JP2005181776A - Nonmagnetic single-component developing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonmagnetic single-component developing method, capable of suppressing degradation in color reproducibility and increase in the consumption of a toner. <P>SOLUTION: In the nonmagnetic single-component developing method of developing electrostatic latent images on an electrostatic latent image carrier 5, by forming a thin layer of the nonmagnetic toner on the surface of a toner carrier 4 by a regulating member 3; the toner carrier has at least a substrate and a surface coating layer, containing a nitrogenous compound on the substrate; and the nonmagnetic toner contains a binder resin, a colorant and a resin having sulfur atoms. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a developing method for developing a latent image formed on an image bearing member such as an electrophotographic photosensitive member or an electrostatic recording dielectric with a non-magnetic one-component developer to visualize the latent image. .

  Conventionally, many methods are known as electrophotographic methods. Generally, a charging process for charging an image carrier using a photoconductive substance and an electrostatic latent image are formed on the charged image carrier. A developing process for developing the electrostatic latent image formed on the image carrier, a transferring process for transferring the developed image to a transfer material by a transfer means, and a transfer process on the transfer material. The target copy is obtained through a fixing step of heating and fixing the transferred image.

  Development methods in electrophotography are mainly divided into a one-component development method and a two-component development method. The two-component development method that requires carrier particles such as glass beads, iron powder, and ferrite needs to maintain a constant toner concentration in the developer, so a device that detects the toner concentration and replenishes the required amount of toner is required. This increases the size and weight of the developing device.

  In the one-component development method, a one-component developer (toner) is used, and a charge is applied to the toner particles by friction between the layer thickness regulating member and the toner particles and friction between the developer carrier and the toner particles, and at the same time, the developer carrier. The toner is applied thinly and conveyed to a developing area where the developer carrying member and the drum are opposed to each other, and the electrostatic latent image on the drum is developed to be visualized as a toner image. Unlike the two-component development method, this one-component development method can reduce the size and weight of the developing device because no carrier particles are required.

  In recent years, devices using electrophotography have been applied to multifunction devices such as printers and fax machines and scanners in addition to conventional copying machines. And with the widespread use of digital cameras and their high image quality, these demanded higher-quality full-color images, and further reduced size, extended service life, and environment to accommodate small offices and ordinary homes. Safety has come to be demanded.

  Especially for printers and fax machines, the developer unit and the electrostatic latent image carrier (hereinafter also referred to as the “drum”) are the drum units centered on the developer unit to reduce the size of the copying machine and simplify maintenance. It is becoming increasingly common to use two process units and process cartridges that integrate them. Therefore, as a developing device used for a process cartridge, a developing device that can aim for a reduction in size and weight using a one-component developer is often used.

With regard to the one-component developing device, contact development is performed by bringing the drum and the developing roller into contact with each other, and development is performed by electrostatically flying toner from the developer carrier onto the electrostatic latent image on the drum at a predetermined interval. There is jumping development to be performed. The developing device according to the present invention is characterized by jumping development. The problem with jumping development is that the chargeability of the toner falls in the second half of the endurance test and the electrostatic flight of the toner deviates from the development area. For this reason, it has been devised to stabilize the flight in the development region using magnetism (see Patent Document 1). However, the use of a magnetic material is likely to narrow the color gamut with color toners. Therefore, it is necessary to stabilize the chargeability of the toner so that it can fly electrostatically. Therefore, in the present invention, by introducing a resin containing sulfur atoms, the toner is easily charged by the friction between the layer regulating member and the toner. Further, it has been found that the addition of a quaternary ammonium salt compound to the resin coating layer on the developer carrying member suppresses the generation of excessive charge in the developer and provides suitable charging characteristics. In other words, it is known as a positive charge control agent of conventional toners, and is positively charged with respect to iron powder, and any of —NH ₂ group, ═NH group, and —NH— bond in its molecular structure. By forming the resin coating layer of the developer carrier using the binder resin contained in the developer, it is possible to effectively prevent the generation of the developer having an excessive charge and the strong adhesion of the developer to the surface of the developer carrier. Thus, it has been found that the triboelectric charge amount of the developer in the present invention can be maintained at a suitable level (see Patent Document 2 and Patent Document 3).

  By placing a non-magnetic one-component developer, in which a polymer containing sulfur atoms is introduced, on a resin coating layer of a developer carrier using this quaternary ammonium salt compound in an appropriate addition amount, a developer carrier is obtained. Since the density can be obtained even with a small amount of applied toner, color reproducibility and toner consumption control can be further improved.

  In a full color image forming apparatus, the resin coating layer of the developer carrying member has the above-described configuration, so that the charge amount of the developer into which the polymer containing sulfur atoms is introduced is stabilized, and image unevenness such as development unevenness and blotch is blurred. Further, it is possible to prevent occurrence of a decrease in image density due to fogging or charge-up. As a result, it has been found that a high-definition image can be obtained by a jumping development method even if toners of respective colors of yellow, cyan, magenta, and black are superimposed.

JP 2003-057942 A Japanese Patent Laid-Open No. 10-326040 JP 11-052711 A

  To provide a non-magnetic one-component developing method capable of suppressing deterioration in color reproducibility and increase in toner consumption due to a decrease in chargeability of a one-component developer in a color toner for repeated use in an electrophotographic developing apparatus. is there.

  The configuration for achieving the object of the present invention is a non-magnetic single component for developing an electrostatic latent image on an electrostatic latent image carrier by forming a thin layer of a non-magnetic developer on the surface of the developer carrier by a regulating member. The developer carrier in the development method has at least a substrate and a surface coating layer containing a nitrogen-containing compound on the substrate, and the nonmagnetic developer contains a binder resin, a colorant, and a resin having a sulfur atom. This is a non-magnetic one-component developing method.

  In a full-color developer for repeated use in an electrophotographic developing apparatus, the chargeability of a one-component developer is improved by adding a positive charge control agent such as an ammonium salt to the resin on the developer carrier. In addition, this means that the density can be obtained even with a small amount of toner on the developer carrying member, and image defects such as fogging can be avoided, so that color reproducibility and toner consumption control can be further improved. is there.

<1> Developer carrier used in the present invention The configuration of the developer carrier used in the present invention will be described. The developer carrying member includes a substrate and a resin coating layer surrounding and covering the substrate. Examples of the shape of the substrate include a cylindrical member, a columnar member, and a belt-like member. In the developing method without contact with the drum, a metal cylindrical member is preferably used, and specifically, a metal cylindrical tube is preferably used. As the metal cylindrical tube, nonmagnetic materials such as stainless steel, aluminum and alloys thereof are preferably used. In addition, as the substrate in the development method in which the drum is brought into direct contact, a cylindrical member having a layer structure containing rubber or elastomer such as urethane, EPDM, or silicone is preferably used.

  The method for forming the resin coating layer on the developer carrying member of the present invention is not particularly limited and can be performed by a usual method. The coating liquid containing the binder resin for the coating layer and the quaternary ammonium salt compound is applied to the base material of the developer carrier by a method such as dipping, spraying, or brushing, and dried. Thus, the developer carrying member used in the present invention can be obtained.

  As a result of repeated investigations on the surface of the developer carrier that imparts triboelectric charge to the developer, a resin coating layer is formed on the substrate of the developer carrier, and the formed resin coating layer is at least negatively charged. By containing a substance, it is possible to effectively prevent generation of excessively charged toner and strong adhesion of the toner to the surface of the developer carrying member with respect to the developer having conductive fine powder, and friction. It has been found that the charge amount can be charged to a suitable level.

  As the binder resin for resin coating used in the resin coating layer in the present invention, known resins can be used. For example, thermoplastic resins such as styrene resins, vinyl resins, polyethersulfone resins, polycarbonate resins, polyphenylene oxide resins, polyamide resins, fluororesins, fiber resins, acrylic resins, epoxy resins, polyester resins, alkyd resins Thermal or photo-curable resins such as phenol resin, melamine resin, polyurethane resin, urea resin, silicone resin, polyimide resin, etc. can be used. Among them, those having releasability such as silicone resin, fluorine resin, or polyether sulfone resin, polycarbonate resin, polyphenylene oxide resin, polyamide resin, phenol resin, polyester resin, polyurethane resin, styrene resin, acrylic resin Those having excellent mechanical properties are more preferred.

Among these, those having negative chargeability are preferably silicone resins, fluororesins, etc., and may be mixed with other binder resins for the purpose of improving mechanical strength. Further, as described above, a binder resin having at least one structure of —NH ₂ group, ═NH group, or —NH— bond may be used together with a quaternary ammonium salt having positive chargeability with respect to iron powder. preferable. By forming the resin coating layer using such a binder resin for the resin coating layer, the effect of the present invention is easily exhibited. In the present invention, when a binder resin having a structure as described above is used as the binder resin for the resin coating layer in the developer carrying member, there is no clear reason why the charge imparting property of the resin coating layer itself changes. Is a quaternary ammonium salt compound that is positively charged with respect to iron powder, and a binder for a resin coating layer having at least one structure of an —NH ₂ group, ═NH group, or —NH— bond By forming a resin coating layer using a resin, a quaternary ammonium salt is taken into the structure of the binder resin for the resin coating layer. At that time, the original structure of the quaternary ammonium salt having a positive polarity is lost, and the binder resin for the resin coating layer incorporating these has a uniform and sufficient negative chargeability, thereby stabilizing the charge. It is thought to contribute.

Examples of the substance having —NH ₂ group include a primary amine represented by R—NH ₂ or a polyamine having them, a first amide represented by RCO—NH ₂ , or a polyamide having them. Examples of the substance having = NH group include a secondary amine represented by R = NH or a polyamine having them, a second amide represented by (RCO) ₂ = NH, or a polyamide having them. Examples of the substance having an —NH— bond include polyurethane having an —NHCOO— bond in addition to the above-described polyamine, polyamide and the like. As the binder resin for the coating layer, an industrially synthesized resin containing one or more of the above substances as a copolymer or a copolymer is suitably used. Of these, from the viewpoint of versatility, phenol resins, polyamide resins, urethane resins and the like produced by adding and condensing phenols and aldehydes using a nitrogen-containing compound as a catalyst can be preferably used.

  Examples of the nitrogen-containing compound used as a catalyst in the production of a phenol resin include an acidic catalyst and a basic catalyst. Examples of the acidic catalyst include ammonium sulfate, ammonium phosphate, ammonium sulfamate, ammonium carbonate, ammonium acetate, maleic acid. Examples thereof include ammonium salts such as ammonium acid or amine salts. Examples of the basic catalyst include ammonia, dimethylamine, diethylamine, diisopropylamine, diisobutylamine, diamylamine, trimethylamine, triethylamine, tri-n-butylamine, triamylamine, dimethylbenzylamine, diethylbenzylamine, dimethylaniline, and diethyl. Aniline, N, N-di-n-butylaniline, N, N-diamilaniline, N, N-di-t-amylaniline, N-methylethanolamine, N-ethylethanolamine, diethanolamine, triethanolamine, dimethyl Ethanolamine, diethylethanolamine, ethyldiethanolamine, n-butyldiethanolamine, di-n-butylethanolamine, triisopropanolamine, ethylenediamine Amino compounds such as hexamethylenetetramine, pyridine such as pyridine, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine and derivatives thereof, quinoline compounds, imidazole, 2-methylimidazole, 2,4- Examples include imidazole such as dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, and derivatives thereof.

  It is also preferable to add a negatively charged substance to these known binder resins. As such a negatively charged substance, conventionally known substances can be used. For example, in addition to silica powder and fluororesin powder, there are organometallic complexes, chelate compounds, monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acid, and aromatic dicarboxylic acid metal complexes. In addition, there are aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

  Among them, the following aluminum compounds of benzylic acid, boron compounds, zinc compounds, chromium compounds and the like are preferably used for charging the developer satisfactorily. Examples of the benzylic acid compound include an aluminum compound of benzylic acid having an unsubstituted group or a substituent represented by the following general formula (11).

（式中、Ｒ⁵とＲ⁶は同一であっても異なっていても良く、各々、直鎖または分岐したアルキル基、アルケニル基、アルコキシル基、ハロゲン原子、ニトロ基、シアノ基、アミノ基、カルボキシル基及び水酸基からなる群から選ばれる置換基を示し、ｍ及びｎは０〜５の整数を示す。）

(In the formula, R ⁵ and R ⁶ may be the same or different, and each represents a linear or branched alkyl group, alkenyl group, alkoxyl group, halogen atom, nitro group, cyano group, amino group, carboxyl group. And represents a substituent selected from the group consisting of a group and a hydroxyl group, and m and n represent an integer of 0 to 5.)

