JP2006259180A - Charge control agent, toner for electrostatic development using the same, developer and developing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To make charge control agent particles fine and to control the particle size distribution of the particles to a narrow range, so that inclusion of coarse particles of >1 μm is avoided. <P>SOLUTION: The objective charge control agent is provided which is particles of a reaction product having an average particle size of 0.1-0.6 μm obtained by reaction using a micro reactor in which solutions of mutually different raw materials are supplied from two or more micro passages for supplying raw materials and which is controlled so that chemical reaction takes place in a passage for reaction formed by uniting the passages. A toner for electrostatic development using the charge control agent, a developer and a developing method are also provided. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a toner charge control agent used as a developer for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing, etc., a toner using the same, and a developer using the same. And a developing method. More specifically, a charge control agent for toner for electrophotography used in a copier, laser printer, plain paper fax machine, etc. using a direct or indirect electrophotographic developing system, and electrophotographic toner using the same, and It relates to the developing method used. Furthermore, a charge control agent used for toner for electrophotography used in full-color copiers, full-color laser printers, full-color plain paper fax machines and the like using a direct or indirect electrophotographic multicolor image development system, and the same The present invention relates to an electrophotographic toner, a developer using the toner, and a developing method.

  In the developing process, the developer used in electrophotography, electrostatic recording, electrostatic printing, etc. is once attached to an image carrier such as a photoreceptor on which an electrostatic charge image is formed, and then After being transferred from the photoreceptor to a transfer medium such as transfer paper in the transfer process, it is fixed on the paper surface in the fixing process. At that time, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner and a one-component developer not requiring a carrier (magnetic toner, non-magnetic toner, Magnetic toner) is known.

  Conventionally, as dry toners used for electrophotography, electrostatic recording, electrostatic printing, and the like, toner binders such as styrene resins and polyester resins are melt-kneaded together with colorants and finely pulverized. .

  Conventionally, in order to obtain high-quality and high-quality images, improvements have been made by reducing the particle size of the toner. However, the particle shape of the production method by ordinary kneading and pulverization is indefinite. Internally, the toner is further pulverized by agitation with the carrier in the developing unit, and when it is used as a one-component developer, contact stress between the developing roller and the toner supply roller, the layer thickness regulating blade, the friction charging blade, etc. Or a phenomenon that the image quality is deteriorated due to the fluidizing agent being embedded in the toner surface. Further, because of its shape, the fluidity as a powder is poor, a large amount of fluidizing agent is required, and the filling rate into the toner bottle is low, which is an obstacle to downsizing. Therefore, the current situation is that the merit of reducing the particle size is not fully utilized. In addition, the pulverization method has a physical particle size limit, and the actual situation is that it cannot cope with further smaller particle size.

  Furthermore, the transfer process of an image formed from multicolor toners to a transfer medium or paper for creating a full-color image has become complicated, and in an irregular shape such as pulverized toner, transferability is increased. Due to the inconvenience, there are problems such as missing in the transferred image and increased toner consumption to compensate for it.

  Accordingly, there is an increasing demand for further improving the transfer efficiency to reduce the toner consumption to obtain a high-quality image without image omission and to reduce the running cost. When transfer efficiency is very good, there is no need for a cleaning unit to remove untransferred toner from the photoconductor or transfer medium, which can reduce the size and cost of the equipment and eliminate waste toner. It is because it has. In order to compensate for the disadvantages of the irregular shape effect, various spherical toner manufacturing methods have been considered.

  As a method for solving these problems, a toner production method using a suspension polymerization method or an emulsion polymerization aggregation method has been studied. Patent Document 1 discusses a method called volumetric shrinkage called a polymer dissolution suspension method. In this method, a toner material is dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified and formed into droplets in an aqueous medium containing a dispersant, and then the volatile solvent is removed. Unlike the suspension polymerization method and emulsion polymerization aggregation method, this method is a versatile resin that can be used, and in particular, a polyester resin useful for a full color process that requires transparency and smoothness of the image area after fixing. It is excellent in that it can be used. However, the dispersant used is strongly adsorbed on the surface of the toner particles, and it is difficult to remove even by a subsequent cleaning operation. If it cannot be completely removed, the chargeability of the toner is largely governed by the dispersant used. There was an evil. That is, the average charge level of the obtained toner is generally low, the charging speed is slow, and it is strongly influenced by humidity. Further, when the dispersant is completely removed, a considerable amount of water is required, and the production efficiency is remarkably lowered.

  In Patent Document 2, the resin used in the polymer dissolution suspension method has a low molecular weight to reduce the viscosity of the dispersed phase, facilitate emulsification, and improve the fixability by carrying out a polymerization reaction in the particles. In particular, the influence of the functional group used for the polymerization reaction is not negligible, and particularly when an isocyanate compound is used, not only the influence of the dispersant described above but also the chargeability of the resulting urethane and urea groups is strongly controlled. It was a thing.

  In order to improve such a poor charging property, the charge control agent used in the conventional pulverized toner is dispersed or dissolved in a monomer or an organic solvent in which a polymer is dissolved in advance. Attempts have also been made to implement control. The charge control agent dissolved in the monomer or the organic solvent is classified into a type that deposits after polymerization or after evaporation of the organic solvent, and a type that is dissolved as it is. It is extremely difficult to control the particle size of the charge control agent to a constant value, and it is almost impossible to uniformly disperse the submicron that is the optimum particle size inside the toner. On the other hand, the charge control agent of the dissolving type does not cause such a problem, but the original effect of the charge control agent is not expressed in the dissolved (molecularly dispersed) state. The adverse effect of the functional group used for the condensation reaction could not be excluded. Furthermore, a charge control agent having the property of being insoluble and dispersed in a monomer or an organic solvent is most effective in terms of charge control. However, the primary particle size of the charge control agent is not reduced to submicron. Since the amount of charge control agent varies greatly from toner particle to toner particle, the charge amount distribution becomes wide and cannot be uniformly dispersed inside the toner. The problem of contaminating the charging member occurs. Therefore, a method of finely dispersing the charge control agent in a monomer or an organic solvent using a wet mill or the like is used, but this method requires enormous energy for pulverization and fine dispersion, and it takes a long time after processing. If stored, re-aggregation will eventually cause a problem that the particle size will increase. Therefore, the dispersion of the charge control agent obtained by such a method is used immediately after the treatment, or the stability for a certain period of time is maintained by using a dispersion stabilizer typified by a surfactant. . However, as described above, such a stabilizer is not only one that deteriorates the charge controllability, particularly the chargeability in a high humidity environment, and has a contradictory effect. There is no area that achieves both stability. In addition, it is impossible to obtain a charge control agent having such a very fine particle size by a conventional manufacturing technique, and it is possible to extend the charge control agent in a monomer or an organic solvent by a simpler and more productive method. It has been strongly desired to produce an electrophotographic toner that is finely dispersed for a period and is excellent in a charge control agent.

