later crushing process, so that the fine particles of excellent physical properties can be obtained as an electrophotographic toner, so that the interface between the particles does not disappear completely, in other words, in the fusion state leaving grain boundaries. It is desirable to.

In the first embodiment in which the heat treatment is performed by heating the suspension of colored spherical fine particles, it is possible to add a flocculant to the suspension as necessary before the heat treatment. By adding a flocculant in this way, aggregation or precipitation of colored spherical microparticles | fine-particles is accelerated | stimulated, and fusion of colored spherical microparticles | fine-particles by heat processing is made easy. On the other hand, in the second and third embodiments in which the heat treatment is performed on agglomerates of the colored spherical fine particles extracted from the suspension medium, the colored spherical fine particles are extracted from the suspension medium. A flocculant is added to the suspension to aggregate or precipitate the colored spherical fine particles. It is advantageous to cause. In other words, the colored spherical fine particles to be used in the present invention are very small as described above with an average particle diameter of about 3 to 50 μm, and it is very difficult to extract this in suspension as it is, and even if it can be carried out, This is because it requires high energy or special devices. Moreover, it is preferable to agglomerate or precipitate the colored spherical microparticles | fine-particles in suspension also in the control of the bulk density of the block-like thing obtained by fusion, and handling property of a lump.

As a flocculant used for such a purpose, a well-known flocculant, for example, inorganic acids, such as hydrochloric acid, organic acids, such as a hydroxyl acid, the water-soluble metal salt which consists of these acids, alkaline earth metal, aluminum, etc. can be used. However, when these colored flocculants are used as the electrophotographic toner, these known flocculents may affect the performance. The present inventors found that the nonsolvent for the colored spherical microparticles can be used as a precipitant when separating or fractionating a high molecular substance, and furthermore, the colored microparticles obtained have no drawbacks when a coagulant is used. Such non-solvents include lower alcohols such as nucleic acids, heptanes, octanes and petroleum ethers. The nonsolvent with respect to colored spherical microparticles | fine-particles here means the solvent which does not melt | dissolve or disperse the resin of the said colored spherical microparticles | fine-particles. In the case of using such a non-solvent or a precipitant, a well-known flocculant may be used in combination within a range without any problem.

In addition, when the insoluble fine particles are added to the suspension of colored spherical fine particles, the present inventors obtain stable agglomeration as in the case of using a known flocculant, and become a block-shaped particle of a desired size, and furthermore, it is possible to perform a stable fusion operation. It was found that the colored fine particles had no defects when the flocculant was used. The water-insoluble fine particles to be used in the present invention are intended to maintain agglomeration or fusion between the colored fine particles in an optimal state, to significantly improve the subsequent pulverization and to express high physical properties by the colored fine particles obtained by pulverizing. Therefore, the particle diameter of the water-insoluble fine particles should be smaller than the colored spherical fine particles, and it is preferable to select and use the particles so as to be 1/2 or less of the particle diameter of the colored spherical fine particles.

Therefore, in a preferred embodiment of the present invention, the non-aqueous fine particles are added to the suspension of the colored fine particles prior to the heat fusion step of the colored spherical fine particles or the step of recovering the colored spherical fine particles from the suspension.

For example, one of the most preferred embodiments of the present invention is to polymerize a polymerizable monomer by suspending it in a suspending medium in the presence of a colorant and / or a magnetic component, thereby obtaining the colored spherical fine particles having an average particle diameter in the range of 3 to 50 μm. In this suspension at the time when the polymerization rate reached 90%

1) After adding water-insoluble fine particles

2) Heat treatment at 50 ~ 98 ℃

The polymerization aging is carried out and the colored spherical fine particles are fused together to form a block, and then the block particles are substantially ground to an average particle diameter of the colored spherical fine particles before fusion.

Next, the water-insoluble fine particles used as one type of flocculant in the present invention will be described in more detail. As the water-insoluble fine particles, various organic fine particles and inorganic fine particles can be used.

Examples of the organic fine particles include crosslinked and uncrosslinked polymer fine particles, organic pigments, charge control agents, waxes, and the like. Examples of the crosslinked and uncrosslinked resin fine particles include styrene resin fine particles, acrylic resin fine particles, methacryl resin fine particles, polyethylene resin fine particles, polypropylene resin fine particles, silicone resin fine particles, polyester resin fine particles, and polyurethane resin fine particles. And polyamide resin fine particles, epoxy resin fine particles, polyvinyl butyral resin fine particles, rosin resin fine particles, terpene resin fine particles, phenolic resin fine particles, melamine resin fine particles, guanimine resin fine particles and the like. As organic pigments, for example, yellow pigments such as nebble yellow, naphthol yellow-S, kanji yellow-10G, benzidine yellow-G, benzidine yellow-GR, quinoline yellow lake, permanent yellow-NCG, tatrazine lake, molybdenum orange, permanent Orange pigments such as orange RK, benzidine orange G, indonesrene brilliant orange GK, permanent red 4R, resol red, pyrazolone red 4R, watching red calcium salt, lake red D, brilliantant carmine 6B, eosin lake, rhodamine lake Red pigments such as B, azaline lake, brilliant carmine B, purple violet such as fast violet B, methyl violet lake, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, pest sky Blue, blue pigment such as incident blue BC, pigment green B, malachite green ray And organic pigments such as, panel yellow green pigments such as green G. Examples of charge control agents include nigrosine, monoazo dyes, zinc, hexadecyl lacsinate, alkyl esters or alkylamides of naphthenic acid, nitrofumic acid, N, N-tetramethyl diamine benzophenone, N, N-tetra And fine particles of a substance which is called a charge control agent in the field of electrophotography, such as methylbenzidine, triazine, and salicylic acid metal compound. Examples of the waxes include fine particles such as polymers having a cyclic softening point of 80 to 180 ° C, high melting point paraffin waxes having a melting point of 60 to 70 ° C, fatty acid esters and partial silicides, higher fatty acids, and higher alcohols. .

Examples of the inorganic fine particles include, for example, alumina, titanium dioxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, various inorganic oxide pigments, chromium oxide, cerium oxide, And powders or particles such as bangara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, calcium carbonate, silica fine powder, silicon carbide, silicon nitride, boron carbide, tungsten carbide, titanium carbide, and carbon black.

Moreover, since the hydrophobic index (Mw: methanol wetness) of 5 or more thing in these water-insoluble microparticles | fine-particles can grind | pulverize favorable spherical microparticles | fine-particles obtained, it is more preferable. The application of spherical fine particles as an electrophotographic toner is also advantageous in terms of charging stability. Examples thereof include conductive inorganic blacks such as hydrophobic silica, hydrophobic titanium, and hydrophobic treatments such as hydrophobic zirconia, Ketjen balck, acetylene black, and furnace black.

The hydrophobicity index as used herein refers to numerical values obtained in the following order.

1) Take 0.2g of sample in 200ml beaker and add 50ml of pure water.

2) Add methanol under the liquid surface while stirring with an electronic stirrer.

3) The end point is the point where the sample is not identified on the liquid level.

4) The hydrophobicity is calculated by the following equation from the amount of methanol required.

Hydrophobicity index (%) = {x / (50 + x)} 100

X) Methanol use amount (ml)

In addition, when the charge stability physical properties of the small particle size toner necessary for expressing a high resolution image are taken into consideration, it is more preferable to select conductive fine particles as the water-insoluble fine particles. As electroconductive fine particles, titanium oxide, tin oxide, electroconductive zinc oxide, titanium black which doped the above-mentioned electroconductive carbon black, antimony oxide, etc. are mentioned.

In order to use for this purpose, it is preferable that the particle diameter of water-insoluble microparticles shall be 0.001-10 micrometers, More preferably, it is 0.005-5 micrometers. When the particle size of the water-insoluble fine particles is smaller than 0.001 μm, the effect by the addition of the fine particles, that is, the cohesiveness or the remarkable improvement in the fluidity and the cleaning property when used as an electrophotographic toner, for example, may not appear. On the other hand, when the particle diameter of the water-insoluble fine particles exceeds 10 µm, the effect of the addition of the non-water-soluble fine particles may be less and the improvement in image resolution when used as an electrophotographic toner may not be seen. The amount of the non-aqueous fine particles can be added in a wide range depending on the type and particle size of the non-aqueous fine particles to be used. However, the effect of the addition of the non-aqueous fine particles is too small. When it is used, since adverse effects on chargeability and environmental stability may be caused, it is preferable to set it as 0.01-100 weight part with respect to 100 weight part of polymerizable monomer components, More preferably, it is 0.1-50 weight part. In addition, the water-insoluble fine particles may be used alone or in combination of two or more thereof, and even in the case where such non-water-soluble fine particles are used, there is no problem in the known coagulant or the non-solvent for the colored spherical fine particles as described above. Of course, it can be used in combination. Moreover, it is free to use a suitable organic solvent for the purpose of further promoting fusion.