  Among these, an aluminum compound of benzyl acid represented by the following general formula (12) is more preferable.

（式中、Ｒ⁵とＲ⁶は同一であっても異なっていても良く、各々、直鎖または分岐したアルキル基、アルケニル基、アルコキシル基、ハロゲン原子、ニトロ基、シアノ基、アミノ基、カルボキシル基及び水酸基からなる群から選ばれる置換基を示し、ｍ及びｎは０〜５の整数を示す。また、Ｙは１価のカチオン、水素、リチウム、ナトリウム、カリウム、アンモニウム及びアルキルアンモニウムを示す。）

(In the formula, R ⁵ and R ⁶ may be the same or different, and each represents a linear or branched alkyl group, alkenyl group, alkoxyl group, halogen atom, nitro group, cyano group, amino group, carboxyl group. A substituent selected from the group consisting of a group and a hydroxyl group, m and n are each an integer of 0 to 5. Y is a monovalent cation, hydrogen, lithium, sodium, potassium, ammonium or alkylammonium. )

  It is also preferable to further contain sulfonic acid-containing acrylamide. For example, 2-acrylamidopropanesulfonic acid, 2-acrylamide-n-butanesulfonic acid, 2-acrylamide-n-hexanesulfonic acid, 2-acrylamide-n-octanesulfonic acid, 2-acrylamido-n-dodecanesulfonic acid, 2 -Acrylamide-n-tetradecanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamido-2-phenylpropanesulfonic acid, 2-acrylamido-2,2,4-trimethylpentanesulfonic acid, 2-acrylamide- 2-methylphenylethanesulfonic acid, 2-acrylamido-2- (4-chlorophenyl) propanesulfonic acid, 2-acrylamido-2-carboxymethylpropanesulfonic acid, 2-acrylamido-2- (2-pyridyl) propanesulfur Acid, 2-acrylamido-1-methylpropanesulfonic acid, 3-acrylamido-3-methylbutanesulfonic acid, 2-methacrylamide-n-decanesulfonic acid, 2-methacrylamide-n-tetradecanesulfonic acid, etc. Can do. Preferably, 2-acrylamido-2-methylpropanesulfonic acid is used.

  The amount of the negatively chargeable substance added to the resin coating layer is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the binder resin for the resin coating layer. When the amount is less than 1 part by mass, the charging stability is not improved by addition. When the amount exceeds 100 parts by mass, the amount in the binder resin for the resin coating layer becomes excessive, and the original binder resin for the resin coating layer is used. These properties are impaired, and the strength of the coating layer is likely to decrease.

As a result of further investigations, it has been found that the addition of a quaternary ammonium salt compound to the resin coating layer suppresses the generation of excessive charge in the developer and provides suitable charging characteristics. That is, it is known as a positive charge control agent for conventional toners, and a quaternary ammonium salt compound that is positively charged with respect to iron powder is used in an appropriate addition amount, and a —NH ₂ group, a —NH group , By using a binder resin having any of —NH— bonds in its molecular structure to form a resin coating layer of the developer carrier, the generation of a developer having an excessive charge or the developer carrier. It has been found that the strong adhesion of the developer to the surface can be effectively prevented and the triboelectric charge amount of the developer in the present invention can be maintained at a suitable level.

  The superior point of this method is that the resin is compared with a system in which powder such as silica, fluororesin powder, negative charge control agent is added to the resin coating layer and dispersed in a matrix to impart charge to the toner. Since the quaternary ammonium salt compound is dissolved in the solvent of the binder resin for the coating layer and can be uniformly present in the resin, a resin coating layer exhibiting uniform and good charge imparting properties is formed on the entire developer carrier. It can be formed. Further, since it is not a powder addition system, it has a good mechanical strength, that is, durability.

  It has been found that by having the resin coating layer of the developer carrying member configured as described above, the charge amount of the developer can be stabilized, and the occurrence of development unevenness, blotch, fog, image density reduction due to charge-up, and the like can be prevented. . As the quaternary ammonium salt compound suitably used in the present invention, those having positive chargeability with respect to iron powder are used. Examples thereof include compounds represented by the following general formula (1).

（式中のＲ₁、Ｒ₂、Ｒ₃、Ｒ₄は、各々、置換基を有しても良いアルキル基、置換基を有しても良いアリール基、アルアルキル基を表し、各々同一でもあるいは異なっていてもよい。Ｘ−は酸の陰イオンを表す。）

(In the formula, R ₁ , R ₂ , R ₃ , and R ₄ each represents an alkyl group that may have a substituent, an aryl group that may have a substituent, and an aralkyl group. Or X- represents an anion of an acid.

  Specific examples of the quaternary ammonium salt compound that is preferably used in the present invention and is positively charged with respect to iron powder include the following general formulas (3) to (10). Of course, the present invention is not limited to these.

  The addition amount of the quaternary ammonium salt compound used in the present invention as described above is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the binder resin for the resin coating layer. If it is less than 1 part by mass, no charge-up prevention due to addition and improvement in charging stability are not observed. If it exceeds 100 parts by mass, the amount of the resin present in the binder resin for the resin coating layer becomes excessive, and the characteristics of the original resin And the film strength is liable to decrease.

  In order to adjust the volume resistance of the resin coating layer, the developer carrier used in the present invention may contain conductive fine powder dispersed in the binder resin for the coating layer. Such conductive fine powder preferably has a number average particle size of 20 μm or less, and more preferably 10 μm or less. In order to avoid unevenness formed on the surface of the binder resin for coating layer, it is more preferable to use conductive fine powder having a number average particle diameter of 1 μm or less.

  The average particle size of the conductive fine powder in the present invention is measured in a measurement range of 0.04 to 2000 μm by attaching a liquid module to an LS-230 type laser diffraction particle size distribution measuring device manufactured by Beckman Coulter. As a measuring method, a trace amount of surfactant is added to 10 ml of pure water, 10 mg of a conductive fine powder sample is added thereto, and the mixture is dispersed for 10 minutes with an ultrasonic disperser (ultrasonic homogenizer). Measured once per second and number of measurements.

  The conductive fine powder used in the present invention includes carbon black such as furnace black, lamp black, thermal black, acetylene black, channel black; titanium oxide, tin oxide, zinc oxide, molybdenum oxide, potassium titanate, antimony oxide. And metal oxides such as indium oxide; metals such as aluminum, copper, silver and nickel; inorganic fillers such as graphite, metal fibers and carbon fibers.

  As an addition amount of the conductive fine powder in the resin coating layer described above, a preferable range is 60 parts by mass or less with respect to 100 parts by mass of the binder resin for the coating layer. A more preferable addition amount is 40 parts by mass or less. When the addition amount exceeds 60 parts by mass, the coating strength is liable to decrease, and the addition of a large amount of non-chargeable particles causes a decrease in the charge amount of the toner.

  As the constitution of the resin coating layer of the developer carrying member used in the present invention, it is preferable to further disperse the lubricating substance in the resin coating layer because the effect of the present invention is further promoted. Examples of the lubricating substance include graphite, molybdenum disulfide, boron nitride, mica, graphite fluoride, silver-niobium selenide, calcium chloride-graphite, talc, and fatty acid metal salts such as zinc stearate. Is preferably used because it does not impair the conductivity of the coating layer. These lubricating substances preferably have a number average particle diameter of preferably about 0.2 to 20 μm, more preferably 0.3 to 15 μm. In the present invention, the average particle size of the lubricating substance is 0.04 to 0.04 to the liquid particle size distribution measuring device manufactured by Beckman Coulter, LS-230, as in the case of measuring the particle size of the conductive fine powder. Measure in the measuring range of 2000 μm. As the addition amount of the lubricating substance, particularly preferable results are given in the range of 10 to 50 parts by mass with respect to 100 parts by mass of the binder resin for the coating layer. When the addition amount exceeds 50 parts by mass, the strength of the coating layer is likely to be reduced, and when a large amount of non-chargeable additive is added, the charge amount of the toner is reduced. On the other hand, if it is less than 10 parts by mass, it is difficult to obtain the effect of adding toner to the developer carrying member.

  Further, the resin coating layer of the developer carrying body stabilizes the surface roughness by dispersing spherical particles in the resin coating layer in addition to the above-mentioned additive substances, and the developer coating amount on the developer carrying body. Can be optimized. The spherical particles maintain a uniform surface roughness on the surface of the coating layer of the developer carrier, and at the same time, even when the surface of the coating layer is worn, there is little change in the surface roughness of the coating layer. There is an effect of making it difficult to cause agent fusion.

  The spherical particles used in the present invention have a number average particle size of 0.3 to 30 μm, preferably 2 to 20 μm. If the number average particle size of the spherical particles is less than 0.3 μm, the effect of imparting uniform roughness to the surface and the effect of stabilizing the charging performance thereby are small, and the rapid and uniform charging to the developer becomes insufficient. . In addition, the developer transport becomes unstable, and further deterioration in transportability due to wear of the coating layer causes developer charging failure, developer contamination, and developer fusion, resulting in ghost deterioration and image density reduction. Is liable to occur, which is not preferable. When the number average particle diameter exceeds 30 μm, the coating layer surface becomes too rough, the developer transport amount becomes large, and it becomes difficult for the developer regulating section to be sufficiently regulated. Charging is difficult to perform sufficiently, and problems such as deterioration in image quality and increase in reversal fog are likely to occur. Furthermore, it is not preferable because the mechanical strength of the coating layer decreases and the durability of the film decreases.

The number average particle diameter of the spherical particles is measured using a LS-230 type laser diffraction particle size distribution measuring device manufactured by Beckman Coulter, in the same manner as the particle diameter measurement of the conductive fine powder. Spherical particles true density of 3 g / cm ³ or less, preferably 2.7 g / cm ³ or less, it is better and more preferably from 0.9~2.3g / cm ^3. That is, when the true density of the spherical particles exceeds ³ g / cm ³ , the dispersibility of the spherical particles in the coating layer becomes insufficient, so that it is difficult to impart uniform roughness to the coating layer surface. Also, since the storage stability of the paint is not good, it is difficult to obtain the surface of the triboelectric charge imparting member having uniform surface irregularities. Even when the true density of the spherical particles is less than 0.9 g / cm ³ , the dispersibility and storage stability of the spherical particles in the coating layer tend to be insufficient.

  The true density of the spherical particles was measured using a dry densitometer Accuvic 1330 (manufactured by Shimadzu Corporation). In the present invention, “spherical” in the spherical particles means that the ratio of the major axis / minor axis of the particles is about 1.0 to 1.5. In the present invention, the ratio of major axis / minor axis is preferably 1. It is preferable to use particles of 0 to 1.2. When the ratio of the major axis / minor axis of the spherical particles exceeds 1.5, the coating layer surface roughness becomes non-uniform, which leads to rapid and uniform charging of the toner and the strength of the conductive coating layer. It is not preferable.

  As the spherical particles used in the present invention, known spherical particles can be used. Examples include spherical resin particles, spherical metal oxide particles, and spherical carbonized particles. Spherical resin particles are obtained, for example, by suspension polymerization, dispersion polymerization, and the like, and a suitable surface roughness can be obtained with a smaller addition amount, and a more uniform surface shape can be easily obtained. Examples of such spherical particles include acrylic resin particles such as polyacrylate and polymethacrylate, polyamide resin particles such as nylon, polyolefin resin particles such as polyethylene and polypropylene, silicone resin particles, phenol resin particles, and polyurethane resins. Examples thereof include resin particles, styrene resin particles, and benzoguanamine particles. The resin particles obtained by the pulverization method may be used after thermally or physically spheroidizing.

An inorganic fine powder may be attached to the surface of the spherical particles or may be fixed. Examples of such inorganic fine powder include oxides such as SiO ₂ , SrTiO ₃ , CeO ₂ , CrO, Ai ₂ O ₃ , ZnO and MgO, nitrides such as Si ₃ N ₄ , carbides such as SiC, CaSO ₄ , Examples thereof include sulfates such as BaSO ₄ and CaCO ₃ , and carbonates. The inorganic fine powder attached to the spherical particles may be used after being treated with a coupling agent. In particular, it is preferable to use spherical particles to which an inorganic fine powder treated with a coupling agent is attached for the purpose of improving the adhesion to the binder resin or imparting hydrophobicity to the particles. Examples of such a coupling agent include a silane coupling agent, a titanium coupling agent, and a zircoaluminate coupling agent. More specifically, as silane coupling agents, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchloro. Silane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethyldiethoxysilane , Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldi Siloxane, 1,3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane having 2 to 12 siloxane units per molecule, each containing a hydroxyl group bound to one silicon atom at each terminal unit Etc. By attaching the inorganic fine powder treated with the coupling agent to the spherical particle surface in this way, dispersibility in the resin coating layer, uniformity of the resin coating layer surface, stain resistance of the resin coating layer, The charge imparting property to the toner, the abrasion resistance of the resin coating layer, and the like can be improved.