  As described above, the conventional charge control agent for general electrophotographic use has been synthesized in an ordinary batch reaction bath. However, the obtained charge control agent has irregular particle sizes, and coarse particles are present. In the process of containing / attaching the charge control agent to the toner particle matrix, various complicated processing operations are required.

JP-A-7-152202 JP-A-11-149179

Therefore, the problems to be solved by the present invention can be listed as follows.
(1) Reducing the size of the charge control agent particles, controlling the particle size distribution of the particles to a narrow range so that large particles exceeding 1 μm are not mixed, and such charge control agent To achieve a uniform adhesion amount of the charge control agent for each toner particle and uniform dispersion inside the toner, thereby reducing variations in the chargeability of the toner and obtaining necessary charging characteristics. Specifically, the present invention provides a toner having a high average charge level, excellent stability over time, an agile charge rate, and being unaffected by the environment such as humidity and temperature, and a method for producing the same (2) Sharp particle size Providing toner with high melt viscosity that has a distribution, spherical shape, and high molecular weight components with sufficient fixability (3) Reproduce the latent image faithfully to reproduce high-quality full-color images (4) the copy efficiency to reproduce high quality full color image (5) to provide a process cartridge having the toner.

The first of the present invention is controlled so that a solution of different raw materials is supplied from at least two or more raw material supply microchannels, and a chemical reaction occurs in a reaction channel in which the channels are integrated. The present invention relates to a charge control agent characterized in that the reaction product obtained by reacting using a microreactor is particles having an average particle size of 0.1 to 0.6 μm.
In the second aspect of the present invention, an aromatic carboxylic acid derivative and a metal compound aqueous solution are respectively supplied from two raw material supply microchannels, and a chemical reaction occurs in a reaction channel in which the channels are integrated. Charging characterized in that it is a metal compound particle of an aromatic carboxylic acid derivative in which the average particle size of the reaction product obtained by reacting using a controlled microreactor is 0.1 to 0.6 μm It relates to a control agent.
A third aspect of the present invention relates to the charge control agent according to claim 2, wherein the aromatic carboxylic acid derivative is selected from the group consisting of a salicylic acid derivative, a naphthoic acid derivative and an oxy-naphthoic acid derivative.
A fourth aspect of the present invention relates to the charge control agent according to claim 3, wherein the aromatic carboxylic acid derivative is a salicylic acid derivative.
The fifth aspect of the present invention relates to the charge control agent according to claim 2, wherein the metal compound aqueous solution is a divalent or higher metal salt aqueous solution.
6th of this invention is related with the charge control agent in any one of Claims 1-3 whose said particle | grain is a thing of 1 micrometer or less at maximum.
A seventh aspect of the present invention relates to a toner for developing an electrostatic charge, comprising at least the charge control agent according to any one of claims 1 to 5.
An eighth aspect of the present invention relates to a developer containing the electrostatic charge developing toner according to claim 7.
According to a ninth aspect of the present invention, each color formed on a single photoreceptor using a plurality of developing devices including a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll. In the method of developing the electrostatic latent image divided into two with a developer corresponding to each color, the developer according to claim 8 is used as the developer.
According to a tenth aspect of the present invention, each color formed on a single photoconductor using a plurality of developing devices including a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll. The developer according to claim 8, wherein the developer is developed with a developer corresponding to each color and transferred to an intermediate transfer member by an electric field, and the developer according to claim 8 is used as the developer. It relates to the developing method.
According to an eleventh aspect of the present invention, a plurality of developing devices including a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll are used, and a plurality of photosensitive members corresponding to the developing device are used. The present invention relates to a developing method, wherein the developer according to claim 8 is used as the developer in a method of developing the formed electrostatic latent image with a developer corresponding to each color.
According to a twelfth aspect of the present invention, a plurality of developing devices including a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll are used, and a plurality of photosensitive members corresponding to the developing device are used. The developer according to claim 8, wherein the developer is developed with a developer corresponding to each color, and transferred to an intermediate transfer member by an electric field. The present invention relates to a developing method.
A thirteenth aspect of the present invention integrally supports at least one means selected from electrophotographic toner or developer storage means, charging means, latent image holding means (photoconductor), developing means, and cleaning means. A process cartridge that is detachably attached to an image forming apparatus main body, wherein the electrostatic charge developing toner according to claim 7 is used as the toner.

  The charge control agent of the present invention is controlled such that a solution of different raw materials is supplied from at least two raw material supply microchannels, and a chemical reaction occurs in a reaction channel in which the channels are integrated. It can manufacture by making it react using the made microreactor.

  When the charge control agent is a metal compound of an aromatic carboxylic acid derivative, the aromatic carboxylic acid derivative and the metal compound aqueous solution are respectively supplied from the two raw material supply microchannels, and the channels are integrated. It can be manufactured by reacting using a microreactor controlled so that a chemical reaction occurs in the reaction channel.

  As the aromatic carboxylic acid derivative, those which are soluble in a monomer or an organic solvent after charging and reaction are desirable. Specific examples include salicylic acid derivatives, naphthoic acid derivatives, and oxy-naphthoic acid derivatives. For example, salicylic acid; methyl substitution (any of the 3, 4, 5, and 6 positions is substituted) salicylic acid, ethyl substitution (any of the 3, 4, 5, and 6 positions are substituted), salicylic acid, butyl substitution (3,4, 5, 5, and so on) Alkyl substituted salicylic acid such as salicylic acid, propyl substituted (any of 3,4,5,6 substituted) salicylic acid, naphthoic acid; methyl substituted (1 or 2-substituted) naphthoic acid, Examples thereof include alkyl-substituted naphthoic acids such as ethyl-substituted (1- or 2-position-substituted) naphthoic acid and butyl-substituted (1- or 2-position substituted) naphthoic acid; oxy-1-naphthoic acid and oxy-2-naphthoic acid. In particular, 3,5-di-t-butylsalicylic acid is preferred.