Agglomeration or precipitation of the colored spherical fine particles in the case where such water-insoluble fine particles are added to the water suspension is added to the suspension of the spherical fine particles, and when heated and maintained for a predetermined time while stirring as necessary, no heating is particularly required. However, in the manufacturing method of the colored fine particle of this invention, since the colored spherical microparticles | fine-particles obtained by suspension polymerization fuse | melted, typically, the interface of particle | grains will be fused once in the range which does not completely disappear, it is within a predetermined range. There is no problem with heating at. That is, in the case where the heat treatment for fusion of the colored spherical fine particles is performed by heating the suspension of the colored spherical fine particles as in the first embodiment, after the addition of the non-aqueous fine particles, the temperature range of 50 to 130 ° C as described above In the aggregation of the colored spherical microparticles which are heated at, the fusion can be continuously generated. As in the second and third embodiments, the heat treatment for fusion of the colored spherical microparticles is carried out in the suspension medium. Also in the case of performing the agglomeration, heating can be performed for a short time at a temperature range of 50 to 130 ° C. or lower during the agglomeration treatment, and a certain fusion state can be generated in the agglomerate extracted into the agglomeration from the suspension. In the first embodiment in which the heating treatment for fusion of the colored spherical fine particles is performed by heating the suspension of the colored spherical fine particles, the colored spherical fine particles can be added to the suspension by using various solid-liquid separation devices by suction filtration, subscription filtration, and centrifugal filtration. The block-like thing formed by fusion | melting is obtained. Wherein the block-like water volume density is more preferably a fusing condition of the range of 0.1-0.9g / cm ^3, especially 0.2 ~ 0.7g / cm ^3.

In addition, the shape and size of the block-like object are not limited, but considering the filtration, drying, pulverization, and the like after the heat fusion treatment, a method of producing 20 to 10,000 μm, more preferably 30 to 1,000 μm, is preferable. If the size is less than 20 μm, very high energy or special equipment is required for particle extraction, and if it exceeds 10,000 μm, more energy is required for grinding. The block-like article thus obtained is then passed through a drying step to a grinding step.

Further, in the second and third embodiments in which the heat treatment for fusion of the colored spherical fine particles is performed on the agglomerates of the colored spherical fine particles extracted from the suspension medium, the above-described liquid-liquid separation of the colored spherical fine particles in the suspension medium is performed as described above. It is preferable to agglomerate the above-mentioned colored spherical fine particles into fine particle aggregates so as to easily separate by using various solid-liquid separators, and the bulk density of the fine particle aggregates is 0.05 to 0.9 g / cm ³ , especially 0.1 to 0.7. It is preferable to set it as about g / cm <^3> .

In addition, the shape and size of the particulate aggregate are not limited, but in consideration of drying and pulverization after the solid-liquid separation and heat treatment as described above, it is preferable to produce particles of 20 to 10,000 μm, more preferably 30 to 1,000 μm. In these examples, the agglomerates of the colored spherical fine particles thus extracted are subjected to heat treatment as described above to obtain a block-like article obtained by fusion of the colored spherical fine particles. Here, the bulk density of the block-like article is more preferably in a fusion state in the range of 0.1 to 0.9 g / cm ³ , especially 0.2 to 0.7 g / cm ³ . The block-like article is then sent to the grinding step via a drying step as in the first embodiment.

In the grinding step, the dried block-like article is ground to an average particle diameter of colored spherical fine particles before actual fusion. Grinding can be used without limitation, a grinder which has been conventionally used to produce powder, particles and the like industrially.

The most ideal form of the grinding | pulverization to the average particle diameter of the colored spherical microparticles | fine-particles before real fusion here is a scanning electron micrograph (60 times magnification) shown in FIG. 1, and it is clear that the interface of the colored spherical microparticles disappears completely. The individual particles of the block-shaped particles formed by fusion of the particles with each other in the range not pulverized are pulverized to the unit of the colored spherical fine particles before fusion, and the colored spherical fine particles before fusion pulverization are returned only to the deformed state.

However, it is practically difficult to uniformly control the fusion state of the fusion interface. As is apparent from the scanning electron micrograph (150 times magnification) shown in FIG. 2, the colored fine particles usually obtained are colored spherical fine particles before fusion pulverization. At the same time as the deformed and partially missing, the missing portion is attached and obtained as a mixture of fine particles. If the average particle diameter of the colored spherical microparticles | fine-particles obtained even in such a mixture is substantially the same as the average particle diameter of the colored spherical microparticles | fine-particles before fusion | melting grinding | pulverization, the property of this colored fine particle will be inferior compared with the case of the most ideal form. At this time, if the average particle diameter of the colored fine particles is within 20% of the passage, preferably within 10% and more preferably within 5% of the average particle diameter of the colored spherical fine particles, the average particle diameter of the colored fine particles and the colored spherical fine particles is Can be regarded as substantially the same.

The colored fine particles thus obtained can be arbitrarily controlled in particle size and particle size distribution, but the average particle size is 3-50 μm, preferably 3.5-20 μm, and the particle size distribution has a coefficient of variation of the particle size of 0-80%, preferably 0 It is preferable to set it as -50%. However, the variation coefficient of particle diameter here is a percentage of the value which the standard deviation divided by the average particle diameter. Although the shape of the said colored fine particle is not restrict | limited, For example, the particle | grains and non-spherical particle | grains which have spherical spherical shape and fine unevenness | corrugation on the surface are mentioned, for example.

The electrophotographic toner according to the present invention is made of the red fine particles, and in order to make the chargeability of the toner proper, the average particle diameter is preferably in the range of 3.5 to 20 µm, preferably 4 to 15 µm. The colored fine particles can be used as an electrophotographic toner as it is.

Moreover, the additive compatible with normal toners, such as a charge control agent and a fluidizing agent for charge adjustment, may be mix | blended suitably.

The method for incorporating the charge control agent is not particularly limited, and any conventionally known method may be employed. For example, when the polymerizable monomer dispersing the colorant is polymerized, a charge control agent may be included in the monomer in advance, or the colored fine particles of the present invention may be post-treated with the charge controlling agent to attach the charge controlling agent to the surface of the colored fine particles. Methods can be employed as appropriate.

Some of the preferred embodiments of the method for producing colored fine particles of the present invention add the above water-insoluble particles to the suspension of the colored spherical fine particles to promote aggregation of the colored spherical fine particles and also to precipitate the solid-liquid separation of the colored spherical fine particles in the precipitate. Although this technique is not limited to the above-described method for producing colored fine particles, a recovery method for separating spherical fine particles obtained by a suspension polymer in a suspension medium, and in particular, various types in which fine particles mainly composed of resin are dispersed in an aqueous suspension. It is widely applicable as a method for recovering fine particles by solid-liquid separation in a suspension obtained by dissolving a dispersion system, for example, by heating and melting a resin component and dispersing it in an aqueous dispersion medium. That is, after the addition of the non-aqueous particles, especially in the case of agglomeration or precipitation without high heating, the spherical fine particles in the generated block form are in a state where the junction point or a little surface bonding occurs at the interface, so that the block is in suspension. Separation of the phases using a common solid-liquid separator as described above, and drying and pulverizing substantially maintains the spherical shape of the fine particles obtained by suspension polymerization, and does not deteriorate the performance of the fine particles as in the case of using a known flocculant. This is because it is possible to obtain fine particles.

This is because the pulverization can be easily pulverized to an average particle diameter of spherical fine particles before aggregation by a little energy using a pulverizer of a relatively simple mechanism. Of course, it is arbitrary as the treatment method after solid-liquid separation, and heat processing for modifying the surface characteristics of microparticles | fine-particles like the manufacturing method of the said colored fine particle can be performed. The fine particle recovery technology from the suspension using such water-insoluble fine particles as a flocculant is produced by the production of fine spherical fine particles having an average particle diameter of 1 to 100 µm, in particular 1 to 50 µm, or the use of a known flocculant, which is difficult to separate by a general centrifugal sedimentation method. It is considered that the deterioration of moisture resistance and the like are particularly useful for producing spherical fine particles used in applications such as electrophotographic toners.

In the above-mentioned recovery method according to the present invention, it is not necessary to perform heat treatment after the addition of the fine particles in order to agglomerate or precipitate the suspended spherical fine particles. However, in view of the operating efficiency, it is possible to perform a heat treatment for heating the suspension to at least the polymer Tg constituting the spherical fine particles, unless excessive fusion of the spherical fine particles is caused.

Hereinafter, the present invention will be described in detail by way of examples, but the examples shown below are merely disclosed for the purpose of explanation of the present invention, and the present invention is not limited to these examples. In addition, unless otherwise indicated, the part in a following example and a comparative example is based on weight.