The spherical particles used in the present invention are more preferably conductive. That is, by imparting conductivity to the spherical particles, it is difficult for charges to accumulate on the particle surface, and it is possible to reduce the adhesion of the developer and to improve the charge imparting property to the developer. In the present invention, the conductivity of the spherical particles is preferably a conductive spherical particle having a volume resistance of 10 ⁶ Ωcm or less, more preferably 10 ⁻³ to 10 ⁶ Ωcm. In the present invention, when the volume resistance of the spherical particles exceeds 10 ⁶ Ωcm, the developer is likely to cause contamination and fusion of the developer with the spherical particles exposed on the surface of the coating layer due to wear as a core, and rapid and uniform charging is achieved. Since it becomes difficult to be performed, it is not preferable.

  As a method for obtaining such conductive spherical particles, the following methods are preferable, but are not necessarily limited to these methods. As a method for obtaining particularly preferable conductive spherical particles used in the present invention, low density and good conductive spherical carbon particles obtained by carbonizing or graphitizing resin spherical particles or mesocarbon microbeads are obtained. The method of obtaining is mentioned. Examples of the resin used for the resin spherical particles include phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, and polyacrylonitrile. In addition, mesocarbon microbeads can be usually produced by washing spherical crystals formed in the process of heating and firing the medium pitch with a large amount of a solvent such as tar, medium oil, and quinoline.

  More preferable methods for obtaining conductive spherical particles include a mechanochemical method on the surface of spherical resin particles such as phenol resin, naphthalene resin, furan resin, xylene resin, divinylbenzene polymer, styrene-divinylbenzene copolymer, and polyacrylonitrile. And a method of obtaining conductive spherical carbon particles by coating bulk mesophase pitch by carbonization and heat-treating the coated particles in an oxidizing atmosphere, followed by firing in an inert atmosphere or vacuum to carbonize and / or graphitize. It is done. The spherical carbon particles obtained by this method have improved crystallization because the coating of the spherical carbon particles obtained by graphitization has progressed.

Any of the above-described methods can control the conductivity of the spherical carbon particles by changing the firing conditions, and is preferably used in the present invention. In addition, the spherical carbon particles obtained by the above method are plated with a conductive metal and / or metal oxide so that the true density of the conductive spherical particles does not exceed ³ g / cm ³ in order to further increase the conductivity. May be given.

  As another method of obtaining the conductive spherical particles used in the present invention, by electrically mixing conductive fine particles having a particle size smaller than the particle size of the core particles made of spherical resin particles at an appropriate blending ratio, After the conductive fine particles uniformly adhere around the core particles by the action of van der Waals force and electrostatic force, the core particle surface is softened by the local temperature rise caused by applying mechanical impact force, and the core particles are softened. Examples thereof include a method of obtaining conductive resin-treated spherical resin particles by forming conductive fine particles on the particle surface.

  Further, as other methods for obtaining conductive spherical particles, there are two methods for obtaining conductive spherical particles in which conductive fine particles are dispersed by uniformly dispersing conductive fine particles in spherical resin particles. One method of uniformly dispersing the conductive fine particles in the spherical resin particles is to knead the binder resin used for the spherical resin particles and the conductive fine particles to disperse the conductive fine particles, and then cool them. Examples thereof include a method of solidifying, pulverizing to a predetermined particle size, and spheronizing by mechanical treatment and thermal treatment to obtain conductive spherical particles. The other is dispersion stability of a monomer composition that is uniformly dispersed by a disperser by adding a polymerization initiator, conductive fine particles and other additives to the polymerizable monomer used for spherical resin particles. A method of obtaining conductive spherical particles by carrying out a polymerization reaction after suspending in an aqueous phase containing an agent with a stirrer or the like so as to have a predetermined particle size.

<2> Developer Used in the Present Invention The method for producing the toner of the present invention is not particularly limited, but more preferably, a polymerized toner that can easily control the particle size distribution and easily obtain a spherical toner is used.

  Among the polymerized toners, a method for producing toner by the aggregation method will be described.

  The resin particle dispersion used in the toner production method by the aggregation method is one in which at least resin particles are dispersed in a dispersant. Examples of the resin used for the resin particles include thermoplastic binder resins, and specifically, homopolymers or copolymers of styrenes such as styrene, parachlorostyrene, and α-methylstyrene (styrene-based resins). ); Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, Homopolymers or copolymers of esters having vinyl groups such as 2-ethylhexyl methacrylate (vinyl resins); Homopolymers or copolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile (vinyl resins) Vinyl acetate such as vinyl methyl ether and vinyl isobutyl ether Homopolymers or copolymers of vinyls (vinyl resins); homopolymers or copolymers of vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone (vinyl resins); ethylene, propylene, Homopolymers or copolymers of olefins such as butadiene and isoprene (olefin resins); non-vinyl condensation resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and the like Examples thereof include graft polymers of non-vinyl condensation resins and vinyl monomers. These resins may be used alone or in combination of two or more.

  Among these resins, vinyl resins are particularly preferable. In the case of a vinyl resin, it is advantageous in that a resin particle dispersion can be easily prepared by emulsion polymerization or seed polymerization using an ionic surfactant or the like. Examples of the vinyl monomer include acrylic acid, methacrylic acid, maleic acid, cinnamic acid, fumaric acid, vinyl sulfonic acid, ethylene imine, vinyl pyridine, vinyl amine, and other vinyl polymer acids and vinyl polymer bases. The monomer used as a raw material is mentioned. In the present invention, the resin particles preferably contain the vinyl monomer as a monomer component, and a styrene-acrylic resin with a small change in toner charge amount in a high temperature and high humidity or low temperature and low humidity environment is preferable. In the present invention, among these vinyl monomers, vinyl polymer acids are more preferable from the viewpoint of ease of formation reaction of vinyl resins, and specifically, acrylic acid, methacrylic acid, maleic acid, cinnamon. A dissociable vinyl monomer having a carboxyl group such as an acid or fumaric acid as a dissociating group is particularly preferred from the viewpoint of controlling the degree of polymerization and the glass transition point. Furthermore, at this time, in order to adjust the molecular weight, a chain transfer agent, a crosslinking agent, or the like can be used in combination.

  As the chain transfer agent, mercaptans such as octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, halogen compounds such as carbon tetrabromide, disulfides and the like are used. Furthermore, as the crosslinking agent, it is possible to use one having two or more unsaturated bonds such as divinylbenzene, divinylnaphthalene, divinyl ether, diethylene glycol methacrylate, ethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, diallyl phthalate, In particular, divinylbenzene is preferably used.

  In the present invention, the radical polymerization initiator can be appropriately used as long as it is water-soluble. For example, persulfates (potassium persulfate, ammonium persulfate, etc.), azo compounds [4,4′-azobis-4-cyanovaleric acid and its salts, 2,2′-azobis (2-amidinopropane) salts, etc.], Examples thereof include peroxide compounds such as hydrogen oxide and benzoyl peroxide. The radical polymerization initiator can be combined with a reducing agent as needed to form a redox initiator. By using a redox initiator, the polymerization activity is increased, the polymerization temperature can be lowered, and the polymerization time can be further shortened.

  The polymerization temperature may be any temperature as long as it is equal to or higher than the lowest radical generation temperature of the polymerization initiator. For example, a range of 50 ° C. to 80 ° C. is used. Moreover, it is also possible to superpose | polymerize at room temperature or the temperature close | similar to it by using the polymerization initiator of normal temperature start, for example, the combination of hydrogen peroxide-reducing agent (ascorbic acid etc.).

  Surfactants that can be used for polymerization include sulfonates (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino-8- Sodium naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sulfonate Sulfate ester salts (sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, etc.), fatty acid salts (sodium oleate, sodium laurate, sodium caprate, sodium caprylate, sodium caproate) , Potassium stearate, calcium oleate), and the like.

  The average particle diameter of the resin particles is preferably 0.01 to 1 μm. When the average particle size of the resin particles exceeds 1 μm, the particle size distribution of the finally obtained toner becomes wide, and free particles are generated, which tends to cause deterioration in performance and reliability. On the other hand, when the average particle diameter is within the above range, there are no disadvantages, and it is advantageous in that uneven distribution among toners is reduced, dispersion in the toner is good, and variations in performance and reliability are reduced.

  As content of the said resin particle in the said resin particle dispersion liquid, it is 5-60 mass% normally, Preferably it is 10-40 mass%. Further, the content of the resin particles in the aggregated particle dispersion when the aggregated particles are formed may be 50% by mass or less, and is preferably about 2 to 40% by mass.

  The colorant particle dispersion is obtained by dispersing at least colorant particles in a dispersant. Examples of the colorant include phthalocyanine pigments, monoazo pigments, bisazo pigments, magnetic powder, and quinacridone pigments. Specific examples thereof include, for example, carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brillianthamine 3B, brillianthamine. 6B, DuPont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments: acridine, xanthene, azo, benzoquinone, azine, anthraquinone, dioxane Various dyes such as gin, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole, and xanthene; . These colorants may be used alone or in combination of two or more.

  The average particle diameter of the colorant particles is preferably 0.5 μm or less, and more preferably 0.2 μm or less. When the average particle size exceeds 0.5 μm, irregular reflection of visible light cannot be prevented. In addition, when coarse particles are present, the coloring power, color reproducibility, and OHP permeability are adversely affected, and the resin particles and the colorant particles do not aggregate in the later-described aggregated particle forming step or are fused even if aggregated. Sometimes desorbed. Therefore, it is not preferable in that the quality of the obtained toner may be deteriorated. On the other hand, when the average particle diameter of the colorant particles is within the above range, there is no such disadvantage as described above, and uneven distribution between the toners is reduced, and dispersion in the toner is good, resulting in variations in performance and reliability. This is advantageous in that it becomes smaller. The content of the colorant particles and the like is about 1 to 10% by mass, more preferably about 2 to 6% by mass in the aggregated particle dispersion when the aggregated particles are formed.

  The release agent particle dispersion is obtained by dispersing at least release agent particles in a dispersant. As the release agent, those having a melting point of 150 ° C. or lower are used, preferably those having a melting point of 40 ° C. to 130 ° C., and particularly preferably those having a melting point of 50 ° C. to 100 ° C. For example, low molecular weight polyolefins such as polyethylene; silicones having a melting point (softening point) upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide; ester waxes such as stearyl stearate Kinds: plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, ester Examples thereof include particles such as minerals such as waxes, petroleum-based waxes, and modified products thereof. The average particle size of the release agent particles is preferably 2.0 μm or less, and more preferably 1.0 μm or less. When the average particle diameter exceeds 2.0 μm, the wax content tends to occur between the toners, which adversely affects the stability of the image over a long period of time. On the other hand, when the average particle diameter of the release agent particles is within the above range, uneven distribution among the toners is reduced, the dispersion in the toners is improved, and variations in performance and reliability are reduced. There is no restriction | limiting in particular as a combination of the said colorant particle, the said resin particle, and a mold release agent particle | grain, According to the objective, it can select suitably suitably. The content of the release agent particles is about 0.5 to 20% by mass in the aggregated particle dispersion when the aggregated particles are formed, and preferably about 1 to 10% by mass. When the content of the release agent particles is larger than 5% by mass, the particle size distribution may be widened to deteriorate the characteristics. In this case, the problem can be solved by performing seed polymerization on the release agent when generating the resin particles.

  In addition to the resin particle dispersion, the colorant particle dispersion, and the release agent dispersion, a particle dispersion obtained by dispersing appropriately selected particles in a dispersant may be further mixed. The particles contained in the particle dispersion are not particularly limited and may be appropriately selected according to the purpose. Examples thereof include internal additive particles, charge control agent particles, inorganic particles, and abrasive particles. In the present invention, these particles may be dispersed in the resin particle dispersion or the colorant particle dispersion. Examples of the charge control agent particles include particles such as quaternary ammonium salt compounds, nigrosine compounds, compounds composed of complexes of aluminum, iron, chromium, zinc, zirconium, and the like. The charge control agent particles in the present invention are preferably those that are difficult to dissolve in water from the viewpoints of controlling ionic strength that affects the stability during aggregation and fusion and recycling wastewater. The content of each particle such as the particle dispersion is about 0.01 to 5% by mass and preferably about 0.5 to 2% by mass in the aggregated particle dispersion when the aggregated particles are formed. . If the content is outside the above range, the effect of dispersing the release agent particles or the like may be insufficient, or the particle size distribution may be widened to deteriorate the characteristics.