Examples of the metal compound include sulfates, hydrochlorides, nitrates, and the like of various metals. There are no particular limitations on the type of metal, but considering the charge control effect and safety, aluminum, zinc, iron, Examples include zirconium, chromium (III), manganese, cobalt, titanium, and silicon. Among these, aluminum, zinc, iron, zirconium, and chromium (III) are preferable.
Specific metal compounds include zinc sulfate, zinc chloride, aluminum sulfate, aluminum chloride, iron sulfate, iron chloride, iron oxychloride, zirconium sulfate, zirconium chloride, zirconium oxychloride, chromium (III) sulfate, chromium chloride (III ) And the like.

The microreactor used in the present invention is, for example, as shown in FIG. 1, and the raw material supply microchannel varies depending on the number of raw materials, but in the present invention, since the raw materials are usually two components, There are two microchannels. These two are integrated at the inlet of the reaction channel, and after a predetermined reaction is started in the reaction channel, the reaction is terminated and a reaction product is collected from the side opposite to the raw material supply microchannel. Table 1 below shows an example of the relationship between the diameter of at least two raw material supply microchannels and the diameter of a reaction channel integrated with the raw material supply microchannels.
The microreactor is laminar and the reaction takes place at the interface. Therefore, if a Y-shaped channel is provided after the reaction, it is possible to separate the liquid vertically.

  Each raw material solution reacts instantaneously in the area where each flow path is in contact, and at the same time, the reaction product is deposited. By controlling the raw material concentration, flow rate, and microchannel diameter, the primary charge control agent deposited is controlled. The particle diameter can be arbitrarily controlled. After the reaction, the organic layer and aqueous layer in which the charge control agent is dispersed can be separated in the microreactor by separating the flow path into two again, and once stored in a container. A liquid separation operation may occur.

  Both the aromatic carboxylic acid derivative and the metal compound are subjected to the reaction in a form dissolved in a solvent. The metal compound is used in the form of an aqueous solution, while the aromatic carboxylic acid derivative is used by dissolving it in a monomer or an organic solvent. A monomer or an organic solvent for dissolving an aromatic carboxylic acid derivative, for example, a salicylic acid derivative, is not particularly limited, but is not completely compatible with water in terms of efficient use of a charge control agent dispersed in an organic layer. What separates is desirable. Examples of such a solvent include styrene monomer, acrylic monomer, toluene, ethyl acetate, tetrahydrofuran, and the like. In the suspension polymerization method, a styrene monomer is desirable, and in the emulsion polymerization aggregation method and the polymer suspension method, ethyl acetate is desirable.

(Charge control resin fine particles)
As the charge controllable resin fine particles, for example, resin fine particle dispersions obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization are preferable. In particular, polystyrene copolymerized with a monomer having a carboxyl group such as methacrylic acid, a copolymer obtained by emulsion polymerization or dispersion polymerization of fluorine-based methacrylate ester or fluorine-based acrylic ester, silicone, benzoguanamine, nylon, etc. And polymer fine particles of a polycondensation system and a thermosetting resin.

  A method for producing a toner using the charge control agent of the present invention or a dispersion of the charge control agent will be described in detail below.

First, a method for adjusting the charge control agent dispersion will be described.
A reactor having at least two or more micro-channels is used, a salicylic acid derivative is supplied as a raw material dissolved in a monomer or an organic solvent from one channel, and an aqueous metal solution is supplied from another channel . The salicylic acid derivative is not particularly limited, but is preferably charged and soluble in a monomer or an organic solvent after the reaction, preferably alkyl-substituted salicylic acid, naphthoic acid, and the like, particularly 3,5-ditertiarybutyl salicylic acid. Most desirable. Similarly, the type of metal is not particularly limited, but considering the charge control effect and safety, mention may be made of aluminum, zinc, iron, zirconium, oxyzirconium, chromium (III), manganese, cobalt, titanium, silicon. I can do it. Among these, aluminum, zinc, iron, oxyzirconium, and chromium (III) are preferable. The monomer or organic solvent in which the salicylic acid derivative is dissolved is not particularly limited. However, in view of efficient use of the charge control agent dispersed in the organic layer, it is desirable to separate the liquid without completely compatibilizing with water. Examples of such a solvent include styrene monomer, acrylic monomer, toluene, ethyl acetate, tetrahydrofuran, and the like. In the suspension polymerization method, a styrene monomer is desirable, and in the emulsion polymerization aggregation method and the polymer suspension method, ethyl acetate is desirable.
The two liquids react instantaneously in the area where each flow channel is in contact, and the reaction product precipitates at the same time. By controlling the raw material concentration, flow rate, and microchannel diameter, the primary particle size of the deposited charge control agent is controlled. It can be controlled arbitrarily. After the reaction, the organic layer and aqueous layer in which the charge control agent is dispersed can be separated in the microreactor by separating the flow path into two again, and once stored in a container. A liquid separation operation may be performed.
Thus, the charge control agent dispersion obtained by synthesizing fine particles of the charge control agent in the monomer or organic solvent using the microreactor may have a maximum particle size of the charge control agent of 1 μm or less. This is important from the viewpoint of dispersibility in the toner, and it is desirable that the average particle diameter is 0.1 μm to 0.6 μm in view of the charge control effect. These charge control agents exhibit sufficient performance when used in a solid content of the charge control agent of 0.01 to 5% by weight based on the solid content of the toner particles.

Next, a method for producing toner base particles using the charge control agent dispersion will be described.
First, in the oil phase of the toner composition of the present invention, a colorant such as a resin, a prepolymer, and a pigment, a release agent, the charge control agent dispersion liquid, and the like are dispersed in a volatile solvent. In order to lower the viscosity of the oil phase and make it emulsifiable, a volatile solvent in which the polyester resin or prepolymer is soluble is used. The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. In addition, the toner shape can be further adjusted by using a solvent that can be dissolved in an aqueous medium such as alcohol or water. The amount of the solvent used is usually 10 to 900 parts by weight with respect to 100 parts by weight of the toner composition.

