JP2007206482A - Image forming method, nonmagnetic single component developer, image forming apparatus, and process cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method for stabilizing and maintaining density and gloss while suppressing fog, toner splashing, cleaning failure, filming and dot-like defects through repeated use. <P>SOLUTION: The image forming method comprises bringing a developer carrier into contact with through a developer or directly the surface of an electrostatic latent image carrier and developing an electrostatic latent image on the surface of the electrostatic latent image carrier with a developer carried by the developer carrier, and the method is characterized in that: the developer carrier has an effective resistance of 1×10<SP>6</SP>to 1×10<SP>11</SP>Ω and ten-point surface average roughness Rz of 6μm to 12 μm; the developer is a nonmagnetic single component developer that contains toner particles containing at least a colorant and a resin essentially comprising polyester and shows an aggregation degree of 20 to 60; the toner particles are obtained by an emulsion polymerization aggregation method including at least an emulsion polymerization process, an aggregation process and an ageing process. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an image forming method, a non-magnetic one-component developer, an image forming apparatus, and a process cartridge used in a recording method using electrophotography, electrostatic recording, or the like. Specifically, after forming a developer image on an electrostatic latent image carrier in advance, the image is formed on a transfer material by transferring it onto a transfer material, such as an image forming method such as a copying machine, a printer, or a fax machine, a non-magnetic one-component developer, image formation The present invention relates to an apparatus and a process cartridge.

  In recent years, apparatuses using electrophotography have been applied to apparatuses such as printers and fax machines in addition to conventional copying machines. Especially for printers and fax machines, it is necessary to reduce the size of the copying machine, and in order to facilitate maintenance, a developer unit centered on the developing device and a drum unit centered on an electrostatic latent image carrier (hereinafter also referred to as “drum”). It is becoming increasingly common to use two process units and process cartridges that integrate them.

  As a developing method used for these process cartridges, there are many one-component developing methods advantageous for downsizing. The one-component developing method uses a one-component developer (hereinafter also referred to as “toner”), friction between a layer thickness regulating member (hereinafter also referred to as “blade”) and toner particles, and a developer carrier (hereinafter referred to as “developing roller”). Is also applied to the developing roller at the same time as a thin film by friction of the toner particles, and the toner is transported to a developing area where the developing roller and the drum face each other, and the electrostatic latent image on the drum is formed. Develop and visualize as a toner image.

  Unlike the two-component development method that requires carrier particles such as glass beads, iron powder, and ferrite, this one-component development method does not require carrier particles, and thus the development apparatus itself can be reduced in size and weight. Furthermore, since the two-component development method needs to keep the toner concentration in the developer constant, a device that detects the toner concentration and replenishes the necessary amount of toner is required, which leads to an increase in the size and weight of the developing device. . In this respect as well, the one-component development method is advantageous for reduction in size and weight. Further, in the case of full color, since it is difficult to use magnetic powder as a color developer, a non-magnetic toner has been used as the developer.

  In addition, with regard to the one-component development system, development is performed by electrostatically flying toner from the development roller to the electrostatic latent image on the drum, with contact development in which development is performed by bringing the drum and the development roller into contact with each other. Although there is jumping development to be performed, contact development is suitably used because toner scattering hardly occurs and toner does not concentrate on the edge of an image like sweeping and edge effects.

  However, in the contact development method, since the developing roller and the drum are in contact with each other, the toner is applied with much stress, and the toner deterioration is promoted. As a result, when an endurance test is performed, fogging, scattering, and dropout due to toner deterioration are likely to deteriorate in the second half of the endurance.

  Further, since the drum and the developing roller are rubbed, a phenomenon called filming in which toner is fused to the drum and the developing roller is likely to occur. Also, in anticipation of toner deterioration, if the toner fluidity is increased from the beginning, or if a true spherical toner is used to improve the transferability, a cleaning defect will occur and a trace of residual toner will appear on the image like rain. If it is steep or severe, streaks may occur from end to end of the image.

  Further, in a full-color image, an image having high image gloss (gloss) without image adverse effects such as changes in density and gloss in the initial stage and the latter half of durability is required as a high image quality.

  Although a method for improving the toner and achieving high image quality and high gloss (high gloss) has been proposed (for example, see Patent Documents 1 and 2), fog and scattering are caused when the toner deteriorates due to a durability test. May worsen or cause a dropout.

  Further, a method for reducing the durability deterioration of the toner while maintaining high image quality (see, for example, Patent Document 3) has also been presented. However, when a long-term durability test is performed, a change in developability due to deterioration of the developing roller is likely to occur. As a result, the amount of toner applied on the developing roller changes, and in the second half of the endurance, there is a risk that the density and image gloss (gloss) differ from the initial image.

JP 2002-108018 A (page 3) JP 2003-5438 A (page 3) JP 2001-134071 A (5th page)

  The present invention provides an image forming method, a toner, a process cartridge, and an image forming apparatus capable of stably maintaining density and gloss while suppressing fogging, toner scattering, poor cleaning, filming, and dropout through durability. For the purpose.

  The above object is achieved by the present invention described below.

That is, according to the present invention, a developer carrier is brought into contact with the surface of the electrostatic latent image carrier directly or via a developer, and the electrostatic latent image on the surface of the electrostatic latent image carrier is developed by the developer carried by the developer carrier. The developer carrying member has an actual resistance value of 1 × 10 ⁶ or more and 1 × 10 ¹¹ Ω or less, and a ten-point average roughness Rz of the surface is 6 μm or more and 12 μm or less, The developer is a non-magnetic one-component developer that includes toner particles containing at least a polyester-based resin and a colorant, and has an aggregation degree of 20 to 60, and the toner particles are at least emulsion polymerized. The present invention relates to an image forming method, a toner, a process cartridge, and an image forming apparatus, which are obtained by an emulsion polymerization aggregation method including a process, an aggregation process, and an aging process.

  According to the present invention having the above-described configuration, it is possible to stably maintain density and gloss while suppressing fogging, toner scattering, poor cleaning, filming, and dropout through durability.

  The image forming method used in the present invention includes an electrostatic latent image carrier that carries an electrostatic latent image, and a developer supplied to the electrostatic latent image carried on the electrostatic latent image carrier to provide an electrostatic latent image. A developer carrier used in a developing method for developing an image, and carrying the developer on the surface at least during development and contacting the surface of the electrostatic latent image carrier directly or via the developer, and the developer carrier And a layer thickness regulating member that regulates the layer thickness of the developer layer on the developer carrying member by contacting directly or via a developer. The image forming method used in the present invention is not particularly limited as long as the above-described requirements are satisfied, and can take various forms. Examples of such an image forming method include various image forming methods such as a copying machine, a printer, and a FAX.

  In addition to the electrostatic latent image carrier and the developing method described later, the image forming method used in the present invention can have various means such as various means and members. For example, the image forming method used in the present invention can be suitably used in a cleaner-less system, but can also 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 at an opening of a waste toner container that opens toward the drum. The removed transfer residual toner is accommodated in a waste toner container.

  The image forming method used in the present invention preferably includes a charging member that is provided in contact with the drum and charges the drum. According to such a configuration, it is possible to prevent generation of ozone when the drum is charged by electric discharge, and it is possible to charge the drum at a lower voltage. It is preferable from the viewpoint of prevention.

  Examples of such a charging member include a charging roller having a cored bar and a conductive elastic layer formed on the peripheral surface of the cored bar, a conductive sleeve, and a magnetic force generated on the peripheral surface of the conductive sleeve. A known contact charging member such as a magnetic brush charging member having magnetic force generating means such as a magnet roll and conductive magnetic particles carried on a conductive sleeve is used.

  Further, in the present invention, a process cartridge in which the electrostatic latent image carrier, the developing device, the charging member, the cleaning member, and the like described above are integrated and detachable from the image forming apparatus main body is also preferably used. It is done. In the process cartridge, known means are adopted as means for integrally configuring the electrostatic latent image carrier and the like, and means for detachably configuring it on the main body.

  The developing method used in the present invention can be used in various forms as long as the above requirements are satisfied. Even in a developing device integrated in the main body of a copying machine, a printer, a FAX, etc., a drum, a cleaner, a developing roller Even if the process cartridge is integrated with a toner storage container, the above-described embodiment can be used as long as the development method satisfies the above requirements, such as a developing device in which a developing roller and a toner storage container are integrated with a process cartridge and a drum unit. Either can be used.

  As the developer carrying member used in the present invention, for example, a developing roller formed by coating the surface of a metal roller with a polymer elastic body or integrally forming a polymer elastic body on a core metal is preferable. The core metal only needs to have a strength that can be withstood during molding or actual use, and the outer diameter is preferably 2 to 10 mm. As the material of the core metal, for example, metals such as iron, aluminum, titanium, copper and nickel, alloys such as stainless steel, duralumin, brass and bronze containing these metals, and composites in which carbon black and carbon fibers are hardened with plastic. Examples thereof include a material that is rigid and exhibits conductivity.

  As the polymer elastic body in the developing roller, various polymer compositions having elasticity are used, for example, EPDM (ethylene-propylene-diene terpolymer), urethane, silicone rubber, nitrile butadiene rubber, chloroprene rubber. Resin selected from styrene butadiene rubber, butadiene rubber, natural rubber, isoprene rubber, etc., and those obtained by dispersing and mixing conductive fine particles such as carbon and titanium oxide as an electric resistance adjusting material in these resins An electrical resistance adjusting resin using an ionic conductive material, for example, an inorganic ionic conductive material such as sodium perchlorate, calcium perchlorate, or sodium chloride is used.

  The thickness of the polymer elastic body is preferably 2.0 to 10 mm. If it is too thick, the resistance value tends to be high, and if it is too thin, the hardness may be too high.

  The polymer elastic body may be provided with a coating layer. This is a surface layer of the developing roller, and is formed of a coating layer forming material in which the above-described positive charge control resin is mixed with a base resin. The above-mentioned positive charge control resin is preferably contained in the coating layer forming material in an amount of 0.01 to 50% by mass, and more preferably 0.05 to 30% by mass.

  As the base resin, known resins can be used. Styrene resin (monopolymer or copolymer containing styrene or styrene-substituted product), acrylic resin (monopolymer or copolymer containing ester of acrylic acid or methacrylic acid) Coalesced), vinyl chloride resin, styrene-vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyester resin, fluororesin, low molecular weight polyethylene, low molecular weight polypropylene, ionomer resin, polyurethane resin, nylon resin , Silicone resin, ketone resin, ethylene-ethyl acrylate copolymer, xylene resin, polyvinyl butyral resin, and the like. Particularly preferred base resins in the practice of the present invention are urethane resin, nylon resin, acrylic resin, fluororesin and the like because they require wear resistance, toner chargeability, toner transportability and the like. One type or two or more types of base resins may be used.