  The average particle size of the above-mentioned particles is preferably 0.01 to 1 μm. When the average particle diameter exceeds 1 μm, the particle diameter distribution of the finally obtained toner is widened, and free particles are generated, which tends to cause deterioration in performance and reliability. On the other hand, when the average particle diameter is within the above range, there are no disadvantages, and the uneven distribution among the toners is reduced, the dispersion in the toners is improved, and the variation in performance and reliability is reduced. Furthermore, in order to control the chargeability of the toner obtained, the charge control particles and the resin particles may be added after the aggregated particles are formed.

  Examples of the dispersant contained in the resin particle dispersion, the colorant particle dispersion, the release agent dispersion, the particle dispersion, and the like include an aqueous medium containing a polar surfactant. Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together. The content of the polar surfactant in the polar dispersant cannot be generally defined and can be appropriately selected according to the purpose. Examples of polar surfactants include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type. . Specific examples of the anionic surfactant include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and the like. Specific examples of the cationic surfactant include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. These may be used individually by 1 type and may use 2 or more types together.

  In the present invention, these polar surfactants and nonpolar surfactants can be used in combination. Examples of nonpolar surfactants include polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based nonionic surfactants, and the like.

  The resin particle dispersion is prepared, for example, as follows. First, the resin in the resin particles is a homopolymer or copolymer (vinyl resin) of a vinyl monomer such as the ester having a vinyl group, the vinyl nitrile, the vinyl ether, or the vinyl ketone. In some cases, a vinyl monomer homopolymer or copolymer (vinyl resin) resin is obtained by emulsion polymerization or seed polymerization of the vinyl monomer in an ionic surfactant. A dispersion is prepared by dispersing particles in an ionic surfactant. When the resin in the resin particles is a resin other than the homopolymer or copolymer of the vinyl monomer, the resin can be used as long as it is soluble in an oily solvent having a relatively low solubility in water. Is dissolved in an oily solvent. This solution is finely dispersed in water together with an ionic surfactant and a polymer electrolyte using a disperser such as a homogenizer. Then, the dispersion liquid which disperse | distributes resin particles other than vinyl resin to an ionic surfactant is prepared by evaporating an oil-based solvent by heating or pressure reduction.

  The dispersion means is not particularly limited, and examples thereof include known dispersion apparatuses such as a rotary shear type homogenizer and a ball mill having a medium, a sand mill, and a dyno mill.

  The colorant particle dispersion, the release agent dispersion, the particle dispersion, and the like are prepared by adding particles such as the colorant particles into a dispersant and dispersing the particles using the means for dispersion. .

(Aggregation process)
In the formation of the aggregated particles, aggregated particles are formed in a mixed solution to prepare an aggregated particle dispersion. The agglomerated particles can be formed in the mixture by adding a pH adjuster, a flocculant, and a stabilizer to the mixture and mixing them, and appropriately adding temperature, mechanical power, and the like.

  Examples of the pH adjuster include alkalis such as ammonia and sodium hydroxide, and acids such as nitric acid and citric acid. Examples of the flocculant include monovalent metal salts such as sodium and potassium; divalent metal salts such as calcium and magnesium; trivalent metal salts such as iron and aluminum; and alcohols such as methanol, ethanol and propanol. It is done. Examples of the stabilizer mainly include the polar surfactant itself or an aqueous medium containing the same. For example, when the polar surfactant contained in the aqueous dispersion is anionic, a cationic one can be selected as the stabilizer.

  The addition / mixing of the flocculant and the like is preferably performed at a temperature below the glass transition point of the resin contained in the mixed solution. When mixing is performed under this temperature condition, aggregation proceeds in a stable state. The mixing can be performed using a known mixing device, a homogenizer, a mixer and the like.

  The average particle size of the aggregated particles formed here is not particularly limited, but is controlled to be approximately the same as the average particle size of the toner to be obtained. The control can be easily performed by appropriately setting and changing the temperature and the stirring and mixing conditions. Through the above-described aggregated particle forming step, aggregated particles having an average particle diameter substantially the same as the average particle diameter of the toner are formed, and an aggregated particle dispersion liquid in which the aggregated particles are dispersed is prepared.

(Heat fusion process)
The thermal fusion process is a process in which the aggregated particles are heated and fused. Before entering the fusing step, the pH adjusting agent, the polar surfactant, the nonpolar surfactant, and the like can be appropriately added in order to prevent fusing between toner particles.

  The heating temperature may be within the range from the glass transition temperature of the resin contained in the aggregated particles to the decomposition temperature of the resin. Therefore, since the heating temperature differs depending on the type of resin of the resin particles and the resin fine particles, it cannot be defined unconditionally, but generally the glass transition point of the resin contained in the aggregated particles or the adhered particles The temperature is 140 ° C. or lower. The heating can be performed using a known heating device / apparatus.

  As the fusion time, a short time is sufficient if the heating temperature is high, and a long time is required if the heating temperature is low. That is, the fusion time depends on the heating temperature and cannot be defined in general, but is generally 30 minutes to 10 hours.

  In the present invention, the toner obtained after completion of the fusing process can be washed and dried under appropriate conditions. In addition, inorganic particles such as silica, alumina, titania, calcium carbonate, and resin particles such as vinyl resin, polyester resin, and silicone resin are added to the surface of the obtained toner by applying a shearing force in a dry state. May be. These inorganic particles and resin particles function as external additives such as fluidity aids and cleaning aids.

  Next, among the polymerized toners, a method for producing the toner of the present invention in the suspension polymerization method will be described.

  First, a release agent, a polar resin, a colorant, a charge control agent, a polymerization initiator, and other additives are added to the polymerizable monomer, and the solution is uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser, or the like. The quantity system is dispersed in a water phase containing a dispersion stabilizer by a usual stirrer, homogenizer, homomixer or the like. At this time, granulation is preferably performed by adjusting the stirring speed and time so that the monomer droplets have a desired developer particle size. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the sedimentation of the particles is prevented by the action of the dispersant. The polymerization temperature is preferably set to 40 ° C. or higher, generally 50 ° C. to 90 ° C. In addition, the temperature may be raised in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers and by-products that cause odors when fixing the developer, the latter half of the reaction or at the end of the reaction. A part of the aqueous medium may be distilled off. After completion of the reaction, the produced developer particles are washed, collected by filtration and dried. In the suspension polymerization method, it is usually preferable to use 300 parts by mass to 3000 parts by mass of water as a dispersion medium with respect to 100 parts by mass of the monomer system.

  Toner particle size distribution control and particle size control can be done by adjusting the pH of the system during granulation, changing the type and addition amount of a sparingly water-soluble inorganic salt and protective colloid, mechanical equipment conditions, For example, it can be achieved by controlling the stirring conditions such as the peripheral speed of the rotor, the number of passes, the shape of the stirring blades, the shape of the container or the solid content concentration in the aqueous solution.

  Examples of the polymerizable monomer used in the present invention include styrene monomers such as styrene, o- (m-, p-) methylstyrene, m- (p-) ethylenestyrene; methyl (meth) acrylate, Propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate (Meth) acrylate monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; monomers such as butadiene, isoprene, cyclohexane, (meth) acrylonitrile, and acrylamide Preferably used.

  Moreover, as a polar resin added at the time of superposition | polymerization, the copolymer of a styrene (meth) acrylic acid, a maleic acid copolymer, a polyester resin, and an epoxy resin are used preferably. In the present invention, in order to prevent fixing offset, it is possible to add wax in the same manner as that used for the agglomerated toner.

  As the release agent, those having a melting point of 150 ° C. or less are used, preferably those having a melting point of 40 ° C. to 130 ° C., and particularly preferably those having a melting point of 40 ° C. to 110 ° C. For example, low molecular weight polyolefins such as polyethylene; silicones having a melting point (softening point) upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, and stearic acid amide; ester waxes such as stearyl stearate Kinds: plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, ester Examples thereof include particles such as minerals such as waxes, petroleum-based waxes, and modified products thereof.

  Examples of the colorant include phthalocyanine pigments, monoazo pigments, bisazo pigments, magnetic powder, and quinacridone pigments. Specific examples thereof include, for example, carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brillianthamine 3B, brillianthamine. 6B, DuPont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments: acridine, xanthene, azo, benzoquinone, azine, anthraquinone, dioxane Various dyes such as gin, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole, and xanthene; . These colorants may be used alone or in combination of two or more.

  Examples of the polymerization initiator used in the present invention include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1). -Carbonitrile), azo polymerization initiators such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutylnitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroxy peroxide, A peroxide polymerization initiator such as 2,4-dichlorobenzoyl peroxide or lauroyl peroxide is used. Although the addition amount of a polymerization initiator changes with the target degree of polymerization, generally 0.5 mass%-20 mass% are added and used with respect to a monomer. The kind of the polymerization initiator is slightly different depending on the polymerization method, but may be used alone or mixed with reference to the 10-hour half-life temperature.

  Examples of the dispersant used when using suspension polymerization include inorganic calcium oxides such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, and hydroxide. Examples thereof include magnesium, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina, magnetic substance, and ferrite. As the organic compound, for example, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, starch and the like are used dispersed in an aqueous phase. These dispersants are preferably used in an amount of 0.2 to 2.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer. These commercially available dispersants may be used as they are, but in order to obtain dispersed particles having a fine and uniform particle size, they can also be obtained by producing the inorganic compound in a dispersion medium under high-speed stirring. . For example, in the case of calcium phosphate, a dispersant preferable for the suspension polymerization method can be obtained by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution under high-speed stirring.

  Moreover, you may use together 0.001-0.1 mass part surfactant for refinement | miniaturization of these dispersing agents. Specifically, commercially available nonionic, anionic and cationic surfactants can be used, such as sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, Calcium oleate is preferably used. In the toner of the present invention, as in the case of the agglomerated toner, in addition to a black colorant such as carbon black or magnetite, any pigment or dye such as yellow, magenta, and cyan colorant can be used as a colorant.

  In the one-component toner of the present invention, a charge control agent can be used to control the charge amount of the toner as in the case of the aggregation toner. As the charge control agent, organometallic complexes and chelate compounds are effective when controlling to negative charge, and salicylic acid, naphthoic acid, dicarboxylic acid, metal compounds of derivatives thereof, and polymers having sulfonic acid in the side chain Compounds, boron compounds, urea compounds, silicon compounds, calixarene, monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid metal complexes can be used. The usage-amount of the said charge control agent is 0.1-15 mass parts with respect to 100 mass parts of binder resin, Preferably it is 0.1-10 mass parts.

  It is essential to add a polymer having a sulfur atom to the toner of the present invention. Among polymers having a sulfur atom, it is particularly preferable to use a polymer having a sulfonic acid group. By adding a polymer having a sulfonic acid group to the toner, the dispersion state of the wax in the binder is improved, the fixability on the low temperature side and the high temperature side is dramatically improved, and the deterioration of the charging property due to the wax is prevented. be able to. Furthermore, since the polarity of the sulfonic acid group also improves the chargeability of the toner, scattering that occurs during fixing can be sufficiently suppressed, and the image density and fog are also improved. Examples of the polymer having a sulfonic acid group used in the present invention include a polymer type compound having a sulfonic acid group in the side chain, and in particular, a methacrylic acid monomer containing a sulfonic acid group has a copolymerization ratio of 2 mass. % Or more, preferably 5% by mass or more, and using a polymer compound comprising a styrene and / or styrene (meth) acrylate copolymer having a glass transition temperature (Tg) of 40 to 90 ° C., The preferred charging characteristics can be enjoyed without affecting the thermal characteristics required of the toner particles. As said (sulfonic) group containing (meth) acrylamide type monomer, what can be represented by following General formula (2) is preferable, and, specifically, 2-acrylamido-2-methylpropanoic acid and 2-methacrylamide-2-methyl are used. And propanoic acid.

［上記一般式（２）中、Ｒ₁は水素原子、又はメチル基を示し、Ｒ₁とＲ₃は、それぞれ水素原子、Ｃ₁〜Ｃ₁₀のアルキル基、アルケニル基、アリール基、又はアルコキシ基を示し、ｎは１〜１０の整数を示す。］

[In the general formula (2), R ₁ represents a hydrogen atom or a methyl group, and R ₁ and R ₃ represent a hydrogen atom, a C _{1 to} C ₁₀ alkyl group, an alkenyl group, an aryl group, or an alkoxy group, respectively. N represents an integer of 1-10. ]

  Next, a method for measuring the physical properties of the toner of the present invention will be described.