The toner particles may be formed by reacting a dispersion in a volatile organic solvent composed of, for example, a prepolymer having an isocyanate group and another toner composition in an aqueous medium with amines. Examples of a method for stably forming a dispersion composed of a prepolymer and a toner composition in an aqueous medium include a method in which a composition of a toner raw material composed of a prepolymer is added to an aqueous medium and dispersed by shearing force. It is done. Colorant, colorant masterbatch, release agent, charge control agent, polyester resin, etc. which are prepolymer and other toner composition (hereinafter referred to as toner raw material) are mixed when forming a dispersion in an aqueous medium. However, it is more preferable to mix the toner raw materials in advance to form an oil phase, and then add and disperse the mixture in the aqueous medium. For the dispersion, an ordinary agitating mixer, more preferably a homogenizer having a high-speed rotating body and a stator, a high-pressure homogenizer, a disperser using a medium such as a ball mill, a bead mill, a sand mill, or the like is used. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.
The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. The emulsifier having rotating blades is not particularly limited, and any emulsifier and disperser that are generally commercially available can be used. For example, Ultra Turrax (manufactured by IKA), Polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Special Machine Industries Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK pipeline homomixer , TK homomic line flow [manufactured by Special Machine Industries Co., Ltd.], colloid mill (manufactured by Shinko Pantech Co., Ltd.), slasher, trigonal wet pulverizer (manufactured by Mitsui Miike Chemical Co., Ltd.), Cavitron (Eurotech Co., Ltd.) ), Fine flow mills (manufactured by Taiheiyo Kiko Co., Ltd.) and other continuous emulsifiers, Claremix (manufactured by MTechnic Co., Ltd.), fill mixes (manufactured by Tokushu Kika Kogyo Co., Ltd.), etc. Etc.

  When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 10 to 98 ° C. Higher temperatures are preferred in that the dispersion of the prepolymer has a lower viscosity and is easier to disperse.

  The amount of the aqueous medium used relative to 100 parts of the toner composition containing the prepolymer is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2000 parts by weight, it is not economical.

  In the aqueous medium, solid fine particles may be dispersed as a dispersant in addition to a surfactant as an emulsification dispersion stabilizer. Further, the stabilization of the dispersed droplets may be adjusted with a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloroacrylate 2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used. When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, after the elongation and / or cross-linking reaction, it is better to dissolve and wash away the remaining solid fine particle dispersant. From the aspect, it is preferable.

  The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

When the particle size distribution at the time of emulsification dispersion is wide, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying, but it is preferably performed in a liquid in terms of efficiency. The obtained unnecessary fine particles or coarse particles can be returned to the kneading step and used for forming particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

By mixing the resulting dried toner powder with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) is modified to reduce the grinding air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron system (Made by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.
The materials used in the above toner manufacturing method will be described in more detail below.

(Surfactant used when producing polymerization toner)
Examples of the anionic surfactant include alkylbenzene sulfonate, α-olefin sulfonate, and phosphate ester.
Cationic surfactants include amine salts such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoses. Quaternary ammonium salt types such as quinolinium salt and benzethonium chloride are listed.
In combination with these, nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethyl Amphoteric surfactants such as ammonium betaine may be used.
The amount of these surfactants used is preferably 0.1 to 10% by weight based on the entire aqueous phase.

(Solid fine particle dispersant)
The solid fine particle dispersant used for the production of the polymerized toner of the present invention is present in an aqueous medium as a solid hardly soluble in water, and is preferably fine particles having an average particle diameter of 0.01 to 1 μm.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
More preferably, tricalcium phosphate, calcium carbonate, colloidal titanium oxide, colloidal silica, hydroxyapatite and the like can also be used. In particular, hydroxyapatite synthesized by reacting sodium phosphate and calcium chloride in water under a basic condition is preferable. Other organic solid fine particle dispersants are copolymerized with a monomer having a carboxyl group, such as methacrylic acid obtained by microcrystals of low molecular weight organic compounds or polymer fine particles such as soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization. Polystyrene particles such as polystyrene, methacrylic acid ester, acrylic acid ester copolymer, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resin.

(Compound having an isocyanate group at the end: Prepolymer)
Examples of the polyester prepolymer (A) having an isocyanate group include a polycondensate of a polyol (1) and a polycarboxylic acid (2) and a polyester having an active hydrogen group, which is further reacted with a polyisocyanate (3). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates such as phenol derivatives, oximes, caprolactams, etc. And a combination of two or more of these.

The ratio of the polyisocyanate (3) to the polyester which is a polycondensate of (1) and (2) is the equivalent ratio [NCO] / [OH of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. ] Is usually 5/1 to 1/1, preferably 4/1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.
The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If the number is less than 1 per molecule, the molecular weight of the urea-modified polyester to be produced becomes low, and the hot offset resistance deteriorates.

[Amines (B)]
As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of B1 to B5 blocked amino groups (B6) include ketimine compounds and oxazoline compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated. In the present invention, the polyester modified with a urea bond may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

(Polyester resin)
In the present invention, an unmodified polyester resin (C) can be contained as a toner binder component together with the prepolymer (A) and the amines (B). By using the polyester resin (C) in combination, the low-temperature fixability and the gloss when used in a full-color device are improved, which is preferable to the single use. Examples of the polyester resin (C) include polycondensates of the polyol (1) and the polycarboxylic acid (2) similar to the polyester component of the prepolymer (A). The same as the polyester component. The polyester resin (C) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, such as a urethane bond. The reaction product of the prepolymer (A) and amines (B) and the polyester resin (C) are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component of the prepolymer (A) and the polyester resin (C) preferably have similar compositions. When the polyester resin (C) is contained, the weight ratio of the prepolymer (A) to the polyester resin (C) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5 / 95-25 / 75, particularly preferably 7 / 93-20 / 80. When the weight ratio of the prepolymer (A) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of the polyester resin (C) is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The polyester resin (C) preferably has a hydroxyl value of 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of the said polyester resin (C) is 1-30 normally, Preferably it is 5-20. By having an acid value, it tends to be negatively charged.