  Further, it is desirable to add carbon black to the coating layer forming material as a resistance adjusting material. Examples of the carbon black used for such purposes include furnace black, lamp black, thermal black, acetylene black, channel black, and the like. The amount of carbon black in the coating layer forming material can be appropriately set according to the characteristics of the target developing roller, and can be contained, for example, in an amount of about 1 to 40% by mass.

  Furthermore, it is preferable to add insulating particles having an average particle diameter of 3 to 30 μm, for example, urethane particles, nylon particles, acrylic particles, silicone particles, etc., to the coating layer forming material as the surface roughening material. The amount of the surface roughening material in the coating layer forming material can be appropriately set according to the characteristics of the intended developing roller, and can be contained, for example, at about 2 to 50% by mass.

  The coating layer forming material containing the above-mentioned components is a spray coating method, a dipping method, etc., which is a paint dispersed using a conventionally known dispersing device using beads such as a sand mill, paint shaker, dyno mill, pearl mill, etc. Is applied to the surface of the elastic layer to form a coating layer. For example, methyl ethyl ketone, toluene, alcohol or the like can be used as the solvent used in the paint.

  The thickness of the coating layer is preferably 2 to 100 μm in consideration of realizing high wear resistance without impairing the flexibility of the elastic layer. More preferably, it is 5-30 micrometers.

  The developing roller preferably has an Asker C hardness of 60 ° or more and 90 ° or less by a JIS-K6301 Asker C scale hardness meter. When the Asker C hardness is less than 60 °, the charge application to the toner tends to be unstable, and fog and scattering may easily occur. When the Asker C hardness is higher than 90 °, filming and fogging due to toner deterioration may be deteriorated. More preferably, the angle is 65 ° to 80 °, and the Asker C hardness of the developing roller can be adjusted by, for example, the thickness of the polymer elastic body.

  The developing roller of the present invention needs to have a surface roughness Rz of 6 to 12 μm. By combining this combination with the toner of the present invention, toner deterioration can be suppressed and good and stable toner transportability can be achieved for a long time. Can be maintained.

  The developing method used in the present invention desirably has a layer thickness regulating member. The layer thickness regulating member is also not particularly limited in its form, but is a blade that is provided in contact with the developing roller and regulates the toner coat amount on the developing roller by regulating the toner carried on the developing roller. Is preferred. Such a configuration is preferable in controlling the toner coat amount on the developing roller. As such a blade, a known blade such as a flexible plate member or a metal plate such as SUS or phosphor bronze is used.

  As the drum used in the present invention, known ones such as an organic photoreceptor and an α-Si photoreceptor can be used from the viewpoint of high image quality such as filming and drum scraping and safety. Se-based photoconductors have problems with heat resistance, wear resistance, mechanical strength, stability over time, and toxicity. In addition to usage, sufficient care must be taken in handling such as disposal.

  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 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.

  The electrophotographic light-receiving member of an α-Si drum is generally a conductive support heated to 50 ° C. to 400 ° C., and vacuum deposition, sputtering, ion plating, heat treatment on the support. A photoconductive layer made of a-Si is formed by a film forming method such as a CVD method, a photo CVD method, or a plasma CVD method. Among these, a plasma CVD method, that is, a method of decomposing a source gas by direct current, high frequency or microwave glow discharge to form an α-Si deposited film on a support is put to practical use. Since this drum has good durability, it is effective in a contact development system in which drum deterioration is relatively likely to occur and a system that requires long-term durability.

  The development of the electrostatic latent image in the present invention is performed by a contact development method in which the electrostatic latent image carrier and the developer carrier are brought into contact directly or via a developer. This is because, when the electrostatic latent image carrier and the developer carrier are not in contact during development, the lines of electric force concentrate on the edge portion of the electrostatic latent image on the electrostatic latent image carrier. This is because the toner is biased and developed at the edge portion of the image, and it is difficult to form an image having a desired image quality.

  In the development of the electrostatic latent image in the present invention, the electrostatic latent image carrier and the developer carrier may be in contact with each other directly or via a developer during development. The body may be installed directly or at a predetermined position in contact with the developer, or the electrostatic latent image carrier and the developer carrier may move relative to each other during development to directly or develop. You may arrange | position in the position which contacts through an agent. In the present invention, steps other than the above-described development step are not particularly limited, and each step in a known image forming method is employed.

  As the image forming method of the present invention, a known method such as a method using an intermediate transfer member or a method directly transferring to a recording material is used.

  Various materials are used for the belt-shaped intermediate transfer member. In the case of so-called plastic belts, although the length changes little due to durability, stress cracking is likely to occur due to durability and the life is extended. It is difficult. In the case of a rubber belt, although there is little stress cracking due to durability, the durability tends to cause elongation due to durability. As a countermeasure, a highly durable belt can be made by putting a highly durable core material into the rubber belt.

  As materials that can be used as an intermediate transfer belt, the resin system is polycarbonate (PC), nylon (PA), polyester (PET), polyethylene naphthalate (PEN), polysulfone (PSU), polyethersulfone (PEI), polyether Imide (PEI), polyether nitrile (PEN), polyether ether ketone (PEEK), thermoplastic polyimide (TPI), thermosetting polyimide (PI), PES alloy, polyvinylidene fluoride (PVdF), ethylene tetrafluoroethylene There are polymers (ETFE), etc. In the case of elastomers, polyolefin-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyurethane-based thermosetting elastomers, polystyrene-based thermoplastics Elastomers, polyamide thermoplastic elastomers, fluorine-based thermoplastic elastomer, polybutadiene thermoplastic elastomer, polyethylene-based thermoplastic elastomers, ethylene vinyl acetate type thermoplastic elastomers, polyvinyl chloride thermoplastic elastomer, and the like.

  As the drum-like intermediate transfer member, the intermediate transfer member comprises 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, silicone elastomer, polyethylene (PE), polypropylene (PP), polystyrene ( PS), acrylic resin, polyamide resin, phenol resin, epoxy resin and the like are preferably used.

  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.

  Examples of the material directly transferred to the recording material include those using an electrostatic conveyance drum or an electrostatic conveyance belt.

  The electrostatic conveyance drum is a method in which the recording material is attracted onto the electrostatic conveyance drum, and the recording material is transferred to the opposite portion of the electrostatic latent image carrier to transfer the toner image. It is necessary to make it large diameter because it needs to be mounted and rotated. In addition, as a material of the electrostatic transfer drum, a material usable for the intermediate transfer drum can be used.

  Further, the electrostatic conveyance belt conveys the recording material to the opposite portion of the drum while adsorbing the recording material by the adsorption roller and transfers the toner image onto the recording material, and can be used for an image forming apparatus provided with a developing device. It is effective because it can be installed in a small space. In addition, materials usable for the intermediate transfer belt can be used.

  Next, a toner manufacturing method will be described.

  The toner of the present invention is difficult to obtain all of the effects of the present invention with a so-called pulverized toner or a true spherical toner by suspension polymerization, and an aqueous solution containing polymer fine particles, colorant fine particles and release agent fine particles as follows. A so-called agglomerated toner obtained by adding, for example, a pH adjusting agent, an aggregating agent and a stabilizer to the dispersion liquid, aggregating a large number of the fine particles, and thermally fusing the agglomerated particles is most preferable.

  In this toner manufacturing method, in the aggregation step, resin particles, colorant particles, or release agent fine particles that are uniformly dispersed in the mixed solution are aggregated to form aggregated particles. In the thermal fusing step, the resin in the aggregated particles is melted and fused to form toner particles.

  Hereinafter, the method for producing the toner of the present invention will be described in detail.

  The resin particle dispersion is obtained by dispersing at least resin particles in a dispersant. Examples of the resin include thermoplastic binder resins. Specifically, homopolymers or copolymers (styrene-based resins) of styrenes such as styrene, parachlorostyrene, and α-methylstyrene; acrylic Methyl acid, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, methacrylic acid 2 -Homopolymers or copolymers of vinyl group esters such as ethylhexyl (vinyl resins); Homopolymers or copolymers of vinyl nitriles such as acrylonitrile and methacrylonitrile (vinyl resins); A single vinyl ether such as ether or vinyl isobutyl ether Polymer or copolymer (vinyl resin); homopolymer or copolymer of vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone (vinyl resin); ethylene, propylene, butadiene, isoprene, etc. Homopolymers or copolymers of olefins (olefin resins); non-vinyl condensation resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and non-vinyl condensation systems thereof Examples thereof include a graft polymer of a resin and a vinyl monomer. These resins have polyester as a main component and may be used alone or in combination of two or more.

  The polyester in the present invention is usually obtained by polycondensation of one or more alcohol monomers (2 or more) and one or more carboxylic acid monomers (2 or more). Examples of the dihydric alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl). Propane, polyoxypropylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4- Alkylene oxide adducts of bisphenol A such as hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopenty Glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, bisphenol A propylene adduct of A, ethylene adduct of bisphenol A, hydrogenated bisphenol A and the like. Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned. These divalent alcohol monomers and trihydric or higher polyhydric alcohol monomers can be used alone or in combination. The acid component is a carboxylic acid component and a divalent monomer such as maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, Examples include sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, n-dodecyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, and anhydrides or lower alkyl esters of these acids. It is done. Examples of the trivalent or higher carboxylic acid component include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and 1,2,4-butanetricarboxylic acid. 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7 , 8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, their acid anhydrides, lower alkyl esters and the like. A single monomer or a plurality of monomers can be used from these divalent carboxylic acid monomers and trivalent or higher carboxylic acid monomers.

  The method for producing the amorphous polyester in the present invention is not particularly limited, and can be produced by esterification and transesterification using the above monomers.

  The polyester-based resin can be produced at a polymerization temperature of 180 to 230 ° C., and the reaction system is reduced in pressure as necessary, and reacted while removing water and alcohol generated during condensation. If the monomer is not dissolved or compatible at the reaction temperature, a high boiling point solvent is added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary solvent is distilled off. If there is a monomer with poor compatibility in the copolymerization reaction, it is advisable to condense the monomer with poor compatibility with the monomer and the acid or alcohol to be polycondensed in advance before polycondensing with the main component. .

  Catalysts that can be used in the production of the polyester resin include alkali metal compounds such as sodium and lithium, alkaline earth metal compounds such as magnesium and calcium, metals such as zinc, manganese, antimony, titanium, tin, zirconium, and germanium. Examples include compounds, phosphorous acid compounds, phosphoric acid compounds, and amine compounds. Specific examples include the following compounds.