Example 1

2,000 parts of deionized water which melt | dissolved 1 part of polyvinyl alcohols in the reaction kiln provided with the stirrer, the inert gas introduction tube, the reflux cooling tube, and the thermometer is put. The mixture which melt | dissolved 80 parts of benzoyl peroxides in the polymerizable monomer which consists of 585 parts of styrene previously adjusted, 390 parts of butyl methacrylates, and 25 parts of glycidyl methacrylate was put therein, and it stirred at high speed, and made it a uniform suspension. Subsequently, it heated at 80 degreeC, injecting nitrogen gas, continued stirring at this temperature for 5 hours, and after performing polymerization reaction, water was removed and the polymer which has an epoxy group as a reactive group was obtained.

400 parts of polymer having epoxy group as reactive group, 150 parts of carbon black MA-100R (manufactured by Samneung Chemical Co., Ltd.) and 50 parts of charge control agent (manufactured by Aizen Spilon Black TRH Botogok Chemical Co., Ltd.) After mixing and reacting under the conditions, the mixture was cooled and pulverized to obtain a carbon black graft polymer as a colorant.

In the same reaction kiln as described above, 8,970 parts of deionized water in which 5 parts of sodium dodecylbenzenesulfonate was dissolved as an anionic surfactant was added. 500 parts of carbon black graft polymers as said coloring agent, 30 parts of azobisisobutylonitrile, and 2, in the polymerizable monomer component which consists of 800 parts of styrene previously adjusted, 200 parts of n-butyl acrylate, and 0.03 part of divinylbenzene previously adjusted to it. The mixture which mix | blended 30 parts of 2'- azobis (2, 4- dimethylvaleronitrile) was put, it stirred for 5 minutes at 8,000 rpm by the TK homomixer (made by Special Vaporization Co., Ltd.), and it was set as a uniform suspension.

Subsequently, it heated at 65 degreeC, injecting nitrogen gas, and continued stirring polymerization reaction at this temperature for 5 hours, and after heating at 75 degreeC for 1 hour, the polymerization rate was 95.0%, the average particle diameter was 5.82 micrometers, and the particle diameter. A suspension (1) of colored spherical fine particles having a coefficient of variation of 20.5% was obtained. 2,095 parts of methanol was added to the suspension (1) of colored spherical microparticles | fine-particles maintained at 75 degreeC, and heating was performed for 1 hour, and the block shaped object which formed the fusion | melting of particle | grains was formed. This was filtered, and 1,500 parts of block-like objects with a bulk density of 0.20 g / cm <^3> were obtained in the fusion state which dried at 50 degreeC for 10 hours using the hot air dryer, and left the grain boundary. The block-like article was ground at a feed amount of 15 kg / hr using a supersonic jet grinder IDS type 2 (manufactured by Pneumatic Co., Ltd.) to obtain colored fine particles (1).

When the obtained colored fine particle (1) was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 5.67 micrometers and the coefficient of variation of the particle diameter was 18.7%. Using the colored fine particles 1 as the electrophotographic toner 1 as it is, the image output was performed by an electrostatic copying machine (type Rico Co., Ltd.).

Example 2

In the same reaction kiln as used in Example 1, 8,970 parts of deionized water in which 30 parts of polyvinyl alcohol (PVA205, manufactured by Kraray Corporation) was dissolved was added. To the polymerizable monomer component consisting of 800 parts of styrene and 200 parts of n-butyl acrylate previously adjusted therein, 50 parts of Brilliant Carmine 6B (manufactured by Night Chemical Co., Ltd.), 30 parts of Azobibisobutylonitrile and 2,2 'as a colorant. -The mixture which mix | blended 30 parts of azobis (2, 4- dimethylvaleronitrile) was put, it stirred for 5 minutes by 6,000 rpm by TK homomixer (made by Special Vaporization Co., Ltd.), and it was set as a uniform suspension.

Next, it heated at 65 degreeC, injecting nitrogen gas, and continued stirring at this temperature for 5 hours. After the suspension polymerization reaction, the mixture was heated at 75 ° C for 1 hour, whereby a suspension (2) of colored spherical fine particles having a polymerization rate of 98.0%, an average particle diameter of 6.42 µm and a coefficient of variation of the particle size of 21.3% was obtained. 13 parts of an aqueous paste charge control agent (Bontron S-34 Orient Chemical Co., Ltd.) having an active ingredient of 35% was added to a suspension of colored spherical fine particles held at 75 ° C, and then heated at 95 ° C for 1 hour. A block-like object formed by fusion of particles was formed. This was filtered, and dried at 50 ° C. for 8 hours using a vacuum dryer, and 1110 parts of block-like article having a bulk density of 0.28 g / cm ³ were obtained in a fused state leaving grain boundaries. The said block-like thing was grind | pulverized at the feed amount of 12 kg / hr using the supersonic jet grinder IDS type 2 (made by Japan Pneumatic Co., Ltd.), and the colored fine particle (2) was obtained.

As a result of measuring the obtained colored fine particle (2) with a Golter counter (gap 10 micrometers), the average particle diameter was 6.15 micrometers and the coefficient of variation of the particle diameter was 23.0%. It was as shown in Table 1 when the image output was performed by the electrostatic copying machine (type 4060 product made by Ricoh) which uses the said colored fine particle 2 as an electrophotographic toner 2 as it is.

Example 3

200 parts of a polymer having an epoxy group as a reactive group obtained in the same manner as in Example 1 and 400 parts of a Mapico BL-200 (manufactured by Titanium Industry Co., Ltd.) as a powdery magnetic substance were mixed under conditions of 160 ° C and 100 rpm using a pressure kneader. Thereafter, the mixture was cooled and pulverized to obtain a polymer-treated magnetic body.

In the same reaction kiln as used in Example 1, 8,970 parts of deionized water in which 5 parts of sodium dodecylbenzenesulfonate was dissolved as an anionic surfactant was added. 700 parts of the said polymerized magnetic body, 30 parts of azobisisobutylonitrile, and 2,2'- azobis to the polymerizable monomer component which consists of 800 parts of styrene previously adjusted, 200 parts of n-butyl acrylate, and 0.1 part of vinyl benzene previously adjusted to it. The mixture which mix | blended 30 parts of (2, 4- dimethylvaleronitrile) was put, it stirred at 8,000 rpm for 5 minutes with TK homomixer (made by Special Vaporization Co., Ltd.), and it was set as a uniform suspension.

Subsequently, it heated at 65 degreeC, injecting nitrogen gas, and continued stirring polymerization reaction at this temperature for 5 hours, and after heating at 75 degreeC for 1 hour, as a result, 98.0% of polymerization rates, an average particle diameter of 5.43 micrometers, and a particle diameter A suspension (3) of colored spherical fine particles having a coefficient of variation of 22.5% was obtained. To the suspension of colored spherical microparticles maintained at 75 ° C, 41 parts of an aqueous paste charge control agent (Bontron S-34, Orient Chemical Co., Ltd.) of 35% of organic components and 5 parts of aluminum chloride of 5% of organic components were added. Thereafter, heat treatment was performed at 95 ° C. for 30 minutes to form a block-like article in which particles were fused together. This was filtered and dried at 50 ° C. for 8 hours using a reduced pressure drier to obtain 1,700 parts of a block-like material having a bulk density of 0.22 g / cm ³ in a fused state leaving grain boundaries. This block-like product was ground at a feed amount of 18 kg / hr using a supersonic jet mill IDS type 2 (manufactured by Nippon Pneumatic Co., Ltd.) to obtain colored fine particles (3).

As a result of measuring the obtained colored fine particle (3) with a Golter counter (gap 100 micrometers), the average particle diameter was 5.24 micrometers and the coefficient of variation of the particle size was 19.8%. Using the colored fine particles 3 as the electrophotographic toner 3 as it is, the image output was performed by an electrostatic copying machine (NP-5000, manufactured by Canon Corporation).

Example 4

Carbon black kraft polymer was obtained by the same method as Example 1, and 8,970 parts of deionized water which melt | dissolved 10 parts of anionic surfactants hytenol N-08 (made by Cheil Industries Co., Ltd.) was added to the flask as mentioned above.

With 500 parts of carbon black graft polymer and azobisisobutyl in a component consisting of 800 parts of styrene, 150 parts of n-butyl acrylate, and 50 parts of polybutadiene NISSO-PB-B-3000 (manufactured by Nippon Procurement Co., Ltd.). A mixture containing 20 parts of nitrile and 10 parts of 2,2'-azobis (2,4-dimethyl valeronitrile) was added thereto, and the same operation as in Example 1 was carried out to find that the polymerization rate was 92% and the average particle diameter was 6.30 µm. The suspension (4) of the colored spherical fine particles having a coefficient of variation of the particle diameter of 19.5% was obtained.

