JP2005345759A - Method for manufacturing magnetic polymerized toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To always keep a specific amount of magnetic iron oxide and to achieve stable triboelectric charging characteristics, even when using a recycling process, it is characterized by adjusting the amount of magnetic iron oxide used in a toner manufacturing process according to the magnetic iron oxide content of extra toner when the extra toner particles generated in a process of manufacturing a magnetic polymerized toner using magnetic iron oxide are recycled. <P>SOLUTION: In a method for manufacturing a magnetic polymerized toner by polymerizing a polymerizable monomer composition containing at least magnetic iron oxide, a polymerizable monomer and a charge control agent, extra toner generated in a process of manufacturing the toner is melted and kneaded, adjusted extra toner powder is obtained, and this adjusted extra toner powder is put again in a polymerizable monomer system. The amount of magnetic iron oxide used in a toner manufacturing process is adjusted according to the magnetic iron oxide content of the extra toner. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a toner used in an electrophotographic method or an electrostatic printing method, and more particularly to a method for producing a toner that can be reused from a non-predetermined toner produced in a toner production process.

  Conventionally, a number of methods are known as electrophotographic methods. In general, an electric latent image is formed on an electrostatic image bearing member (hereinafter referred to as a “photosensitive member”) using a photoconductive substance by various means. Then, the latent image is developed with toner to form a visible image. If necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat and pressure. To obtain a copy. In this case, the residual toner on the photosensitive member that has not been transferred onto the transfer material is generally removed by a cleaning mechanism composed of a regulating blade or a fur brush.

  As a developing method for visualizing an electric latent image using toner, a cascade developing method as seen in Patent Document 1, a magnetic brush method as seen in Patent Documents 2 to 5, and a Patent Documents 6 and 7 can be found. Many developing methods such as a powder cloud method, a fur brush developing method, and a liquid developing method are known.

  In recent years, output devices using these electrophotographic methods are printers as output means due to the popularization of digital cameras, personal computers, home faxes, etc., where demand has been increasing in recent years, in addition to so-called copying machines that copy conventional documents. Equipment is becoming mainstream in the market.

  LED and LBP printers are the mainstream in the recent market as printers, and with higher recording image quality as the direction of technology, higher resolutions, that is, conventional 300, 400 dpi, 600, 800, and more Has become a higher resolution of 1200, 2400 dpi. Accordingly, with this development, higher definition has been demanded.

  In addition, since these digital devices are widely used in homes for home use, maintenance can be performed more easily, and at the same time, higher reliability has been strictly pursued. However, not only the improvement of hardware technology but also improvement of toner technology cannot be expected.

  In general, as a method for producing a toner, a colorant such as a dye and a pigment and an additive such as a charge control agent are melt-mixed in a thermoplastic resin and uniformly dispersed, and then pulverized and pulverized by a fine pulverizer and a classifier. A method for producing a toner having a desired particle size by classification, that is, a pulverization method is known.

In the toner by these pulverization methods, there is a limitation when adding a releasing material such as wax. That is, in order to achieve a sufficient level of dispersibility of the releasable substance,
1. 1. It is necessary to maintain a certain viscosity at the kneading temperature with the resin. For example, the content of the releasable substance should be about 5 parts by mass or less. Due to such restrictions, there is a limit to the fixability of the toner by the pulverization method.

  In this kneading and pulverization method, it is not easy to completely disperse solid fine particles such as a colorant in a resin. Depending on the degree of dispersion, the toner composition may be distributed, resulting in fluctuations in toner development characteristics. May come. Furthermore, in general, the resolution, solid portion uniformity, gradation reproducibility, etc. of an image formed with toner largely depend on the properties of the toner, particularly its particle size, and a higher quality image can be obtained with smaller particle size particles. Recent printers and high-quality copiers often use small particle size toner. However, in order to reduce the toner particle size by the pulverization method, a volume average diameter of about 5.0 μm is the limit due to the capability of the pulverizer.

  Further, in this pulverized toner, a classification step is essential in order to obtain a predetermined particle size and particle size distribution. In addition to the predetermined particle size toner, fine powder and coarse powder are generated by this step. Various ideas have been made for reuse. As for the coarse powder, it is pulverized again into a fine powder in the manufacturing process, but the generated toner fine powder is placed in the conventional raw material mixing process due to the environmental aspect and production cost as described in Patent Document 8 and the like. It was recycled after quantitative recycling. However, in this method, when the toner fine powder is melted and kneaded again by the kneader, the resin molecular cutting in the toner fine powder occurs again, and the fixing performance such as hot offset when the toner is fixed on the paper due to the decrease in the molecular weight of the resin component. In addition, deterioration of the durability performance of the toner due to a decrease in mechanical strength was caused, which was not preferable. In order to improve these, various devices such as Patent Document 9 have been proposed for the reuse of the toner component, such as processing the fine powder before it is put into the kneading process, and the fine powder is thrown into the kneading process for reuse. Is widely practiced as a known technique from the viewpoint of a method for producing a toner with good economic efficiency and productivity.

  On the other hand, a method for producing a toner (hereinafter, polymerized toner) is proposed in which a polymerizable monomer composition having at least a polymerizable monomer is subjected to suspension polymerization and toner particles are obtained at the same time (Patent Document 10). ). In this suspension polymerization method, a polymerizable monomer and a colorant (in addition, a polymerization initiator, a crosslinking agent, and other additives as necessary) are uniformly dissolved or dispersed to form a monomer composition. The monomer composition is dispersed in a continuous phase (for example, an aqueous phase) containing a dispersion stabilizer by using a suitable stirrer and simultaneously undergoes a polymerization reaction to obtain toner particles having a desired particle size. Since there are no restrictions on the items described in the above pulverized toner and various advantages, it has recently attracted particular attention.

  In other words, regarding the content and dispersibility of the release agent, in the polymerized toner, since the release agent component can be included in the toner particles, the content can be increased as compared with the pulverized toner, and the dispersibility is satisfied at the same time. You can make it. Further, the dispersibility of the colorant is not particularly problematic because it can be uniformly dissolved or dispersed together with other additives in the polymerizable monomer. Furthermore, since the desired particle size and particle size distribution can be controlled depending on the dispersion / granulation conditions, there is an advantage that the toner can be made into a small particle size toner.

  However, this polymerized toner also has problems to be solved as described below.

  In the polymerized toner, particle aggregation occurs during the reaction depending on the polymerization reaction conditions and the toner formulation, and the polymer particle aggregate adheres to the reaction vessel wall surface, the stirring blade, or the like. In addition, it is not easy to completely eliminate the inclusion of these coarse particles even under production conditions where a sharp particle size distribution width is provided by the dispersion / granulation process and particle aggregation is suppressed as much as possible by various techniques. .

  On the other hand, depending on the concentration and addition conditions of the dispersant in the aqueous phase used to give a sharp particle size distribution range, polymerization occurs in the aqueous phase and the size is 0.1 to 1 μm or smaller. Of ultrafine particles. In these ultrafine particles, the dispersion of additives such as colorants is non-uniform, and this presence causes problems in terms of toner image characteristics (solid density, density uniformity, fog, etc.). Further, in the toner in which the ultrafine particles are adhered to the toner surface, the fluidity, charge controllability, etc. of the toner change, so that a problem is similarly generated on the image characteristics of the toner.

  From another point of view, the polymerized toner is a batch type because of its production method. When toner particles outside the range of a predetermined particle size distribution and particle size distribution width are generated in some form, Since the particles are designed as a core-shell structure of at least two layers by inclusion of a releasable component, a low energy fixing component, etc., it cannot be simply reused like a pulverized toner. This is an important examination item to be solved in terms of toner yield. In this regard, Patent Document 11 proposes that non-predetermined toner particles are dissolved in a monomer and reused. However, in this proposal, only the soluble component in the toner other than the predetermined toner is used as the polymerizable monomer, and the insoluble component cannot be used. Therefore, the recycling rate is not 100%, and further improvement of the recycling rate is required. It has been.

  On the other hand, polymerized toner obtained by using magnetic iron oxide instead of colorant can easily make the toner fine particles, and further, the resulting toner has a spherical shape and excellent fluidity and high image quality. It is advantageous for the conversion.

  However, when the polymerized toner contains magnetic iron oxide, its fluidity and charging characteristics are significantly lowered. This is because the magnetic particles are generally hydrophilic and thus easily exist on the toner surface. In order to solve this problem, it is important to modify the surface characteristics of the magnetic iron oxide.

  Many proposals have been made regarding surface modification for improving dispersion of a magnetic substance in a polymerized toner. For example, various silane coupling agent treatment techniques for magnetic materials have been proposed in Patent Documents 12 to 15 and the like, and Patent Documents 16 and 17 disclose techniques for treating silicon element-containing magnetic particles with a silane coupling agent. Yes.

  However, although the dispersibility in the toner is improved to some extent by these treatments, there is a problem that it is difficult to uniformly hydrophobize the surface of the magnetic material. The generation of unmodified magnetic particles cannot be avoided, and is insufficient to improve the dispersibility in the toner to a good level.

  Further, Patent Document 18 has already disclosed a special toner in which magnetic particles are contained only in specific parts inside the particles.

  However, Patent Document 18 does not mention the circularity of the disclosed toner.

  Further, to summarize the toner configuration disclosed in Patent Document 18, it is composed of a structure in which a resin layer having no magnetic particles is formed in the vicinity of the toner particle surface with a certain thickness or more. This means that the toner surface layer portion where no magnetic particles are present is present in a considerable proportion. However, in other words, such a developer, when the average particle size is as small as 10 μm, for example, is that it is difficult to enclose a sufficient amount of magnetic particles because the volume in which magnetic particles can exist is small. Moreover, in such a developer, in the developer particle size distribution, the ratio of the surface resin layer in which no magnetic particles are present differs between the developer particles having a large particle size and the developer particles having a small particle size. The content of the magnetic substance contained in the developer is also different, and the developability and transferability are also different depending on the particle size of the developer, that is, selective developability depending on the particle size is easily observed. Therefore, when printing is performed for a long time with a magnetic developer having a non-uniform particle size, particles that contain a large amount of magnetic material and are difficult to be developed, that is, developer particles having a large particle size are likely to remain, and the image density and image quality are lowered. It will continue to worsen the fixability.

  In addition, in the case of magnetic polymerized toner manufactured using magnetic iron oxide, toner particles outside the predetermined particle size distribution and particle size distribution range may be generated in some form, as in the above-described polymerized toner manufacturing process. These particles are designed as particles having a core-shell structure of at least two layers by inclusion of a releasable component, a low energy fixing component, etc., and therefore cannot be simply reused like a pulverized toner. Further, if only the soluble component in the toner other than the predetermined toner is used for the polymerizable monomer and the insoluble component is not used, the recycling rate is not 100%, and further improvement of the recycling rate is required. Yes.

  From such a background, in order to achieve an increase in manufacturing yield while maintaining toner quality by reusing non-predetermined toner particles in the polymerized toner using the colorant and the magnetic polymerized toner using the magnetic iron oxide. , By kneading and pulverizing non-predetermined toner particles (fine powder, coarse powder, polymerization kettle deposits, etc.) to be reused to produce non-predetermined toner adjustment powder, it becomes easily soluble in the polymerizable monomer, Means have also been proposed in which uniform dissolution / dispersion in the polymerizable monomer is possible.

  According to this means, the non-predetermined toner particles are heated and melt-kneaded using a twin-screw extruder or the like, so that shearing force and shearing force are applied, and insoluble molecular chains in the non-predetermined toner are cut. It is considered that the insoluble matter is eliminated and the dissolution in the polymerizable monomer is facilitated.

  By using this means, particularly in a polymerized toner using a colorant, it becomes possible to reuse non-predetermined toner without deteriorating its quality, and it is achieved to increase the yield in the manufacturing process. The magnetic polymerization toner using magnetic iron oxide does not always achieve reuse of the non-predetermined toner by the above means.