  For example, sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, manganese acetate, manganese naphthenate, titanium tetraethoxide, titanium Tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide, antimony trioxide, triphenylantimony, tributylantimony, tin formate, tin oxalate, tetraphenyltin, dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide, zirconium tetrabutoxide, naphthene Zirconate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octylate, germanium oxide, triphenyl Phosphite, tris (2,4-di -t- butyl-phenyl) phosphite, ethyltriphenylphosphonium bromide, triethylamine, compounds such as triphenyl amine.

  The method for producing the crystalline polyester resin is not particularly limited, and can be produced by a general polyester polymerization method in which an acid component and an alcohol component are reacted. For example, direct polycondensation, transesterification, etc. They are manufactured using different types of monomers. The molar ratio (acid component / alcohol component) when the acid component reacts with the alcohol component varies depending on the reaction conditions and the like, and cannot be generally stated, but is usually about 1/1.

  In addition, when a polyester containing a double bond is used as a copolymerization component, in the emulsification step, the aggregation step, and the coalescence step, when the polyester resin is heated to the melting point or higher, or after completion of each step, It may be heated separately to cause the crosslinking reaction. When the crosslinking reaction is performed, for example, an unsaturated crystalline polyester resin obtained by copolymerizing a double bond component as a binder resin is used, and a radical reaction is caused in the resin to introduce a crosslinked structure. At this time, a polymerization initiator shown below may be used.

  Examples of the polymerization initiator include t-butyl peroxy-2-ethylhexanoate, cumyl perpivalate, t-butyl peroxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, di-t. -Butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane 1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (t-butylperoxyca) Bonyl) cyclohexane, 2,2-bis (t-butylperoxy) octane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, , 3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylper) Oxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di-t-butyldiperoxyisophthalate, 2,2-bis (4,4-di-t-butylperoxy) (Cyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxyhexahydrotereph Tartrate, di-t-butylperoxyazelate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate), di-t-butylper Oxytrimethyl adipate, tris (t-butylperoxy) triazine, vinyltris (t-butylperoxy) silane, 2,2'-azobis (2-methylpropionamidine dihydrochloride), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine], 4,4′-azobis (4-cyanovaleric acid) and the like.

  These polymerization initiators can be used alone or in combination of two or more. The amount and type of the polymerization initiator are selected depending on the amount of unsaturated sites in the polymer and the type and amount of the coexisting colorant.

  The polymerization initiator may be mixed with the polymer in advance before the emulsification step, may be added after the emulsification step, or may be incorporated into the aggregate in the aggregation step. Further, it may be introduced after the coalescence process or after the coalescence process. In the case of introduction after the aggregation step, coalescence step, or coalescence step, a solution in which the polymerization initiator is dissolved or emulsified is added to a particle dispersion (resin particle dispersion or the like). These polymerization initiators may be added with known crosslinking agents, chain transfer agents, polymerization inhibitors and the like for the purpose of controlling the degree of polymerization.

  As described above, according to the method for producing an electrophotographic toner of the present invention, since there is no hydrolysis in the emulsification step, a crystalline polyester resin having a high molecular weight can be obtained, and an electrophotographic toner having a low fixing temperature can be obtained.

  Surfactants that can be used for polymerization and dispersion include sulfonates (sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, 3,3-disulfonediphenylurea-4,4-diazo-bis-amino- Sodium 8-naphthol-6-sulfonate, ortho-carboxybenzene-azo-dimethylaniline, 2,2,5,5-tetramethyl-triphenylmethane-4,4-diazo-bis-β-naphthol-6-sulfone Acid salts), sulfate 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, potassium stearate, calcium oleate), and the like.

  The volume average particle diameter of the resin particles is usually 1 μm or less and preferably 0.01 to 1 μm. When the volume average particle size exceeds 1 μm, the particle size distribution of the finally obtained toner is broadened or free particles are generated, which tends to cause a decrease in performance and reliability. On the other hand, when the volume average particle size 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 improved, and variations in performance and reliability are reduced. .

  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, xanthene, etc. . These colorants may be used alone or in combination of two or more.

  The volume average particle size of the colorant particles is preferably 0.5 μm or less, and more preferably 0.2 μm or less. When the volume average particle diameter exceeds 0.5 μm, irregular reflection of visible light cannot be prevented, and when coarse particles are present, coloring power, color reproducibility, and OHP permeability are adversely affected, and agglomeration described later. In the particle forming step, the resin particles and the colorant particles are not aggregated, or even when aggregated, they may be detached at the time of fusion, which is not preferable in that the quality of the obtained toner may be deteriorated. On the other hand, when the volume average particle diameter is in the above range, there is no disadvantage, and the uneven distribution among the toners is reduced, the dispersion in the toner is good, and the variation in performance and reliability is advantageous. is there.

  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 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.

  The volume average particle size of the release agent particles is preferably 2.0 μm or less, and more preferably 1.0 μm or less. If the volume average particle size exceeds 2.0 μm, the toner content tends to be affected by the wax content, which adversely affects the stability of the image over a long period of time. On the other hand, when the volume average particle size is within the above range, uneven distribution between toners is reduced, dispersion in the toner 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 the said mold release agent particle | grains, According to the objective, it can select suitably.

  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 depending on the intended 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.

  Any method can be used as a method for dispersing the release agent particles and the colorant particles. For example, a rotary shear type homogenizer, a media disperser, or the like can be used. An aqueous dispersion can be prepared using an emulsifier, or an organic solvent dispersion can be prepared using a dispersant.

  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 made of materials that are difficult to dissolve in water from the viewpoints of controlling ionic strength that affects the stability during aggregation and fusion and reusing wastewater.

  The volume average particle diameter of each of the above-mentioned particles is usually 1 μm or less, and preferably 0.01 to 1 μm. When the volume average particle size exceeds 1 μm, the particle size distribution of the finally obtained toner is broadened or free particles are generated, which tends to cause a decrease in performance and reliability. On the other hand, when the volume average particle size 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 improved, and variations in performance and reliability are reduced. .

  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 dispersant having the polarity cannot be generally defined and can be appropriately selected according to the purpose.

  Examples of the polar surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type Is mentioned. 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 the nonpolar surfactant include nonionic surfactants such as polyethylene glycol, alkylphenol ethylene oxide adducts, and polyhydric alcohols.

  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 content of the colorant particles and the like is about 1 to 10% by mass and preferably about 2 to 6% by mass in the aggregated particle dispersion when the aggregated particles are formed.

  The content of the release agent particles and the like 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 is larger than 5% by mass, the particle size distribution is widened and the characteristics may be deteriorated. In this case, for example, when the resin particles are produced, the above problem can be solved by performing seed polymerization on the release agent.

  The content of each particle such as the additive particles is about 0.01 to 5% by mass and about 0.5 to 2% by mass in the aggregated particle dispersion when the aggregated particles are formed. preferable. When the content is out of the above range, the effect of dispersing the release agent particles or the like may not be sufficient, or the particle size distribution may be widened and the characteristics may be deteriorated.

  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.

  The resin particle dispersion is prepared, for example, as follows. That is, 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 a homopolymer or copolymer of the vinyl monomer, the resin can be dissolved in an oily solvent having a relatively low solubility in water. The resin is dissolved in the oily solvent, and the solution is finely dispersed in water together with an ionic surfactant and a polymer electrolyte using a disperser such as a homogenizer, and then heated or decompressed to remove the oily solvent. By transpiration, a dispersion liquid in which resin particles made of resin other than vinyl resin are dispersed in an ionic surfactant is prepared.

  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 liquid, the release agent dispersion liquid, the particle dispersion liquid, and the like are prepared, for example, by adding particles such as the colorant particles to a dispersant and dispersing the particles using the dispersion means. Is done.

(Aggregation process)
In the aggregated particle formation, aggregated particles are formed in the mixed solution to prepare an aggregated particle dispersion. The agglomerated particles can be formed in the mixed solution by adding, for example, a pH adjusting agent, a flocculant, and a stabilizer to the mixed solution 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 the mixing is performed under this temperature condition, aggregation proceeds in a stable state. The mixing can be performed using, for example, 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 usually controlled to be about the same as the average particle size of the toner to be obtained. The control can be easily performed, for example, 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 size substantially the same as the average particle size 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 from the glass transition temperature of the resin contained in the aggregated particles to the decomposition temperature of the resin. Therefore, the temperature of the heating differs depending on the type of resin of the resin particles and the resin fine particles, and cannot be generally defined. However, in general, the glass of resin contained in the aggregated particles or the adhered particles Transition point temperature to 140 ° C. In addition, the said heating can be performed using a publicly known heating apparatus and instrument.

  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 temperature of the heating and cannot be defined in general, but is generally 30 minutes to 10 hours.

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

(Other configurations)
The surface of the electrophotographic toner of the present invention may be covered with a surface layer. It is desirable that the surface layer does not significantly affect the mechanical properties and melt viscoelastic properties of the entire electrophotographic toner. For example, if the surface layer of non-melting or high melting point covers the electrophotographic toner thickly, the low-temperature fixability due to the use of the crystalline polyester resin cannot be sufficiently exhibited. Therefore, it is desirable that the film thickness of the surface layer is as thin as possible, and specifically, it is preferable to be in the range of 0.001 to 1 μm.

  In order to form a thin surface layer in the above range, a method of chemically treating the surface of particles containing binder resin, fine particles thereof, colorant, inorganic fine particles added as necessary, and other materials Are preferably used.

  Examples of the component constituting the surface layer include silane coupling agents, isocyanates, or vinyl monomers, resins, fine particles thereof, and the like, and it is preferable that a polar group is introduced into the component, By chemically bonding, the adhesive force between the toner and a transfer medium such as paper increases.

  The polar group may be any polar functional group, for example, carboxyl group, carbonyl group, epoxy group, ether group, hydroxyl group, amino group, imino group, cyano group, amide group, imide group , Ester groups, sulfone groups and the like.

  Chemical treatment methods include, for example, a strong oxidizing substance such as peroxide, a method of oxidizing by ozone oxidation, plasma oxidation, etc., a method of bonding a polymerizable monomer containing a polar group by graft polymerization, seed polymerization, etc. Can be mentioned.

<Non-magnetic one-component developer>
The volume average particle diameter of the toner is preferably 4 to 10 μm, and more preferably 5 to 8 μm. When the average particle size is less than 4 μm, the chargeability tends to be insufficient, and the developability may be lowered. When the average particle size is more than 10 μm, the resolution of the image may be lowered.