In the present invention, the glass transition point (Tg) of the toner binder is usually 50 to 70 ° C., preferably 55 to 65 ° C. If it is less than 50 ° C., the heat resistant storage stability of the toner is deteriorated, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the urea-modified polyester resin, which is a reaction product of the prepolymer (A) and the amines (B), the dry toner of the present invention has heat resistance even when the glass transition point is low as compared with known polyester-based toners. It shows a tendency of good storage stability. As the storage elastic modulus of the toner binder, the temperature (TG ′) at which 10000 dyne / cm ² is obtained at a measurement frequency of 20 Hz is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner binder, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or lower, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or more. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

(Coloring agent)
As the colorant of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide , Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow ( 5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithobon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. In addition to the above-mentioned modified and unmodified polyester resins, the binder resin kneaded together with the production of the master batch is a polymer of styrene such as polystyrene, poly p-chlorostyrene, and polyvinyl toluene, and its substituted products. Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Polymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α -Methyl chloromethacrylate copolymer Styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. are used alone or in combination it can.

  This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
Further, a wax may be contained together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention, and examples thereof include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbons (paraffin wax, sazol wax, etc.); carbonyl group-containing waxes. Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18 -Octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

(Toner production method)
The toner can be produced by the following method, but is not limited thereto.
When preparing the toner, in order to improve the fluidity, storage stability, developability, and transferability of the toner base particles, the toner base particles manufactured as described above are further mixed with hydrophobic silica fine powder, etc. Add and mix external additives such as For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and vice versa.

  Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.

  To further adjust the shape of the obtained toner, a toner binder, a method of adjusting the shape mechanically using a hybridizer, mechanofusion, etc. A so-called spray drying method is a method in which a toner material is dissolved and dispersed in a solvent in which a toner binder is soluble, and then a solvent is removed using a spray drying apparatus to obtain a spherical toner. Moreover, although the method of making it spherical by heating in an aqueous medium is mentioned, it is not limited to this.

(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, and thermosetting resins Examples include polymer particles.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 to 10 weights of toner with respect to 100 parts by weight of carrier. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resin such as vinyl, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

  The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

  The present invention uses a plurality of developing devices provided with a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll, and is divided into each color formed on a single photoconductor. In the method of developing the electrostatic latent image with a developer corresponding to each color, when the developer containing the charge control agent of the present invention is used as the developer, a high-quality image can be obtained.

  In addition, the present invention uses a plurality of developing devices provided with a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll, for each color formed on a single photoconductor. In the developing method in which the divided electrostatic latent image is developed with a developer corresponding to each color and transferred to an intermediate transfer member by an electric field, the developer containing the charge control agent of the present invention is used as the developer. Then, a high quality image can be obtained.

  The present invention uses a plurality of developing devices provided with a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll, and is formed on a plurality of photoreceptors corresponding to the developing device. In the method of developing the electrostatic latent image divided into each color with a developer corresponding to each color, a high-quality image can be obtained by using the developer containing the charge control agent of the present invention as the developer. Can do.

  In addition, the present invention uses a plurality of developing devices including a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll, and is formed on a plurality of photoreceptors corresponding to the developing device. In the developing method in which the electrostatic latent image divided into each color is developed with a developer corresponding to each color and transferred to the intermediate transfer member by an electric field, the charge control agent of the present invention is contained as the developer. When a developer is used, a high quality image can be obtained.

  Further, the present invention integrally supports at least one means selected from an electrophotographic toner or a developer storing means, a charging means, a latent image holding means (photoconductor), a developing means, and a cleaning means. In the process cartridge that is detachable from the forming apparatus main body, the electrostatic charge developing toner according to claim 8 can be used as the toner.

(1) According to the present invention, a charge control agent that is fine and has a narrow particle size distribution, that is, very high uniformity can be obtained.
(2) By using such a charge control agent, non-uniformity in the amount of charge control agent between toner particles is eliminated, and the charge control agent can be uniformly dispersed inside the toner.
(3) As a result, by using the charge control agent of the present invention, it is possible to give the toner excellent characteristics in charge rising property, charge stability, and sharpness of charge amount distribution. By doing so, it was possible to obtain an extremely high quality image excellent in fine line reproducibility and to widen the fixing temperature range.
(4) The present invention eliminates the need for an inefficient method in which a conventional charge control agent is finely dispersed in a monomer or an organic solvent using a wet mill, and the charge control agent particles are stable simultaneously with the reaction. Therefore, even after storage for a long time after the reaction, almost no reaggregation is observed, and the charge control agent particles are stable for a long time.
(5) In the present invention, by producing a micro-reactor, a charge control agent having a particle diameter smaller than that of a charge control agent produced by an ordinary batch reaction, or a dispersion in which the charge control agent is finely dispersed is used as it is. When used as a solvent for production, the resulting toner has excellent charging performance.

  Hereinafter, the present invention will be described with reference to examples and comparative examples, but the present invention is not limited thereto. In addition, all the description of the following part is a weight part.

Production Example 1
(Synthesis of polyester resin)
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of terephthalic acid and 2 parts of dibutyltin oxide are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and polycondensed at 230 ° C. for 8 hours at normal pressure. The reaction was further performed at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain an unmodified polyester having a peak molecular weight of 4800. 100 parts of this resin was dissolved and mixed in 100 parts of ethyl acetate to obtain an ethyl acetate solution of a toner binder. A portion was dried under reduced pressure, the polyester resin was isolated, and Tg and acid value were measured. The Tg was 58 ° C. and the acid value was 8.

Production Example 2
[Synthesis of terminally isocyanated polyester (prepolymer)]
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide were placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 230 ° C. for 8 hours at normal pressure. The reaction was further carried out at a reduced pressure of 10 to 15 mmHg for 5 hours, followed by cooling to 160 ° C., and 32 parts of phthalic anhydride was added thereto and reacted for 2 hours. Next, the mixture was cooled to 80 ° C. and reacted with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours to obtain (terminal) isocyanated polyester.

Production Example 3
(Synthesis of ketimine compounds)
A reaction vessel equipped with a stir bar and a thermometer was charged with 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone, and reacted at 50 ° C. for 5 hours to obtain a ketimine compound. The amine value of this ketimine compound was 418.