  In the present invention, the degree of circularity is measured by a toner-based circle equivalent diameter-circularity scattergram measured by a flow type particle image measuring apparatus. In the present invention, “FPIA-1000” (Toa) Measurement was performed using a medical electronic company), and calculation was performed using the following formula.

      Circularity = circumference with the same projected area as the particle image / perimeter of the particle projection image

  Here, the “particle projected area” is an area of a binarized toner particle image. As a specific measurement method, 10 ml of ion-exchanged water from which impure solids and the like are previously removed is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, and then further measurement is performed. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser “UH-50 type” (manufactured by SMT Co., Ltd.) equipped with a 5Φ titanium alloy chip as a vibrator is subjected to a dispersion treatment for 5 minutes, and a measurement dispersion liquid and To do. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more.

  To measure the shape of the toner, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 3000 to 10,000 / μl, and 1000 or more toner particles are obtained. measure. After the measurement, the average circularity of the toner is obtained using this data.

  The volume average particle size and number average particle size of the developer can be measured by various methods such as Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Co.). In the present invention, Coulter Counter TA-II type is used. (Coulter Co., Ltd.) is used, an interface (manufactured by Nikka) and a personal computer (manufactured by NEC) that output number distribution and volume distribution are connected, and a 1% NaCl aqueous solution is prepared using first-grade sodium chloride as the electrolyte. . 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 subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toners of 2 μm or more are measured using the Coulter counter TA-II with a 100 μm aperture as an aperture. The volume distribution and the number distribution were calculated. Then, the volume-based volume average particle diameter (Dv: the median value of each channel is a representative value of the channel) obtained from the volume distribution, the coefficient of variation (S1) of the number-based average particle diameter obtained from the number distribution, and the volume The volume-based coarse powder amount (12.7 μm or more) obtained from the distribution and the number-based fine powder amount (5 μm or less) obtained from the number distribution were obtained.

  The variation coefficient is obtained by dividing the standard deviation in the number distribution by the number-based average particle diameter.

  The charge amount of the developer was measured by the following method. The carrier is vinylidene fluoride-tetrafluoroethylene copolymer (copolymer amount 8: 2) and styrene-methyl 2-ethylhexyl methacrylate (copolymer ratio 45:20:35) of 50:50. A Cu—Zn—Fe-based magnetic ferrite carrier (average particle diameter of 40 μm) coated with about 0.5 mass% by mass is used.

  0.4 g of developer and 19.6 g of the above ferrite-coated carrier are weighed, and the toner and carrier are put in a polyethylene container having a capacity of 50 ml, and shaken by hand 150 times at a frequency of 3 reciprocations per second. About 0.5 to 1.5 g of the mixture is placed in a metal measuring vessel with a 500 mesh screen at the bottom, and a metal lid is applied. The mass of the entire measurement container at this time is measured and is defined as W1. Next, in the suction machine, the suction pressure is set to 2 KPa by suction from the suction port and adjusting the air volume control valve. In this state, the toner is removed by suction for 2 minutes. The value indicated by the ammeter KEITHLEY 616 DIGITAL ELECTROMETER at this time is defined as a charge amount Q. The mass of the whole suction machine is measured again and is defined as W2 (g). The triboelectric charge amount of the toner is calculated based on the following formula.

      Frictional charge Q (mC / kg) = Q / (W1-W2)

<3> Image Forming Method of the Present Invention The image forming method of the present invention comprises a charging step in which a voltage is applied to a charging member to charge the image carrier, and a static image in which an electrostatic latent image is formed on the charged image carrier. An electrostatic latent image forming step, and a developing step including the following (a) to (d):
(A) A step of supporting the developer contained in the developer container on the developer carrier (b) A step of regulating the layer thickness of the developer on the developer carrier by a developer layer thickness regulating member ( c) a step of carrying and transporting the developer having a regulated layer thickness to a developing region where the developer carrying member and the image carrying member are opposed to each other; and (d) the developer on the developer carrying member being statically placed on the image carrying member. A process of forming a toner image by transferring to an electrostatic latent image A transfer process of electrostatically transferring a toner image formed on the surface of the image carrier onto a transfer material, and heating and fixing the toner image transferred onto the transfer material A fixing step.

  An image forming apparatus using the image forming method of the present invention will be described below with reference to FIG. 1, but the present invention is not limited to these. FIG. 1 is a schematic diagram of a developing device used in the present invention using a non-magnetic one-component developer. In FIG. 1, an electrophotographic photosensitive drum 5 that is an image carrier for holding an electrostatic latent image is rotated in the direction of an arrow. The developing sleeve 4 as the developer carrying member carries the developer T having the non-magnetic toner supplied by the hopper 1 as the developing container and rotates in the direction of the arrow so that the developing sleeve 4 and the photosensitive drum 5 are The developer T is transported to the developing area D that is facing. In the hopper 1, a stirring blade 8 for stirring the developer 4 is provided.

  The developer 4 obtains a triboelectric charge that can develop the electrostatic latent image on the photosensitive drum 5 by friction between the developers and the resin coating layer on the developing sleeve 4. In the example of FIG. 1, in order to regulate the layer thickness of the developer T conveyed to the development region D, a material having rubber elasticity such as urethane rubber, silicone rubber, or the like, or phosphor bronze, stainless steel as the developer layer thickness regulating member A developer layer thickness regulating member 3 made of an elastic plate made of a metal elastic material such as steel is used, and a thin layer of developer is formed by elastically pressing the developer sleeve 4 in the counter direction via the developer. Forming. In this way, the thickness of the thin layer of the developer T formed on the developing sleeve 4 may be thinner than the minimum gap α between the developing sleeve 4 and the photosensitive drum 5 in the developing region D. preferable.

  The developing sleeve 4 is preferably installed facing the photosensitive drum 5 with a separation distance of 100 to 1000 μm. If the separation distance of the developing sleeve 4 from the photosensitive drum 5 is smaller than 100 μm, the change in development characteristics of the toner with respect to the fluctuation of the separation distance becomes large, and it is difficult to mass-produce an image forming apparatus that satisfies stable image quality. Become. When the separation distance of the developing sleeve 4 from the image carrier is greater than 1000 μm, the recoverability of the transfer residual toner to the developing device is lowered, and fogging due to poor recovery tends to occur. Further, since the followability of the toner with respect to the electrostatic latent image on the image carrier is lowered, the image quality is lowered such as a lower resolution and a lower image density. Preferably 120-500 micrometers is good. In the image forming apparatus of the present invention, a gap (hereinafter referred to as “SD gap”) is provided between the developing sleeve 4 and the photosensitive drum 5 at the developing position, and a jumping developing method which is non-contact development is preferably used. It is done. The SD gap is preferably set to 100 to 500 μm by a drum abutting roller rotatably supported on the developing roller shaft. If the SD gap is less than 100 μm, the electric field tends to leak from the developer carrying member to the latent image holding member, and it becomes difficult to develop the latent image. On the other hand, if it is 500 μm or more, the toner is difficult to fly and the fog tends to be deteriorated.

  The contact pressure of the developer layer thickness regulating member 3 with respect to the developing sleeve 4 is a linear pressure of 4.9 to 49 N / m (5 to 50 g / cm), which stabilizes the regulation of the developer and the developer layer thickness. Is preferable in that it can be made suitable. When the contact pressure of the developer layer thickness regulating member 3 is less than 4.9 N / m of linear pressure, the regulation of the developer becomes weak, causing fogging and toner leakage. When the linear pressure exceeds 49 N / m, damage to the toner is increased, which tends to cause toner deterioration and fusion to the sleeve and blade.

  In order to cause the developer T carried on the developing sleeve 4 to fly, an AC bias voltage is applied to the developing sleeve 4 by a power source 6 as a biasing means. When a DC voltage is used as the developing bias, a voltage having a value between the potential of the image portion of the electrostatic latent image (the region visualized with the developer T attached) and the potential of the background portion is set as the developing sleeve 4. It is preferable to apply to. In order to increase the density of the developed image and improve the gradation, an oscillating electric field whose direction is alternately reversed may be formed in the developing region D by applying an AC bias voltage to the developing sleeve 4. In this case, it is preferable to apply to the developing sleeve 4 an AC bias voltage in which a DC voltage component having an intermediate value between the developed image portion potential and the background portion potential is superimposed.

  In the case of normal development in which toner is attached to a high potential portion of an electrostatic latent image having a high potential portion and a low potential portion for visualization, toner charged to a polarity opposite to that of the electrostatic latent image is used. In the case of reversal development in which toner is attached to a low potential portion of an electrostatic latent image having a high potential portion and a low potential portion for visualization, a toner charged with the same polarity as that of the electrostatic latent image is used. High potential and low potential are expressed by absolute values. In any of these cases, the developer T is charged by friction with the developing sleeve 4.

  The charging step in the present invention is a step of charging the image carrier by applying a voltage to a charging member that forms a contact portion with the image carrier and comes into contact therewith. First, the surface of the photosensitive drum 5 as an image carrier is charged to a negative polarity by a contact charging roller 9 as a primary charging means.

  The electrostatic latent image forming means for forming an electrostatic latent image on the charging surface of the image carrier is preferably an image exposure means. An electrostatic latent image is formed on the photosensitive drum 5 by image scanning by the laser beam exposure 10. The image exposure means for forming the electrostatic latent image is not limited to the laser scanning exposure means for forming a digital electrostatic latent image, and other light emission such as normal analog image exposure and LEDs. An element may be used. Further, any combination of a light emitting element such as a fluorescent lamp and a liquid crystal shutter can be used as long as it can form an electrostatic latent image corresponding to image information.

  Next, the electrostatic latent image is visualized with the developer on the developer carrying member. When the transfer material P is conveyed and arrives at the transfer portion, it is charged by the voltage application means 13 from the back surface (the surface opposite to the photosensitive drum side) of the transfer material P by a contact transfer means (roller) 12 as a transfer means. As a result, the developed image formed on the surface of the photosensitive drum 5 is transferred onto the transfer material P by the transfer roller 12. Next, the transfer material P separated from the photosensitive drum 5 is conveyed to heat and pressure roller fixing devices 14 and 15 as fixing means, and the developed image on the transfer material P is fixed by the fixing device. An example of the fixing means is film fixing.

  In the image forming apparatus of the present invention, it is preferable to use a partition 7 that restricts toner flying between the developing sleeve and the drum at the developing position in order to suppress toner scattering and fogging. The partition 7 is preferably attached so as to limit the barrel-shaped electric field between the developing sleeve and the drum. More preferably, it is preferable that the upstream portion of the drum is regulated so that the line connecting the developing sleeve 4 and the center of the drum 5 is not blocked in the developing region. The partition may be set between the developing sleeve and the drum like a window frame so as to limit the developing region. The partition may be a thin plate or a film and may be developed from the upstream side of the developing sleeve 4 to the developing region. It may be inserted into the. Further, it may be installed in the developing area on the drum so as to be in contact with the drum. The partition material at this time may be a thin metal plate such as a SUS plate or phosphor bronze plate, or a resin film such as PET, PE, or PP film.

  The non-magnetic one-component developing device used in the present invention can be used in various forms as long as the above requirements are satisfied. Even in the developing device integrated in the main body of a copying machine, a printer, a FAX, etc., the drum and Even a process cartridge in which a cleaner, a developing sleeve, and a toner storage container are integrated, such as a developing apparatus in which a process cartridge in which a developing roller toner storage container is integrated and a drum unit are separated from each other, as long as the developing apparatus satisfies the present invention. Either can be used.

  These image forming configurations are very effective for installation on a desk or in a narrow space because not only the apparatus can be downsized but also ozone is hardly generated. However, it has been found that fogging, toner scattering, halftone gradation, fine line reproducibility, and the like are likely to occur as image adverse effects. Incidentally, in a tandem type full-color image forming apparatus as shown in FIG. 2, transferring directly from a drum to a recording material is effective for high-definition superposition of toner of each color. However, it is necessary to fundamentally improve the image defect because the image defect is easily emphasized in the image as it is.

  The cause of this is not clear, but since the curvature of the developing region D increases as the developing sleeve and drum are reduced in diameter, it is easy for the developer to fly out of the developing region in jumping development. it is conceivable that. In addition, when a small-diameter developing sleeve is used, a range in which the developer slides between the developing sleeve and the layer regulating member is narrowed, and the developer cannot obtain sufficient charge. As a result, it is considered that fogging, toner scattering, and fine line reproducibility are deteriorated. In order to prevent fogging, scattering, fine line reproducibility, gradation, charging member contamination, and the like when using a non-magnetic one-component toner in jumping development, which is the image forming configuration of the present invention, developer particles It is important to charge each one uniformly.