  The toner resin is mainly composed of polyester, preferably 70% by mass or more, and preferably higher in content, but at least 50% of the resin component needs to be a polyester component. At this time, the resin other than the polyester component may be a resin obtained by graft polymerization on a polyester chain or may be simply mixed. If the polyester component is less than 50%, not only the gloss of the fixed image is lowered, but color development is inferior, or toner deterioration is promoted to cause fogging, scattering, and filming.

  The molecular weight Mp of the polyester which is the main component of the toner of the present invention is preferably 5000 to 30000 in terms of weight average molecular weight. If the weight average molecular weight is less than 5,000, the toner may aggregate during storage and cause toner to fall off, or fog, filming, and scattering due to toner deterioration may occur. Further, if the weight average molecular weight is larger than 30000, the gloss of the fixed image is inferior, or if the toner is an agglomerated toner, the toner may be pulverized in the developing machine, causing fogging or poor cleaning.

  Therefore, in order to more effectively maintain the stable density and gloss, which are the greatest characteristics of the toner of the present invention, it is desirable to define the molecular weight within the above range, whereby the roughness of the developing roller and the actual resistance value are determined. It is possible to make the best use of the adjustment effect of.

  The binder resin of the present invention is preferably a crystalline resin. When a crystalline resin is used, the resin melts cleanly at a constant temperature, which is effective in increasing the fixing strength and increasing the gloss in a fixed image. In addition, when the resin is set to the same melting temperature, the toner using the crystalline resin is more resistant to toner deterioration and more advantageous for the storage stability of the toner. Among them, the crystalline resin is not particularly limited as long as it is a resin having crystallinity, and specifically includes a crystalline polyester resin and a crystalline vinyl resin. Crystalline polyester resins are preferred from the viewpoints of adhesiveness, chargeability, and adjustment of the melting point within a preferred range. An aliphatic crystalline polyester resin having an appropriate melting point is more preferable.

  In the present invention, “crystallinity” refers to a substance having a clear endothermic peak rather than a stepwise endothermic amount change in differential scanning calorimetry (DSC).

  As melting | fusing point of the said crystalline resin, it is preferable that it is 60-120 degreeC, and it is more preferable that it is 70-100 degreeC. When the melting point is less than 60 ° C., powder aggregation is likely to occur or the storability of a fixed image may be deteriorated. On the other hand, if the temperature exceeds 120 ° C., low-temperature fixing may not be possible.

As the external additive used in the present invention, known inorganic fine powders or resin particles are used. In order to improve charging stability, developability, fluidity, and storage stability, silica, alumina, titania or a double oxide thereof may be used. It is preferably selected from inorganic fine powders. Further, silica is more preferable. For example, such silica is used both of so-called dry process produced by vapor phase oxidation of silicon halides and alkoxides or dry silica called fumed silica, and so-called wet silica produced from alkoxide, water glass, etc. Although possible, dry silica is preferred because it has few silanol groups on the surface and inside of the silica fine powder, and has little production residue such as Na ₂ O, SO ₃ ^2- . In dry silica, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. Is also included.

  The amount of silica used as an external additive in the present invention is preferably 0.4% to 5% in terms of the total toner mass ratio. If the amount of silica is less than 0.4%, the fluidity and chargeability of the toner may be inferior, and fog, roughness, and vertical stripes may be deteriorated. On the other hand, if it exceeds 5%, the fluidity is too high to cause toner leakage, filming on the drum, or deterioration of fixability.

  The amount of silica in the present invention is an optimal amount for uniformly coating the toner particles of the present invention having unevenness in an optimal range, and thereby the fluidity and chargeability of the toner of the present invention are effectively maintained for a long time. The This also makes it possible to adjust the roughness of the developing roller and the actual resistance value very effectively, and a stable high-quality image can be maintained over a long period of time.

  In addition, the external additive used in the present invention has a silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, a silane coupling agent, and a functional group as necessary for the purpose of hydrophobization and chargeability control. It is possible and preferable to treat with a treating agent such as a silane coupling agent, an organic silicon compound, an organic titanium compound, etc. or in combination with various treating agents.

  For example, silane coupling agents typically include dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethylchlorosilane, vinyltriethoxysilane, γ -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, dimethylvinylchlorosilane and the like. The inorganic fine powder is treated with a silane coupling agent by dry treatment in which the vaporized silane coupling agent is reacted with a cloud of inorganic fine powder by stirring or the like, or a silane cup in which the inorganic fine powder is dispersed in a solvent. It can be processed by a generally known apparatus such as a wet method in which a ring agent is dropped.

  It is particularly preferable that the external additive used in the present invention is further treated with at least silicone oil.

  The average particle diameter of the silicone oil-treated external additive is preferably 0.1 μm or less, more preferably 0.002 to 0.05 μm. The oil treatment amount of the silicone oil-treated inorganic fine powder is preferably 1 to 30% by mass, particularly preferably 1 to 20% by mass with respect to the external additive to be treated. A preferable range of the amount of the silicone oil-treated external additive added to the toner is 0.3 to 3.0% by mass, and particularly preferably 0.5 to 2% by mass. Furthermore, the oil viscosity of the silicone oil is preferably 1 to 10000 cSt, and more preferably 50 to 1000 cSt.

  Examples of the silicone oil used in the present invention include dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil. A known technique is used for the apparatus for treating the silicone oil. For example, the silica fine powder and the silicone oil may be directly mixed using a mixer such as a Henschel mixer, or by an apparatus for spraying the silicone oil onto the base silica. good. Alternatively, it may be prepared by dissolving or dispersing silicone oil in an appropriate solvent, mixing the base silica fine powder, and then removing the solvent.

  In the one-component developer of the present invention, other additives, for example, a lubricant powder such as a polyfluorinated ethylene powder, a zinc stearate powder, a polyvinylidene fluoride powder; a cerium oxide powder within a range that does not substantially adversely affect the developer. Polishing agents such as silicon carbide powder and strontium titanate powder; fluidity imparting agents such as titanium oxide powder and aluminum oxide powder; anti-caking agents or conductive materials such as carbon black powder, zinc oxide powder and tin oxide powder A small amount of an imparting agent, or organic fine particles and inorganic fine particles having reverse polarity can be used as a developability improver.

  As the external addition method, a conventionally known method such as a Henschel mixer can be used.

  The toner of the present invention can maintain stable chargeability for a long period of time by defining the following BET specific surface area within an optimal range.

  The measurement of the BET specific surface area is performed using a known apparatus such as a degassing apparatus Bacuprep 061 (manufactured by Micromesotech) or a BET measuring apparatus Gemini 2375 (manufactured by Micromesotech). The BET specific surface area in the present invention is a value of a multipoint BET specific surface area. Specifically, the procedure is as follows.

  After measuring the mass of the empty sample cell, the sample to be measured is filled so as to be about 1.0 to 2.0 g. Further, the sample cell filled with the sample is set in the degassing apparatus, and degassing is performed at room temperature for 3 hours. After completion of degassing, the mass of the entire sample cell is measured, and the accurate mass of the sample is calculated from the difference from the empty sample cell. Next, empty sample cells are set in the balance port and analysis port of the BET measuring apparatus. A dewar bottle containing liquid nitrogen is set at a predetermined position, and P0 is measured by a saturated vapor pressure (P0) measurement command. After the P0 measurement is completed, the sample cell prepared for degassing is set in the analysis port, and after inputting the sample mass and P0, the measurement is started by the BET measurement command. After that, the BET specific surface area is automatically calculated.

The optimum BET specific surface area value (BET value) of the toner of the present invention is 1.5 to 3.5 m ² / g.

  If the BET value is less than 1.5, the chargeability and fluidity may be inferior, and fogging, scattering, and dropping off may be worsened, or transferability may be inferior. On the other hand, if the ratio is larger than 3.5, the resistance due to friction increases, and filming on the drum may be deteriorated. Further, there is a possibility that the image density may be thin due to improvement in fluidity or charge-up.

  The volume average particle size of the toner is, for example, a Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Inc.), etc., and an interface (manufactured by Nikkiki) that outputs number distribution and volume distribution and PC9801 personal computer (manufactured by NEC). It is possible to measure with a measuring device connected to. In this measurement, an electrolytic solution is used. As this electrolytic solution, for example, a 1% NaCl aqueous solution prepared using primary sodium chloride or ISOTON R-II (manufactured by Coulter Scientific Japan) can be used.

  As a measurement 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. Using a 100 μm aperture as the aperture, the volume and number of toners of 2 μm or more are measured by the Coulter Counter TA-II type. The volume distribution and the number distribution are calculated. Then, the volume average particle diameter obtained from the volume distribution according to the present invention and the number average particle diameter obtained from the number distribution are obtained.

  On the other hand, a contact-type surface roughness meter [manufactured by Kosaka Laboratory Ltd .: Surfcoder SE-3300] was used to measure the surface roughness of the developer carrier (developing roller). In such a measuring instrument, the ten-point average roughness Rz (JIS B0601) and the uneven peak crest Sm (JIS B0601) on the surface of the developing sleeve can be simultaneously measured in one measurement. The measurement conditions are a cutoff value of 0.8 mm, a measurement length of 2.5 mm, a feed speed of 0.1 mm / second, and a magnification of 5000 times. Here, the roughness Rz qualitatively represents the height difference between the uneven peaks and valleys on the surface of the developing sleeve.

  In the present invention, a desirable range of Rz is 6 or more and 12 μm or less. If Rz is less than 6, the toner transportability is inferior, and there is a risk that the image density is thin and the gloss of the fixed image is low. On the other hand, if the size is larger than 12 μm, the toner is excessively conveyed, so that fogging and scattering are deteriorated, and there is a possibility that the blurring may occur. In addition, since a large amount of toner remains, cleaning failure is likely to occur.

  In the present invention, the actual resistance value of the developing roller is measured by applying a load of 500 g on each end (total pressure 1 kg) to the core of the developing roller, and an aluminum drum having the same diameter as the photosensitive drum as the image carrier to be used ( In this embodiment, the developing roller is pressure-bonded to 30 mm. Keep the aluminum drum grounded. Then, the aluminum drum is rotated at 100 mm / sec and the developing roller is rotated at 170 mm / sec, 200 V is applied to the developing roller conductive cored bar, and the resistance between the developing roller and the aluminum drum is set to the actual resistance value.