  Also in magnetic polymerized toner, a non-predetermined toner particle is melted and kneaded to apply shearing force and shearing force, etc., and insoluble matter in the non-predetermined toner is broken to eliminate insoluble matter, and the polymerizable monomer Although the same effect as that of a polymerized toner using a colorant can be obtained with respect to the ease of dissolution in the body, the surface property of the magnetic iron oxide in the magnetic polymerized toner depends on the surface properties of the magnetic iron oxide. Dispersibility varies greatly.

  From various studies so far, due to fluctuations in the surface treatment conditions of magnetic iron oxide, toner production conditions, etc., when the amount of magnetic iron oxide prescribed at the time of toner production is included, inclusion of magnetic iron oxide in the desired particle size distribution The amount of magnetic iron oxide in the non-predetermined toner is likely to vary, and the non-predetermined toner particles are heated as described above, melted and kneaded using a twin screw extruder, etc., and dissolved in the polymerizable monomer. Even when the toner is used, the amount of magnetic iron oxide contained in the non-predetermined toner may vary depending on the production process, and the amount of magnetic iron oxide in the magnetically polymerized toner obtained after reuse changes. In particular, there is a great concern that the triboelectric charging characteristics, which are essential for exhibiting good behavior in the electrophotographic process, become unstable, causing fogging at non-image sites and image defects such as image unevenness.

JP-A-11-109755 JP-A-5-061259 Japanese Patent Laid-Open No. 5-100468 Japanese Patent Application Laid-Open No. 5-100472 Japanese Patent Laid-Open No. 5-100491 JP-A-5-0274779 Japanese Patent Laid-Open No. 5-080584 Japanese Patent Laid-Open No. 5-34976 JP-A-8-69126 Japanese Patent Publication No. 36-10231 JP-A-10-301330 Japanese Patent Laid-Open No. 59-200254 Japanese Patent Laid-Open No. 59-200256 JP 59-200237 A JP 59-224102 A JP-A-63-250660 JP-A-10-239897 JP-A-7-209904

  An object of the present invention is to provide a method for producing a polymerized toner that solves the above-described problems.

  That is, the present invention provides a method for producing a polymerized toner, characterized in that in the method for producing a polymerized toner, non-predetermined toner particles generated in the toner production process are reused, and particularly a magnetic toner using magnetic iron oxide. When reusing the non-predetermined toner particles generated in the production process of the polymerized toner, the amount of magnetic iron oxide used in the toner production process is adjusted by the content of magnetic iron oxide in the non-predetermined toner. The purpose is to always maintain a constant amount of magnetic iron oxide even when using a process, and to derive stable triboelectric charging characteristics.

  Furthermore, an object of the present invention is to provide a method for producing a toner for developing an electrostatic charge image that achieves recycling of polymerized toner from the viewpoint of ecology, is economical and wasteless, has high image density, is stable, and has no fog. To do.

The present invention relates to a method for producing a magnetic polymer toner obtained by polymerizing a polymerizable monomer composition containing at least magnetic iron oxide, a polymerizable monomer, and a charge control agent.
A non-predetermined toner produced in the toner production process is melt-kneaded to obtain a non-predetermined toner adjustment powder, and the non-predetermined toner adjustment powder is reintroduced into the polymerizable monomer system. The present invention relates to a method for producing a magnetically polymerized toner, characterized in that the amount of magnetic iron oxide used in the toner production process is adjusted by the content of magnetic iron oxide in the outer toner.

  According to the present invention, the recovered toner of aggregated coarse powder and ultrafine powder generated in the production process of the magnetic polymerization toner, and the toner that is restricted in use that is generated due to process fluctuations are kneaded to obtain a non-predetermined toner adjustment powder, The non-predetermined toner adjustment powder can be reused through a process of putting it in a polymerizable monomer system, and the toner production method can contribute to ecology and economy.

  The toner of the present invention is a magnetic polymerized toner obtained by polymerizing a polymerizable monomer composition containing magnetic iron oxide, and is a non-predetermined toner produced in the process of producing the magnetic polymerized toner. Is reused at the time of production of the magnetic polymerization toner.

  Specifically, a process for reusing the non-predetermined toner according to the present invention in the production process of the magnetic polymerization toner will be described below. FIG. 1 is a flowchart showing the overall flow of the manufacturing method of the present invention.

  Non-predetermined toner to be reused (fine powder, coarse powder, polymerization kettle deposits, etc.) is melt-kneaded and pulverized to produce a non-predetermined toner adjustment powder. At the time of melt-kneading, a shearing force, a shearing force, and the like are applied to the non-predetermined toner, and molecular chains insoluble in the non-predetermined toner are cut. At this time, it is preferable to perform kneading until the insoluble matter disappears by kneading, and by making it easily soluble in the polymerizable monomer, uniform dissolution and dispersion in the polymerizable monomer is possible. It becomes.

  Depending on the form of the non-predetermined toner used in the melt-kneading process, it is conceivable that the amount of magnetic iron oxide contained will fluctuate as described above. In particular, in the case of fine powder, coarse powder, etc., the amount ratio of magnetic iron oxide contained is likely to vary greatly from the particle size.

  Therefore, in the present invention, in consideration of the content of magnetic iron oxide in these non-predetermined toners, the amount of magnetic iron oxide contained in one or a plurality of non-predetermined toners is measured. By adjusting the amount of magnetic iron oxide used, the amount of magnetic iron oxide of the magnetically polymerized toner obtained is constant even when the recycling step is used.

  In the present invention, the content of magnetic iron oxide in the non-predetermined toner was measured with a thermal analyzer, TGA-7, manufactured by PerkinElmer. In the measurement method, the toner is heated from normal temperature to 900 ° C. at a temperature increase rate of 25 ° C./min in a nitrogen atmosphere, and the weight loss from 100 ° C. to 750 ° C. is defined as the binder resin amount, and the residual mass is approximately calculated. The amount of magnetic material was used.

  When a plurality of non-predetermined toners are used in the melt-kneading step, premixing is performed using a mixer such as a Henschel mixer (manufactured by Mitsui Miike Kogyo Co., Ltd.) or a Nauter mixer (manufactured by Hosokawa Micron Co., Ltd.). However, if there is one type of toner other than the predetermined toner, the preliminary mixing may not be performed.

  The premixing conditions are preferably 2/3 or less of the maximum speed of the mixer used, and the mixing time is preferably within 2 minutes. If the rotational speed is longer than that and the mixing time is longer than the above conditions, there is a risk that non-predetermined toner may be fused to the inner wall of the mixer layer during continuous operation. Moreover, it is preferable to use a rotary blade or the like used in the mixer having a low shearing force.

  Preferably, the non-predetermined toner (one or a plurality) obtained through the premixing step is melt kneaded using the following kneading apparatus or the like to obtain non-predetermined toner adjusting powder.

  The apparatus used in the kneading step may be a commercially available apparatus, and examples thereof include three rolls and a screw kneader. The purpose of the kneading step is to cleave molecular chains by imparting a high share to non-predetermined toner. For this reason, the kneading temperature is preferably lower, and the amount of non-predetermined toner fed to the kneading device is also fed until it can be discharged in order to retain more in the kneading zone in the kneading device and give a mechanical share. Increasing the amount is considered to have higher molecular chain scission ability.

  The kneading temperature is preferably between about 90 ° C. and 110 ° C. as the kneading device set temperature, although it varies depending on the device used. Therefore, it is necessary to determine the conditions such as the kneader scale.

  When the set temperature is lower than 90 ° C., the non-predetermined toner does not melt and the apparatus is overloaded, and the apparatus cannot be started. On the other hand, when the temperature is 110 ° C. or higher, the toner outside the predetermined range is excessively melted, making it difficult to apply an appropriate share in the kneading device. If the feed amount is increased to obtain the share, the toner outside the predetermined amount is oversaturated in the kneading device. This leads to a vicious circle such as being unable to feed non-predetermined toner.

  When melt kneading is performed within the set temperature range of the kneading apparatus, the actual temperature of the discharged material is preferably 130 ° C. or higher. If the actual temperature of the discharged material is 130 ° C or higher with respect to the set temperature, it means that the kneaded material has a sufficient share in the kneader and self-heating is generated. Therefore, the effect of breaking the molecular chain can be sufficiently obtained, and an unspecified toner adjustment powder with few insoluble components can be obtained.

  On the other hand, if the product temperature of the discharged product is 130 ° C. or less or a value close to the set temperature of the kneading device, there is no sufficient kneading zone in the kneading device, and the toner outside the predetermined range is melted without taking a share. Since the shearing force cannot be obtained, the effect of cutting the molecular chain (reducing insoluble components) is hardly obtained.

  The product temperature of the discharged product is measured using a sensor probe type thermometer.

  The obtained kneaded product is cooled using a cooling roller or the like, passed through a coarse crushing step, and then used a crusher device such as a speed mill (manufactured by Okada Seiko Co., Ltd.) or the like so as to have a particle diameter of about 2 mm to 5 mm. An external toner adjusting powder was obtained.

  The ratio of the non-predetermined toner adjusting powder component to be re-introduced into the polymerizable monomer system is preferably 0.1% by mass to 20% by mass, more preferably 0.1% by mass to 5% by mass with respect to the toner raw material. % Is good. The toner raw material component described here means a polymerizable monomer, magnetic iron oxide (colorant), a resin component, a release agent, an initiator, etc. That is, the toner raw material means the total mass of these components. .

  When the ratio of the non-predetermined toner adjusting powder component to be re-introduced into the polymerizable monomer system exceeds 20% by mass, dissolution or swelling tends to be non-uniform, and even if the dissolution or swelling time is prolonged, non-uniformity Is not changed, the viscosity of the solution is remarkably increased, and the particle size distribution during the granulation process becomes broad, which is not preferable. Further, if the ratio of the non-predetermined toner adjusting powder component to be re-introduced into the polymerizable monomer system is less than 0.1% by mass, there is no economic advantage to deliberately recycle and it is meaningless.

  The step of dispersing and dissolving the obtained non-prescribed toner adjusting powder in the polymerizable monomer system will be described below.

  Non-prescribed toner adjustment powder, if the magnetic iron oxide to be used is familiar and easily dispersible with the polymerizable monomer, it can be dissolved in the polymerizable monomer system with a normal container and stirrer, A non-specified toner adjusting powder is put into a container together with a polymerizable monomer, a colorant, and, if necessary, an additive such as a charge control agent, a release agent, and a polar resin, and uniform polymerization is performed. A functional monomer dispersion is obtained. In particular, in the case of magnetic iron oxide or the like that has been subjected to surface treatment, dispersion by a media-type mill as in the past is not preferable because the surface treatment portion is destroyed. It is important that the stirring device used at this time has at least two different stirring blades. In other words, use a blade that effectively stirs and mixes the entire treated product with a blade that is effective in dispersing magnetic iron oxide and non-specified toner adjustment powder, and uniformly dissolves the dispersion of magnetic iron oxide and wax in the same container. Mixing can be performed. At this time, as a specific blade shape to be used, a disk turbine blade, a jet-type homogenizer (Claremix: made by M Technique Co., Ltd., TK homomixer: made by Tokushu Kika Kogyo Co., Ltd.) to a blade that effectively applies a shearing force ), And the like. Among these, a disc turbine blade is preferable. When mass production is assumed, the jet-type homogenizer has a high apparatus cost and is not preferable in terms of cost reduction of the manufacturing apparatus. Further, there are various blade shapes in the disk turbine blade, and among these, an etched turbine is particularly preferable. The etched turbine has a plurality of edges on the outer periphery, and this edge is preferable because it dissolves the aggregation of the pigment and is very effective for dissolving the toner adjustment powder outside the predetermined range. Moreover, an anchor wing | blade etc. are mentioned as a wing | blade which stirs and mixes the whole tank uniformly.