When the suspension of the obtained colored spherical microparticles | fine-particles was heat-processed at 90 degreeC for 2 hours, the block-like thing which fuse | melted particle | grains was formed. This was filtered, dried at 50 ° C. for 10 hours using a hot air dryer, and 1,500 parts of a block-like material having a bulk density of 0.31 g / cm ³ was obtained in a fused state leaving grain boundaries. The above block-like article was ground at a feed amount of 17 kg / hr using a supersonic jet mill IDS type 2 (manufactured by Nippon Pneumatic Co., Ltd.) to obtain colored fine particles (4).

As a result of measuring the obtained colored fine particle (4) with a Golter counter (gap 100 micrometers), the average particle diameter was 6.14 micrometers and the coefficient of variation of the particle size was 20.8%. Using the colored fine particles 4 as the electrophotographic toner 4 as it was, the image was output by an electrostatic copying machine (type 4060 Ricoh Co., Ltd.).

Example 5

In the same flask as used in Example 1, 8,970 parts of deionized water in which 5 parts of dodecylbenzenesulfonic acid was dissolved with an anionic surfactant was added. 500 parts of carbon black graft polymer, 30 parts of azobisisobutylonitrile, and 2,2'- azobis (2) as a coloring agent to the polymerizable monomer component of 800 parts of styrene and 200 parts of acrylic acid n-butyl previously adjusted thereto A mixture containing 30 parts of, 4-dimethylvaleronitrile) and 30 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added thereto, and the mixture was stirred at 8,000 rpm by a TK homomixer. It stirred for 5 minutes and made it a uniform suspension.

Subsequently, it heated at 65 degreeC, injecting nitrogen gas, continued stirring polymerization at this temperature for 5 hours, and after heating at 75 degreeC for 1 hour, as a result, 95.0% of polymerization rates, an average particle diameter of 5.92 micrometers, and a particle diameter A suspension (5) of colored spherical fine particles having a coefficient of variation of 23.0% was obtained. After adding 200 parts of 1N hydrochloric acid to the suspension 5 of colored spherical microparticles | fine-particles hold | maintained at 75 degreeC, and heat-processing was performed at 85 degreeC for 3 hours, the particle | grains which fuse | melted particle | grains were formed. This was filtered, and it dried at 50 degreeC using the vacuum dryer for 8 hours, and obtained 1,500 parts of block-like objects with a bulk density of 0.35 g / cm <^3> in the fusion state which left the grain boundary. The block-like article was ground at a feed amount of 13 kg / hr using a supersonic jet mill ISD type 2 (manufactured by Pneumatic Co., Ltd.) to obtain colored fine particles (5).

As a result of measuring the obtained colored fine particle (5) with a Golter counter (gap 100 micrometers), the average particle diameter was 5.65 micrometers and the coefficient of variation of the particle size was 21.2%. The colored fine particles 5 were used as the electrophotographic toner as they were, and image output was performed by an electrostatic copying machine (type 4060 Ricoh Co., Ltd.).

Example 6

Example 4 50 parts of HTPALON 20 (EI duPont de Nemors & chlorosulfonated polyethylene) instead of 50 parts of polybutadiene 20 parts of azobisisobutylonitrile and 2,2'-azobis (2,4-dimethylvaleronitrile ) The same operation as in Example 4 was carried out except that 30 parts of benzoyl peroxide was used instead of 10 parts. As a result, a suspension (6) of colored spherical fine particles having a polymerization rate of 92%, an average particle diameter of 6.02 µm and a coefficient of variation of the particle diameter of 21.2% was obtained. Got it. 3 parts of calcium chloride was added to the suspension 6 of colored spherical microparticles | fine-particles hold | maintained at 75 degreeC, and the heat processing was performed at 95 degreeC for 1 hour, and the particle | grains which fuse | melted particle | grains were formed. The resultant was filtered and dried at 50 ° C. for 8 hours using a vacuum dryer to obtain 1,500 parts of block-like material having a bulk density of 0.21 g / cm ³ in a fused state leaving grain boundaries. The said block-like thing was grind | pulverized at the feed amount of 18 kg / hr using the supersonic jet grinder IDS type 2 (made by Japan Pneumatic Co., Ltd.), and the colored fine particle (6) was obtained.

When the obtained colored fine particle 6 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 6.10 micrometers and the coefficient of variation of the particle size was 22.0%. The colored fine particles 6 were used as the electrophotographic toner as they were, and image output was performed by an electrostatic copying machine (type 4060 Ricoh Co., Ltd.).

Example 7

A polymerization rate of 96 was obtained by the same operation as in Example 1, except that 10 parts of Nonipol 200 (manufactured by Samyang Chemical) was used as the anionic surfactant instead of 5 parts of the dodecylbenzenesulfonate as the anionic surfactant used in Example 1. The suspension (7) of the colored spherical microparticles | fine-particles which are%, the average particle diameter of 5.75 micrometers, and the coefficient of variation of a particle diameter is 19.5%. Thereafter, the mixture was maintained at 60 ° C, and 750 parts of heptane was added thereto, followed by heat treatment for 1 hour, whereby particles formed by fusion were formed. The resultant was filtered and dried at 50 ° C. for 10 hours using a hot air dryer to obtain 1,500 parts of a block-like material having a bulk density of 0.22 g / cm ³ in a fused state leaving grain boundaries.

The block-like material was ground at a feed amount of 15 kg / hr using a supersonic jet grinder IDS type 2 (manufactured by Pneumatic Co., Ltd.) to obtain colored fine particles (7).

As a result of measuring the obtained colored fine particle 7 with a Golter counter (gap 100 micrometers), the average particle diameter was 5.65 micrometers and the coefficient of variation of the particle size was 20.7%. The colored fine particles 7 were used as the electrophotographic toner 7 as it was, and image output was performed by an electrostatic copying machine (type 4060 Ricoh Co., Ltd.).

Example 8

By the same method as in Example 1, a suspension of colored spherical fine particles (1) was obtained. To a suspension of colored spherical microparticles (1) kept at 75 ° C, 500 parts of a dispersion of 10 parts of Ketjen Black EC (Ketchen Black International Co., Ltd.), which is a conductive carbon black having a hydrophobicity index of 12.3, was previously dispersed in 1000 parts of deionized water, After heating for 1 hour, particles were fused to form a block-like article. This was filtered and dried at 50 ° C. for 10 hours using a hot air dryer to obtain 1,500 parts of a block-like material having a bulk density of 0.18 g / cm ³ in a fused state leaving grain boundaries. The block-like material was ground at a feed amount of 16 kg / hr using a supersonic jet grinder IDS type 2 (manufactured by Pneumatic Co., Ltd.) to obtain colored fine particles (8). As a result of measuring the obtained colored fine particle (8) with a Golter counter (gap 100 micrometers), the average particle diameter was 5.78 micrometers and the coefficient of variation of the particle size was 17.5%. Using the colored fine particles 8 as an electrophotographic toner as it was, the image was output by an electrostatic copying machine (type 4060 Ricoh Co., Ltd.).

Example 9

Instead of adding 500 parts to the water dispersion of Ketchen Black EC in Example 8, Ketchen is a conductive carbon black showing 10 parts of hydrophobic aerosil R 972 (manufactured by Aerosil Japan) having a hydrophobic index of 50.5 and a hydrophobicity index of 12.3. 53.8 parts of black EC (Ketchen Black International Co., Ltd. product) 123.8 parts of the dispersion liquid disperse | distributed to 150 parts of methanol previously was added, and the block operation was carried out similarly to Example 8 except having heated for 1.5 hours.

This was filtered, dried for 8 hours at 50 ° C. using a reduced pressure dryer, and 1,500 parts of a block-like material having a bulk density of 0.17 g / cm ³ was obtained in a fused state leaving grain boundaries. The block-like material was ground at a feed amount of 20 kg / hr using a supersonic jet mill IDS type 2 (manufactured by Pneumatic Co., Ltd. Japan) to obtain colored fine particles (9).

When the obtained colored fine particle 9 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 5.81 micrometers and the coefficient of variation of the particle diameter was 17.1%. Using the colored fine particles 9 as the electrophotographic toner 9 as it is, image output was performed by an electrostatic copying machine (NP5000, manufactured by Canon Corporation).

Example 10

In the same manner as in Example 2, a suspension (2) of colored spherical fine particles was obtained. 13 parts of an aqueous paste charge control agent (manufactured by Bontron S-34 Orient Chemical Co., Ltd.) and hydrophobic aerosil R 972 (manufactured by Japan Ezeil Co., Ltd.) having 35% of an active ingredient in a suspension of colored fine particles maintained at 75 ° C. 82.5 parts of a dispersion obtained by dispersing 10 parts of methanol in 100 parts of methanol was added and heat-treated at 95 ° C. for 1 hour to form a block-like article in which particles were fused together.

This was filtered and dried at 50 ° C. for 8 hours using a reduced pressure dryer to obtain 1,110 parts of a block-like product having a bulk density of 0.26 g / cm ³ in a fused state leaving grain boundaries.