At this time, the actual resistance value is preferably 1 × 10 ^{6 to} 1 × 10 ¹¹ Ω. If the actual resistance value is less than 1 × 10 ⁶ Ω, there is a possibility that tribo is not sufficiently applied to the toner, and fogging and scattering may be deteriorated. On the other hand, if it is larger than 1 × 10 ¹¹ Ω, the toner is likely to be overcharged, and the image density is thin and the gloss of the fixed image tends to be reduced.

  In the present invention, the glossiness indicating the degree of gloss is determined based on the specifications described in JIS Z 8741 (mirror gloss measurement method) and JIS K 7105 (plastic optical property test method). It is a value measured using PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.) under the condition of a light incident angle of 75 degrees.

  In the present invention, the molecular weight distribution of a chromatogram by GPC (gel permeation chromatography) using THF as a solvent is measured under the following conditions.

That is, the column is stabilized in a heat chamber at 40 ° C., THF (tetrahydrofuran) as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 ml / min, and about 100 μl of a THF sample solution is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK, and at least about 10 standard polystyrene samples is suitable. is there. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, a combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko KK TSKgel G1000H (HXL), G2000H (HXL), G3000H (HXL), G4000H (HXL), G5000H (HXL), G6000H (HXL), G7000H (HXL), and TSKguardcolumn can be given.

  The sample is prepared as follows.

  Put the sample in THF, let stand for several hours, shake well and mix well with THF (until the sample is no longer united), and let stand for more than 12 hours. At this time, the standing time in THF is set to be 24 hours or longer. Thereafter, a sample processing filter (pore size 0.45-0.5 μm, for example, Mysori Disc H-25-5 manufactured by Tosoh Corp., Excro Disc 25CR manufactured by Gelman Science Japan Corp., etc.) can be used, A sample of GPC is used. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

  In the present invention, the degree of aggregation is used as one means for measuring the flow characteristics of a sample (such as a toner having an external additive), and it is determined that the greater the value of the degree of aggregation, the worse the fluidity of the sample.

  As a measuring device, a powder tester (manufactured by Hosokawa Micron Corporation) having a digital vibrometer (Digivibro Model 1332) is used. As a measuring method, 200 mesh, 390 mesh, and 635 mesh sieve are placed on the shaking table in the order of narrow opening, that is, the 635 mesh, 390 mesh, and 200 mesh sieve are stacked so that the 200 mesh sieve comes to the top. To do.

5 g of accurately weighed sample is added to the set 200 mesh sieve, the input voltage to the shaking table is set to 21.7 V, the displacement value of the digital shaking meter is set to 0.130, and the shaking table at that time Is adjusted to fall within the range of 55 to 65 μm (rheostat scale about 2.5), and vibration is applied for about 15 seconds. Thereafter, the mass of the sample remaining on each sieve is measured, and the degree of aggregation is obtained based on the following equation.
Aggregation degree = mass of sample on 200 mesh sieve / 5 g × 100 +
Sample weight on 390 mesh sieve / 5g × 100 × 3/5 +
Sample mass on 635 mesh sieve / 5g × 100 × 1/5

  At this time, the preferable range of the degree of aggregation is 20 or more and 60 or less, and more preferably 30 or more and less than 55. If the degree of aggregation is less than 20, there is a tendency that the charge imparted to the toner tends to be non-uniform, the scattering may be deteriorated, and the fluidity is increased, so that cleaning failure may occur. On the other hand, when the value is larger than 60, the toner is not easily charged, and the fog is likely to be deteriorated or the blur is likely to occur.

  In the DSC measurement according to the present invention, since the heat exchange of the toner is measured and its behavior is observed, it is necessary to measure with a differential scanning calorimeter with high accuracy of internal heat input compensation type from the measurement principle. For example, DSC-7 manufactured by Perkin Elmer can be used.

  The measurement method is performed according to ASTM D3418-82. The DSC curve used in the present invention is a DSC curve that is measured when the temperature is lowered once and the temperature is raised in the range of a temperature rate of 10 ° C./min and a temperature of 0 to 200 ° C. .

  The endothermic peak temperature is a peak temperature in the plus direction in the DSC curve, that is, a point at which the differential value of the peak curve becomes 0 when changing from positive to negative.

  Next, an example of the image forming apparatus of the present invention will be further described with reference to FIGS. The same parts as those in the image forming apparatus are denoted by the same reference numerals and description thereof is omitted.

  An example of a color image forming apparatus (copier or laser beam printer) using an electrophotographic process will be described with reference to FIG.

  FIG. 1 shows a drum-shaped photoconductor as a first image carrier, which is rotationally driven in the direction of an arrow at a predetermined peripheral speed (process speed).

  In the rotating process, the photosensitive member 1 is uniformly charged to a predetermined polarity and potential by the primary charger 2, and then subjected to exposure 3 by an image exposure means 3 (not shown). In this manner, an electrostatic latent image corresponding to the first color component image (for example, a yellow toner image) of the target color image is formed.

  Next, the electrostatic latent image is developed into a yellow toner image which is the first color by the first developing device (yellow toner developing device 41). At this time, the second to fourth developing units, that is, the magenta toner developing unit 42, the cyan toner developing unit 43, and the black toner developing unit 44 are not operated and do not act on the photoconductor 1. One color yellow toner image is not affected by the second to fourth developing units.

  The intermediate transfer belt 20 is rotationally driven in the direction of the arrow at the same peripheral speed as that of the photoreceptor 1.

The yellow toner image of the first color formed on the photoreceptor 1 passes from the bias power source 29 to the intermediate transfer belt 20 via the roller 62 in the process of passing through the nip portion between the photoreceptor 1 and the intermediate transfer belt 20. The image is sequentially transferred onto the outer peripheral surface of the intermediate transfer belt 20 by an electric field formed by the applied bias. This process is called primary transfer, the roller 62 is called a primary transfer roller, and the applied bias is called a primary transfer bias.
The surface of the photoreceptor 1 that has finished transferring the first color yellow toner image corresponding to the intermediate transfer belt 20 is cleaned by the cleaning device 13.

  Similarly, the second color magenta toner image, the third color cyan toner image, and the fourth color black toner image are sequentially superimposed and transferred onto the intermediate transfer belt 20, and the full color toner corresponding to the target color image is obtained. An image is formed.

  Next, the color toner image is transferred to a transfer material, and this process is called secondary transfer. Reference numeral 63 denotes a secondary transfer roller which is supported in parallel with the secondary transfer counter roller 64 and arranged in a state in which it can be separated from the lower surface of the intermediate transfer belt 20.

  A primary transfer bias for transferring the toner image from the photoreceptor 1 to the intermediate transfer belt 20 is applied from a bias power supply 29 with a polarity opposite to that of the toner. The applied voltage is, for example, in the range of +100 V to +2 kV.

  In the primary transfer process of the first to third color toner images from the photoreceptor 1 to the intermediate transfer belt 20, the secondary transfer roller 63 can be separated from the intermediate transfer belt 20.

  The full-color image transferred onto the intermediate transfer belt 20 is contacted with the intermediate transfer belt 20 by the secondary transfer roller 63, and a predetermined portion is contacted between the sheet feeding roller 11 and the intermediate transfer belt 20 and the secondary transfer roller 63. At this timing, the transfer material P is fed, and the secondary transfer bias is applied from the bias power supply 28 to the secondary transfer roller 63, whereby the transfer material P is secondarily transferred. The transfer material P onto which the toner image has been transferred is introduced into the fixing device 15 and is heated and fixed.

  After the image transfer onto the transfer material P is completed, the toner (transfer residual toner) remaining on the intermediate transfer belt is scraped off by the cleaning blade 50 and is carried to a waste toner box.

  FIG. 2 is a configuration diagram showing developing cartridges 18a, 18b, 18c, and 18d that respectively store toners of Y, M, C, and Bk, which are developing means of this embodiment, and these developing cartridges 18a to 18d are shown in FIG. The rotary type color printer which is the image forming apparatus shown in FIG. 1 is configured to be detachable by opening and closing a developing cartridge replacement cover (not shown).

  The Y toner developing cartridge 18a will be described below for the sake of simplicity, but the same applies to the developing cartridges 18b, 18c, and 18d for other colors.

  The developing cartridge 18a of this embodiment shown in FIG. 2 is a reversal developing unit in which non-magnetic one-component Y toner is accommodated as a developer.

  The developing cartridge 18a is developed in contact with the photosensitive drum 1 while being rotated in the direction of arrow e in the drawing, and toner supply means for supplying toner to the developing roller 9a by rotating in the direction f in the drawing. A supply roller 16a, a developing blade 17a as a developer regulating member for regulating the toner application amount and the charge amount on the developing roller 9a, a stirring member 12a for feeding and stirring the toner to the supply roller 16a, and the like.

  FIG. 3 shows an image forming apparatus equipped with a contact one-component developing device (hereinafter simply referred to as a developing device) that performs development by a non-magnetic one-component DC contact developing method (this image forming device is an electrophotographic laser beam printer). It is a schematic block diagram which shows.

  The image forming apparatus includes a drum-type electrophotographic photosensitive member (hereinafter referred to as a photosensitive drum) 1 as an image carrier. A charging roller 2, a developing device 18, a transfer roller 4, and a cleaning blade 5 are installed around the photosensitive drum 1, and an exposure device 6 is disposed outside the charging roller 2 and the developing device 18. . A fixing device 15 is disposed downstream of the transfer nip between the photosensitive drum 1 and the transfer roller 4 in the transfer material conveyance direction.

  The photosensitive drum 1 is, for example, a negatively charged organic photoconductor, and has a photoconductor layer (not shown) on an aluminum drum base (not shown), and in a direction indicated by an arrow (clockwise) at a predetermined peripheral speed. The charging roller 2 that is driven to rotate and contacts in the rotation process is uniformly charged with negative polarity.

  A charging roller 2 as a charging unit is rotatably contacted with the surface of the photosensitive drum 1 and uniformly charges the photosensitive drum 1 to a predetermined negatively charged potential by a charging bias applied from a charging bias power source (not shown).

  The developing device 18 is a contact one-component developing device that performs development with a non-magnetic toner T as a one-component developer. The developing roller 9 as a freely rotatable developer carrier, the rotatable elastic roller 16 in pressure contact with the developing roller 9, the regulating blade 17 having elasticity in contact with the developing roller 9, and the toner T in the developing container 8 are agitated. A stirring member 12 is provided. The regulating blade 17 is in contact with the developing roller 9 on the downstream side in the rotation direction of the developing roller 9 with respect to the pressure contact portion between the developing roller 9 and the elastic roller 16.