Production Example 4
(Preparation of charge control agent dispersion 1)
A microreactor (microreactor device manufactured by Micro Chemical Engineering Co., Ltd.) used in the embodiment of the present invention shown in FIG. 1 has a 50 to 200 μm width, 40 to 90 μm depth, and 80 to 120 mm reaction channel on a glass substrate. This is a reaction apparatus in which a microchannel having a long length is formed, two reaction fluids are allowed to flow therethrough, and the two reaction fluids can cause a chemical reaction in an interface region. The diameter of the raw material supply microchannel a, the diameter of the raw material supply microchannel b, and the diameter of the reaction channel of the microreactor shown in FIG. 1 are both 50 μm wide and 40 μm deep. Was used. The reaction flow path can be adjusted very accurately by a Peltier temperature controller (IOK-01). For example, when the set temperature is 20 ° C., the upper surface temperature of the integrated glass chip (ICC-DY15) When the set temperature was 20.3 to 20.4 ° C. and 35 ° C., the chip upper surface temperature was in the range of 34.6 to 34.9 ° C. Using this microreactor, an ethyl acetate solution of 3,5-ditertiary butylsalicylic acid was reacted with an aqueous zinc sulfate solution to synthesize a 3,5-ditertiary butylsalicylate zinc compound as follows.
A 1.0 wt% ethyl acetate solution of 3,5-ditertiary butylsalicylic acid is introduced from the inlet 1 of the raw material supply microchannel a, and a 1.0 wt% zinc sulfate aqueous solution is introduced from the raw material supply microchannel b inlet 2. Were introduced at a flow rate of 2.0 ml / hr using a microsyringe pump and discharged from the outlet after the reaction. FIG. 2 shows an optical micrograph of the joined portion of the raw material supply microchannel a and the raw material supply microchannel b at this time. The liquid mixture containing the obtained reaction product was collected in a beaker, and this was allowed to stand and liquid-separated to obtain an ethyl acetate dispersion having a target charge control agent. When the average particle size of the dispersion obtained with a laser type particle size distribution measuring instrument was measured, it was 0.35 μm, and even the largest particles did not exceed 1 μm.

Production Example 5
(Preparation of charge control agent dispersion 2)
Using a two-fluid microreactor shown in FIG. 1, an ethyl acetate solution of 3,5-ditertiary butylsalicylic acid is reacted with an aqueous zinc sulfate solution, and a 3,5-ditertiary butylsalicylate zinc compound is reacted as follows. And synthesized.
A 5.0 wt% ethyl acetate solution of 3,5-ditertiary butylsalicylic acid is introduced from the inlet 1 of the raw material supply microchannel a, and 5.0 wt% of zinc sulfate is introduced from the inlet 2 of the raw material supply microchannel b. The aqueous solution was introduced using a micro syringe pump at a flow rate of 10.0 ml / hr, and discharged from the outlet after the reaction. FIG. 3 shows an optical micrograph of the joining portion of the raw material supply microchannel a and the raw material supply microchannel b at this time. The liquid mixture containing the obtained reaction product was collected in a beaker, and this was allowed to stand and liquid-separated to obtain an ethyl acetate dispersion having a target charge control agent. This was diluted 5-fold with ethyl acetate. The average particle size of the dispersion obtained with a laser type particle size distribution measuring instrument was 3.2 μm, and the maximum particle size exceeded 10 μm.

Production Example 6
(Preparation of charge control agent dispersion 3)
Using a two-fluid microreactor shown in FIG. 1, an ethyl acetate solution of 3,5-ditertiary butylsalicylic acid is reacted with an aqueous aluminum chloride solution, and the 3,5-ditertiary butylsalicylate aluminum compound is reacted as follows. And synthesized.
A 1.0 wt% ethyl acetate solution of 3,5-ditertiary butylsalicylic acid is introduced from the inlet 1 of the raw material supply microchannel a, and 1.0 wt% of aluminum chloride is introduced from the inlet 2 of the raw material supply microchannel b. The aqueous solution was introduced using a micro syringe pump at a flow rate of 2.0 ml / hr, and discharged from the outlet after the reaction. The liquid mixture containing the obtained reaction product was collected in a beaker, and this was allowed to stand and liquid-separated to obtain an ethyl acetate dispersion having a target charge control agent. When the average particle size of the dispersion obtained with a laser type particle size distribution measuring instrument was measured, it was 0.35 μm, and even the largest particles did not exceed 1 μm.

Production Example 7
(Preparation of charge control agent dispersion 4)
Using a two-fluid microreactor shown in FIG. 1, an ethyl acetate solution of 3,5-ditertiary butylsalicylic acid is reacted with an aqueous solution of zirconium oxychloride, and 3,5-ditertiary butylsalicylic zirconia compound is converted into the following: And synthesized.
A 1.0 wt% ethyl acetate solution of 3,5-ditertiary butylsalicylic acid is introduced from the inlet 1 of the raw material supply microchannel a, and 1.0 wt% of oxychlorination from the inlet 2 of the raw material supply microchannel b. The aqueous zirconium solution was introduced at a flow rate of 2.0 ml / hr using a microsyringe pump, and discharged from the outlet after the reaction. The liquid mixture containing the obtained reaction product was collected in a beaker, and this was allowed to stand and liquid-separated to obtain an ethyl acetate dispersion having a target charge control agent. The average particle size of the dispersion obtained with a laser-type particle size distribution measuring instrument was measured to be 0.35 μm, and even the largest particles did not exceed 1 μm.

Production Example 8
(Preparation of charge control agent dispersion 5)
Using a two-fluid microreactor shown in FIG. 1, an ethyl acetate solution of 3,5-ditertiary butylsalicylic acid and a zinc sulfate aqueous solution are reacted to form a 3,5-ditertiary butylsalicylate zinc compound as follows. And synthesized.
A 2.0 wt% ethyl acetate solution of 3,5-ditertiary butylsalicylic acid is introduced from the inlet 1 of the raw material supply microchannel a, and 2.0 wt% of zinc sulfate from the inlet 2 of the raw material supply microchannel b. The aqueous solution was introduced using a microsyringe pump at a flow rate of 2.0 ml / hr, and discharged from the outlet after the reaction. FIG. 4 shows an optical micrograph of the joined portion of the raw material supply microchannel a and the raw material supply microchannel b at this time. The mixed solution containing the obtained reaction product was collected in a beaker, and allowed to stand, followed by liquid separation to obtain an ethyl acetate dispersion having a target charge control agent. When the average particle size of the dispersion obtained with a laser type particle size distribution measuring instrument was measured, it was 0.57 μm, and even the largest particles did not exceed 1 μm.