This block-like object was ground at a feed amount of 13 kg / hr using a supersonic jet grinder IDS type 2 (manufactured by Pneumatic Co., Ltd.) to obtain colored fine particles (10).

As a result of measuring the obtained colored fine particle 10 with a Golter counter (gap 100 micrometers), the average particle diameter was 6.35 micrometers and the coefficient of variation of the particle size was 19.0%. Using the colored fine particles 10 as the electrophotographic corner 10 as it was, as shown in Table 1 as a result of image output by an electrostatic copying machine (type Rico Co., Ltd.).

Example 11

In the same manner as in Example 3, a suspension (3) of colored spherical fine particles was obtained. R202 (Aero Japan) having 41 parts of an aqueous paste charge control agent (Bontron S-34 Orient Chemical Co., Ltd.) having 35% of an active ingredient and a hydrophobicity index 69.5 in a suspension of the colored constituent spherical fine particles held at 75 ° C. After adding 110 parts of a dispersion liquid previously dispersed in 100 parts of methanol to 10 parts of a Jigsa yarn, heat treatment was performed at 95 ° C. for 30 minutes to form a block-like material in which particles were fused together. This was filtered and dried at 50 ° C. for 8 hours using a reduced pressure dryer to obtain 1,700 parts of a block-like material having a bulk density of 0.20 g / cm ³ in a fused state leaving grain boundaries. The block-like material was ground at a feed amount of 20 kg / hr using a supersonic jet grinder IDS type 2 (manufactured by Pneumatic Co., Ltd.) to obtain colored fine particles (11).

When the obtained colored fine particle 11 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 5.24 micrometers and the coefficient of variation of the particle size was 19.8%. Using the colored fine particles 11 as the electrophotographic corner 11 as it is, the image output was performed by an electrostatic copying machine (NP-5000, manufactured by Canon Corporation).

Example 12

In the same manner as in Example 4, a suspension (4) of colored spherical fine particles was obtained.

20 parts of tin oxide T-1 (product of Samneung Metal Co., Ltd.) doped with antimony oxide was put into the obtained suspension of colored spherical microparticles | fine-particles, and it heat-processed at 90 degreeC for 2 hours, The particle | grains which melt | dissolved particle | grains were fused together. Formed. This was filtered, and dried at 50 ° C. for 10 hours using a hot air dryer to obtain 1,500 parts of a block-like material having a bulk density of 0.30 g / cm ³ in a fused state leaving grain boundaries. The block-like article was ground at a feed amount of 18 kg / hr using a supersonic jet grinder IDS type 2 (manufactured by Japan Pneumatic Co., Ltd.) to obtain colored fine particles (12).

When the obtained colored fine particle 11 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 6.20 micrometers and the coefficient of variation of the particle size was 20.0%. The colored fine particles 12 were used as the electrophotographic corners 12 as they were, and image output was performed by an electrostatic copying machine (type 4060 Ricoh Co., Ltd.).

Example 13

By the same method as in Example 5, a suspension (5) of colored spherical fine particles was obtained. 10 parts of water-insoluble fine particles obtained by hydrophobizing titanium oxide P25 (manufactured by Aerosil Japan Co., Ltd.) to hydrophobic resin up to 15 were added to 100 parts of a dispersion and 100 parts of heptane. Then, when heat-processing was performed at 85 degreeC for 3 hours, the block-like thing which melt | dissolved particle | grains was formed. This was filtered and dried at 50 ° C. for 8 hours using a reduced pressure dryer to obtain 1,500 parts of a block-like material having a bulk density of 0.34 g / cm ³ in a fused state leaving grain boundaries. The block-like material was ground at a feed amount of 13 kg / hr using a supersonic jet grinder IDS type 2 (manufactured by Pneumatic Co., Ltd.) to obtain colored fine particles (13). When the obtained colored fine particle 13 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 5.73 micrometers and the coefficient of variation of the particle size was 20.5%. Using the colored fine particles 13 as the electrophotographic toner 13 as it is, image output was performed by an electrostatic copying machine (type Rico Co., Ltd.).

Example 14

By the same method as in Example 6, a suspension (6) of colored spherical fine particles was obtained. 15 parts of zirconium oxide NS-3Y (manufactured by Nippon Catalysts Co., Ltd.) and 15 parts of Mapico BL-400 (manufactured by Titanium Industry Co., Ltd.), which is a powdery magnetic substance, in 180 parts of methanol When the mixture was added and heated at 95 ° C. for 1 hour, particles were fused to form a block-like article. This was filtered and dried at 50 ° C. for 8 hours using a reduced pressure dryer to obtain 1,500 parts of a block-like article having a bulk density of 0.19 g / cm ³ in a fused state leaving grain boundaries. The block-like material was ground at a feed amount of 19.5 kg / hr using a supersonic jet grinder IDS type 2 (manufactured by Pneumatic Co., Ltd.) to obtain colored fine particles (14).

When the obtained colored fine particle 14 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 6.21 micrometers and the coefficient of variation of the particle size was 21.5%. Using the colored fine particles 14 as the electrophotographic toner 14 as it is, image output was performed by an electrostatic copying machine (type 4060 Ricoh Co., Ltd.).

Example 15

A suspension (7) of colored spherical fine particles was obtained in the same manner as in Example 7. Then, 200 parts of heptane maintained at 60 ° C, 12 parts of hydrophobic aerosil R 809 (made by Aerosil Japan) having a hydrophobic resin of 64.5, 12 parts of R 805 (made by Aerosil Japan) having a hydrophobic index of 50, and 4.5 parts of Ketjenblack EC (Ketchen Black International Co., Ltd.), which is conductive carbon black, were added to 313 parts of a dispersion liquid previously dispersed in 285 parts of methanol, and heated for 2 hours to form a block-like article in which particles were fused together. This was filtered, dried at 50 ° C. for 10 hours using a hot air dryer, and 1,500 parts of a block-like material having a bulk density of 0.21 g / cm ³ was obtained in a fused state leaving grain boundaries. The block-like material was ground at a feed amount of 16 kg / hr using a supersonic jet grinder IDS type 2 (manufactured by Pneumatic Co., Ltd.) to obtain colored fine particles (15).

When the obtained colored fine particle 15 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 5.65 micrometers and the coefficient of variation of the particle size was 20.7%. The colored fine particles 15 were used as the electrophotographic toner 15 as it was, and image output was performed by an electrostatic copying machine (type Rico Co., Ltd.).

Example 16

Instead of using a TK homomixer, the product was passed five times at 15,000 rpm by Ebara Milder MDN-303V Co., Ltd.) to make a uniform suspension, and the suspension polymerization reaction was heated at 65 ° C. for 5 hours or at 75 ° C. for 2 hours. A suspension (1 ') of colored spherical fine particles having a mean particle size of 5.82 µm and a coefficient of variation of 20.5% in particle size was obtained in the same manner as in Example 1. 60 parts of an aqueous aluminum chloride solution of 5% of the active ingredient was added to the suspension to agglomerate the colored spherical fine particles, and then separated by filtration using a centrifuge, and the resulting mass was kept at a temperature of 90 ° C. and a relative temperature of 98%. When heat-humidification was performed for 10 minutes, the lump of the block-like thing which melt | dissolved particle | grains was formed. The block was dried at 50 deg. This was a fused state leaving grain boundaries, and a block-like material having a bulk density of 0.4 g / cm ³ was obtained at 1,500 parts. After crushing the said block-like thing finely, it was grind | pulverized at the feed amount of 1 kg / hr using the supersonic jet grinder IDS type 2 (made by Japan Pneumatic Co., Ltd.), and the colored fine particle 16 was obtained.

As a result of measuring the obtained colored fine particles 16 with a Golter counter (gap 100 μm), the average particle size was 5.65 μm and the coefficient of variation of the particle size was 18.8%. Using the colored fine particles 16 as the electrophotographic toner 16 as it is, image output was performed by an electrostatic copying machine (type Rico Co., Ltd.).

Example 17

A suspension of colored spherical fine particles having an average particle diameter of 6.42 µm and a coefficient of variation of 21.3% in particle size (2 ') by the same method as in Example 2, except that the suspension polymerization reaction was heated at 65 ° C for 5 hours and at 75 ° C for 2 hours. ) 13 parts of an aqueous paste charge control agent (Bontron S-34, product of Orient Chemical Co., Ltd.) of 35% of the active ingredient was added to the suspension (2 ') of colored spherical fine particles held at 75 ° C, followed by coloring by adding 1,110 parts of methanol. The precipitate obtained by precipitating spherical fine particles was separated by filtration and subjected to heat and humidification treatment for 20 minutes under an atmosphere maintained at a temperature of 80 ° C. and a relative temperature of 90% to form a block-like article in which particles were fused together. The block was dried at 50 deg.