  The toner T agitated by the agitating member 12 is supplied to the surface of the developing roller 9 by an elastic roller 16 that rotates in pressure contact with the developing roller 9. The toner supplied to the surface of the developing roller 9 is conveyed along with the rotation of the developing roller 9 and is charged by friction at the contact portion between the regulating blade 17 and the developing roller 9 to be thinned on the surface of the developing roller 9. The The thinned toner is conveyed by the rotation of the developing roller 9 and is attached to the electrostatic latent image formed on the photosensitive drum 1 at a contact portion (developing portion) with the photosensitive drum 1 to be visualized. . The toner that has not contributed to the development on the developing roller 9 is peeled off by the elastic roller 16.

  The transfer roller 4 serving as a transfer unit forms a transfer nip by contacting the surface of the photosensitive drum 1 with a predetermined pressing force, and the photosensitive drum 1 and the transfer roller 4 by a transfer bias applied from a transfer bias power source (not shown). The toner image on the surface of the photosensitive drum 1 is transferred to the transfer material P at the transfer nip.

  The cleaning blade 5 removes transfer residual toner remaining on the surface of the photosensitive drum 1 after transfer.

  The exposure apparatus 6 includes a laser driver (not shown), a laser diode, a polygon mirror 14, and the like, and laser light modulated in accordance with a time-series electric digital image signal of image information input to the laser driver is a laser diode. The laser beam is scanned by the polygon mirror 14 that is rotated at a high speed and the surface of the photosensitive drum 1 is image-exposed 3 through the optical lens system 19 to form an electrostatic latent image corresponding to the image information.

  The fixing device 15 includes a rotatable fixing roller 15a and a pressure roller 15b. The transfer material P is nipped and conveyed at a fixing nip between the fixing roller 15a and the pressure roller 15b, and the surface of the transfer material P is fixed. The toner image transferred to is heated and pressed to fix it thermally.

  Next, an image forming operation by the image forming apparatus will be described.

  At the time of image formation, the photosensitive drum 1 is rotationally driven at a predetermined peripheral speed in the direction of the arrow by a driving unit (not shown), and the surface is uniformly charged by the charging roller 2. Then, an image exposure 3 is given on the charged photosensitive drum 1 by the exposure device 6 to form an electrostatic latent image corresponding to the input image information.

  Then, the electrostatic latent image formed on the photosensitive drum 1 is exposed to light by the developing roller 9 of the developing device 18 to which a developing bias having the same polarity as the charging polarity (negative polarity) of the photosensitive drum 1 is applied in the developing unit. The toner T charged with the same polarity as the charging polarity (negative polarity) of the drum 1 is attached to be visualized as a toner image. When the toner image on the photosensitive drum 1 reaches the transfer nip between the photosensitive drum 1 and the transfer roller 4, a transfer material P such as paper is fed one by one by the pickup roller 11 in accordance with this timing. It is conveyed to the transfer nip by a roller (not shown) or the like.

  The toner image on the photosensitive drum 1 is transferred to the transfer material P conveyed to the transfer nip by the transfer roller 4 to which a transfer bias having a polarity opposite to that of the toner (positive polarity) is applied. Then, the transfer material P onto which the toner image has been transferred is conveyed to the fixing device 15 where the toner image is heated and pressed against the transfer material P at the fixing nip between the fixing roller 15a and the pressure roller 15b, and then discharged. The paper is discharged onto the paper tray 21 and a series of image forming operations is completed.

  Further, the transfer residual toner remaining on the surface of the photosensitive drum 1 after the toner image transfer is removed by the cleaning blade 5 and collected in the waste toner storage container 13.

  In the present invention, by adjusting the actual resistance value and surface roughness Rz of the developing roller, and the chargeability and fluidity of the toner, the toner amount supplied from the developing roller is stably maintained throughout the durability. It is characterized in that the same high image quality can be obtained even after the developing roller and toner in the latter half of the durability deteriorate. This means that the same density and high gloss can be achieved even if the same image is output in the initial stage and the latter half of the durability, and an image with the same density and high gloss can be obtained even when one or more colors are changed to a new one.

  Although all of this reason is not clear, I think that this purpose is achieved by the following mechanism in consideration of the situation.

  In the present invention, the actual resistance value of the developing roller is increased and the surface roughness Rz is increased, so that the physical conveyance amount of the toner is initially increased, and the electrostatic conveyance amount is gradually increased as the developing roller deteriorates. The overall transport amount is lowered while bringing the physical transport amount closer. On the other hand, the toner uses a so-called agglomerated toner to make the physical conveyance of the developing roller slightly more advantageous, while using the unevenness of the toner to suppress a decrease in the charge amount when the toner is deteriorated, and electrostatic conveyance. Is maintained until endurance. In addition, the toner resin is made of polyester and the charge amount is slightly increased, and the aggregation degree is increased more than usual so that the charge amount imparted to the toner in the development process is maintained at a high level. It became possible to obtain a stable and high image quality. In addition, a slight decrease in the charge amount and increase in the degree of aggregation due to toner deterioration contribute to an increase in the toner conveyance amount, and it is considered that the decrease in the conveyance amount due to the development roller deterioration described above is complemented. It seems that the same density and high gloss can be maintained while maintaining the same developability from the beginning to the end while the developing roller and the toner deteriorate due to this.

  The present invention will be specifically described below with reference to examples and comparative examples. “Parts” in the following examples and the like are “parts by mass”.

-Preparation of resin 1 (crystalline polyester)-
In a 1 L flask, 0.98 mol of dimethyl sebacate and 0.02 mol of acid component of 5-t-butylisophthalic acid, ethylene glycol (2.0 mol), and dibutyltin oxide (0.08 g) as a catalyst were added. After putting, the air in the container was depressurized by a depressurization operation, and further an inert atmosphere was established with nitrogen gas, followed by refluxing at 180 ° C. for 5 hours with mechanical stirring. Thereafter, excess ethylene glycol was removed by distillation under reduced pressure, the temperature was gradually raised to 230 ° C., and the mixture was stirred for 2 hours. When the mixture became viscous, the molecular weight was confirmed by GPC, and Mp = 12000 was obtained. By the way, vacuum distillation was stopped and air-cooled to obtain a crystalline polyester resin (1). The melting point of this resin was 69 ° C. (DSC peak top).

-Preparation of resin 2 (non-crystalline polyester)-
In a 1 L flask, dimethyl terephthalate (0.85 mol), dimethyl isophthalate 5-sodium sulfonate (0.14 mol), propylene glycol (1.4 mol), dipropylene glycol (0.4 mol), diethylene glycol (0.2 mol) ) And dibutyltin oxide (0.07 g), and the reaction was carried out in the same manner as described above. At this time, Mp was 12000, and melting | fusing point was 61 degreeC.

-Preparation of resin 3 (crystalline polyester)-
A 1 L flask was charged with 0.98 mol of sebacic acid and 0.02 mol of acid component of dimethyl 5-sulfonate sodium, ethylene glycol (2.0 mol), and dibutyltin oxide (0.08 g) as a catalyst. Thereafter, the reaction was carried out in the same manner as described above. At this time, Mp was 4500, and melting | fusing point was 69 degreeC.

-Preparation of resin 4 (crystalline polyester)-
In a 1 L flask, 0.85 mol of dimethyl sebacate and 0.15 mol of n-octadecenyl succinic anhydride, ethylene glycol (2.0 mol), and dibutyltin oxide (0.08 g) as a catalyst Then, the reaction was carried out in the same manner as described above. At this time, Mp was 48000, and melting | fusing point was 68 degreeC.

--Preparation of resin particle dispersion 1--
200 parts of the resin 1 was dissolved in 250 parts of tetrahydrofuran, and 5 parts of potassium hydroxide was dissolved in 10 parts of ion-exchanged water and added. While stirring this tetrahydrofuran solution at room temperature, 1000 parts of ion-exchanged water was added dropwise. The mixed solution was heated to about 75 ° C. to remove tetrahydrofuran to obtain a resin particle dispersion 1 having an average particle size of 0.09 μm.

--Preparation of resin particle dispersion 2--
200 parts of the resin 2 was dissolved in 250 parts of tetrahydrofuran, and 5 parts of potassium hydroxide was dissolved in 10 parts of ion-exchanged water and added. While stirring this tetrahydrofuran solution at room temperature, 1000 parts of ion-exchanged water was added dropwise. The mixed solution was heated to about 75 ° C. to remove tetrahydrofuran to obtain a resin particle dispersion 2 having an average particle size of 0.11 μm.

--Preparation of resin particle dispersion 3--
To 200 parts of the resin 3, 1000 parts of ion-exchanged water, 5 parts of potassium hydroxide and 8 parts of a 10% aqueous dodecylbenzenesulfonate solution were added. The mixture was heated to 90 ° C. and stirred at 10,000 rpm using a homogenizer to obtain a resin particle dispersion 3 having an average particle size of 0.18 μm.

--Preparation of resin particle dispersion 4--
To 200 parts of the resin 4, 1000 parts of ion-exchanged water, 5 parts of potassium hydroxide and 8 parts of a 10% aqueous dodecylbenzenesulfonate solution were added. The mixture was heated to 90 ° C. and stirred at 10,000 rpm using a homogenizer to obtain a resin particle dispersion 4 having an average particle size of 0.20 μm.

--Preparation of resin particle dispersion 5--
-73 parts of styrene-25 parts of n-butyl acrylate-2 parts of divinyl benzene-2 parts of acrylic acid A nonionic surfactant (manufactured by Sanyo Kasei Co., Ltd .: Nonipol 400) 1.5 was mixed and dissolved. Parts and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 2.5 parts dissolved in 120 parts of ion-exchanged water, dispersed in a flask, emulsified, and slowly mixed for 10 minutes Then, 10 parts of ion-exchanged water in which 0.7 part of ammonium persulfate was dissolved was added thereto, followed by nitrogen replacement, and then heated in an oil bath until the contents reached 70 ° C. while stirring the inside of the flask. Emulsion polymerization was continued as it was for 5 hours to prepare a resin particle dispersion 5 in which resin particles having an average particle diameter of 0.22 μm were dispersed.

--- Preparation of release agent particle dispersion--
・ Ester wax (melting point: 65 ° C.) 50 parts ・ Anionic surfactant 5 parts (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
・ Ion-exchanged water 200 parts or more was heated to 95 ° C. and dispersed using a homogenizer (IKA: ULTRA TALLAX T50), then dispersed with a pressure discharge homogenizer, and the average particle size was 0.5 μm. A release agent particle dispersion was prepared by dispersing a release agent.