  In the present invention, among the nonmagnetic one-component developer having at least a binder resin, a colorant, a release agent, and a toner particle containing a polymer containing a sulfur atom and an inorganic fine particle, the circularity, the central particle size, and the fine powder When the amount and the amount of coarse powder are within a certain range as shown below, toner particles are uniformly distributed when rubbed with a developer carrier containing a conductive compound such as a quaternary ammonium salt and a layer regulating member. The range is suitable for charging, and the above-described adverse effects are eliminated. Specifically, the average circularity of the toner particles is 0.940 or more and 0.995 or less, and the volume average particle diameter in the Coulter counter is 4.5 μm or more and 10 μm or less, and the number average particle diameter is 5% or less. A ratio of 12.7 μm or more in volume average particle diameter is 5% or less.

As a result, the developer is less deteriorated in durability and is not fused to the layer regulating member when a small-diameter developing sleeve is used, and fog and toner scattering are reduced. Further, even when a partition that restricts the flying of the toner is provided, it becomes difficult to adhere to the partition. At this time, it is also preferable to adjust the rotation speed of the developing sleeve 4 so that the surface speed of the developing sleeve 4 is substantially equal to or close to the speed of the surface of the photosensitive drum 5. In the developing region D, an AC bias may be applied to the developing sleeve 4 as a developing bias voltage. It is preferable that an AC electric field of at least 3 × 10 ⁶ to 10 × 10 ⁶ V / m and a frequency of 100 to 5000 Hz is applied as a developing bias between the developing sleeve 4 and the photosensitive drum 5 with a peak-to-peak electric field strength. .

  In the present invention, by adjusting the surface resistance of the image carrier, the image carrier can be more stably and uniformly charged. For the purpose of making charge injection more efficient or accelerating by adjusting the surface resistance of the image carrier, it is also preferable to provide a charge injection layer on the surface of the electrophotographic photosensitive member.

The image bearing member is an electrophotographic photosensitive member, and the volume resistance of the outermost surface layer of the electrophotographic photosensitive member is 1 × 10 ⁹ Ωcm or more and 1 × 10 ¹⁴ Ωcm or less. In the charging method using direct injection, charges can be exchanged more efficiently by reducing the resistance on the charged object side. On the other hand, in order to hold an electrostatic latent image as an image carrier for a certain period of time, the volume resistance value of the outermost surface layer is preferably 1 × 10 ⁹ Ω · cm or more. In order to hold an electrostatic latent image without being disturbed by a minute latent image even in a high humidity environment, the resistance value is preferably 1 × 10 ¹⁰ Ω · cm or more. As the image bearing member, a drum-like one is preferably composed of a rigid conductive support and an elastic layer covering the surface.

  As the conductive support, metals such as aluminum, iron, copper and stainless steel, alloys, conductive resins in which carbon, metal particles, etc. are dispersed can be used, and the shape thereof is cylindrical or the center of the cylinder. And those having a shaft penetrated, those having a cylindrical inner reinforcement, and the like.

  The elastic layer is not particularly limited, but styrene-butadiene rubber, high styrene rubber, butadiene rubber, isoprene rubber, ethylene-propylene copolymer, nitrile butadiene rubber (NBR), chloroprene rubber, butyl rubber, silicone rubber. Elastomer rubbers such as fluorine rubber, nitrile rubber, urethane rubber, acrylic rubber, epichlorohydrin rubber and norbornene rubber are preferably used. A resin such as a polyolefin resin, a silicone resin, a fluorine resin, or a polycarbonate, and a copolymer or a mixture thereof may be used. Further, a surface layer in which lubricating powder having high lubricity and water repellency is dispersed in an arbitrary binder may be provided on the surface of the elastic body.

  The lubricant is not particularly limited, but various fluororubbers, fluoroelastomers, fluorocarbons and polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymers in which fluorine is bonded to graphite or graphite. (ETFE) and fluorine compounds such as tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), silicone compounds such as silicone resin particles, silicone rubber and silicone elastomer, polyethylene (PE), polypropylene (PP), polystyrene ( PS), acrylic resin, polyamide resin, phenol resin, epoxy resin and the like are preferably used.

The image carrier is preferably a photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as amorphous selenium, CdS, ZnO ₂ , amorphous silicone, or an organic photosensitive material. A photoreceptor having a layer is particularly preferably used. The organic photosensitive layer may be a single layer type in which the photosensitive layer contains a charge generation material and a material having charge transport performance in the same layer, or may be a function-separated type photosensitive layer having a charge transport layer and a charge generation layer. good. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated in this order on a conductive substrate is one preferred example. The charge injection layer preferably has a form in which conductive fine particles are dispersed in a resin.

As a form of providing the charge injection layer,
(I) A charge injection layer is provided on an inorganic photoreceptor such as selenium or amorphous silicone or a single layer type organic photoreceptor;
(Ii) As a charge transport layer of a function-separated organic photoreceptor, a layer having a surface layer having a charge transport agent and a resin also serves as a charge injection layer (for example, a charge transport agent in a resin as a charge transport layer) And the conductive particles are dispersed, or the charge transport layer has a function as a charge injection layer depending on the charge transport agent itself or its presence state);
(Iii) Although a charge injection layer is provided as the outermost surface layer on the function-separated organic photoreceptor, the volume resistance of the outermost surface layer is in a preferable range;
This is very important.

  The charge injection layer is composed of a layer of an inorganic material such as a metal vapor deposition film or a resin layer in which conductive fine particles are dispersed in a binder resin, and includes a dipping coating method, a spray coating method, a roll coating method, and a beam. It is formed by coating by an appropriate coating method such as a coating method. Further, it may be constituted by mixing or copolymerizing a resin having high light-transmitting ionic conductivity with an insulating binder, or may be constituted by a single resin having medium resistance and photoconductivity. Among these, the outermost surface layer of the image carrier is preferably a resin layer in which conductive fine particles made of at least a metal oxide are dispersed. In other words, by configuring the outermost surface layer of the image bearing member in this way, the surface resistance of the electrophotographic photosensitive member can be reduced to transfer charges more efficiently, and the surface resistance can be reduced. Thus, it is preferable because blurring or flow of the latent image due to diffusion of the latent image charge can be suppressed while the image carrier holds the electrostatic latent image.

  The layer thickness of the charge injection layer is preferably 0.1 to 10 μm, more preferably 5 μm or less for obtaining the sharpness of the latent image, and 1 μm or more from the viewpoint of durability of the charge injection layer. It is more preferable that The binder of the charge injection layer can be the same as the binder of the lower layer, but in this case, the coating surface of the lower layer (for example, the charge transport layer) may be disturbed when the charge injection layer is applied. Therefore, it is necessary to select a formation method in particular. In the present invention, the volume resistance value in the outermost surface layer of the image carrier is measured by vapor deposition of gold on the surface and a layer having the same composition as the outermost surface layer of the image carrier on a turbo-ethylene terephthalate (PET) film. Is measured by applying a voltage of 100 V in a volume resistance measuring device (4140B pA MATER manufactured by Hewlett-Packard Company) in an environment of a temperature of 23 ° C. and a humidity of 65%.

  One preferred embodiment of the photoreceptor as an image carrier used in the present invention will be described below. As the conductive substrate, a cylindrical shape of a metal such as aluminum or stainless steel; a plastic having a coating layer of aluminum alloy or indium oxide-tin oxide alloy; paper or plastic impregnated with conductive particles; plastic having a conductive polymer; Cylinders and films are used.

  On these conductive substrates, for the purpose of improving the adhesion of the photosensitive layer, improving the coating property, protecting the substrate, coating defects on the substrate, improving the charge injection from the substrate, or protecting the photosensitive layer from electrical breakdown. An undercoat layer may be provided. Undercoat layer is polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, phenol resin, casein, polyamide, copolymer nylon, glue, gelatin, It is formed of a material such as polyurethane or aluminum oxide. The thickness of the undercoat layer is usually 0.1 to 10 μm, preferably 0.1 to 3 μm.

  The charge generation layer is composed of azo pigments, phthalocyanine pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, squarylium dyes, pyrylium salts, thiopyrylium salts, triphenylmethane dyes or selenium or amorphous silicone. A charge generating material such as an inorganic material is dispersed in an appropriate binder and applied, or formed by vapor deposition. Of these, phthalocyanine pigments are preferred for adjusting the sensitivity of the photoreceptor to a sensitivity suitable for the present invention. Examples of the binder include polycarbonate resin, polyester resin, polyvinyl butyral resin, polystyrene resin, acrylic resin, methacrylic resin, phenol resin, silicone resin, epoxy resin, and vinyl acetate resin. The amount of the binder contained in the charge generation layer is 80% by mass or less, preferably 0 to 40% by mass. The thickness of the charge generation layer is preferably 5 μm or less, particularly preferably 0.05 to 2 μm.

  The charge transport layer has a function of receiving charge carriers from the charge generation layer in the presence of an electric field and transporting them. The charge transport layer is formed by dissolving a charge transport material in a solvent together with a binder resin as required, and coating, and the film thickness is generally 5 to 40 μm. Examples of the charge transporting substance include polycyclic aromatic compounds such as biphenylene, anthracene, pyrene and phenanthrene in the main chain or side chain; nitrogen-containing cyclic compounds such as indole, carbazole, oxadiazole and pyrazoline; hydrazone compound; styryl compound; Selenium; selenium-tellurium; amorphous silicone; cadmium sulfide and the like. Examples of binder resins for dispersing these charge transport materials include polycarbonate resins, polyester resins, polymethacrylic acid esters, polystyrene resins, acrylic resins and polyamide resins; organic photoconductive materials such as poly-N-vinylcarbazole and polyvinylanthracene. A functional polymer. In addition, a conductive agent may be added to the surface layer binder in order to control resistance. Examples of the conductive agent include various conductive inorganic fine particles and carbon black, an ionic conductive agent, a conductive resin, and a conductive particle-dispersed resin.

  The drum used in the present invention can be either Se-based or amorphous silicon-based, but it is preferable to use an organic photoreceptor from the viewpoint of high image quality such as filming and drum scraping and safety. As resins forming the organic photoreceptor, various polycarbonate resins, polystyrene resins, polyarylate resins, polyphenylene ether acrylic resins, phenol resins, alkyd resins, diaryl phthalate resins, epoxy resins, vinyl chloride resins, methacrylate ester resins, polyamide resins, A polyphenylene oxide resin, a polysulfone resin, or the like can be used, but a polycarbonate resin or a polyarylate resin is more preferable as the main component of the binder resin used for the drum surface layer. The reason is that the polycarbonate resin and the polyarylate resin are structurally higher in mechanical strength than general resins used for the surface layer of other electrophotographic photosensitive members. In addition, the affinity with the toner and the discharge product is kept low, which is also effective for preventing fusion.

  As the surface layer, a layer in which conductive fine particles are dispersed in a resin may be provided in order to make charge injection more efficient or promote. Examples of the conductive fine particles include metals and metal oxides. Preferably, there are ultrafine particles such as zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin oxide-coated titanium oxide, tin-coated indium oxide, antimony-coated tin oxide, or zirconium oxide. These may be used alone or in combination of two or more.

  Further, the image forming apparatus used in the present invention can have constituent elements such as various means and members in addition to the electrostatic latent image carrier and the developing device described later. For example, the image forming apparatus used in the present invention can be suitably used in a cleaner-less system, but may have a cleaning member that is provided in contact with the drum and removes transfer residual toner on the drum. It is. According to such a configuration, the surface of the electrostatic latent image carrier can be cleaned before the completion of one image forming process and the start of the next image forming process. This is preferable for preventing image defects caused by. As such a cleaning member, for example, a known cleaning member such as an elastic blade such as rubber, a rotatable roll-shaped brush member, or a roll member whose surface is formed by an elastic layer is used. The cleaning member is generally provided in an opening portion of a waste toner container that opens toward the drum, and accommodates the removed transfer residual toner in the waste toner container.

  EXAMPLES Hereinafter, although a manufacture example and an Example demonstrate this invention concretely, these do not limit this invention at all.

<Example of photoconductor production>
A photoconductor using an organic photoconductive material for negative charging (hereinafter referred to as “OPC photoconductor”) was produced. An aluminum cylinder having a diameter of 30 mm was used as the substrate of the photoreceptor. The following layers were sequentially laminated on this cylinder by dip coating to prepare a photoreceptor.