This was a fused state leaving grain boundaries, and a block-like material having a bulk density of 0.70 g / cm ³ was obtained 1,110 parts. After crushing the said block-like thing finely, it was grind | pulverized at the feed amount of 8.0 kg / hr using the supersonic jet grinder IDS type 2 (made by Japan Pneumatic Co., Ltd.), and the colored fine particle 17 was obtained.

When the obtained colored fine particle 17 was measured with the Golter counter (100 micrometers in gap), the average particle diameter was 6.15 micrometers and the coefficient of variation of the particle size was 23.3%. Using the colored fine particles 17 as the electrophotographic toner 17 as it is, image output was performed by an electrostatic copying machine (type 4060 Ricoh Co., Ltd.).

Example 18

A suspension of colored spherical fine particles having an average particle diameter of 5.43 μm and a coefficient of variation of 22.5% in particle diameter by the same method as Example 3 except that the suspension polymerization reaction was performed by heating at 65 ° C. for 5 hours and at 75 ° C. for 2 hours (3) Got ')

41 parts of an aqueous paste charge control agent (Bontron S-34, Orient Chemical Co., Ltd.) with 35% of the active ingredient and 60 parts of an aqueous aluminum chloride solution with 5% of the active ingredient were added to the suspension (3 ') of the colored spherical fine particles held at 75 ° C. After addition and coagulation of the colored spherical fine particles, the mass obtained by filtration and separation was subjected to heat and humidification for 5 minutes under an atmosphere maintained at a temperature of 95 ° C. and a relative temperature of 100%. Formed. The block was dried at 50 deg. This was a block-like article having a bulk density of 0.35 g / cm ³ as a fusion state leaving grain boundaries, and 1,700 parts were obtained. After crushing the said block-like thing finely, it was grind | pulverized at the feed amount of 13 kg / hr using the supersonic jet grinder IDS type 2 (made by Japan Pneumatic Co., Ltd.), and the colored fine particle 18 was obtained.

When the obtained colored fine particle 18 was measured with the Golter counter (100 micrometers in gap), the average particle diameter was 5.22 micrometers and the coefficient of variation of the particle size was 19.3%. The colored fine particles 18 were used as the electrophotographic toner 18 as it was, and image output was performed by an electrostatic copying machine (NP-5000, manufactured by Canon Corporation).

Example 19

A suspension of colored spherical fine particles having a mean particle size of 6.30 µm and a coefficient of variation of 19.5% in particle diameter (4 ') by the same method as in Example 4 except that the suspension polymerization reaction was performed at 65 ° C for 5 hours and at 75 ° C for 2 hours. ) 60 parts of aluminum chloride aqueous solution of 5% of the active ingredient was added to the obtained suspension of colored spherical fine particles to agglomerate the colored spherical fine particles, followed by filtration and separating the mass obtained at a temperature of 85 ° C. and a relative temperature of 100%. When heat-humidification was performed for 20 minutes under, lumps of the block-shaped object which the particle | grains were fused together were formed. The block was dried at 50 deg. This was a fused state leaving a grain boundary and 1,500 parts of a block-like thing with a bulk density of 0.31 g / cm <^3> .

After crushing this block-like thing, it was grind | pulverized at the feed amount of 15 kg / hr using the supersonic jet grinder IDS type 2 (made by Japan Pneumatic Co., Ltd.), and the colored fine particle 19 was obtained.

When the obtained colored fine particle 19 was measured with the Golter counter (100 micrometers in gap), the average particle diameter was 6.24 micrometers and the coefficient of variation of the particle diameter was 20.8%. The colored fine particles 19 were used as the electrophotographic toner 19 as it was, and image output was performed by an electrostatic copying machine (type 4060 Ricoh Co., Ltd.).

Example 20

A suspension of colored spherical fine particles having a mean particle size of 5.92 µm and a coefficient of variation of 23.0% in particle diameter (5 ') by the same method as Example 5 except that the suspension polymerization reaction was performed at 65 ° C for 5 hours and at 75 ° C for 2 hours. ) 1,500 parts of methanol was added to the suspension, the colored fine particles were precipitated, and the lump obtained by filtration and separation was subjected to heat and humidification for 35 minutes under an atmosphere maintained at 70 ° C. and 95% relative temperature. Was formed. This block-like thing was dried at 50 degreeC.

This was a fused state leaving grain boundaries, and a block-like material having a bulk density of 0.55 g / cm ³ was obtained at 1,500 parts. After crushing the block-like object finely, using a supersonic jet grinder IDS type 2 (manufactured by Pneumatic Co., Ltd. Japan) at a feed amount of 10.5 kg / hr, a colored fine particle 20 was obtained.

As a result of measuring the obtained colored fine particle 20 with a Golter counter (gap 100 micrometers), the average particle diameter was 5.67 micrometers and the coefficient of variation of the particle size was 21.5%. Using the colored fine particles 20 as the electrophotographic toner 20 as it is, image output was performed by an electrostatic copying machine (type Rico Co., Ltd.).

Example 21

A suspension of colored spherical fine particles having an average particle diameter of 6.02 μm and a coefficient of variation of 21.2% in particle diameter by the same method as in Example 6 except that the suspension polymerization reaction was performed at 65 ° C. for 5 hours and at 75 ° C. for 2 hours (6 ′). ) 180 parts of calcium chloride aqueous solution of 5% of the active ingredient was added to the suspension to aggregate colored spherical fine particles, and the resulting mass was subjected to heat and humidification for 3 minutes under an atmosphere maintained at 110 ° C and 100% relative temperature. Agglomerated with each other to form a block-like thing. This block-like thing was dried at 50 degreeC. This was a fused state leaving a grain boundary and a block-like object having a bulk density of 0.51 g / cm ³ to obtain 1,500 parts. The block-like material was crushed finely and then pulverized at a feed amount of 9.5 kg / hr using a supersonic jet grinder IDS type 2 (manufactured by Pneumatic Co., Ltd.) to obtain colored fine particles 21.

When the obtained colored fine particle 21 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 6.15 micrometers and the coefficient of variation of the particle size was 22.5%. The colored fine particles 21 were used as the electrophotographic toner 21 as it was, and image output was performed by an electrostatic copying machine (type Rico Co., Ltd.).

Example 22

A suspension of colored spherical fine particles having a mean particle size of 5.75 µm and a coefficient of variation of 19.5% in particle diameter (7 ') by the same method as in Example 7 except that the suspension polymerization reaction was performed at 65 ° C for 5 hours and at 75 ° C for 2 hours. ) 180 parts of calcium chloride aqueous solution of 5% of the active ingredient was added to the suspension, aggregated by filtration, and the resulting mass was subjected to heat and humidification for 15 minutes under a pressurized atmosphere maintained at 85 ° C and 90% relative temperature. Agglomerated to form a block of the block-like thing. This block-like thing was dried at 50 degreeC. This was a fused state leaving grain boundaries, and a block-like material having a bulk density of 0.62 g / cm ³ was obtained at 1,500 parts. After crushing this block-like thing, it was grind | pulverized at the feed amount of 7 kg / hr using the supersonic jet grinder IDS type 2 (made by Japan Pneumatic Co., Ltd.), and the colored fine particle 22 was obtained.

When the obtained colored fine particle 22 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 5.65 micrometers and the coefficient of variation of the particle size was 21.7%. Using the colored fine particles 22 as the electrophotographic toner 22 as it is, image output was performed by an electrostatic copying machine (type Rico Co., Ltd.).

Example 23

Instead of adding 60 parts of an aqueous aluminum chloride solution of 5% of the active ingredient used in Example 16, an R 972 dispersed methanol solution obtained by dispersing 10 parts of hydrophobic aerosil R 972 (manufactured by Aerosil Japan) in advance with respect to 100 parts of methanol was prepared. 82.5 parts of addition was performed to aggregate to obtain a lump separated by filtration.

Thereafter, the same operation as in Example 16 was carried out to obtain 1,500 parts of a block-like article having a bulk density of 0.39 g / cm ³ as a fusion state leaving grain boundaries. After crushing this block-like object, it was grind | pulverized at the feed amount of 10 kg / hr using the supersonic jet grinder IDS type 2 (made by Japan Pneumatic Co., Ltd.), and the colored fine particle 23 was obtained.

When the obtained colored fine particle 23 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 5.64 micrometers and the coefficient of variation of the particle diameter was 18.7%. Using the colored fine particles 23 as the electrophotographic toner 8 as it is, image output was performed by an electrostatic copying machine (type Rico Co., Ltd.).

In addition, the colored fine particles were agglomerated under the same conditions as described above, and the block water phase having a bulk density of 0.33 g / cm ³ obtained by drying as it was without being subjected to heat-humidification to the mass obtained by filtration and separation was pulverized using a hammer mill to obtain colored fine particles ( 23 '), it was a very high spherical particle. Table 2 shows the results of measuring the charge amount of the colored spherical fine particles 23 '.