-Preparation of colorant particle dispersion 1-
・ C. I. Pigment Red 122 20 parts, anionic surfactant 2 parts (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 parts or more were mixed and dispersed using a sand grinder mill. When the particle size distribution in this 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 larger coarse particles 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. Colorant particle dispersion 4 was prepared in the same manner as colorant particle dispersion 1, except that Pigment Red 122 was changed to carbon black.

--Preparation of charge control particle dispersion--
20 parts of a metal compound of di-alkyl-salicylic acid (charge control agent, Bontron E-84, manufactured by Orient Chemical Industries)
・ Anionic surfactant 2 parts (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 parts or more were mixed and dispersed using a 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.

-Preparation of capsule dispersion-
-Styrene 340 parts-n-butyl acrylate 60 parts-Acrylic acid 6 parts-Dodecanethiol 24 parts Mixing and dissolving the above 6 parts of nonionic surfactant Nonipol and 10 parts of anionic surfactant in 550 g of ion-exchanged water The dissolved product was dispersed and emulsified in a flask and slowly mixed, and then 50 parts of ion-exchanged water in which 4 parts of ammonium persulfate was dissolved was added to perform nitrogen substitution. Thereafter, the contents were heated to 70 ° C. while stirring the flask, and emulsion polymerization was continued for 5 hours. As a result, a resin dispersion for capsules having an average particle size of 0.155 μm, a glass transition point of 59 ° C., and Mw of 12000 was obtained.

(Toner Production Example 1)
<Preparation of liquid mixture>
-Resin particle dispersion 1 360 parts-Colorant dispersion 1 40 parts-Release agent dispersion 70 parts The above was put into a 1 liter separable flask equipped with a stirrer, a condenser, and a thermometer and stirred. The mixture was adjusted to pH = 5.2 using 1N potassium hydroxide.

<Agglomerated particle formation>
To this mixed solution, 2 parts of a 10% aqueous sodium chloride solution was added dropwise as a flocculant, and the flask was heated to 50 ° C. while stirring in the heating oil bath. At this temperature, 3 parts of the resin particle dispersion 1 and 10 parts of the charge control agent particle dispersion were added and held for 30 minutes. Thereafter, 15 parts of the capsule dispersion was slowly added, heated to 55 ° C. and held for 30 minutes.

<Fusion process>
Thereafter, 70 parts of a 15% aqueous solution of dodecylbenzenesulfonate was slowly added thereto, and the liquid temperature was raised to 80 ° C. and held for 5 hours. After cooling, filtration, sufficient washing with ion exchange water, and drying were performed to obtain a magenta toner base 1. The average particle diameter of the toner base 1 was about 6.8 μm. To 100 parts of this toner, 1.7 parts of hydrophobic silica having a BET specific surface area value of 200 (m ² / g) was externally added with a Henschel mixer FM10B under the condition of 4000 rpm × 5 minutes to obtain toner 1. .

  Similarly, cyan toner, yellow toner, and black toner were prepared using the colorant dispersions 2, 3, and 4, respectively. Since the physical properties of the toners of the respective colors are almost the same, the physical property values of the magenta toner relating to the toner 1 are shown in Table 1.

(Toner Production Example 2)
Toner 2 was obtained in the same manner except that resin particle dispersion 1 of toner production example 1 was changed to resin particle dispersion 2. The physical properties are shown in Table 1.

(Toner Production Example 3)
Toner 3 was obtained in the same manner except that one half of the resin particle dispersion 1 was changed to the resin particle dispersion 2 during preparation of the mixed liquid in Toner Production Example 1.

(Toner Production Example 4)
Toner 4 was obtained in the same manner except that resin particle dispersion 1 of toner production example 1 was changed to resin particle dispersion 3. The physical properties are shown in Table 1.

(Toner Production Example 5)
Toner 5 was obtained in the same manner except that resin particle dispersion 1 of toner production example 1 was changed to resin particle dispersion 4. The physical properties are shown in Table 1.

(Toner Production Example 6)
Toner 6 was obtained in the same manner except that the hydrophobic silica of Toner Production Example 1 was changed to 1.0 part. The physical properties are shown in Table 1.

(Toner Production Example 7)
Toner 7 was obtained in the same manner except that the amount of hydrophobic silica in Toner Production Example 1 was changed to 2.3 parts. The physical properties are shown in Table 1.

(Toner Production Example 8)
Toner 8 was obtained in the same manner except that the external addition time in Toner Production Example 1 was changed to 3 minutes. The physical properties are shown in Table 1.

(Toner Production Example 9)
Toner 9 was obtained in the same manner except that the external addition time in Toner Production Example 1 was changed to 10 minutes. The physical properties are shown in Table 1.

(Toner Production Example 10)
100 parts of crystalline polyester resin (1), C.I. I. 4.0 parts of Pigment Red 122 pigment and 5.0 parts of a metal compound of di-alkyl-salicylic acid (Bontron E-84) were melt-kneaded with a roll mill, cooled, coarsely pulverized, finely pulverized, and classified to obtain glass transition temperature. (Tg) Toner base 10 having a volume average particle size of 7.5 μm at 68 ° C. was obtained. The obtained toner base 10 was externally added with hydrophobic silica in the same manner as in Toner Production Example 1 to obtain Toner 10. The physical properties are shown in Table 1.

(Toner Production Example 11)
Add 3 parts of tricalcium phosphate to 900 parts of ion-exchanged water heated to 60 ° C, and stir at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo) to create an aqueous medium. did.

The following formulation was put into a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), heated to 60 ° C., and then stirred at 9,000 rpm to dissolve and disperse.
-Styrene 160 parts-n-butyl acrylate 40 parts-C.I. I. 18 parts of Pigment Red 122 and 4 parts of aluminum salicylate compound (Bontron E-88: manufactured by Orient Chemical Co., Ltd.)
-Stearyl stearate wax (DSC main peak 60 ° C) 30 parts-Divinylbenzene 0.5 part In this, 5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) is dissolved and polymerized. A monomer composition was prepared.

  The polymerizable monomer composition was put into the aqueous medium, and granulated by stirring at 8,000 rpm using a TK homomixer at 60 ° C. in a nitrogen atmosphere.

  Then, the temperature was raised to 70 ° C. over 2 hours while stirring by transferring to a propeller type stirring device, and further 4 hours later, the temperature was raised to 80 ° C. at a rate of temperature rise of 40 ° C./Hr and reacted at 80 ° C. for 5 hours. To produce polymer particles. After completion of the polymerization reaction, the slurry containing the particles was cooled, washed with 10 times the amount of water as the slurry, filtered, dried, and then classified to obtain magenta toner base particles 1 having a volume average particle size of 6.7 μm. This was externally added in the same manner as in Toner Production Example 1 to obtain Toner 11. The physical properties are shown in Table 1.

(Toner Production Example 12)
A toner 12 was obtained in the same manner except that the resin particle dispersion 1 of Toner Production Example 1 was changed to the resin particle dispersion 5. The physical properties are shown in Table 1.

(Toner Production Example 13)
Toner 13 was obtained in the same manner except that the external addition time in Toner Production Example 1 was changed to 2 minutes. The physical properties are shown in Table 1.

(Toner Production Example 14)
Toner 14 was obtained in the same manner except that the external addition time in Toner Production Example 1 was changed to 15 minutes. The physical properties are shown in Table 1.

(Development roller production example 1)
As a developing roller, a solid silicone in which 9 parts of carbon black per 100 parts of silicone rubber and 3.0 parts of an organic peroxide vulcanizing agent are dispersed as an electronic conductive layer on a stainless steel core having a diameter of 12 mm. A rubber layer of 2 mm is formed and sufficiently cured, and 10 μm of an ion conductive layer in which 2 parts of lithium perchlorate is dispersed in 100 parts of polyamide resin is formed, and an elastic developing roller 1 having a diameter of 16 mm is formed. did.

The rubber hardness of the developing roller 1 was 72 degrees (Asker C). Further, the surface roughness of the developing roller 1 was 9.0 μm in terms of 10-point average roughness Rz, and the actual resistance value was 7.6 × 10 ⁸ Ω.

(Development roller production example 2)
The developing roller 2 was obtained in the same manner except that the organic peroxide vulcanizing agent in the developing roller production example 1 was changed to 2.3 parts. The physical properties are shown in Table 2.

(Development roller production example 3)
The developing roller 3 was obtained in the same manner except that the organic peroxide vulcanizing agent in the developing roller production example 1 was changed to 3.5 parts. The physical properties are shown in Table 2.

(Development roller production example 4)
The developing roller 4 was obtained in the same manner except that the carbon black of the developing roller production example 1 was changed to 10 parts. The physical properties are shown in Table 2.

(Developing roller production example 5)
The developing roller 5 was obtained in the same manner except that the carbon black of the developing roller production example 1 was changed to 8 parts. The physical properties are shown in Table 2.

(Developing roller production example 6)
A developing roller 6 was obtained in the same manner except that the lithium perchlorate in Developer Example 1 was changed to 1.5 parts. The physical properties are shown in Table 2.

(Developing roller production example 7)
A developing roller 7 was obtained in the same manner except that the lithium perchlorate in Developer Example 1 was changed to 2.5 parts. The physical properties are shown in Table 2.

<Example 1>
Using the printer shown in FIG. 1, the developing roller 1 was incorporated in the cartridge shown in FIG. 2, 150 g of toner 1 was charged, and 8000 continuous printing tests were performed at a printing ratio of 1%. At that time, the yellow toner is obtained by replacing the colorant particle dispersion 1 of the toner 1 with the colorant particle dispersion 3, the cyan toner is replaced with the colorant particle dispersion 2, and the black toner is the colorant particle dispersion. 4 was prepared in the same manner as Magenta Toner 1 and evaluated at the same time. Thereafter, four colors were similarly prepared for the toner 2 and the subsequent toners and subjected to simultaneous evaluation. In any of the tests, the initial, 1000th and 8000th image patterns, the non-printed image pattern, the two-color solid image overlay pattern, and the halftone image were printed as samples, and the images at that time and transferred on the drum The remaining toner was also confirmed. Moreover, image evaluation was performed as follows.