Example 1
In a sealed pot, 100 parts of ethyl acetate dispersion 1 of the above charge control agent, 100 parts of an ethyl acetate solution of polyester resin, 5 parts of carnauba wax, 4 parts of copper phthalocyanine blue pigment were used, and 5 mmφ zirconia beads were used. Then, ball mill dispersion was performed for 24 hours to obtain a toner composition. In a beaker, 600 parts of ion exchange water, 60 parts of tricalcium phosphate and 3 parts of sodium dodecylbenzenesulfonate were uniformly dissolved and dispersed. Next, the internal temperature of the beaker was kept at 20 ° C., and the toner composition was added and emulsified with stirring for 3 minutes while stirring at 12000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo). Subsequently, this mixed liquid was transferred to a flask equipped with a stirring bar and a thermometer, and the solvent was removed at 30 ° C. under reduced pressure of 50 mmHg for 8 hours. It was confirmed by gas chromatography that ethyl acetate in the dispersion was 100 ppm or less. Thereafter, the dispersion was cooled to room temperature, and 120 parts of 35% concentrated hydrochloric acid was added to dissolve tricalcium phosphate. Thereafter, the mixture was stirred for 1 hour at room temperature, filtered, and the operation of redispersing the obtained cake in distilled water and filtering was repeated three times. The obtained cake was further redispersed in distilled water to a solid content of 10% by weight. Thereto, a 1% by weight aqueous solution of stearylamine acetate was gradually added with stirring so that the pure content of stearylamine acetate was 0.3% by weight with respect to the toner solids. Thereafter, the mixture was stirred for 1 hour at room temperature and then separated by filtration. The obtained cake was dried under reduced pressure at 40 ° C. for 24 hours to obtain toner particles. Then, 100 parts of toner particles were mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain an electrostatic charge developing toner of the present invention. The physical properties of the electrostatic charge developing toner are shown in Table 1 below.

Comparative Example 1
A comparative toner for electrostatic charge development was obtained in the same manner as in Example 1 except that the same amount of the charge control agent dispersion 2 was added instead of the charge control agent dispersion 1 of Example 1. The physical properties of the electrostatic charge developing toner are shown in Table 1 below.

Example 2
In a sealed pot, 100 parts of an ethyl acetate solution of the polyester resin obtained in Production Example 1, 100 parts of the charge control agent dispersion 1 produced in Production Example 4, 5 parts of carnauba wax, 4 parts of copper phthalocyanine blue pigment Was ball milled for 24 hours using 5 mmφ zirconia beads. Thereafter, 20 parts of the terminal isocyanated polyester (prepolymer) obtained in Production Example 2 was added in terms of solid content and mixed by stirring to obtain a toner composition. In a beaker, 600 parts of ion exchange water, 60 parts of tricalcium phosphate and 3 parts of sodium dodecylbenzenesulfonate were uniformly dissolved and dispersed. Next, while maintaining the internal temperature of the beaker at 20 ° C. and stirring at 12000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), an oil phase in which 1 part of a ketimine compound was mixed immediately before emulsification was prepared. The resulting mixture was stirred and emulsified for 3 minutes. Subsequently, this mixed liquid was transferred to a flask equipped with a stirring bar and a thermometer, and the solvent was removed at 30 ° C. under reduced pressure of 50 mmHg for 8 hours. It was confirmed by gas chromatography that ethyl acetate in the dispersion was 100 ppm or less. Thereafter, the dispersion was cooled to room temperature, and 120 parts of 35% concentrated hydrochloric acid was added to dissolve tricalcium phosphate. Thereafter, the mixture was stirred for 1 hour at room temperature, filtered, and the operation of redispersing the obtained cake in distilled water and filtering was repeated three times. The obtained cake was further redispersed in distilled water to a solid content of 10% by weight. Thereto, a 1% by weight aqueous solution of stearylamine acetate was gradually added with stirring so that the pure content of stearylamine acetate was 0.3% by weight with respect to the toner solids. Thereafter, the mixture was stirred at room temperature for 1 hour and then separated by filtration. The obtained cake was dried under reduced pressure at 40 ° C. for 24 hours to obtain toner particles. Subsequently, 100 parts of toner particles were mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain the toner of the present invention. The physical properties of the electrostatic charge developing toner are shown in Table 1 below.

Comparative Example 2
A comparative toner was obtained in the same manner as in Example 2 except that the charge control agent dispersion 2 was used instead of the charge control agent dispersion 1 in Example 2. The physical properties of the electrostatic charge developing toner are shown in Table 1 below.

Example 3
An electrostatic charge developing toner of the present invention was obtained in the same manner as in Example 2 except that the charge control agent dispersion 3 was used instead of the charge control agent dispersion 1 of Example 2. The physical properties of the electrostatic charge developing toner are shown in Table 1 below.

Example 4
An electrostatic charge developing toner of the present invention was obtained in the same manner as in Example 2 except that the charge control agent dispersion 4 was used instead of the charge control agent dispersion 1 of Example 2. The physical properties of the electrostatic charge developing toner are shown in Table 1 below.

Example 5
A toner for electrostatic charge development of the present invention was obtained in the same manner as in Example 2 except that a dispersion obtained by diluting the charge control agent dispersion 1 of Example 2 twice with ethyl acetate was used. The physical properties of the electrostatic charge developing toner are shown in Table 1 below.

Example 6
An electrostatic charge developing toner of the present invention was obtained in the same manner as in Example 2 except that the charge control agent dispersion 5 was used in place of the charge control agent dispersion 1 in Example 2. The physical properties of the electrostatic charge developing toner are shown in Table 1 below.

(Evaluation of the obtained toner)
5 parts by weight of each of the prepared color toners of Examples 1 to 6 and Comparative Examples 1 and 2 and 95 parts by weight of the following carrier were mixed with a blender for 10 minutes to prepare a developer.