Example 24

By the same method as in Example 8, a suspension (1 ') of colored spherical fine particles was obtained. 60 parts of aluminum chloride aqueous solution of 5% of the active ingredient was added to the suspension, aggregated, and filtered by a continuous suction filter, and 5,000 parts of 85% of hot water were continuously added to the lump obtained on the same filter, followed by washing and hot water heating. The lumps of the block-like object which the particle | grains fuse | melted by each other were formed. The block was dried at 50 deg. This was a block-like material with a bulk density of 0.42 g / cm ³ as a fusion state leaving grain boundaries, and 1,500 parts were obtained. After crushing this block-like thing, it was grind | pulverized at the feed amount of 11 kg / hr using the supersonic jet grinder IDS type 2 (made by Japan Pneumatic Co., Ltd.), and the colored fine particle 24 was obtained.

When the obtained colored fine particle 24 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 5.60 micrometers and the coefficient of variation of the particle size was 18.7%. Using the colored fine particles 24 as an electrophotographic toner 24 as it is, the image was output by an electrostatic copying machine (type 4060 Ricoh Co., Ltd.).

Example 25

By the same method as in Example 10, a suspension (2 ') of colored spherical fine particles was obtained. To the suspension of colored fine particles (2 '), 13 parts of an aqueous paste charge control agent (Bontron S-34, product of Orient Chemical Co., Ltd.) having 35% of an active ingredient was added, and then 1,110 parts of methanol was added to precipitate colored spherical fine particles. When 4,000 parts of hot water at 80 ° C. were continuously added to the lump obtained on the same filter while filtration was separated by a filtration suction filter, hot water heating was performed to form a lump of block-like material in which particles were fused together. The block was dried at 50 deg. This was a fused state leaving grain boundaries, and a block-like material having a bulk density of 0.70 g / cm ³ was obtained 1,110 parts. After crushing this block-like object, it was grind | pulverized at the feed amount of 8 kg / hr using the supersonic jet grinder IDS type 2 (made by Japan Numatic Industry Co., Ltd.), and the colored fine particle 25 was obtained.

As a result of measuring the obtained colored fine particle 25 with a Golter counter (gap 100 micrometers), the average particle diameter was 6.18 micrometers and the coefficient of variation of the particle size was 23.0%. The colored fine particles 25 were used as the electrophotographic toner 25 as it was, and image output was performed by an electrostatic copying machine (type 4060, manufactured by Rico Co., Ltd.), as shown in Table 1.

Example 26

By the same method as in Example 11, suspension (3 ') of colored spherical fine particles was obtained. 41 parts of an aqueous paste charge control agent (Bontron S-34, product of Orient Chemical Industry Co., Ltd.) of 35% of active ingredient and 60 parts of aluminum chloride aqueous solution of 5% of active ingredient were added to the suspension (3 ') of colored fine particles, and then aggregated. The suspension was filtered and separated with a continuous pressure filter, and 3,000 parts of hot water at 110 ° C. was continuously added to the lump obtained on the same filter, washed with hot water to form a lump of blocks formed by fusion of the particles.

The block was dried at 50 deg. This was a fused state that left grain boundaries and had a block density of 0.35 g / cm ³ and obtained 1,700 parts. The block-like material was crushed finely and then pulverized at a feed amount of 13 kg / hr using a supersonic jet grinder IDS type 2 (manufactured by Pneumatic Co., Ltd.) to obtain colored fine particles 26.

When the obtained colored fine particle 26 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 5.24 micrometers and the coefficient of variation of the particle size was 19.0%. The colored fine particles 26 were used as the electrophotographic toner 26 as it was, and image output was performed by an electrostatic copying machine (NP-5000, manufactured by Canon Corporation).

Example 27

By the same method as in Example 12, a suspension (4 ') of colored spherical fine particles was obtained. 60 parts of aluminum chloride aqueous solution of 5% of the active ingredient was added to the suspension of the colored fine particles (4 ') to aggregate, and 4,500 parts of 85 ° C hot water was continuously added to the mass obtained on this centrifuge while being filtered off with a centrifuge. When the hot water heating process was performed, the agglomerates of the block-like object by which the particles were fused were formed. The block was dried at 50 deg. This was a fused state leaving a grain boundary, and a block-like object having a bulk density of 0.33 g / cm ³ was obtained at 1,500 parts. After crushing this block-like object, it was grind | pulverized at the feed amount of 15 kg / hr using the supersonic jet grinder IDS type 2 (made by Japan Pneumatic Co., Ltd.), and the colored fine particle 27 was obtained.

As a result of measuring the obtained colored fine particle 27 with a Golter counter (gap 100 micrometers), the average particle diameter was 6.23 micrometers and the coefficient of variation of the particle size was 20.5%. The colored fine particles 27 were used as the electrophotographic toner 27 as it was, and image output was performed by an electrostatic copying machine (type 4060, manufactured by Ricoh Co., Ltd.).

Example 28

By the same method as in Example 13, a suspension (5 ') of colored spherical fine particles was obtained. 1,500 parts of methanol was added to the suspension (5 ') to precipitate colored fine particles, followed by filtration and separation with a centrifuge, followed by continuous addition of 6,000 parts of hot water at 75 ° C., followed by washing and hot water heating. Agglomerates of block-like objects obtained by fusion of the particles were formed.

The block was dried at 50 deg. This was a fused state leaving grain boundaries, and a block-like material having a bulk density of 0.55 g / cm ³ was obtained at 1,500 parts. After crushing this block-like object, it was grind | pulverized at the feed amount of 10.5 kg / hr using the supersonic jet grinder IDS type 2 (made by Nipmatic Co., Ltd.), and the colored fine particle 28 was obtained.

When the obtained colored fine particle 28 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 5.65 micrometers and the coefficient of variation of the particle size was 21.6%. Using the colored fine particles 28 as an electrophotographic toner 28 as it is, the image was output by an electrostatic copying machine (type 4060 Ricoh Co., Ltd.).

Example 29

By the same method as in Example 14, a suspension (6 ') of colored spherical fine particles was obtained. 180 parts of 5% calcium chloride aqueous solution of 5% active ingredient was added to the suspension (6 '), aggregated, and separated by filtration using a continuous pressure filter. Then, 4,000 parts of 115 ° C. hot water were continuously added to the suspension, followed by washing and hot water heating. The lumps of the block-like object which the particle | grains fuse | melted by each other were formed. This block-like thing was dried at 50 degreeC. This was a fused state leaving a grain boundary, and a block-like object having a bulk density of 0.58 g / cm ³ was obtained at 1,500 parts.

The block-like material was crushed finely and then pulverized using a supersonic jet grinder IDS type 2 (manufactured by Japan Pneumatic Co., Ltd.) at a feed amount of 9.5 kg / hr to obtain colored fine particles (29).

As a result of measuring the obtained colored fine particle 29 with a Golter counter (gap 100 micrometers), the average particle diameter was 6.12 micrometers and the coefficient of variation of the particle size was 22.3%. The colored fine particles 29 were used as the electrophotographic toner 29 as it was, and image output was performed by an electrostatic copying machine (type 4060, manufactured by Ricoh Co., Ltd.).

Example 30

By the same method as in Example 15, a suspension 7 'of colored spherical fine particles was obtained. 1,500 parts of methanol and 1,000 parts of industrial ethanol were added to the suspension 7 'to precipitate colored fine particles, followed by filtration and separation with a continuous suction filter, and continuously adding 2,500 parts of 90 ° C hot water to the lump obtained on this filter and washing the product. When the hot water heating process was performed, the agglomerates of the block-like object by which the particles were fused were formed. This block-like thing was dried at 50 degreeC. This was a fused state leaving grain boundaries, and a block-like material having a bulk density of 0.62 g / cm ³ was obtained at 1,500 parts. After crushing this block-like object, it was grind | pulverized at the feed amount of 7 kg / hr using the supersonic jet grinder IDS type 2 (made by Japan Pneumatic Co., Ltd.), and the colored fine particle 30 was obtained.

When the obtained colored fine particle 30 was measured with the Golter counter (gap 100 micrometers), the average particle diameter was 5.61 micrometers and the coefficient of variation of the particle size was 21.5%. Using the colored fine particles 30 as the electrophotographic toner 30 as it is, image output was performed by an electrostatic copying machine (type 4060, manufactured by Ricoh Co., Ltd.).

Example 31

Instead of adding 60 parts of an aqueous aluminum chloride solution of 5% of the active ingredient used in Example 24, 10 parts of hydrophobic aerosil R972 (Aerosil Co., Ltd.) and Ketchen Black EC are conductive carbon blacks. (143 parts of dispersion liquid which disperse | distributed 3 parts of Ketchen Black International Co., Ltd. was added, it aggregated, it filtered, and obtained the lump. Thereafter, the same operation as in Example 24 was carried out to obtain 1,500 parts of a block-like article having a bulk density of 0.30 g / cm ³ as a fusion state that left grain boundaries. The block-like material was crushed finely and then pulverized at a feed amount of 12 kg / hr using a supersonic jet grinder IDS type 2 (manufactured by Japan Pneumatic Co., Ltd.) to obtain colored fine particles 31.