  As described above, since the dispersion step and the dissolution step are processed in the same container, the cost can be reduced as compared with the conventional case, and the stirring device used at this time has at least two different stirring blades. The polymerizable monomer dispersion can be continuously applied to the polymerizable monomer dispersion until just before the granulation step in which the toner is produced by introducing the polymerizable monomer dispersion into the aqueous medium that is the next step. Furthermore, since the inside of the tank can be uniformly stirred and mixed, re-aggregation of the pigment and sedimentation of magnetic iron oxide at the bottom of the tank can be prevented, and the magnetic iron oxide is homogeneously dispersed in the toner and has a sharp particle size distribution. Toner can be manufactured efficiently.

  By introducing the polymerizable monomer dispersion thus obtained into a normal polymerization toner production process cycle (granulation dispersion, polymerization, solid-liquid separation), unnecessary toner components generated in the toner production process can be recycled. The toner can be used, and an economical and wasteless toner production method that is excellent in terms of ecology is provided.

  In the polymerizable monomer containing the reusable component, the encapsulated release agent component and the colorant, other additives and relatively low molecular weight resin soluble in the polymerizable monomer, etc. It is included. These are uniformly dissolved in the polymerizable monomer, and are dissolved and dispersed together with the raw materials starting with a new batch of polymerizable monomer components in the dispersion and dissolution process, which is particularly problematic for non-uniformity. Not.

  In addition, by strictly controlling the amount of added toner particles (toner particles that are restricted for reuse), the amount of polymerizable monomer components and other raw materials added as a new batch can be calculated backward. The stability of the toner formulation can be maintained.

  Furthermore, due to the presence of a relatively low molecular weight component in the re-dissolved toner, the apparent mass% of the low molecular weight resin component in the produced polymerized toner particles increases, which improves the low-temperature fixability of the toner. Also has useful benefits.

  The magnetic iron oxide used in the magnetic polymerization toner of the present invention will be described below.

  In the magnetic iron oxide used in the magnetic polymer toner of the present invention, when the particle surface is hydrophobized, the coupling agent is added while being dispersed in an aqueous medium so that the magnetic iron oxide particles have a primary particle size. It is very preferable to use a method of surface treatment while decomposing. This hydrophobization treatment method is less likely to cause coalescence of magnetic iron oxide particles than the treatment in the gas phase, and the repulsive action between the magnetic iron oxide particles due to the hydrophobization treatment works, so that the magnetic iron oxide is almost primary. Surface treatment in the state of particles.

  The method of treating the surface of magnetic iron oxide while hydrolyzing the coupling agent in an aqueous medium does not require the use of a coupling agent that generates gas, such as chlorosilanes and silazanes. In the gas phase, magnetic iron oxide particles can be easily combined with each other, and a highly viscous coupling agent, which has been difficult to be processed well, can be used.

Examples of the coupling that can be used in the surface treatment of magnetic iron oxide according to the present invention include a silane coupling agent and a titanium coupling agent. More preferably used is a silane coupling agent, which has the general formula Rm SiYn
[Wherein, R represents an alkoxy group, m represents an integer of 1 to 3, Y represents a hydrocarbon group such as an alkyl group, a vinyl group, a glycidoxy group, or a methacryl group, and n represents an integer of 1 to 3. Show. ]. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl Diethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxy Silane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, n-butyltrimethoxysilane, isobutyl Le trimethoxysilane, trimethyl methoxysilane, hydroxypropyl Ritori silane, n- hexadecyl trimethoxysilane, n- octadecyl trimethoxysilane and the like.

  Among them, it is preferable to use a silane coupling agent having a double bond to improve the dispersibility of magnetic iron oxide, such as phenyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyl. Trimethoxysilane is more preferred. This is considered to be because, particularly when suspension polymerization is carried out, if the treatment is performed with a coupling agent having a double bond, the familiarity between the magnetic iron oxide and the polymerizable monomer is improved. The dispersibility of the magnetic iron oxide becomes good.

However, using only these coupling agents having a double bond makes it difficult to impart sufficient hydrophobicity to magnetic iron oxide, and magnetic iron oxide having insufficient hydrophobicity is exposed on the toner surface. Due to the influence, the toner has a wide particle size distribution. The reason for this is not clear, but it is thought to be due to inferior hydrophobicity of the coupling agent itself, reactivity with the active group on the surface of the magnetic iron oxide, and poor coverage with the surface of the magnetic iron oxide. For this reason, in order to obtain sufficient hydrophobicity, it is more preferable to use together an alkyltrialkoxysilane coupling agent represented by the following formula.
_{C p H 2p + 1 -Si- (} OC q H 2q + 1) 3
[Wherein p represents an integer of 2 to 20, and q represents an integer of 1 to 3]

  When p in the above formula is smaller than 2, the hydrophobizing treatment is easy, but it is difficult to sufficiently impart hydrophobicity, and it becomes difficult to suppress the exposure of the magnetic particles from the toner particles. On the other hand, when p is larger than 20, the hydrophobicity is sufficient, but the coalescence of the magnetic iron oxide particles increases, making it difficult to sufficiently disperse the magnetic iron oxide particles, and the particle size distribution is broad. become.

  On the other hand, when q is larger than 3, the reactivity of the silane coupling agent is lowered, and the hydrophobicity is not sufficiently performed.

  In particular, p in the formula represents an integer of 2 to 20 (more preferably an integer of 3 to 15), and q represents an integer of 1 to 3 (more preferably an integer of 1 or 2). A coupling agent should be used.

  The treatment amount is 0.05 to 20 parts by mass, preferably 0.1 to 10 parts by mass of the silane coupling agent with respect to 100 parts by mass of magnetic iron oxide. It is preferable to adjust the amount of the treatment agent in accordance with the reactivity of.

  Here, the aqueous medium is a medium containing water as a main component. Specific examples of the aqueous medium include water itself, water added with a small amount of a surfactant, water added with a pH adjusting agent, and water added with an organic solvent. As the surfactant, a nonionic surfactant such as polyvinyl alcohol is preferable. The surfactant is preferably added in an amount of 0.1 to 5% by mass with respect to water. Examples of the pH adjuster include inorganic acids such as hydrochloric acid, and examples of the organic solvent include alcohols.

  In the case where a plurality of types of silane coupling agents are used, a plurality of types of coupling agents are added simultaneously or with a time difference to perform magnetic iron oxide treatment.

  In the magnetic iron oxide thus obtained, no aggregation of particles is observed, and the surface of each particle is uniformly hydrophobized, so that the dispersibility of the magnetic iron oxide is good.

The magnetic iron oxide used in the magnetic polymerization toner of the present invention may contain elements such as phosphorus, cobalt, nickel, copper, magnesium, manganese, aluminum, and silicon. Magnetic iron oxide is composed mainly of iron oxide such as triiron tetroxide and γ-iron oxide, and these are used alone or in combination of two or more. These magnetic iron oxides preferably have a BET specific surface area of ² to 30 m ² / g, particularly 3 to 28 m ² / g, and a Mohs hardness of 5 to 7 by the nitrogen adsorption method.

  The magnetic iron oxide used in the magnetic polymerization toner of the present invention is preferably used in an amount of 10 to 200 parts by mass with respect to 100 parts by mass of the binder resin. More preferably, 20 to 180 parts by mass are used. If it is less than 10 parts by mass, the coloring power of the toner is poor, and it is difficult to suppress fogging. On the other hand, when the amount exceeds 200 parts by mass, not only the retention by the magnetic force on the toner carrier is increased and the developability is lowered, but it is difficult not only to uniformly disperse the magnetic iron oxide into individual toner particles, but also the fixability. It will decline.

  For example, in the case of magnetite, the magnetic iron oxide used in the magnetic polymerization toner according to the present invention is produced by the following method.

  An aqueous solution containing ferrous hydroxide is prepared by adding an alkali such as sodium hydroxide to the ferrous salt aqueous solution in an amount equivalent to or greater than the iron component. While maintaining the pH of the prepared aqueous solution at pH 7 or higher (preferably pH 8 to 14), air is blown in, and the aqueous ferrous hydroxide is oxidized while heating the aqueous solution to 70 ° C. or higher, whereby the core of the magnetic iron oxide particles First, a seed crystal is formed.

  Next, an aqueous solution containing about 1 equivalent of ferrous sulfate is added to the slurry-like liquid containing seed crystals based on the amount of alkali added previously. While maintaining the pH of the solution at 6 to 14, the reaction of ferrous hydroxide proceeds while blowing air, and magnetic iron oxide particles are grown with the seed crystal as the core. As the oxidation reaction proceeds, the pH of the liquid shifts to the acidic side, but the pH of the liquid is preferably not less than 6. Adjust the pH of the solution at the end of the oxidation reaction, stir well so that the magnetic iron oxide becomes primary particles, add the coupling agent, mix and stir well, filter after stirring, dry, Hydrophobic treated magnetic iron oxide particles are obtained by crushing. Alternatively, after the oxidation reaction is completed, the iron oxide particles obtained by washing and filtering are redispersed in another aqueous medium without drying, and then the pH of the redispersion is adjusted and the silane is stirred well. A coupling agent may be added to perform the coupling treatment. In any case, it is important to perform the surface treatment after the oxidation reaction without passing through the drying step, which is an important point in the toner of the present invention.

  As the ferrous salt, iron sulfate generally produced as a by-product in the production of sulfuric acid titanium, iron sulfate produced as a by-product with the surface cleaning of the steel sheet can be used, and iron chloride or the like can be used.

  In the method for producing magnetic iron oxide by the aqueous solution method, an iron concentration of 0.5 to 2 mol / l is generally used from the viewpoint of preventing the viscosity from increasing during the reaction and the solubility of iron sulfate. Generally, the lower the iron sulfate concentration, the finer the particle size of the product. Further, in the reaction, the larger the amount of air and the lower the reaction temperature, the easier the atomization.

  By using the magnetically polymerized toner made of the hydrophobic magnetic iron oxide produced in this way, stable toner charging property can be obtained, transfer efficiency is high, and high image quality and high stability are possible. .

  Examples of the polymerizable monomer constituting the polymerizable monomer system used in the magnetic polymerization toner of the present invention include the following.

  Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate, ethyl acrylate, Acrylic esters such as n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. , Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, Methacrylic acid dimethyl aminoethyl methacrylate esters such as diethylaminoethyl methacrylate and other acrylonitrile-methacrylonitrile-monomer acrylamide.

  In the production of the toner according to the present invention, a resin may be added to the monomer system for polymerization. For example, hydrophilic monomers such as amino groups, carboxylic acid groups, hydroxyl groups, sulfonic acid groups, glycidyl groups, and nitrile groups cannot be used to dissolve in aqueous suspension and cause emulsion polymerization because monomers are water-soluble. When it is desired to introduce a monomer component containing a group into the toner, a random copolymer of these and a vinyl compound such as styrene or ethylene, a block copolymer, a graft copolymer, or the like, Alternatively, it can be used in the form of a polycondensate such as polyester or polyamide, or a polyaddition polymer such as polyether or polyimine.

  The alcohol component and acid component which comprise the polyester resin used for this invention are illustrated below.

  As alcohol components, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexane Diol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, bisphenol derivatives;

［式中、Ｒはエチレン又はプロピレン基であり、ｘ，ｙはそれぞれ１以上の整数であり、且つｘ＋ｙの平均値は２〜１０である。］

[Wherein, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10. ]

  Or hydrogenated compound of formula (I), or diol of formula (II);

、或いは式（ＩＩ）の化合物の水添物のジオールが挙げられる。

Or hydrogenated diol of the compound of formula (II).