(Career)
Core material: Spherical ferrite particles having an average particle size of 50 μm Coating material constituent materials: Aminosilane coupling agent and silicone resin Aminosilane coupling agent and silicone resin are dispersed in toluene to adjust the dispersion, and then in a heated state. The core material was spray coated, fired and cooled, and carrier particles having an average coated resin film thickness of 0.2 μm were prepared.

(Charge rise)
In a test room at a temperature of 20 ° C. and a humidity of 50%, 100 parts of the carrier and 5 parts of the toner of the present invention were charged into a stainless steel pot and rotated and mixed at a constant rotational speed on a ball mill frame. The developer was stopped after 15 seconds from the start of rotation, and the charge amount (μC / g) of the obtained developer was measured with a blow-off device.

(Saturated charge)
The charge amount (μC / g) of the developer after stirring for 10 minutes was measured with a blow-off device in the same manner as the charge rising property.

[High-temperature and high-humidity environment (HH) saturation charge amount]
100 parts of the carrier and 5 parts of the toner of the present invention are allowed to stand for 1 hour in an environmental test room at a temperature of 30 ° C. and a humidity of 90%, charged in a stainless steel pot in the environmental test room, and fixed on the ball mill frame in the environmental test room. And mixed with rotation. The rotation was stopped 10 minutes after the start of rotation, and the charge amount (μC / g) of the obtained developer was measured with a blow-off device.

(Charge amount distribution)
The charge amount distribution of the toner was measured by a charge amount distribution measuring device (E-Spart Analyzer EST-2 type manufactured by Hosokawa Micron Corporation). As an index indicating the distribution of the charge amount, the distribution width at a position having a height that is half the most frequent (peak), that is, a so-called half width (q / d) is shown.

(Fine line reproducibility)
For fine line reproducibility, this developer is placed in a tandem, intermediate transfer type commercial color copier (IMAGIO COLOR 5000; manufactured by Ricoh Co., Ltd.) in a modified machine from which the fixing oil portion has been removed. Running was performed using 6000 paper manufactured by the company. Compare the original 10th image and the 30,000th image thin line with the original, and observe it with an optical microscope at a magnification of 100x, and evaluate it in 4 stages while comparing the line missing state with the stage sample. did. In either case, the image quality is higher in the order of ◎>○>△> ×. In particular, the evaluation of x is a level that cannot be adopted as a product.

(Fixing temperature range)
As for the fixability, after running 30,000 sheets as in the thin line reproducibility test, the surface temperature of the fixing roller was changed from 120 ° C to 200 ° C to output a solid color image, and the toner on the image was transferred to tape. The degree of soiling was evaluated by comparison with a four-stage sample. The fixing temperature at which the contamination of the tape was below the standard was defined as the minimum fixing temperature, the temperature at which image gloss began to decrease due to hot offset was defined as the maximum fixing temperature, and the difference was defined as the fixing temperature range.

It is the schematic for demonstrating a microreactor. 14 is a schematic photograph of a joining portion of a raw material supply microchannel a and a raw material supply microchannel b of a microreactor in Production Example 4. FIG. 10 is a schematic photograph of a joining portion of a raw material supply microchannel a and a raw material supply microchannel b of a microreactor in Production Example 5. FIG. 10 is a schematic photograph of a joining portion of a raw material supply microchannel a and a raw material supply microchannel b of a microreactor in Production Example 8. FIG.

Explanation of symbols

a Raw material inlet 1
b Raw material inlet 2
c Discharge port

Claims (13)

  Reaction is performed using a microreactor that is controlled so that a chemical reaction takes place in a reaction channel in which the solution is fed from at least two raw material supply microchannels. A charge control agent, wherein the average particle size of the reaction product obtained is 0.1 to 0.6 μm.   Using a microreactor that is controlled so that a chemical reaction takes place in a reaction channel in which the aromatic carboxylic acid derivative and the metal compound aqueous solution are respectively supplied from two raw material supply microchannels. A charge control agent, wherein the reaction product obtained by reacting is a metal compound particle of an aromatic carboxylic acid derivative having an average particle size of 0.1 to 0.6 μm.   The charge control agent according to claim 2, wherein the aromatic carboxylic acid derivative is selected from the group consisting of a salicylic acid derivative, a naphthoic acid derivative and an oxy-naphthoic acid derivative.   The charge control agent according to claim 3, wherein the aromatic carboxylic acid derivative is a salicylic acid derivative.   The charge control agent according to claim 2, wherein the metal compound aqueous solution is a divalent or higher metal salt aqueous solution.   The charge control agent according to any one of claims 1 to 3, wherein the particles are at most 1 µm or less.   An electrostatic charge developing toner comprising at least the charge control agent according to claim 1.   A developer containing the electrostatic charge developing toner according to claim 7.   Using a plurality of developing devices having a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll, an electrostatic latent image divided into each color formed on a single photoconductor 9. A method for developing an image with a developer corresponding to each color, wherein the developer according to claim 8 is used as the developer.   Using a plurality of developing devices having a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll, an electrostatic latent image divided into each color formed on a single photoconductor The developing method according to claim 8, wherein the developer is developed with a developer corresponding to each color and transferred to an intermediate transfer member by an electric field, wherein the developer according to claim 8 is used as the developer.   Using a plurality of developing devices equipped with a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll, the color is divided into each color formed on a plurality of photoreceptors corresponding to the developing device. In the method for developing the electrostatic latent image with a developer corresponding to each color, the developer according to claim 8 is used as the developer.   Using a plurality of developing devices equipped with a developing roll and a developing blade that uniformly regulates the layer thickness of the developer supplied onto the developing roll, the color is divided into each color formed on a plurality of photoreceptors corresponding to the developing device. In the developing method in which the electrostatic latent image is developed with a developer corresponding to each color and transferred to the intermediate transfer member by an electric field, the developer according to claim 8 is used as the developer. Method. At least one means selected from electrophotographic toner or toner storage means, charging means, latent image holding means (photoconductor), developing means, and cleaning means is integrally supported and attached to and detached from the main body of the image forming apparatus. 8. A process cartridge according to claim 7, wherein the toner for developing electrostatic charge according to claim 7 is used as the toner.