As a result of measuring the obtained colored fine particles 31 with a Golter counter (gap 100 micrometers), the average particle diameter was 5.45 micrometers and the coefficient of variation of the particle size was 17.8%. The colored fine particles 31 were used as the electrophotographic toner 31 as it was, and image output was performed by an electrostatic copying machine (type 4060, manufactured by Ricoh Co., Ltd.).

In addition, a block-like article having a bulk density of 0.26 g / cm ³ obtained by drying as it is without being subjected to heat-humidification to a mass obtained by agglomeration of colored fine particles by separate operation as described above and subjected to filtration and separation is pulverized by using a hammer mill and colored. The fine particles 31 'were obtained, which were very high spherical particles. Table 2 shows the results of measuring the charge amount of the colored spherical fine particles 31 '.

Comparative Example 1

After adding 5 parts of aluminum chloride in the state which hold | maintained 10,480 parts of the suspensions (4) of the colored spherical microparticles obtained in Example 4 at 75 degreeC, it heat-processes at 150 degreeC for 30 minute (s) under pressurization, and formed the block-like thing which fused together. It was. The resultant was filtered, dried at 50 ° C. for 8 hours using a vacuum dryer, and finely pulverized. The resultant powder was pulverized at a feed amount of 4 kg / hr using the same model as in Example 4 to obtain 1,500 parts of comparative colored fine particles (a).

Image output by an electrostatic copying machine (type 4060, manufactured by Rico Co., Ltd.) using the properties of the particles of the comparative colored fine particles (a) and the comparative colored fine particles (a) as they are as comparison electrophotographic toners (a). The result was as shown in Table 1.

Comparative Example 2

The suspension of colored spherical microparticles | fine-particles was obtained by operation similar to Example 4. However, since suspension polymerization reaction was 65 degreeC for 4 hours, the polymerization rate was 86%.

When the suspension of the obtained colored spherical fine particles was further heat-processed at 90 degreeC for 2 hours, the whole of the colored spherical fine particles became a big aggregate, and post-processing was difficult.

Comparative Example 3

2,228 parts of styrene acrylic resin (TB-1000F Samyang Hwasung Co., Ltd.), 187 parts of carbon black MA-100R (manufactured by Samneung Hwaseong Co., Ltd.) and 25 parts of charge control agent (Aizen Spilon Black TRH) were premixed with a Henschel mixer, The mixture was melt mixed at 150 for 30 minutes and then cooled to obtain a toner mass. The toner lump is crushed into 0.1 mm to 2 mm with a pulverizer, and the remaining toner is pulverized with a feed amount of 5 kg / hr using the same model as in Example 1 to grind the pulverized product into a wind classifier (DS-2 type). Japan Pneumatic Co., Ltd.) was obtained, and 1,500 parts of comparative colored fine particles (b) were obtained.

Image output by the electrostatic copying machine (type 4060, manufactured by Rico Co., Ltd.) using the properties of the particles of the comparative colored fine particles (c) and the comparative colored fine particles (c) as they are as comparison electrophotographic toners (c). The result was as shown in Table 1.

[Comparative Example 5]

The filter cake of colored spherical fine particles obtained by the same operation as in Example 19 was subjected to heat and humidification for 20 minutes under an atmosphere maintained at a temperature of 85 ° C. and a relative temperature of 60%, whereby particles formed almost no fused blocks. It was. The said block-like thing was dried at 50 degreeC, and 1,500 parts were obtained. This was crushed finely and ground to a feed amount of 20 kg / hr using the same model as in Example 4 to obtain a comparative colored fine particle (d). As a result of observing the said colored fine particle for comparison (d) with a scanning electron microscope photograph, 90% or more of particle | grains were spherical, and the effect of heat-humidification treatment was not at all.

Image output by an electrostatic copying machine (type 4060, manufactured by Rico Co., Ltd.) using the properties of the particles of the comparative colored fine particles (d) and the comparative colored fine particles (d) as they are as the comparative electrophotographic toner (d). The results were as shown in Table 1.

Comparative Example 6

3,000 parts of 135 degreeC hot water was continuously added to the lump obtained on this filter, while filtration of the colored spherical fine particle aggregate liquid obtained by the same operation as Example 27 by this continuous pressure filter, and a hot water heating process was performed with washing | cleaning, and a particle was fused together. The agglomerates were formed in a block. The said block-like thing was dried at 50 degreeC, and 1,500 parts were obtained. This was crushed finely and ground to a feed amount of 2 kg / hr using the same model as in Example 27 to obtain colored fine particles for comparison (e).

Image output by an electrostatic copying machine (type 4060, manufactured by Rico Co., Ltd.) by using the properties of the particles of the comparative colored fine particles (e) and the comparative colored fine particles (e) as they are as comparison electrophotographic toners (e). The results were as shown in Table 1.

Comparative Example 7

8,000 parts of hot water at 45 ° C. were continuously added to the mass obtained on the filter, while the colored spherical fine particle aggregate liquid obtained by the same operation as in Example 27 was separated by filtration with a centrifugal separator. Unblocked material was formed. The said block-like thing was dried at 50 degreeC, and 1,500 parts were obtained. This was crushed finely and ground to a feed amount of 20 kg / hr using the same model as in Example 27 to obtain a comparative colored fine particle (f).

Image output by an electrostatic copying machine (type 4060, manufactured by Rico Co., Ltd.) using the properties of the particles of the comparative colored fine particles (f) and the comparative colored fine particles (f) as they are as a comparison electrophotographic toner (f). The result was as shown in Table 1.

Comparative Example 8

To the suspension (1 ') obtained in Example 16, 100 parts of an aqueous aluminum chloride solution of an organic component was added, coagulated, and obtained by agglomeration by filtration to obtain a block-like product having a bulk density of 0.23 g / cm ³ obtained by drying as it was without performing a humidification treatment. And the grinder was used to obtain comparative microparticles (g).

Table 2 shows the results of measuring the charge amount using this.

TABLE 1

(Note 1) Grinding throughput

It was set as the grinding | pulverization process amount with the feed amount at the time of using the supersonic jet grinder IDS type 2 (made by Nippon Numatic Co., Ltd.).

(Note 2)

Particle diameter: Measured by a Gulter counter (Gulter Electronics INC product: TA-II type).

Coefficient of variation: measured by a Gulter counter (Gulter Electronics INC product: TA-II type).

Friction charge amount: Blow-off powder charge measuring device using iron carrier (Donghwa Iron Co., Ltd. product: DSP-128) and mixture (toner concentration 5% by weight) (Toshiba Chemical Co., Ltd. product: Model TB-200) Measured by

Fluidity: The fluidity of the toner was visually evaluated.

(Note 3)

By using the electrostatic copying machine image output (type 4060 Ricoh Corporation or NP-5000, Canon Corporation) The images obtained by copying 1 were evaluated.

Flow: The presence or absence of the phenomenon that the ground became spotty by toner was examined.

Fine wire reproducibility: fax test chart No. 1 was evaluated by the read state of the image obtained by copying.

Cleanability: Facsimile Test Chart No. 1 was evaluated by the image obtained by copying.

TABLE 2

Claims (8)

The polymerizable monomer is suspended in a suspension medium in the presence of a colorant and / or a magnetic component to carry out suspension polymerization to obtain colored spherical fine particles having an average particle diameter of 3-50 μm, and water-insoluble fine particles are added to the suspension containing the colored spherical fine particles. And then fusion of the fine particles into blocks to form a block by heating under a wet condition of 50-130 ° C., and containing the colored fine particles obtained by crushing the block-like particles to the size of the average particle diameter of the colored spherical fine particles before fusion. Electrophotographic toner. The electrophotographic toner according to claim 1, wherein the heat treatment is carried out simultaneously with the polymerization property at a temperature of 50-98 占 폚. The method according to claim 1, wherein the water-insoluble fine particles are added to the suspension when the polymerization rate of the colored spherical fine particles is 90% or more, and the heat treatment is carried out simultaneously with the polymerization aging at a temperature of 50 to 98 ° C. An electrophotographic toner characterized by the above-mentioned. The electrophotographic toner according to claim 1, wherein the relative humidity condition during the heat treatment is 70-100%. The electrophotographic toner according to claim 1, wherein the colorant is a carbon black graft polymer. The electrophotographic toner according to claim 1, wherein the block-like particles have a bulk density of 0.1-0.9 g / cm ³ . The electrophotographic toner according to claim 1, wherein the average particle size is 3 to 50 m. 8. The electrophotographic toner according to claim 7, wherein the coefficient of variation of the particle diameter is 0.0%.