  As the divalent carboxylic acid, benzene dicarboxylic acid or village anhydride such as phthalic acid, terephthalic acid, isophthalic acid or phthalic anhydride; alkyl dicarboxylic acid such as succinic acid, adipic acid, sebacic acid or azelaic acid or anhydride thereof, Furthermore, succinic acid substituted with an alkyl or alkenyl group having 6 to 18 tannes or an anhydride thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or an anhydride thereof may be used.

  Furthermore, polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ethers of novolac type phenol resins can be cited as the alcohol component, and trimellitic acid, pyromellitic acid, 1,2,3,4- Examples thereof include polyvalent carboxylic acids such as butanetetracarboxylic acid, benzophenonetetracarboxylic acid and anhydrides thereof.

  It is preferable that 45-55 mol% of the said polyester resin is an alcohol component, and 55-45 mol% is an acid component in all the components.

  In the present invention, as long as the physical properties of the toner particles obtained are not adversely affected, it is also preferable to adjust the physical properties by using two or more kinds of polyester resins together, for example, by modifying with silicone or a fluoroalkyl group-containing compound. To be done.

  Moreover, when using the high molecular polymer containing such a polar functional group, the average molecular weight is preferably 5,000 or more.

  Resins other than those mentioned above may be added to the monomer system. Examples of the resin used include styrene such as polystyrene and polyvinyltoluene, and homopolymers of substitution products thereof; styrene-propylene copolymer, styrene -Vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer Polymer, styrene-vinyl methyl ether copolymer, styrene -Styrene such as vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Copolymer: polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol Resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins and the like can be used alone or in combination.

  As addition amount of these resin, 1-20 mass parts is preferable with respect to 100 mass parts of monomers. If the amount is less than 1 part by mass, the effect of addition is small, while if it is added more than 20 parts by mass, it becomes difficult to design various physical properties of the polymerized toner.

  Further, a polymer having a molecular weight different from the molecular weight range of the toner obtained by polymerizing the monomer may be dissolved in the monomer for polymerization.

  The polymerization initiator used in the production of the magnetic polymerization toner of the present invention has a half-life of 0.5 to 30 hours at the time of the polymerization reaction, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the polymerization reaction is carried out with a part addition amount, a polymer having a maximum between 10,000 and 100,000 in molecular weight can be obtained, and the toner can be provided with desirable strength and suitable melting characteristics. Examples of polymerization initiators include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo-based or diazo-based polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, Examples thereof include peroxide-based polymerization initiators such as cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, and t-butylperoxy 2-ethylhexanoate.

  In producing the magnetic polymerization toner of the present invention, a crosslinking agent may be added, and a preferable addition amount is 0.001 to 15% by mass with respect to 100 parts by mass of the polymerizable monomer.

  Here, as the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol diacrylate and ethylene glycol diacrylate. Carboxylic acid ester having two double bonds such as methacrylate and 1,3-butanediol dimethacrylate; divinyl compound such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and having three or more vinyl groups Are used alone or as a mixture.

  The magnetic polymerization toner obtained in the present invention can also be suitably used in the present invention by a seed polymerization method in which a monomer is further adsorbed to the polymer particles once obtained and then polymerized using a polymerization initiator. At this time, a polar compound can be dispersed or dissolved in the monomer to be adsorbed.

  When the magnetic polymer toner of the present invention is produced, it is one of the preferable usage forms to contain a release agent, and wax is mainly used as the release agent.

  Examples of the wax that can be used in the magnetic polymerization toner of the present invention include paraffin wax, microcrystalline wax, petroleum wax such as petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon wax and derivatives thereof by Fischer-Tropsch method, polyethylene And natural waxes such as carnauba wax and candelilla wax and derivatives thereof. Derivatives here include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, higher fatty alcohols, fatty acids such as stearic acid and palmitic acid or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes and animal waxes can also be used.

  In the toner of the present invention, the content of the wax component is preferably in the range of 0.5 to 50 parts by mass with respect to 100 parts by mass of the binder resin. When the content of the wax component is less than 0.5 parts by mass, the effect of suppressing the low temperature offset is poor, and when it exceeds 50 parts by mass, the long-term storage stability is lowered and the dispersibility of other toner materials is deteriorated. Lead to deterioration of fluidity and image characteristics.

  Furthermore, a charge control agent may be blended in the magnetic polymerization toner of the present invention. Known charge control agents can be widely used. Further, when the toner is produced using a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable. Specific compounds include, as negative charge control agents, metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, metal salts or metal complexes of azo dyes or azo pigments, sulfones Examples thereof include a polymer compound having an acid or carboxylic acid group in the side chain, a boron compound, a urea compound, a silicon compound, and a calixarene. Examples of positive charge control agents include quaternary ammonium salts, polymer compounds having the quaternary ammonium salt in the side chain, guanidine compounds, nigrosine compounds, imidazole compounds, and the like. As a method for incorporating the charge control agent into the toner, there are a method of adding it inside the toner base particles and a method of adding it externally. The amount of these charge control agents used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. When added internally, it is preferably used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin. In addition, when externally added, the amount is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.3 part by mass with respect to 100 parts by mass of the toner.

  In the suspension polymerization method, which is a preferred method for producing the magnetic polymerization toner of the present invention, generally, the above-described toner composition, that is, a magnetic iron oxide, a crosslinking agent, a release agent, and a charge control agent in the polymerizable monomer. Etc., components necessary for the toner and other additives, for example, an organic solvent, a high molecular weight polymer, a dispersing agent, etc., which are added to reduce the viscosity of the polymer produced by the polymerization reaction, are added as appropriate to dissolve or disperse uniformly. The caulked monomer system is suspended in an aqueous medium containing a dispersion stabilizer. At this time, the particle size of the obtained toner particles becomes sharper by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired toner particle size all at once. The polymerization initiator may be added at the same time when other additives are added to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Further, during the granulation, a polymerization initiator dissolved in a polymerizable monomer or a solvent can be added immediately after the granulation and before starting the polymerization reaction.

  After granulation, stirring may be performed using a normal stirrer to such an extent that the particle state is maintained and particle floating and sedimentation are prevented.

  In the production of the magnetic polymer toner of the present invention, known surfactants and organic / inorganic dispersants can be used as dispersion stabilizers. Among them, inorganic dispersants are unlikely to produce harmful ultrafine powders, and due to their steric hindrance. Since the dispersion stability is obtained, the stability is not easily lost even if the reaction temperature is changed, and the toner can be preferably used because it is easily washed and does not adversely affect the toner.

  Examples of such inorganic dispersants include polyvalent metal phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate, carbonates such as calcium carbonate and magnesium carbonate, calcium metasuccinate, calcium sulfate and barium sulfate. Inorganic oxides such as inorganic salts, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite and alumina can be mentioned.

  These inorganic dispersants are desirably used alone in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. However, although it is difficult to generate ultrafine particles, it is somewhat difficult to atomize the toner. Therefore, you may use 0.001-0.1 mass part surfactant together.

  Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

  When these inorganic dispersants are used, they may be used as they are, but in order to obtain finer particles, the inorganic dispersant particles can be generated and used in an aqueous medium. For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution can be mixed with high-speed stirring to produce water-insoluble calcium phosphate, which enables more uniform and fine dispersion. At the same time, a water-soluble sodium chloride salt is produced as a by-product. However, if a water-soluble salt is present in the aqueous medium, dissolution of the polymerizable monomer in water is suppressed, and an ultrafine toner based on emulsion polymerization is produced. Since it becomes difficult to generate | occur | produce, it is more convenient. Since it becomes an obstacle when removing the remaining polymerizable monomer at the end of the polymerization reaction, it is better to replace the aqueous medium or desalinate with an ion exchange resin. The inorganic dispersant can be almost completely removed by dissolving with an acid or an alkali after completion of the polymerization.

  In the polymerization step, the polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. When the polymerization is carried out in this temperature range, the release agent to be sealed inside is precipitated by phase separation, and the encapsulation becomes more complete. In order to consume the remaining polymerizable monomer, it is possible to raise the reaction temperature to 90 to 150 ° C. at the end of the polymerization reaction.

  Further, the polymerized toner obtained after the completion of the polymerization can be obtained by filtering, washing and drying by a known method, mixing the inorganic fine powder and adhering it to the surface. Moreover, it is one of the desirable forms of this invention to put a classification process in a manufacturing process and to cut coarse powder and fine powder.

  The coarse powder, fine powder, etc. cut in this step are used as “non-predetermined toner” in the recycling process during the production process of the magnetic polymerization toner according to the present invention.

  The magnetic polymer toner according to the present invention is preferably mixed with an inorganic fine powder or a hydrophobic inorganic fine powder as a fluidity improver. For example, titanium oxide fine powder, silica fine powder, and alumina fine powder are preferably added and used, and silica fine powder is particularly preferred.

  As the inorganic fine powder used in the magnetic polymerization toner of the present invention, those having a primary average particle size in the range of 4 to 80 nm are preferable because good results can be obtained. When the primary average particle size of the inorganic fine powder is larger than 80 nm, good toner fluidity cannot be obtained, and the toner particles are likely to be non-uniformly charged, and the triboelectric chargeability under low humidity becomes non-uniform. Therefore, problems such as an increase in fog, a decrease in image density, and a decrease in durability cannot be avoided. When the average primary particle size of the inorganic fine powder is smaller than 4 nm, the agglomeration property between the inorganic fine particles is increased, and the aggregate is not a primary particle but an aggregate having a wide particle size distribution having a strong agglomeration property that is difficult to break even by crushing treatment. It is easy to behave, and image defects are likely to occur due to development of the aggregate, damage to the image carrier or toner carrier, and the like. In order to make the charge distribution of the toner particles more uniform, the average primary particle size of the inorganic fine powder is preferably 6 to 35 nm.

  The measurement method of the average primary particle size of the inorganic fine powder is a photograph of the toner magnified by a scanning electron microscope, and further an element contained in the inorganic fine powder by an elemental analysis means such as XMA attached to the scanning electron microscope. The number average primary particle size can be determined by measuring 100 or more primary particles of inorganic fine powder that are attached to or separated from the toner surface while comparing the photograph of the toner mapped in step (1).

  The silica fine powder used in the present invention uses both a so-called dry process produced by vapor phase oxidation of a silicon halogen compound or dry silica called fumed silica and so-called wet silica produced from water glass. Although possible, dry silica is preferred because it has few silanol groups on the surface and inside and no production residue.

  Furthermore, the silica fine powder used in the present invention is preferably hydrophobized because of its characteristics in a high temperature and high humidity environment. When the inorganic fine powder added to the toner particles absorbs moisture, the charge amount of the toner particles decreases and the image density decreases. The hydrophobizing treatment is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, an organosilicon compound such as a silicone oil or an organotitanium compound is used after a dry silica fine powder produced by vapor phase oxidation of a silicon halide compound is treated with a silane coupling agent or simultaneously with a silane coupling agent. A method of treating with a treating agent such as singly or in combination.

  Examples of silane coupling agents used for hydrophobizing treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, and allylphenyldichlorosilane. , Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, Dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyl Examples thereof include tetramethyldisiloxane and 1,3-diphenyltetramethyldisiloxane.

Examples of the organosilicon compound include silicone oil. Preferred silicone oils, those viscosity at 25 ° C. is 10~200,000mm ² / s, more preferably from 3,000~80,000mm ² / s. If it is less than 10 mm ² / s, the inorganic fine particles are not stable, and the image quality tends to deteriorate due to heat and mechanical stress. If it exceeds 200,000 mm ² / s, uniform processing tends to be difficult.

  As the silicone oil used, for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil are preferable.

  Silicone oil treatment can be performed by, for example, mixing silica fine powder treated with a silane coupling agent and silicone oil directly using a mixer such as a Henschel mixer, or injecting silicone oil onto the base silica. Depending on how you do it. Alternatively, the silicone oil may be dissolved or dispersed in a suitable solvent, and then mixed with the base silica fine powder to remove the solvent. A method using a sprayer is more preferable in that the formation of inorganic fine particle aggregates is relatively small.