  The first layer is a conductive layer, and is provided with a conductive particle-dispersed resin layer (tin oxide) having a thickness of about 20 μm, which is provided for leveling defects on the aluminum substrate and preventing the occurrence of moire due to reflection of laser exposure. And mainly titanium oxide powder dispersed in a phenol resin.

The second layer is a positive charge injection preventing layer, and serves to prevent the positive charge injected from the aluminum substrate from canceling out the negative charge charged on the surface of the photoreceptor, and 10 ⁶ Ω · cm by methoxymethylated nylon. This is a medium resistance layer having a thickness of about 1 μm adjusted to a certain degree.

  The third layer is a charge generation layer, which is a layer having a thickness of about 0.3 μm in which a disazo pigment is dispersed in a petital resin, and generates positive and negative charge pairs upon receiving laser exposure.

  The fourth layer is a charge transport layer, which is a layer having a thickness of about 25 μm in which a hydrazone compound is dispersed in a polycarbonate resin, and is a P-type semiconductor. Accordingly, negative charges charged on the surface of the photoreceptor cannot move through this layer, and only positive charges generated in the charge generation layer can be transported to the surface of the photoreceptor.

  The fifth layer is a charge injection layer, in which conductive tin oxide ultrafine particles and tetrafluoroethylene resin particles having a particle diameter of about 0.25 μm are dispersed in a photocurable acrylic resin. Specifically, 100 mass% of tin oxide particles having a particle size of about 0.03 μm, doped with antimony and reduced in resistance to the resin, 20 mass% of tetrafluoroethylene resin particles, and 1. 1% by mass is dispersed. The coating solution thus prepared was applied to a thickness of about 2.5 μm by a spray coating method to form a charge injection layer.

The volume resistance of the outermost surface layer of the photoreceptor thus obtained was 5 × 10 ¹² Ω · cm, and the contact angle of the photoreceptor surface with water was 103 degrees.

<Manufacture of developer>
<Production example of polymer containing sulfur atom>
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 200 parts by mass of methanol as a solvent, 150 parts by mass of methyl ethyl ketone and 50 parts by mass of isopropanol, and styrene 78 as a monomer. Part by mass, 15 parts by mass of n-butyl acrylate, and 7 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added and heated to 70 ° C. with stirring. A solution obtained by diluting 1 part by mass of 2,2′-azobis (2-methylbutyronitrile), which is a polymerization initiator, with 20 parts by mass of methyl ethyl ketin was added dropwise over 1 hour, and stirring was continued for 5 hours. , 2'-azobis (2-methylbutyronitrile) diluted with 20 parts by mass of methyl ethyl ketone was added dropwise over 30 minutes and stirred for another 5 hours to complete the polymerization. The polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less using a cutter mill equipped with a 150 mesh screen. The obtained sulfur-containing polymer had a glass transition temperature of 75 ° C. and a weight average molecular weight of 28,000.

<Toner Production Example 1>
--Preparation of resin particle dispersion 1--
-Styrene 70 parts by mass-Methyl methacrylate 5 parts by mass-n-butyl acrylate 25 parts by mass-Acrylic acid 2 parts by mass Mixing and dissolving the above, a nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Nonipol) 400) 1.5 parts by weight and 3.5 parts by weight of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) dissolved in 120 parts by weight of ion-exchanged water were dispersed in a flask. After emulsifying and slowly mixing for 10 minutes, 10 parts by mass of ion-exchanged water in which 1.0 part by mass of ammonium persulfate was dissolved was added, and after nitrogen substitution, the contents were stirred while stirring the inside of the flask. It heated with the oil bath until it became 70 degreeC, emulsion polymerization was continued as it was for 5 hours, and the resin particle dispersion liquid 1 which disperse | distributed the resin particle whose average particle diameter is 0.1 micrometer was prepared.

--Preparation of resin particle dispersion 2--
-76 parts by mass of styrene-24 parts by mass of n-butyl acrylate-2 parts by mass of acrylic acid-1.5 parts by mass of dodecyl mercaptan The above is mixed and dissolved, and a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) 1.5 parts by mass and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 1.0 part by mass were dissolved in 100 parts by mass of ion-exchanged water and dispersed in a flask. Emulsified, slowly mixed for 10 minutes, charged with 10 parts by mass of ion-exchanged water in which 1.0 part by mass of ammonium persulfate was dissolved, and replaced with nitrogen, then the contents in the flask were stirred. Was heated in an oil bath until the temperature reached 70 ° C., and emulsion polymerization was continued for 5 hours to prepare a resin particle dispersion 2 in which resin particles having an average particle diameter of 0.86 μm were dispersed. .

--- Preparation of release agent particle dispersion--
-Ester wax (melting point 65 ° C) 50 parts by mass-Anionic surfactant 5 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion-exchanged water 200 parts by mass The above was heated to 95 ° C and dispersed using a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then dispersed with a pressure discharge homogenizer, with an average particle size of 0.48 µm. A release agent particle dispersion was prepared by dispersing the release agent.

-Preparation of colorant particle dispersion 1-
・ C. I. Pigment Red 122 20 parts by mass, anionic surfactant 2 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 mass parts The above was mixed and it disperse | distributed using the sand grinder mill. When the particle size distribution in the colorant particle dispersion 1 was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size of the contained colorant particles was 0.2 μm and 1 μm. No coarse particles exceeding were observed.

-Preparation of colorant particle dispersion 2-
C. I. Pigment Red 122 is C.I. I. A colorant particle dispersion 2 was prepared in the same manner as the colorant particle dispersion 1, except that the pigment blue was changed to 15: 3.

-Preparation of colorant particle dispersion 3-
C. I. Pigment Red 122 is C.I. I. A colorant particle dispersion 3 was prepared in the same manner as the colorant particle dispersion 1 except that the pigment yellow 17 was used.

-Preparation of colorant particle dispersion 4-
C. I. A colorant particle dispersion 4 was prepared in the same manner as the colorant particle dispersion 1 except that the pigment red 122 was changed to carbon black (Degussa: Printex L6).

--Preparation of charge control particle dispersion--
20 parts by mass of a metal compound of di-alkyl-salicylic acid (charge control agent, Bontron E-84, manufactured by Orient Chemical Industries)
・ Sulfur atom-containing polymer (Acrybase FCA-1001-NS: manufactured by Fujikura Kasei Co., Ltd.) 0.5 part by mass ・ Anionic surfactant 2 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 mass parts The above was mixed and it disperse | distributed using the sand grinder mill. When the particle size distribution in the charge control particle dispersion 1 was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size of the charge control particles contained was 0.2 μm and 1 μm. No coarse particles exceeding were observed.

(Mixed solution preparation)
・ 360 parts by weight of resin particle dispersion 1 ・ 40 parts by weight of colorant dispersion 1 ・ 70 parts by weight of release agent dispersion The above is put into a 1 liter separable flask equipped with a stirrer, a condenser and a thermometer. Stir. The mixture was adjusted to pH = 5.2 using 1N potassium hydroxide.

(Agglomerated particle formation)
As a flocculant, 150 parts by mass of a 10% sodium chloride aqueous solution was dropped into this mixed solution, and the mixture was heated to 57 ° C. while stirring the inside of the flask in a heating oil bath. At this temperature, 3 parts by mass of the resin particle dispersion 1 and 10 parts by mass of the charge control agent particle dispersion were added. After maintaining at 50 ° C. for 2 hours, it was confirmed by observation with an optical microscope that aggregated particles having an average particle diameter of about 6.5 μm were formed.

(Fusion process)
Then, after adding 3 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC), the stainless steel flask was sealed and the stirring was continued using a magnetic seal up to 95 ° C. Heated and held for 4 hours. Then, after cooling, the reaction product was filtered, thoroughly washed with ion-exchanged water, and then the toner particle size was adjusted by wet classification (Microcut ECA1000 manufactured by Matsubo). Thereafter, filtration, fluidized bed drying at 45 ° C. is performed, the shape is adjusted by dispersing in a gas phase of 200 ° C. with a spray dryer, classification is performed again by a DS classifier (manufactured by Nippon Pneumatic Co., Ltd.), and magenta toner base material is obtained. Particle 1 was obtained. Magenta toner 1 was obtained by adding 1.5 parts by weight of hydrophobic silica (R974, manufactured by Aerosil Co.) to 100 parts by weight of this toner with a Henschel mixer FM10B.

  Cyan toner 1, yellow toner 1, and black toner 1 were obtained in the same manner except that the colorant dispersion 1 was changed to the colorant dispersions 2, 3, and 4, respectively, at the stage of adjusting the mixture. Table 1 shows the particle diameter and the circularity of the yellow toner 1, the cyan toner 1, the magenta toner 1, and the black toner 1.

<Toner Production Example 2>
After adding 450 parts by mass of a 0.1 mol / liter-Na ₃ PO ₄ aqueous solution to 400 parts by mass of ion-exchanged water and heating to 50 ° C., using a TK homomixer (manufactured by Special Machine Industries), 10000 rpm Was stirred. To this was added 68 parts by mass of a 1.0 mol / liter-CaCl ₂ aqueous solution to obtain an aqueous medium containing a calcium phosphate salt.

on the other hand,
(Monomer) Styrene 75 parts by mass
25 parts by mass of n-butyl acrylate (colorant) Yellow colorant (CI Pigment Yellow 180)
6 parts by mass (charge control agent) oxycarboxylic acid (di-tert-butylsalicylate aluminum compound: manufactured by Orient) 1 part by mass of a polymer having a sulfur atom (Acrybase FCA-1001-NS: manufactured by Fujikura Kasei) 0.5 Mass part (polar resin) Saturated polyester 10 parts by mass (polycondensate of propylene oxide modified bisphenol A and isophthalic acid, Tg = 70 ° C., Mw = 12000, Mw / Mn = 2.4, acid value: 10)
(Release agent) Behenyl stearate 15 parts by mass (Crosslinking agent) Divinylbenzene 1.2 parts by mass The above materials are heated to 50 ° C. and uniformly at 9000 rpm using a TK homomixer (made by Tokushu Kika Kogyo). Dissolved in and dispersed. In this, 3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved as a polymerization initiator to prepare a polymerizable monomer composition.

  The polymerizable monomer composition was put into the aqueous medium and stirred at 8000 rpm with a TK homomixer in a nitrogen atmosphere at 50 ° C. to granulate the polymerizable monomer composition. Then, while stirring with a paddle stirring blade, the temperature was raised to 60 ° C. in 2 hours and reacted for 5 hours. Then, it heated up at 80 degreeC with the temperature increase rate of 40 degreeC / hr, and was made to react for 5 hours. After completion of the polymerization reaction, the remaining monomer was distilled off under reduced pressure, and after cooling, hydrochloric acid was added and stirred for 6 hours. Thereafter, filtration, washing with ion exchange water, drying, and classification were performed to obtain yellow toner particles 2. Yellow toner 2 was obtained by adding 1.5 parts by mass of hydrophobic dry silica and 0.2 parts by mass of titanium oxide fine particles 1 to 100 parts by mass of the non-magnetic toner base particles with a Henschel mixer FM10B.

  Next, using the same method except that the colorant was changed to magenta colorant (CI Pigment Red 150), cyan colorant (CI Pigment Blue 15: 3), and carbon black, magenta was used. Toner 2, cyan toner 2 and black toner 2 were produced. Table 1 shows the particle sizes and the circularity of the yellow toner 2, the cyan toner 2, the magenta toner 2, and the black toner 2.

<Toner Production Example 3>
In Toner Production Example 2, a toner was produced in the same manner except that oxycarboxylic acid was not added. The obtained toners are designated as yellow toner 3, cyan toner 3, magenta toner 3 and black toner 3, respectively. The particle diameter and circularity of each toner are shown in Table 1.

<Toner Production Example 4>
In Toner Production Example 2, a toner was produced in the same manner except that the amount of divinylbenzene added was changed to 5 parts by mass. The obtained toners are designated as yellow toner 4, cyan toner 4, magenta toner 4 and black toner 4, respectively. The particle diameter and circularity of each toner are shown in Table 1.

<Toner Production Example 5>
In Toner Production Example 2, the toner was produced in the same manner as in Toner Production Example 3 except that the amount of initiator added was changed to 10 parts by mass. The obtained toners are designated as yellow toner 5, cyan toner 5, magenta toner 5 and black toner 5, respectively. The particle diameter and circularity of each toner are shown in Table 1.