(1) Fog The fog density (%) is calculated from the difference between the whiteness of the white portion of the printout image and the whiteness of the transfer paper measured by “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.), and the durability. Image fog at the end of the evaluation was evaluated. The filter used was amber light for cyan, blue for yellow, and green for magenta and black.
A: Very good Less than 1.0% B: Good 1.0% or more to less than 1.5% C: Somewhat difficult 1.5% or more to less than 3.0% D: Bad 3.0% or more

(2) Toner scattering A: Very good No scattering at all B: Good Slightly scattering (level that is slightly dirty when traced with fingers)
C: Slightly difficult To see that toner is scattered D: Poor Other developing cartridges and peripheral members are dirty

(3) Thin image density Using ordinary transfer paper (75 g / m ² ) for ordinary copying machines, the initial and 1000th and 8000th solid images in the image output test are output, and the density Was measured with an average of 5 points, and evaluated as follows according to the concentration reduction rate at that time. The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00.
A: Very good Less than 10% B: Good 10% or more, less than 17% C: Somewhat difficult 17% or more, less than 25% D: Bad 25% or more

(4) Gloss Using a plain paper for ordinary copying machine (75 g / m ² ), a solid image was output in an image output test, and the glossiness was measured by measuring the average of 5 points. In the present invention, the glossiness indicating the degree of gloss is determined based on the specifications described in JIS Z 8741 (mirror gloss measurement method) and JIS K 7105 (plastic optical property test method). This is a value measured using a gloss meter PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.) under the condition of a light incident angle of 75 degrees.
A: Very good 40 or more and less than 55 B: Good 25 or more and less than 40 C: Somewhat difficult 10 or more and less than 25 D: There is a problem Less than 10

  In the present invention, the range up to evaluation B was set as a favorable range.

(5) Poor cleaning A: Very good No occurrence B: Good Occurred but minor C: Somewhat difficult, but not intermittent printing D: Poor What

(6) Filming Evaluation was performed as follows according to the number of filming marks per 100 cm ^{2 in} an image when 1000 sheets were continuously printed.
A: Very good No occurrence at all B: Good Less than 0.5 places C: Somewhat difficult 0.5 or more places Less than 1.5 places D: Unusable 1.5 places or more

(7) Blow-off drop A: Very good No occurrence B: Good Visually faint toner lump traces up to 3 in all evaluation processes C: Slightly difficult All visible toner lump traces visible Up to 3 items in the evaluation process or faint
What is occurring in less than 10 sheets D: Unusable 4 or more obvious toner lump marks or 10 or more faint toner traces
Living things

<Example 2>
Evaluation was performed in the same manner as in Example 1 except that the toner was changed to toner 2. The configuration is shown in Table 3, and the results are shown in Table 4.

<Example 3>
Evaluation was performed in the same manner as in Example 1 except that the toner was changed to toner 3. The configuration is shown in Table 3, and the results are shown in Table 4.

<Example 4>
Evaluation was performed in the same manner as in Example 1 except that the toner was changed to toner 4. The configuration is shown in Table 3, and the results are shown in Table 4.

<Example 5>
Evaluation was conducted in the same manner as in Example 1 except that the toner was changed to toner 5. The configuration is shown in Table 3, and the results are shown in Table 4.

<Example 6>
Evaluation was performed in the same manner as in Example 1 except that the toner was changed to toner 6. The configuration is shown in Table 3, and the results are shown in Table 4.

<Example 7>
Evaluation was performed in the same manner as in Example 1 except that the toner was changed to toner 7. The configuration is shown in Table 3, and the results are shown in Table 4.

<Example 8>
Evaluation was performed in the same manner as in Example 1 except that the toner was changed to toner 8. The configuration is shown in Table 3, and the results are shown in Table 4.

<Example 9>
Evaluation was performed in the same manner as in Example 1 except that toner 9 was used. The configuration is shown in Table 3, and the results are shown in Table 4.

<Example 10>
Evaluation was performed in the same manner as in Example 1 except that the developing roller was changed to the developing roller 2. The configuration is shown in Table 3, and the results are shown in Table 4.

<Example 11>
Evaluation was conducted in the same manner as in Example 1 except that the developing roller 3 was used as the developing roller. The configuration is shown in Table 3, and the results are shown in Table 4.

<Comparative Example 1>
Evaluation was performed in the same manner as in Example 1 except that the developing roller 4 was used as the developing roller. The configuration is shown in Table 3, and the results are shown in Table 4.

<Comparative example 2>
Evaluation was performed in the same manner as in Example 1 except that the developing roller was changed to the developing roller 5. The configuration is shown in Table 3, and the results are shown in Table 4.

<Comparative Example 3>
Evaluation was conducted in the same manner as in Example 1 except that the developing roller was replaced with the developing roller 6. The configuration is shown in Table 3, and the results are shown in Table 4.

<Comparative example 4>
Evaluation was conducted in the same manner as in Example 1 except that the developing roller was changed to the developing roller 7. The configuration is shown in Table 3, and the results are shown in Table 4.

<Comparative Example 5>
Evaluation was conducted in the same manner as in Example 1 except that the toner was changed to toner 10. The configuration is shown in Table 3, and the results are shown in Table 4.

<Comparative Example 6>
Evaluation was performed in the same manner as in Example 1 except that the toner was changed to toner 11. The configuration is shown in Table 3, and the results are shown in Table 4.

<Comparative Example 7>
Evaluation was conducted in the same manner as in Example 1 except that the toner was changed to toner 12. The configuration is shown in Table 3, and the results are shown in Table 4.

<Comparative Example 8>
Evaluation was performed in the same manner as in Example 1 except that the toner was changed to toner 13. The configuration is shown in Table 3, and the results are shown in Table 4.

<Comparative Example 9>
Evaluation was performed in the same manner as in Example 1 except that the toner was changed to toner 14. The configuration is shown in Table 3, and the results are shown in Table 4.

It is explanatory drawing which shows an example of the color image forming apparatus using an electrophotographic process. FIG. 4 is an explanatory diagram illustrating a configuration of a developing cartridge that stores toner. 1 is a schematic configuration diagram illustrating an image forming apparatus including a contact one-component developing device.

Explanation of symbols

1 Photosensitive drum (image carrier)
DESCRIPTION OF SYMBOLS 2 Charging roller 3 Exposure optical path 4 Transfer roller 5 Cleaning means 6 Exposure means 8 Toner container 9, 9a, 9b, 9c, 9d Developing roller (developer carrier)
DESCRIPTION OF SYMBOLS 10 Paper feed guide 11 Paper feed roller 12, 12a, 12b, 12c, 12d Stirring member 13 Waste toner container 14 Exposure device 15 Fixing device 16, 16a, 16b, 16c, 17d Toner supply roller 17, 17a, 17b, 17c, 17d Regulating blade 18, 18a, 18b, 18c, 18d Process cartridge 20 Intermediate transfer belt 21 Discharge tray 28, 29 Transfer bias power supply 41, 42, 43, 44 Developer 50 Belt cleaning means 62, 63 Transfer rollers 64, 65, 66 Tension roller P Transfer paper

Claims (10)

Image formation in which a developer carrier is brought into contact with the surface of the electrostatic latent image carrier directly or via a developer, and the electrostatic latent image on the surface of the electrostatic latent image carrier is developed by the developer carried by the developer carrier. A method,
The developer carrying member has an actual resistance value of 1 × 10 ⁶ or more and 1 × 10 ¹¹ Ω or less, and a 10-point average roughness Rz of 6 μm or more and 12 μm or less,
The developer is a non-magnetic one-component developer having toner particles containing at least a polyester-based resin and a colorant, and having an aggregation degree of 20 or more and 60 or less, and the toner particles include at least a polymer. It is obtained by an emulsion aggregation method obtained through a process of agglomerating fine particles and colorant fine particles to form a fine particle aggregate and a ripening step of causing fusion between the fine particles in the fine particle aggregate An image forming method.   2. The image forming method according to claim 1, wherein the main component of the resin of the non-magnetic one-component developer is a crystalline polyester resin.   3. The image forming method according to claim 1, wherein a peak molecular weight of the polyester resin of the non-magnetic one-component developer is 5,000 or more and 30,000 or less.   4. The image forming method according to claim 1, wherein the measured value of the specific surface area of the non-magnetic one-component developer is 1.5 or more and 3.5 or less.   The image forming method according to claim 1, wherein the nonmagnetic one-component developer has an aggregation degree of 30 or more and 55 or less.   The image forming method according to claim 1, wherein the developer carrying member has an Asker C hardness of 60 ° or more and 90 ° or less.   The image forming method according to claim 1, wherein the image forming method is used as a full color. Image formation in which a developer carrier is brought into contact with the surface of the electrostatic latent image carrier directly or via a developer, and the electrostatic latent image on the surface of the electrostatic latent image carrier is developed by the developer carried by the developer carrier. The developer carrying member used in the method has an actual resistance value of 1 × 10 ^{6 to} 1 × 10 ¹¹ Ω and a surface ten-point average roughness Rz of 6 μm to 12 μm. A non-magnetic one-component developer containing toner particles containing at least a resin mainly containing a colorant and a cohesion degree of 20 or more and 60 or less,
By the emulsion polymerization aggregation method in which the toner particles are obtained through a process of aggregating at least polymer fine particles and colorant fine particles to form a fine particle aggregate and a ripening step of causing fusion between the fine particles in the fine particle aggregate. A non-magnetic one-component developer obtained. An electrostatic latent image carrier that carries an electrostatic latent image; and a developer carrier that contacts the surface of the electrostatic latent image carrier directly or via a developer and develops the electrostatic latent image with the carried developer; An image forming apparatus having
The developer carrying member has an actual resistance value of 1 × 10 ⁶ or more and 1 × 10 ¹¹ Ω or less, and a 10-point average roughness Rz of 6 μm or more and 12 μm or less,
The developer is a non-magnetic one-component developer having toner particles containing at least a polyester-based resin and a colorant, and having an aggregation degree of 20 or more and 60 or less, and the toner particles include at least a polymer. It is obtained by an emulsion polymerization aggregation method obtained through a process of agglomerating fine particles and colorant fine particles to form a fine particle aggregate and a ripening step of causing fusion between the fine particles in the fine particle aggregate. An image forming apparatus. An electrostatic latent image carrier that carries an electrostatic latent image; and a developer carrier that contacts the surface of the electrostatic latent image carrier directly or via a developer and develops the electrostatic latent image with the carried developer; A process cartridge used in an image forming apparatus having
The developer carrying member has an actual resistance value of 1 × 10 ⁶ or more and 1 × 10 ¹¹ Ω or less, and a 10-point average roughness Rz of 6 μm or more and 12 μm or less,
The developer is a non-magnetic one-component developer having toner particles containing at least a polyester-based resin and a colorant, and having an aggregation degree of 20 or more and 60 or less, and the toner particles include at least a polymer. It is obtained by an emulsion polymerization aggregation method obtained through a process of agglomerating fine particles and colorant fine particles to form a fine particle aggregate and a ripening step of causing fusion between the fine particles in the fine particle aggregate. Feature process cartridge.

Images