  The treatment amount of the silicone oil is 1 to 40 parts by mass, preferably 3 to 35 parts by mass with respect to 100 parts by mass of silica.

  The amount of these inorganic fine particles added to the magnetic polymer toner is preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the magnetic polymer toner, and the addition amount of less than 0.1% by mass is sufficient. Since fluidity is not imparted and the charge rising property due to frictional charging between the toner particles is deteriorated, it causes fogging to the non-image area. On the other hand, when the content is 3.0% by weight or more, the heat conductivity to the toner is lowered, which causes a problem that the fixing property is deteriorated.

  The content of the inorganic fine powder can be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

  In addition, the magnetic polymer toner of the present invention may further contain other additives such as a lubricant powder such as a polyethylene fluoride powder, a zinc stearate powder, and a polyvinylidene fluoride powder, or cerium oxide within a range that does not substantially adversely affect the toner. Abrasives such as powders, silicon carbide powders, strontium titanate powders, or fluidity-imparting agents such as titanium oxide powders and aluminum oxide powders, anti-caking agents, and organic particles of opposite polarity and inorganic fine particles are improved in developability. A small amount can be used as an agent. These additives can also be used after hydrophobizing the surface.

(1) Method for Measuring Toner Particle Size The average particle size and particle size distribution of toner can be measured by various methods such as Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Co., Ltd.). Using Multisizer (manufactured by Coulter), connecting an interface (manufactured by Nikka) and a PC9801 personal computer (manufactured by NEC) that outputs number distribution and volume distribution, the electrolyte is 1% NaCl using first grade sodium chloride. Prepare an aqueous solution. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is dispersed for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toners are measured by using the 100 μm aperture as the aperture by the Coulter Multisizer. The volume distribution and the number distribution are calculated. Then, the number average particle diameter (D1) obtained from the number distribution, the volume-based volume average diameter obtained from the volume distribution (D4: the median value of each channel is a representative value for each channel), and the volume basis obtained from the volume distribution. The volume distribution of 12.7 μm or more is obtained.

(2) Confirmation of dispersibility in the polymerizable monomer dispersion The polymerizable monomer dispersion immediately before the granulation step is sampled, placed on a slide glass and stretched thinly, and immediately observed with an optical microscope. The dispersion state was confirmed visually. When the dispersion is uniform, the sample is uniform, and no solid components such as colorants and other additives are observed. On the other hand, when the dispersion is non-uniform or insufficient, solid components are scattered and the resin residue can be visually confirmed.

(3) Observation of white spheres during granulation

  The polymerizable monomer dispersion at the time of the granulation step was sampled, placed on a slide glass and stretched thinly, and the state of granulation was confirmed visually by observing the state immediately with an optical microscope. When the dispersion is uniform, the particle sample is uniform, but when the dispersion is nonuniform or insufficient, white spheres can be visually confirmed.

(4) Method for measuring THF-insoluble content The THF-insoluble content refers to the mass ratio of the ultra-high polymer component (substantially crosslinked polymer) that has become insoluble in the THF solvent in the resin composition in the toner particles. The THF-insoluble content is defined by the values measured as follows.

About 1.5 gram of the toner sample is weighed (W1 g), put into a cylindrical filter paper (for example, Toyo Filter Paper No. 86R), passed through a Soxhlet extractor, extracted for 20 hours using 100 to 200 ml of toluene as a solvent, After evaporating the extracted soluble component, vacuum drying is performed at 100 ° C. for several hours, and the amount of the THF soluble resin component is weighed (W2 g). The mass of a component insoluble in THF such as a pigment in the toner is defined as (W3 g). The THF-insoluble content can be obtained from the following formula.
THF insoluble content = {W1- (W3-W2)} / (W1-W3) × 100

(5) Method for measuring fog on paper The measurement of fog was carried out using REFECTECTOMER MODELTC-6DS manufactured by Tokyo Denshoku. The filter was calculated from the following formula using a green filter.
Fog (reflectance) (%) = reflectance on standard paper (%)-reflectance of sample non-image area (%)

  If the fog is 2.0% or less, a good image is obtained.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but this does not limit the present invention in any way. In addition, all the parts in the following mixing | blending are a mass part.

(Production Example 1 of surface-treated magnetic iron oxide)
An aqueous solution containing ferrous hydroxide was prepared by mixing a ferrous sulfate aqueous solution with a caustic soda solution of 1.0 to 1.1 equivalents with respect to iron ions.

  While maintaining the aqueous solution at pH 9, air was blown and an oxidation reaction was performed at 80 to 90 ° C. to prepare a slurry liquid for generating seed crystals.

Subsequently, after adding ferrous sulfate aqueous solution to this slurry liquid so that it may become 0.9-1.2 equivalent with respect to the original alkali amount (sodium component of caustic soda), the slurry liquid is maintained at pH 8 and air The pH is adjusted to about 6 at the end of the oxidation reaction, and the silane coupling agent [n-C ₄ H ₉ Si (OCH ₃ ) ₃ ] is added to 0.5 parts of magnetic iron oxide. Part was added and stirred well. The produced hydrophobic iron oxide particles were washed, filtered and dried by a conventional method, and then the agglomerated particles were pulverized to obtain surface-treated magnetic iron oxide 1.

(Production example 2 of surface-treated magnetic iron oxide)
The oxidation reaction proceeds in the same manner as in Production Example 1, and the magnetic iron oxide particles generated after the oxidation reaction are washed, filtered, taken out once, redispersed in another water without drying, and then the pH of the redispersion is adjusted. Then, 0.5 part of a silane coupling agent [n-C ₆ H ₁₃ Si (OCH ₃ ) ₃ ] was added with sufficient stirring to perform a coupling treatment. The produced hydrophobic iron oxide particles were washed, filtered and dried by a conventional method, and then the agglomerated particles were lightly crushed to obtain surface-treated magnetic iron oxide 2.

(Production Example 3 of Surface-treated Magnetic Iron Oxide)
A surface-treated magnetic iron oxide 3 was obtained in the same manner as in Production Example 2 except that [n-C ₁₀ H ₂₁ Si (OCH ₃ ) ₃ ] was used as the silane coupling agent.

<Example 1>
[Main process]
A dispersion / dissolution apparatus shown in FIG. 2 was used.

Styrene: 80 parts Negative charge control agent (monoazo dye-based Fe compound) 1 part n-butyl acrylate: 20 parts Unsaturated polyester resin: 1 part Saturated polyester resin: 5 parts Surface treated magnetic iron oxide 1: 80 parts Is introduced into the treated product tank (22), hot water is introduced into the treated product tank jacket (21) from the hot water / cooling water introduction port (27), discharged from the discharge port (28), and treated product (23 ) Is heated to about 60 ° C. over 30 minutes, the motor (24) is operated, the agitation shaft (25) is rotated at about 36.7 rpm, and the anchor blade (30) is rotated at about 1.5 rpm to give a pigment. Started to disperse. Further, the agitating blade (26) was an edged turbine shown in FIG. 5 and had a treatment tank inner diameter of 600 mm and a stirring blade diameter of 130 mm, and d / D = 0.22. At this time, the peripheral speed of the stirring blade (16) was about 15 m / s.

  Next, when the temperature of the treated product reached 60 ° C., 10 parts of ester wax (maximum endothermic peak value in DSC 72 ° C.): 10 parts were added and the operation was continued. After 90 minutes, the polymerization initiator benzoyl par Oxide: 5 parts was added to obtain a particulate polymerizable monomer mixture.

On the other hand, in a container equipped with a high-speed stirring device TK-homomixer, 450 parts by mass of 0.1 mol-Na3PO4 aqueous solution and 16 parts by mass of 1N hydrochloric acid were added to 720 parts of ion-exchanged water, and the rotation speed was adjusted to 200 rps. It was warmed to ℃. To this was added 68 parts by mass of a 1.0 mol / liter-CaCl 2 aqueous solution to prepare a dispersion medium system containing a slight sparingly water-soluble dispersant Ca ₃ (PO ₄ ) ₂ . The finely divided polymerizable monomer mixture heated to a temperature of 60 ° C. was put into a dispersion medium system heated to a temperature of 60 ° C., and granulated for 15 minutes while rotating the TK-homomixer at 240 rpm.

  Then, the stirrer was changed from the high-speed stirrer to the propeller stirring blade, the temperature was raised to 80 ° C., and the reaction was performed for 8 hours. After the polymerization was completed, a part of the slurry was sampled, a small amount of sampling was performed, the particle size distribution was measured, and the droplets during granulation were observed with an optical microscope. As a result, no white spheres were present and the white spheres were uniformly dispersed. The results are shown in Table 2.

  After the polymerization reaction weight, the residual monomer was distilled off under reduced pressure. After cooling, diluted hydrochloric acid was added to dissolve the dispersant, and solid-liquid separation, water washing, filtration, drying, and classification were performed to obtain a magnetic polymerization toner. . After classification, when the particle size distribution of fine powder and coarse powder having a predetermined external particle size was measured with a Coulter Multisizer, the average particle sizes of the fine powder and coarse powder were D4 = 4.65 μm and 16.00 μm, respectively. At the end of the polymerization, a small amount of sampling was performed, and the particle size distribution was measured with a Coulter Multisizer. The results are shown in Table 2.

  Thereafter, 100 parts of the magnetic polymerized toner and silica having a primary particle diameter of 12 nm were treated with hexamethyldisilazane and then treated with silicone oil, and a hydrophobic silica fine powder having a treated BET value of 120 m 2 / g. 0 part was mixed with a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) to prepare as a developer.

  Using this developer, an image was printed in a low humidity environment (15 ° C./10% RH) and a high humidity environment (30 ° C./80% RH) with a modified LBP 1760 manufactured by Canon Inc. After the completion of image output, the image density was measured at the initial stage and after 1000 sheets were passed. The evaluation results are shown in Table 2.

[Example of production of non-prescribed toner adjustment powder 1]
The process of reusing fine powder and coarse powder after classification, which are non-predetermined particle toner, bug fine powder attached to the blower of the classifier, and scale (classified as other) attached to the wall surface of the kettle after the reaction will be described below.

  The fine powder, coarse powder and others obtained in the [main process] step of Example 1 were used as the non-predetermined toner in the reuse process. However, in the non-predetermined toner adjustment powder 1, only the fine powder (4.65 μm) was used. It was re-interested.

First, the amount of magnetic iron oxide in fine powder was approximately determined from TGA-7.
Magnetic iron oxide content in fine powder = 59 parts

  In the non-predetermined toner adjustment powder 1, only fine powder is used as the non-predetermined toner, so that no premixing is performed.

  The amount of non-predetermined toner fed to the kneading apparatus was set to 5 kg for one batch because of the batch on the apparatus scale.

  Next, the non-predetermined toner was fed to a general kneader (PCM-35, manufactured by Ikekai Tekko Co., Ltd.) and kneaded, and kneaded until there was no insoluble matter. Thereafter, the toner was pulverized by a general pulverizer (speed mill, manufactured by Okada Seiko Co., Ltd.) to obtain an unspecified toner adjustment powder 1 having a diameter of about 2 mm. The kneader is not limited to the apparatus as long as it has a strong shearing ability. Details of the quantity ratio are shown in Table 1.

  Here, it can be seen that the amount of magnetic iron oxide in the non-predetermined toner varies from 80 parts of the surface-treated magnetic iron oxide charged in Example 1.

  That is, when the non-predetermined toner adjustment powder is used as it is at the time of reuse, if the amount of the surface-treated magnetic iron oxide in the polymerization process is 80 parts, the content of the surface-treated magnetic iron oxide after reuse is As a result, the desired triboelectric charging characteristics and the like cannot be obtained.