<Toner Production Example 6>
In Toner Production Example 2, 30 parts by mass of toluene was added at the time of polymerization, and after completion of the polymerization, the toner was produced in the same manner as in Toner Production Example 1 except that toluene was removed in the drying step. Unlike the spherical particles obtained by the conventional suspension polymerization method, the obtained toner has a distorted shape by removing toluene in the drying step, and the average circularity of the toner has a low value. The obtained toner was yellow toner 7, cyan toner 7, magenta toner 7 and black toner 7 and the particle diameter and circularity are shown in Table 1.

<Toner Production Example 7>
Manufactured in the same manner as in Toner Production Example 2, except that the toner particle classification conditions in Toner Production Example 2 were changed. The results are shown in Table 2. The obtained toner was yellow toner 8, cyan toner 8, magenta toner 8 and black toner 8, and the particle size and circularity are shown in Table 1.

<Toner Production Example 8>
Manufactured in the same manner as in Toner Production Example 2, except that the toner particle classification conditions in Toner Production Example 2 were changed. The results are shown in Table 2. The obtained toner was yellow toner 9, cyan toner 9, magenta toner 9 and black toner 9, and the particle size and circularity are shown in Table 1.

<Toner Production Example 9>
Manufactured in the same manner as in Toner Production Example 2, except that the toner particle classification conditions in Toner Production Example 2 were changed. The results are shown in Table 2. The obtained toner was yellow toner 10, cyan toner 10, magenta toner 10 and black toner 10, and the particle diameter and circularity are shown in Table 1.

<Comparative Toner Production Example 1>
In Toner Production Example 2, it was produced in the same manner as in Toner Production Example 1 except that no polymer having a sulfur atom was added. The obtained toner was yellow toner 6, cyan toner 6, magenta toner 6 and black toner 6 and the particle size and circularity are shown in Table 1.

<Manufacture of developer carrier>
<Development sleeve production example 1>
The production of the developing sleeve will be described.

The following materials were dispersed with zirconia particles having a diameter of 2 mm using a sand mill for 3 hours, and then the zirconia particles were separated by sieving, and the solid content was adjusted to 33% with isopropanol to obtain a paint 1.
Carbon 20 parts by mass Graphite 70 parts by mass Phenol resin intermediate produced using ammonia as a catalyst (solid content 50%) 500 parts by mass Quaternary ammonium salt compound represented by formula (3) 20 parts by mass 20 parts by mass of spherical carbon particles having an average particle size of 5.2 μm and 130 parts by mass of isopropanol The triboelectric charge amount with the iron powder of the quaternary ammonium salt compound is a commercially available triboelectric charge meter (TB-200 type manufactured by Toshiba Chemical). It was positive polarity when calculated | required by the blow-off method using. Further, spherical carbon particles A were used as spherical particles. The physical properties are shown in Table 2. The number average particle size was 5.2 μm, the true density was 1.51 g / cm ³ , the volume resistance was 7.5 × 10 ⁻² Ωcm, and the major axis / minor axis ratio was 1.15.

  The coating material 1 was sprayed to form a resin coating layer of about 10 μm on an aluminum cylinder having a diameter of 20 mm, and then heated and cured at 150 ° C./30 minutes with a hot air drier to produce a developer carrier 1. Table 2 shows the paint formulation and the physical properties of the developer carrier 1.

<Development sleeve production examples 2 and 3>
In the preparation of the resin coating layer of the developing sleeve, a coating material was prepared in the same manner as in the manufacturing example 1 of the developing sleeve except that the quaternary ammonium salt compound represented by the formulas (4) and (5) was used. By forming a resin coating layer on the cylindrical body, developer carriers 2 and 3 were obtained. When the charge amount of the quaternary ammonium salt compound represented by formula (4) and formula (5) was measured by blow-off using iron powder in the same manner as in Production Example 1, it was positive. Table 2 shows paint formulations and physical properties of the developer carriers 2 and 3.

<Development sleeve production example 4>
The same as in Production Example 1 of the developing sleeve, except that the amount of addition of the quaternary ammonium salt compound represented by the formula (3) used for the resin coating layer of the developing sleeve was changed from 20 parts by mass to 10 parts by mass to prepare a paint. Thus, developer carrier 4 was obtained. Table 2 shows the coating formulation and physical properties of the developer carrier 4.

<Development sleeve production example 5>
The same as in Production Example 1 of the developing sleeve, except that the amount of addition of the quaternary ammonium salt compound represented by the formula (3) used for the resin coating layer of the developing sleeve was changed from 20 parts by weight to 40 parts by weight to prepare a paint. Thus, developer carrier 5 was obtained. Table 2 shows the coating formulation and physical properties of the developer carrier 5.

<Development sleeve production example 6>
The addition amount of spherical particles used in the resin coating layer of the developing sleeve was changed to 30 parts by mass of the spherical carbon particles (A) used in Production Example 1 of the developing sleeve to 5 parts by mass. Except for this, a developer carrier 6 was produced in the same manner as in Production Example 1. Table 2 shows the coating formulation and physical properties of the developer carrier 6.

<Development sleeve production example 7>
The addition amount of the spherical particles used in the resin coating layer of the developing sleeve was changed to 30 parts by mass of the spherical carbon particles (A) used in Developer Production Example 1 to 50 parts by mass. Except for this, the developer carrying member 7 was produced in the same manner as in Example 1. Table 2 shows the coating formulation and physical properties of the developer carrier 7.

<Development sleeve production example 8>
In the production of the resin coating layer of the developer carrying member, a developer carrying member 8 was produced in substantially the same manner as in Production Example 1 of the developing sleeve except that graphite was not used. The raw materials used are as follows.
Carbon 20 mass parts Phenol resin intermediate produced using ammonia as a catalyst (solid content 50%) 500 mass parts Quaternary ammonium salt compound represented by formula 3 20 mass parts Spherical carbon particles (A) 20 mass parts・ 130 parts by mass of isopropanol

  Table 2 shows the coating formulation and physical properties of the developer carrier 8.

<Development sleeve production example 9>
A cylindrical sleeve made of aluminum having a diameter of 20 mm was subjected to sand blasting, and the surface was roughened to a surface roughness Ra of 1.3 μm to obtain a developing sleeve 9. Table 2 shows the coating formulation and physical properties of the developer carrier 9.

<Image forming apparatus>
As the image forming apparatus, an LBP5500 (manufactured by Canon Inc.) modified as shown in FIG. 2 was used. This modified machine uses a non-magnetic one-component developer as a developer, and is a device arranged so that the developer layer on the developer carrier and the image carrier are not in contact with each other. As for the developing device configuration of the evaluation machine, a PET partition is inserted between the drum and the developing roller as shown in FIG. 1 with respect to the original cartridge, and the auxiliary charging roller and the developing roller mounted on the developing roller are removed. A developing sleeve was attached and 200 g of toner was charged. In addition, the diameter of the roller on the left and right of the developing roller was changed to a larger one, and the SD gap between the developing roller and the drum was 220 μm. Further, a DC and AC superimposed voltage was applied to the developing sleeve to perform jumping development. The alternating electric field at that time was a peak-to-peak voltage of 1800 V and a frequency of 3000 Hz. A rubber roller charger in which conductive carbon is dispersed and coated with a nylon resin, and a photoreceptor having the above-described charge injection layer were used.

<Image evaluation>
Evaluation was performed by continuously printing 10,000 sheets at a printing ratio of 2% in an N / N durability environment of 23 ° C. and 50% RH. As the transfer material P, 75 g / m ² paper was used. As a result, a high transferability was exhibited in the initial stage, no transfer of characters or lines was lost during transfer, and a good image without fogging on non-images was obtained.

(1) Image density The solid black image density of cyan was measured with a reflection density RD914 (manufactured by Macbeth), and an average value of 5 points was taken as the image density.

(2) Toner charge amount (Q / M) and toner transport amount (M / S)
The toner carried on the developing sleeve is sucked and collected by a metal cylindrical tube and a cylindrical filter. At that time, the charge amount Q stored in the condenser, the collected toner weight M, and the toner are sucked through the metal cylindrical tube. From the area S, the charge amount per unit mass Q / M (mC / kg; μC / g) and the toner mass M / S (mg / cm ² ) per unit area are calculated, and the toner charge amount (Q / M) is calculated. ) And toner transport amount (M / S).

(3) Fog The fog was measured with a solid white image using a REFECTMETER MODEL TC-6DS manufactured by Tokyo Denshoku. The filter used was a green filter, and fog was calculated from the following formula. If the fog is 2.0% or less, a good image is obtained.
Fog (reflectance) (%) = reflectance on standard paper (%)-reflectance of sample non-image area (%)
A: fog 0 to 3%
B: Fog 3 to 5%.
C: fog 5 to 10%
D: fog 10% or more

(4) Roughness Image defects due to primary charging failure due to transfer residual toner, that is, charging unevenness, were evaluated on a halftone image. The difference in shading that appears on the halftone image was visually evaluated according to the following criteria.
A: No difference in shading is observed.
B: A slight shading difference is observed.
C: Practical use is possible although there is a slight difference in shade.
D: The difference in shading is noticeable and impractical.

<Examples 1 to 5>
The yellow, cyan, magenta, and black process cartridges equipped with the developing sleeve 1 were filled with the toners of the respective colors produced in the toner production examples 1 to 5, respectively, and the durability use test was performed with a modified LBP5500. The evaluation results are shown in Table 3.

<Example 6>
Evaluation was conducted in the same manner as in Example 2 except that the roller of the developing unit was changed and the SD gap was changed to 300 μm. The results are shown in Table 3.

<Example 7>
Evaluation was performed in the same manner as in Example 2 except that the partition of the developing unit was eliminated. The results are shown in Table 3.

<Examples 8 to 14>
The yellow, cyan, magenta, and black process cartridges equipped with the developing sleeves 2 to 8 were filled with the toners of the respective colors produced in the toner production example 2, and the durability use test was performed with a modified LBP5500. The evaluation results are shown in Table 3.

<Examples 15 to 18>
The yellow, cyan, magenta, and black process cartridges equipped with the developing sleeve 1 were filled with the toners of the respective colors produced in the toner production examples 6 to 9, and the endurance use test was performed with a modified LBP5500. The evaluation results are shown in Table 3.

<Comparative Example 1>
The yellow, cyan, magenta, and black process cartridges equipped with the developing sleeve 1 were filled with the respective color toners produced in Comparative Toner Production Example 1 and tested for durability using a modified LBP5500. The evaluation results are shown in Table 3.

<Comparative example 2>
The yellow, cyan, magenta, and black process cartridges equipped with the developing sleeve 9 were filled with the toners of the respective colors produced in the toner production example 2, and the durability use test was performed with a modified LBP5500. The evaluation results are shown in Table 3.

It is the schematic of a developing device. 1 is a schematic view of a full-color image forming apparatus.

Explanation of symbols

1 ... Toner container (hopper)
2 ... Toner supply roller 3 ... Layer thickness regulating member 4 ... Development sleeve 5 ... Drum 6 ... Bias applying means 7 ... Partition 8 ... Stirring blade 9 ... Contact charging roller 10 ... Laser oscillation source 11 Cleaning member 12 Transfer roller 13 Bias applying means 14 Heating roller 15 Pressure roller α SD gap P Recording material

Claims (5)

In the non-magnetic one-component developing method for developing the electrostatic latent image on the electrostatic latent image carrier by forming a thin layer of non-magnetic toner on the surface of the toner carrier by the regulating member,
The toner carrier has at least a substrate and a surface coating layer containing a nitrogen-containing compound on the substrate, and the non-magnetic toner contains a binder resin, a colorant, and a resin having a sulfur atom. A non-magnetic one-component developing method.   2. The nonmagnetic one-component developing method according to claim 1, wherein the nitrogen-containing compound contained in the surface layer of the toner carrier is a quaternary ammonium salt.   The non-magnetic toner-containing resin containing a sulfur atom is in the form of a copolymer such as a random copolymer, a block copolymer, or a graft copolymer with a vinyl compound such as styrene or ethylene having a sulfonic acid group. Or a polycondensate such as polyester or polyamide, or a polyaddition polymer such as polyether or polyimine.   The non-magnetic toner has an average circularity of 0.940 to 0.995, a volume average particle size of 4.5 μm to 10 μm, a number average particle size of 5 μm or less in a ratio of 30% or less, and a volume average particle size of 12. 4. The nonmagnetic one-component developing method according to claim 1, wherein the ratio of 7 [mu] m or more is 5% or less. The non-magnetic toner has an average particle size of 0.970 or more and 0.995 or less, a volume average particle size of 5 to 9 μm, and a number average particle size of 5 μm or less in a ratio of 25% or less and a volume average particle size. The nonmagnetic one-component developing method according to any one of claims 1 to 3, wherein a ratio of 12.7 µm or more is 3% or less.

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