  Therefore, in the present invention, the amount of magnetic iron oxide in the non-predetermined toner is derived in the polymerization step in which the non-predetermined toner is reused, and by increasing or decreasing the amount, the surface-treated magnetic iron oxide introduced in the polymerization step in the reuse process The amount ratio is adjusted by increasing / decreasing, and the amount of magnetic iron oxide is equal to the prescription amount in the toner after reuse.

  The correction method will be described below using the non-predetermined toner adjustment powder as an example.

  First, the content of magnetic iron oxide in the non-predetermined toner derived by TGA-7 measurement is 59 parts. Since the prescription amount in the actual preparation is 80 parts, it can be seen that the ratio is 0.74. If the prescription amount is 100%, the shortage rate is 0.26, and the amount of magnetic iron oxide to which the shortage is added is 0.26 × 0.8 × 100 = 20.8. The amount added to 80 parts of the surface-treated magnetic iron oxide sometimes used is 20.8 parts, for a total of 100.8 parts.

  The same means is used in the following non-predetermined toner adjustment powder production examples, and the corrected amount of surface-treated magnetic iron oxide is shown in Table 1.

<Example 2>
The same operation as in Example 1 was performed except that the formulation was changed as follows. The amount of the surface-treated magnetic iron oxide 1 was increased from 80 parts to 100.8 parts by changing 5% of the toner raw material of Example 1 to 202 parts to the non-prescribed toner adjustment powder 1 with respect to 202 parts of the toner raw material. Table 2 summarizes the evaluation results of the toner.
Non-specified toner adjustment powder 1: 10 parts (5% of toner raw material)
Styrene: 80 × 0.95 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.95 parts n-butyl acrylate: 20 × 0.95 parts Unsaturated polyester resin: 1 × 0.95 parts saturated Polyester resin: 5 × 0.95 parts Surface-treated magnetic iron oxide 1: 100.8 × 0.95 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.95 parts benzoyl peroxide: 5 × 0.95 parts

<Example 3>
The same operation as in Example 2 was performed except that the formulation was changed as follows. The amount of the surface-treated magnetic iron oxide 1 was increased from 80 parts to 100.8 parts by changing 10% of the toner raw material of Example 2 to 202% to the non-prescribed toner adjustment powder 1. Table 2 summarizes the evaluation results of the toner.
Non-specified toner adjustment powder 1: 20 parts (10% of toner raw material)
Styrene: 80 × 0.90 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.90 parts n-butyl acrylate: 20 × 0.90 parts Unsaturated polyester resin: 1 × 0.90 parts saturated Polyester resin: 5 × 0.90 parts Surface-treated magnetic iron oxide 1: 100.8 × 0.90 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.90 parts benzoyl peroxide: 5 × 0.90 parts

<Example 4>
The same operation as in Example 2 was performed except that the formulation was changed as follows. The amount of the surface-treated magnetic iron oxide 1 was increased from 80 parts to 100.8 parts by changing 20% of the toner raw material of Example 2 to 202% to the non-prescribed toner adjustment powder 1. Table 2 summarizes the evaluation results of the toner.
Non-specified toner adjustment powder 1: 40 parts (20% of toner raw material)
Styrene: 80 × 0.80 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.80 parts n-butyl acrylate: 20 × 0.80 parts Unsaturated polyester resin: 1 × 0.80 parts saturated Polyester resin: 5 × 0.80 parts Surface-treated magnetic iron oxide 1: 100.8 × 0.80 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.80 parts benzoyl peroxide: 5 × 0.80 parts

<Example 5>
The same operation as in Example 2 was performed except that the formulation was changed as follows. The amount of the surface-treated magnetic iron oxide 1 was increased from 80 parts to 100.8 parts by changing 30% of the toner raw material of Example 2 to 30% to the non-prescribed toner adjustment powder 1. Table 2 summarizes the evaluation results of the toner.
Non-specified toner adjustment powder 1: 60 parts (30% of toner raw material)
Styrene: 80 x 0.70 parts
Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.70 part n-butyl acrylate: 20 × 0.70 part Unsaturated polyester resin: 1 × 0.70 part Saturated polyester resin: 5 × 0.70 Part
Surface-treated magnetic iron oxide 1: 100.8 × 0.70 parts ester wax (maximum endothermic peak at 72 ° C. in DSC): 10 × 0.70 parts benzoyl peroxide: 5 × 0.70 parts

<Example 6>
In the same manner as in Example 3, the amount of the surface-treated magnetic iron oxide 1 was increased from 80 parts to 100.8 parts by changing 10% of the toner raw material of Example 3 to 202% of the toner raw material of Example 3 to the non-prescribed toner adjustment powder 1. did.
Non-specified toner adjustment powder 1: 20 parts (10% of toner raw material)
Styrene: 80 × 0.90 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.90 parts n-butyl acrylate: 20 × 0.90 parts Unsaturated polyester resin: 1 × 0.90 parts saturated Polyester resin: 5 × 0.90 parts Surface-treated magnetic iron oxide 1: 100.8 × 0.90 parts

  After filling 20 kg of media particles (31) (made of zirconia) having a diameter of 1 mm (filling amount 55%) into the media-type disperser shown in FIG. 3, the above components are put into the treatment tank (32), and the atmospheric pressure state Then, the treatment tank (32) was stirred at a peripheral speed of 1.5 m / s for 60 minutes for dispersion. Subsequently, it transferred to the apparatus shown in FIG. 4, and started the motor (40), heating up to 60 degree | times over 30 minutes, and started stirring of the stirring blade (41) at 1.5 rps.

  Next, when the temperature of the treated product reached 60 ° C., ester wax (maximum endothermic peak value of 72 ° C. in DSC: 72 ° C.): 10 × 0.90 parts were added, and the operation was continued. Initiator benzoyl peroxide: 5 × 0.90 parts were added to obtain a finely polymerizable monomer mixture. After this, the same operation as in Example 1 was performed. Table 2 summarizes the evaluation results of the toner.

[Method for Producing Non-Prescribed Toner Adjustment Powder 2]
Separately, fine powder (4.55 μm) and coarse powder (16.00 μm) obtained in the same steps as in [Main process] of Example 1 were used in the reuse process as non-predetermined toner.

First, the amount of magnetic iron oxide in fine powder and coarse powder was approximately determined from TGA-7.
Magnetic iron oxide content in fine powder = 57 parts Magnetic iron oxide content in coarse powder = 69 parts

  Next, the amount ratio of the non-predetermined toner fed to the kneading apparatus is determined.

  The above fine powder and coarse powder are uniformly mixed with a general mixer (Henschel mixer, ribbon mixer, etc.) at a mixing ratio of fine powder = 0.64 and coarse powder = 0.36 from the production results. To obtain a non-predetermined toner mixture.

  Further, the non-predetermined toner mixture was fed to a general kneader (PCM-35, manufactured by Ikegai Iron Works Co., Ltd.) and kneaded until kneading disappeared. Thereafter, the toner was pulverized by a general pulverizer (speed mill, manufactured by Okada Seiko Co., Ltd.) to obtain an unspecified toner adjustment powder 2 having a diameter of about 2 mm. Details of the quantitative ratio are shown in Table 1.

<Example 7>
The same operation as in Example 2 was performed except that the formulation was changed as follows. The amount of the surface-treated magnetic iron oxide 1 was increased from 80 parts to 97.2 parts by changing 5% of the toner raw material of Example 2 to 202% to the non-prescribed toner adjustment powder 2. Table 2 summarizes the evaluation results of the toner.
Non-specified toner adjustment powder 2: 10 parts (5% of toner raw material)
Styrene: 80 × 0.95 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.95 parts n-butyl acrylate: 20 × 0.95 parts Unsaturated polyester resin: 1 × 0.95 parts saturated Polyester resin: 5 × 0.95 parts Surface-treated magnetic iron oxide 1: 90.2 × 0.95 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.95 parts benzoyl peroxide: 5 × 0.95 parts

[Method for Producing Non-Prescribed Toner Adjustment Powder 3]
Separately, fine powder (4.49 μm), coarse powder (16.00 μm) and others (12.53 μm, bug fine powder and scale) obtained in the same steps as in [Main process] of Example 1 were re-used as non-predetermined toners. We decided to use it for the usage process.

First, the amount of fine powder, coarse powder and other magnetic iron oxides were approximately determined from TGA-7.
Magnetic iron oxide content in fine powder = 64 parts Magnetic iron oxide content in coarse powder = 75 parts Other magnetic iron oxide content = 79 parts

  Next, the amount ratio of the non-predetermined toner fed to the kneading apparatus is determined.

  The above fine powder, coarse powder and others are mixed with a general mixer (Henschel mixer) according to the actual production value, with fine powder = 0.62, coarse powder = 0.31, other = 0.07. , A ribbon type mixer, etc.) to obtain a non-predetermined toner mixture.

  Further, the non-predetermined toner mixture was fed to a general kneader (PCM-35, manufactured by Ikegai Iron Works Co., Ltd.) and kneaded until kneading disappeared. Thereafter, the toner was pulverized by a general pulverizer (speed mill, manufactured by Okada Seiko Co., Ltd.) to obtain a non-prescribed toner adjustment powder 3 having a diameter of about 2 mm. Details of the quantitative ratio are shown in Table 1.

<Example 8>
The same operation as in Example 3 was performed except that the formulation was changed as follows. The amount of the surface-treated magnetic iron oxide 1 was increased from 80 parts to 87.2 parts by changing 10% of the toner raw material of Example 3 to the non-prescribed toner adjustment powder 3 for 202%. Table 2 summarizes the evaluation results of the toner.
Non-specified toner adjustment powder 3: 20 parts (10% of toner raw material)
Styrene: 80 × 0.90 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.90 parts n-butyl acrylate: 20 × 0.90 parts Unsaturated polyester resin: 1 × 0.90 parts saturated Polyester resin: 5 × 0.90 parts Surface-treated magnetic iron oxide 1: 87.2 × 0.90 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.90 parts benzoyl peroxide: 5 × 0.90 parts

<Example 9>
The same operation as in Example 4 was performed except that the formulation was changed as follows. The amount of the surface-treated magnetic iron oxide 1 was increased from 80 parts to 87.2 parts by changing 20% of the toner raw material of Example 4 to 20% to the non-prescribed toner adjustment powder 3. Table 2 summarizes the evaluation results of the toner.
Non-specified toner adjustment powder 3: 40 parts (20% of toner raw material)
Styrene: 80 × 0.80 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.80 parts n-butyl acrylate: 20 × 0.80 parts Unsaturated polyester resin: 1 × 0.80 parts saturated Polyester resin: 5 × 0.80 parts Surface-treated magnetic iron oxide 1: 87.2 × 0.80 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.80 parts benzoyl peroxide: 5 × 0.80 parts

[Method for Producing Non-Prescribed Toner Adjustment Powder 4]
Separately, fine powder (4.83 μm), coarse powder (16.00 μm) and others (13.56 μm, bug fine powder and scale) obtained in the same steps as those in [Main process] of Example 1 were re-used as non-predetermined toners. We decided to use it for the usage process.

First, the amount of fine powder, coarse powder and other magnetic iron oxides were approximately determined from TGA-7.
Magnetic iron oxide content in fine powder = 50 parts Magnetic iron oxide content in coarse powder = 85 parts Other magnetic iron oxide content = 88 parts

  Next, the amount ratio of the non-predetermined toner fed to the kneading apparatus is determined.

  The above-mentioned fine powder, coarse powder and others are obtained from the actual production values. Fine powder, coarse powder and others are mixed at a mixing ratio of fine powder = 0.60, coarse powder = 0.35, other = 0.05. , A ribbon type mixer, etc.) to obtain a non-predetermined toner mixture.

  Further, the non-predetermined toner mixture was fed to a general kneader (PCM-35, manufactured by Ikegai Iron Works Co., Ltd.) and kneaded until kneading disappeared. Thereafter, the toner was pulverized by a general pulverizer (speed mill, manufactured by Okada Seiko Co., Ltd.) to obtain an unspecified toner adjustment powder 4 having a diameter of about 2 mm. Details of the quantitative ratio are shown in Table 1.

[Method for Producing Non-Prescribed Toner Adjustment Powder 5]
Separately, fine powder (4.71 μm) and coarse powder (16.00 μm) obtained in the same steps as those in [Main process] of Example 1 were used in the reuse process as non-predetermined toner.

First, the amount of magnetic iron oxide in fine powder and coarse powder was approximately determined from TGA-7.
Magnetic iron oxide content in fine powder = 88 parts Magnetic iron oxide content in coarse powder = 70 parts

  Next, the amount ratio of the non-predetermined toner fed to the kneading apparatus is determined.

  The above fine powder and coarse powder are uniformly mixed with a general mixer (Henschel mixer, ribbon mixer, etc.) at a mixing ratio of fine powder = 0.61 and coarse powder = 0.35 from the actual production values. To obtain a non-predetermined toner mixture.

  Further, the non-predetermined toner mixture was fed to a general kneader (PCM-35, manufactured by Ikegai Iron Works Co., Ltd.) and kneaded until kneading disappeared. Thereafter, the toner was pulverized by a general pulverizer (speed mill, manufactured by Okada Seiko Co., Ltd.) to obtain an unspecified toner adjusting powder 5 having a diameter of about 2 mm. Details of the quantitative ratio are shown in Table 1.

[Method for Producing Non-Prescribed Toner Adjustment Powder 6]
Separately, fine powder 1 (4.71 μm) and fine powder 2 (4.83 μm) obtained in the same steps as those in [Main process] of Example 1 were used in the reuse process as non-predetermined toners.
First, the amount of magnetic iron oxide in fine powder and coarse powder was approximately determined from TGA-7.
Magnetic iron oxide content in fine powder 1 = 88 parts Magnetic iron oxide content in fine powder 2 = 50 parts

  Next, since the amount ratio of the non-predetermined toner fed to the kneading apparatus is the same type of non-predetermined toner, the fine powder 1 and the fine powder 2 are mixed at a mixing ratio of fine powder 1 = 0.5 and fine powder = 0.5. Using a mixer (Henschel mixer, ribbon mixer, etc.), the mixture was uniformly mixed to obtain a toner mixture other than the predetermined toner.

  Further, the non-predetermined toner mixture was fed to a general kneader (PCM-35, manufactured by Ikegai Iron Works Co., Ltd.) and kneaded until kneading disappeared. Thereafter, the toner was pulverized by a general pulverizer (speed mill, manufactured by Okada Seiko Co., Ltd.) to obtain an unspecified toner adjusting powder 6 having a diameter of about 2 mm. Details of the quantitative ratio are shown in Table 1.

[Method for Producing Non-Prescribed Toner Adjustment Powder 7]
Separately, coarse powder 1 (16.00 μm) and coarse powder 2 (16.00 μm) obtained in the same steps as those in [Main process] of Example 1 were used as non-predetermined toners in the reuse process.

First, the amount of magnetic iron oxide in fine powder and coarse powder was approximately determined from TGA-7.
Amount of magnetic iron oxide in coarse powder 1 = 69 parts Amount of magnetic iron oxide in coarse powder 2 = 85 parts

  Next, since the amount ratio of the non-predetermined toner fed to the kneading apparatus is the same non-predetermined toner, the coarse powder 1 and the coarse powder 2 are mixed at a mixing ratio of coarse powder 1 = 0.5 and coarse powder = 0.5. Then, the mixture was uniformly mixed by a general mixer (Henschel mixer, ribbon type mixer, etc.) to obtain a non-predetermined toner mixture.

  Further, the non-predetermined toner mixture was fed to a general kneader (PCM-35, manufactured by Ikekai Tekko Co., Ltd.) and kneaded, and kneaded until there was no insoluble matter. Thereafter, the toner was pulverized by a general pulverizer (speed mill, manufactured by Okada Seiko Co., Ltd.) to obtain an unspecified toner adjusting powder 7 having a diameter of about 2 mm. Details of the quantitative ratio are shown in Table 1.

<Example 10>
The same operation as in Example 7 was performed except that the formulation was changed as follows. The amount of the surface-treated magnetic iron oxide 1 was increased from 80 parts to 88.0 parts by changing 5% of the toner raw material 202 of Example 7 to the toner powder 4 outside the predetermined amount. Table 2 summarizes the evaluation results of the toner.
Non-specified toner adjustment powder 4: 10 parts (5% of toner raw material)
Styrene: 80 × 0.95 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.95 parts n-butyl acrylate: 20 × 0.95 parts Unsaturated polyester resin: 1 × 0.95 parts saturated Polyester resin: 5 × 0.95 parts Surface-treated magnetic iron oxide 1: 88.0 × 0.95 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.95 parts benzoyl peroxide: 5 × 0.95 parts

<Example 11>
The same operation as in Example 7 was performed except that the formulation was changed as follows. The amount of the surface-treated magnetic iron oxide 1 was increased from 80 parts to 80.8 parts by changing 5% of the toner raw material of Example 7 to 202% to the non-prescribed toner adjustment powder 5 with respect to 202 parts of the toner raw material. Table 2 summarizes the evaluation results of the toner.
Non-specified toner adjustment powder 5: 10 parts (5% of toner raw material)
Styrene: 80 × 0.95 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.95 parts n-butyl acrylate: 20 × 0.95 parts Unsaturated polyester resin: 1 × 0.95 parts saturated Polyester resin: 5 × 0.95 parts Surface-treated magnetic iron oxide 1: 80.8 × 0.95 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.95 parts benzoyl peroxide: 5 × 0.95 parts

<Example 12>
In Example 6, toner was obtained and evaluated in the same manner except that non-predetermined toner adjustment powder 2 was used instead of non-predetermined toner adjustment powder 1 and the amount of surface-treated magnetic iron oxide was 97.2 parts. . The evaluation results are summarized in Table 2.

<Example 13>
In Example 6, toner was obtained and evaluated in the same manner except that non-predetermined toner adjustment powder 3 was used instead of non-predetermined toner adjustment powder 1 and the amount of surface-treated magnetic iron oxide was 87.2 parts. . The evaluation results are summarized in Table 2.

<Example 14>
In Example 6, instead of the non-predetermined toner adjustment powder 1, the non-predetermined toner adjustment powder 4 for 5% of the toner raw material was used, and the amount of the surface-treated magnetic iron oxide was changed to 88.0 parts. A toner was obtained and evaluated. The evaluation results are summarized in Table 2.

<Example 15>
In Example 6, instead of the non-specified toner adjustment powder 1, the non-specific toner adjustment powder 5 for 5% of the toner raw material was used, and the amount of the surface-treated magnetic iron oxide was changed to 80.8 parts. A toner was obtained and evaluated. The evaluation results are summarized in Table 2.

<Example 16>
In Example 6, instead of the non-predetermined toner adjustment powder 1, the non-predetermined toner adjustment powder 3 for 5% of the toner raw material was used, and the amount of the surface-treated magnetic iron oxide was changed to 87.2 parts. A toner was obtained and evaluated. The evaluation results are summarized in Table 2.

<Example 17>
In Example 2, toner was obtained and evaluated in the same manner except that surface-treated magnetic iron oxide 2 was used instead of surface-treated magnetic iron oxide 1 and the amount of surface-treated magnetic iron oxide was 97.2 parts. . The evaluation results are summarized in Table 2.

<Example 18>
In Example 7, toner was obtained and evaluated in the same manner except that surface-treated magnetic iron oxide 2 was used instead of surface-treated magnetic iron oxide 1 and the amount of surface-treated magnetic iron oxide was 97.2 parts. . The evaluation results are summarized in Table 2.

<Example 19>
In Example 10, a toner was obtained and evaluated in the same manner except that the surface-treated magnetic iron oxide 2 was used instead of the surface-treated magnetic iron oxide 1 and the amount of the surface-treated magnetic iron oxide was 97.2 parts. . The evaluation results are summarized in Table 2.

<Example 20>
In Example 2, a toner was obtained and evaluated in the same manner except that the surface-treated magnetic iron oxide 3 was used instead of the surface-treated magnetic iron oxide 1 and the amount of the surface-treated magnetic iron oxide was 87.2 parts. . The evaluation results are summarized in Table 2.

<Example 21>
In Example 7, a toner was obtained and evaluated in the same manner except that the surface-treated magnetic iron oxide 3 was used instead of the surface-treated magnetic iron oxide 1 and the amount of the surface-treated magnetic iron oxide was 87.2 parts. . The evaluation results are summarized in Table 2.

<Example 22>
In Example 10, a toner was obtained and evaluated in the same manner except that the surface-treated magnetic iron oxide 3 was used instead of the surface-treated magnetic iron oxide 1 and the amount of the surface-treated magnetic iron oxide was changed to 87.2 parts. . The evaluation results are summarized in Table 2.

<Example 23>
In Example 2, toner was obtained and evaluated in the same manner except that non-prescribed toner adjustment powder 6 was used instead of non-predetermined toner adjustment powder 1 and the amount of surface-treated magnetic iron oxide was 90.4 parts. . The evaluation results are summarized in Table 2.

<Example 24>
In Example 2, toner was obtained and evaluated in the same manner except that non-prescribed toner adjustment powder 7 was used instead of non-predetermined toner adjustment powder 1 and the amount of surface-treated magnetic iron oxide was 83.2 parts. . The evaluation results are summarized in Table 2.

<Example 25>
In Example 3, toner was obtained and evaluated in the same manner except that non-predetermined toner adjustment powder 6 was used instead of non-predetermined toner adjustment powder 1 and the amount of surface-treated magnetic iron oxide was 90.4 parts. . The evaluation results are summarized in Table 2.

<Example 26>
In Example 3, toner was obtained and evaluated in the same manner except that non-predetermined toner adjustment powder 7 was used instead of non-predetermined toner adjustment powder 1 and the amount of surface-treated magnetic iron oxide was 83.2 parts. . The evaluation results are summarized in Table 2.

<Example 27>
In Example 14, a toner was obtained and evaluated in the same manner except that the non-predetermined toner adjustment powder 6 was used instead of the non-predetermined toner adjustment powder 4 and the amount of the surface-treated magnetic iron oxide was 90.4 parts. . The evaluation results are summarized in Table 2.

<Example 28>
In Example 14, a toner was obtained and evaluated in the same manner except that the non-predetermined toner adjustment powder 7 was used in place of the non-predetermined toner adjustment powder 4 and the amount of surface-treated magnetic iron oxide was 83.2 parts. . The evaluation results are summarized in Table 2.

<Comparative Example 1>
The same operation as in Example 2 was performed except that the formulation was changed as follows. For 202 parts of the toner raw material of Example 2, 5% was changed to fine powder (unkneaded product) used for non-prescribed toner adjustment powder 1, and the amount of surface-treated magnetic iron oxide was 100.8 parts. Table 3 summarizes the evaluation results of the toner.
Non-specified toner mixture (fine powder): 10 parts (5% of toner raw material)
Styrene: 80 × 0.95 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.95 parts n-butyl acrylate: 20 × 0.95 parts Unsaturated polyester resin: 1 × 0.95 parts saturated Polyester resin: 5 × 0.95 parts Surface-treated magnetic iron oxide 1: 100.8 × 0.95 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.95 parts benzoyl peroxide: 5 × 0.90 parts

<Comparative example 2>
The same operation as in Example 7 was performed except that the formulation was changed as follows. For 202 parts of the toner raw material of Example 7, 5% was changed to fine powder and coarse powder (unkneaded product) used for the non-prescribed toner adjustment powder 2, and the amount of surface-treated magnetic iron oxide was 97.2 parts. did. Table 3 summarizes the evaluation results of the toner.
Non-specified toner mixture (fine powder + coarse powder): 10 parts (5% of toner raw material)
Styrene: 80 × 0.95 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.95 parts n-butyl acrylate: 20 × 0.95 parts Unsaturated polyester resin: 1 × 0.95 parts saturated Polyester resin: 5 × 0.95 parts Surface-treated magnetic iron oxide 1: 97.2 × 0.95 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.95 parts benzoyl peroxide: 5 × 0.95 parts

<Comparative Example 3>
The same operation as in Example 8 was performed except that the formulation was changed as follows. For 202 parts of the toner raw material of Example 8, 5% is changed to fine powder, coarse powder and other (unkneaded product) used for the non-prescribed toner adjustment powder 3, and the amount of surface-treated magnetic iron oxide is 87.2. The part. Table 3 summarizes the evaluation results of the toner.
Non-specified toner mixture (fine powder + coarse powder + other): 10 parts (5% of toner raw material)
Styrene: 80 × 0.95 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.95 parts n-butyl acrylate: 20 × 0.95 parts Unsaturated polyester resin: 1 × 0.95 parts saturated Polyester resin: 5 × 0.95 parts Surface-treated magnetic iron oxide 1: 87.2 × 0.95 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.95 parts benzoyl peroxide: 5 × 0.95 parts

<Comparative example 4>
A toner was obtained in the same manner as in Example 2 except that only the magnetic iron oxide particles not subjected to the surface treatment were used instead of the surface-treated magnetic iron oxide 1. Table 3 summarizes the evaluation results of the toner.

<Comparative Example 5>
A toner was obtained in the same manner as in Example 7 except that only the magnetic iron oxide particles not subjected to the surface treatment were used instead of the surface-treated magnetic iron oxide 1. Table 3 summarizes the evaluation results of the toner.

<Comparative Example 6>
A toner was obtained in the same manner as in Example 10 except that only the magnetic iron oxide particles not subjected to the surface treatment were used instead of the surface-treated magnetic iron oxide 1. Table 3 summarizes the evaluation results of the toner.

<Comparative Example 7>
Instead of the surface-treated magnetic iron oxide 1, only magnetic iron oxide particles that are not subjected to surface treatment are used, and 5% of the toner raw material 202 of Example 6 is used for the non-predetermined toner adjustment powder 1. A toner was obtained in the same manner as in Example 6 except that the amount was 100.8 parts. Table 3 summarizes the evaluation results of the toner.

<Comparative Example 8>
Instead of the surface-treated magnetic iron oxide 1, only the magnetic iron oxide particles not subjected to the surface treatment are used, and the toner raw material 202 parts of Example 12 is used for the non-prescribed toner adjustment powder 2 for 5%. A toner was obtained in the same manner as in Example 12 except that the amount was 97.2 parts. Table 3 summarizes the evaluation results of the toner.

<Comparative Example 9>
Instead of the surface-treated magnetic iron oxide 1, only the magnetic iron oxide particles not subjected to the surface treatment are used, and the toner raw material 202 parts of Example 13 is used for the non-prescribed toner adjustment powder 3 for 5%. A toner was obtained in the same manner as in Example 13 except that the amount was changed to 87.2 parts. Table 3 summarizes the evaluation results of the toner.

<Comparative Example 10>
A toner was obtained in the same manner as in Example 3 except that only the magnetic iron oxide particles not subjected to the surface treatment were used instead of the surface-treated magnetic iron oxide 1. Table 3 summarizes the evaluation results of the toner.

<Comparative Example 11>
A toner was obtained in the same manner as in Example 4 except that only the magnetic iron oxide particles not subjected to the surface treatment were used instead of the surface-treated magnetic iron oxide 1. Table 3 summarizes the evaluation results of the toner.

<Comparative Example 12>
A toner was obtained in the same manner as in Example 5 except that only the magnetic iron oxide particles not subjected to the surface treatment were used instead of the surface-treated magnetic iron oxide 1. Table 3 summarizes the evaluation results of the toner.

<Comparative Example 13>
The same operation as in Example 23 was performed except that the formulation was changed as follows. The amount of the surface-treated magnetic iron oxide was changed to 202% of the toner raw material of Example 23 by changing the fine powder 1 (unkneaded product) and fine powder 2 (unkneaded product) used for the non-prescribed toner adjustment powder 6 to 5%. Was 90.4 parts. Table 3 summarizes the evaluation results of the toner.
Non-specified toner mixture (fine powder 1 + fine powder 2): 10 parts (5% of toner raw material)
Styrene: 80 × 0.95 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.95 parts n-butyl acrylate: 20 × 0.95 parts Unsaturated polyester resin: 1 × 0.95 parts saturated Polyester resin: 5 × 0.95 parts Surface-treated magnetic iron oxide 1: 90.4 × 0.95 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.95 parts benzoyl peroxide: 5 × 0.90 parts

<Comparative example 14>
The same operation as in Example 24 was performed except that the formulation was changed as follows. The surface-treated magnetic iron oxide was prepared by changing 5% of the toner raw material 202 of Example 24 to coarse powder 1 (unkneaded product) and coarse powder 2 (unkneaded product) used for the toner powder 7 other than the predetermined toner. Was 83.2 parts. Table 3 summarizes the evaluation results of the toner.
Non-specified toner mixture (coarse powder 1 + coarse powder 2): 10 parts (5% of toner raw material)
Styrene: 80 × 0.95 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.95 parts n-butyl acrylate: 20 × 0.95 parts Unsaturated polyester resin: 1 × 0.95 parts saturated Polyester resin: 5 × 0.95 parts Surface-treated magnetic iron oxide 1: 83.2 × 0.95 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.95 parts benzoyl peroxide: 5 × 0.90 parts

<Comparative Example 15>
The same operation as in Example 27 was performed except that the formulation was changed as follows. The amount of the surface-treated magnetic iron oxide was changed to 202% of the toner raw material of Example 27 by changing the fine powder 1 (unkneaded product) and fine powder 2 (unkneaded product) used for the non-prescribed toner adjustment powder 6 to 5%. Was 90.4 parts. Table 3 summarizes the evaluation results of the toner.
Non-specified toner mixture (fine powder 1 + fine powder 2): 10 parts (5% of toner raw material)
Styrene: 80 × 0.95 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.95 parts n-butyl acrylate: 20 × 0.95 parts Unsaturated polyester resin: 1 × 0.95 parts saturated Polyester resin: 5 × 0.95 parts Surface-treated magnetic iron oxide 1: 90.4 × 0.95 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.95 parts benzoyl peroxide: 5 × 0.90 parts

<Comparative Example 16>
The same operation as in Example 28 was performed except that the formulation was changed as follows. The surface-treated magnetic iron oxide was prepared by replacing 5 parts of the toner raw material of Example 28 with the coarse powder 1 (unkneaded product) and coarse powder 2 (unkneaded product) used for the non-prescribed toner adjustment powder 7. Was 83.2 parts. Table 3 summarizes the evaluation results of the toner.
Non-specified toner mixture (coarse powder 1 + coarse powder 2): 10 parts (5% of toner raw material)
Styrene: 80 × 0.95 parts Negative charge control agent (monoazo dye-based Fe compound) 1 × 0.95 parts n-butyl acrylate: 20 × 0.95 parts Unsaturated polyester resin: 1 × 0.95 parts saturated Polyester resin: 5 × 0.95 parts Surface-treated magnetic iron oxide 1: 83.2 × 0.95 parts ester wax (maximum endothermic peak in DSC 72 ° C.): 10 × 0.95 parts benzoyl peroxide: 5 × 0.90 parts

<Comparative Example 17>
In Example 2, the evaluation was performed in the same manner except that the amount of the surface-treated magnetic iron oxide was not adjusted and 80 parts was used as it was. Table 3 summarizes the evaluation results of the toner.

<Comparative Example 18>
In Example 7, the evaluation was performed in the same manner except that the amount of the surface-treated magnetic iron oxide was not adjusted and 80 parts was used as it was. Table 3 summarizes the evaluation results of the toner.

<Comparative Example 19>
In Example 10, the evaluation was performed in the same manner except that the amount of the surface-treated magnetic iron oxide was not adjusted and 80 parts was used. Table 3 summarizes the evaluation results of the toner.

<Comparative Example 20>
In Example 11, the evaluation was performed in the same manner except that the amount of the surface-treated magnetic iron oxide was not adjusted and 80 parts was used as it was. Table 3 summarizes the evaluation results of the toner.

Dispersibility observation A: No solid component.
B: Some solid components are observed.
C: Although a solid component is observed, there is no practical problem.
D: A level in which a solid component is observed, which is undesirable in practice.

Number variation coefficient At the end of the reaction process, sampling was performed, the particle size distribution was measured, and the number variation coefficient was calculated. A smaller value indicates a sharper particle size distribution.
A: Less than 28.0% B: 28.1% or more and less than 32.0% C: 32.1% or more and less than 36.0% D: 36.1% or more

Observation of white spheres during granulation A: No white spheres.
B: Some white spheres are observed.
C: A white sphere is observed, but there is no practical problem.
D: A level in which white spheres are observed, which is undesirable in practice.

Image Resolution Image resolution was evaluated based on the reproducibility of small-diameter isolated dots at 600 dpi, which is easy to close due to a latent image electric field and difficult to reproduce after 1000 sheets of durability.
A: Less than 5 defects in 100 B: 6-10 defects in 100 C: 11-20 defects in 100 D: More than 20 defects in 100

It is a flowchart which shows the whole flow of the manufacturing method of this invention. It is a figure which shows an example of the dispersion | distribution / dissolution apparatus used for implementation of this invention. It is a figure which shows an example of the media mill dispersion | distribution measure used for implementation of this invention. It is a figure which shows an example of the stirring apparatus used for implementation of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 21 Tank jacket 22 Tank 23 Process 24 Motor 25 Stirring shaft 26 Stirring blade 27 Warm water / cooling water inlet 28 Hot water / cooling water outlet 29 Motor 30 Anchor 31 Media particle 32 Tank 40 Motor 41 Stirring shaft 42 Baffle plate 43 Stirring blade 44 Tank

Claims (7)

In a method for producing a magnetic polymerization toner obtained by polymerizing a polymerizable monomer composition containing at least magnetic iron oxide, a polymerizable monomer, and a charge control agent,
A non-predetermined toner produced in the toner production process is melt-kneaded to obtain a non-predetermined toner adjustment powder, and the non-predetermined toner adjustment powder is reintroduced into the polymerizable monomer system. A method for producing a magnetic polymerized toner, characterized in that the amount of magnetic iron oxide used in the toner production process is adjusted by the content of magnetic iron oxide in the outer toner.   2. The magnetic material according to claim 1, wherein the non-predetermined toner is at least a fine powder, a coarse powder, a bag filter recovered powder, and a polymerized kettle adhering powder having a desired external particle size distribution generated in the production process of the magnetic polymer toner. A method for producing a polymerized toner.   3. The method for producing a magnetic polymerization toner according to claim 1, wherein the non-predetermined toner fed to the kneading apparatus is composed of at least one kind and a plurality of non-predetermined toners.   4. The method for producing a magnetic polymerization toner according to claim 1, wherein the non-predetermined toner fed to the kneading apparatus is composed of at least one kind and a plurality of non-predetermined toners.   The ratio of the non-predetermined toner adjusting powder component to be re-introduced into the polymerizable monomer system is 0.1% by mass to 20% by mass with respect to the toner raw material. A method for producing the magnetic polymerized toner according to claim.   The ratio of the non-predetermined toner adjustment powder component to be re-introduced into the polymerizable monomer system is 0.1% by mass to 10% by mass with respect to the toner raw material. A method for producing the magnetic polymerized toner according to claim.   The stirrer used in the step of re-introducing the non-predetermined toner adjusting powder into the polymerizable monomer system and dispersing / dissolving it has at least two different stirring blades. 7. A method for producing a magnetic polymerization toner according to any one of items 6 to 9.

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