WO1998026332A1 - Support pour electrophotographie et revelateur utilisant un tel support - Google Patents

Support pour electrophotographie et revelateur utilisant un tel support Download PDF

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Publication number
WO1998026332A1
WO1998026332A1 PCT/JP1997/004563 JP9704563W WO9826332A1 WO 1998026332 A1 WO1998026332 A1 WO 1998026332A1 JP 9704563 W JP9704563 W JP 9704563W WO 9826332 A1 WO9826332 A1 WO 9826332A1
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WO
WIPO (PCT)
Prior art keywords
carrier
resin
magnetic powder
toner
electrophotographic
Prior art date
Application number
PCT/JP1997/004563
Other languages
English (en)
Japanese (ja)
Inventor
Shigeo Matsuzaki
Takashi Arakane
Kazuo Murakata
Susumu Kikuchi
Original Assignee
Idemitsu Kosan Co., Ltd.
Kyocera Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Idemitsu Kosan Co., Ltd., Kyocera Corporation filed Critical Idemitsu Kosan Co., Ltd.
Priority to EP97947898A priority Critical patent/EP0883035B1/fr
Priority to DE69724592T priority patent/DE69724592T2/de
Publication of WO1998026332A1 publication Critical patent/WO1998026332A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
    • G03G9/1139—Inorganic components of coatings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
    • G03G9/1132—Macromolecular components of coatings
    • G03G9/1133—Macromolecular components of coatings obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
    • G03G9/1132—Macromolecular components of coatings
    • G03G9/1135—Macromolecular components of coatings obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/1136—Macromolecular components of coatings obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon atoms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/10—Developers with toner particles characterised by carrier particles
    • G03G9/113—Developers with toner particles characterised by carrier particles having coatings applied thereto
    • G03G9/1138—Non-macromolecular organic components of coatings

Definitions

  • the present invention relates to an electrophotographic carrier and an electrophotographic developer using the same. More specifically, the present invention relates to an electrophotographic carrier used for developing an electrostatic latent image in an image forming method using electrophotography, and an electrophotographic developer using the same. Background art
  • the electrostatic latent image developing method for electrophotography has been developed as a one-component magnetic jumping developing method, a one-component non-magnetic contact developing method, or by mixing an insulating non-magnetic toner with magnetic carrier particles to rub the toner.
  • a two-component developing system in which a developer is conveyed while being charged, and is developed by being brought into contact with an electrostatic latent image.
  • the granular carrier used in such a two-component developing system prevents toner filming on the carrier surface, forms a uniform carrier surface, extends the life of the developer, adjusts the amount of damage or charge on the photoreceptor carrier, etc.
  • it is customary to coat a magnetic carrier core material with a suitable material.
  • the conventional resin-coated carrier is not satisfactory in terms of durability because the coating easily peels off due to impacts such as stirring during use.
  • the present inventor has conducted polymerization of an olefin monomer directly on carrier core particles such as ferrite.
  • a technology for forming a olefin resin-based coating was developed and proposed earlier (for example, Japanese Patent Application Laid-Open No. Hei 2-18771).
  • Polyolefin resin-coated carriers obtained by this method have a strong coating between the core material and the coating, because the coating is formed directly on the carrier core particles, and the image quality deteriorates even after long-term continuous copying. And has excellent durability and spent resistance.
  • this polyolefin-based resin-coated carrier cannot control the charge polarity and adjust the charge amount, etc., and also causes the external additive to be spent due to the adhesion of the toner external additive. However, it did not necessarily have sufficient durability, for example, due to problems such as the occurrence of problems.
  • Japanese Patent Application Laid-Open No. 53-10042 discloses a method in which a carrier coating resin contains a nigricin to improve the negative charge amount.
  • Japanese Patent Application Laid-Open No. 61-9661 discloses an example in which a fluidity improving agent is added to improve the fluidity.
  • Japanese Patent Application Laid-Open No. 2-210365 discloses a technique in which one of conductive particles, inorganic filler particles, and a charge controlling agent is added to prevent uniform chargeability and prevent spent. I have.
  • the present invention has been made in view of the above-described problems, and makes it possible to freely adjust a charge amount and a static resistance while taking advantage of the excellent characteristics of a carrier having a polyolefin-based resin coating, and to achieve stable density.
  • An object of the present invention is to provide an electrophotographic carrier and an electrophotographic developer using the same, which can obtain an image and effectively prevent the external additive from being spent on the toner due to adhesion of the external additive. And Disclosure of the invention
  • an electrophotographic carrier having a carrier core having magnetism and a coating layer made of a high molecular weight polyethylene resin covering the surface of the carrier core;
  • a coating layer made of a high-molecular-weight polyethylene resin is used as at least the outermost shell layer, a layer containing a magnetic powder that is a convex polyhedron whose three-dimensional shape is surrounded by six or more planes and / or curved surfaces, or this magnetic powder and silica And an electrophotographic carrier characterized by having a layer containing fine particle resin.
  • the carrier for electrophotography according to claim 1 wherein the average particle size of the magnetic powder is in the range of 0.1 to 1 ⁇ m.
  • the resistance value is 1 0 2 to 1 0 "electrophotographic carrier which is a Omega ⁇ cm is provided.
  • the electrophotographic carrier is 2 to 40% by weight based on the total amount of the carrier and the toner.
  • the present invention provides an electrophotographic developer comprising a toner mixed at a ratio of / 0 .
  • FIG. 1 is an explanatory diagram showing the dependence of the image density on the magnetic field potential in Application Example 1 of the present invention.
  • FIG. 2 is an explanatory diagram showing the results of continuous printing evaluation in Application Example 2 of the present invention.
  • the electrophotographic carrier of the present invention has a carrier core material and a coating layer made of a high molecular weight polyethylene resin that coats the surface of the carrier core material, and at least the coating layer made of the high molecular weight polyethylene resin has
  • the outermost shell layer has a layer containing magnetic powder which is a convex polyhedron surrounded by planes or curves having three or more three-dimensional shapes, or a layer containing this magnetic powder and silica and / or fine particle resin.
  • the carrier core material used in the present invention is not particularly limited, and those known as two-component carriers for electronic photography, such as ferrite, magnetite, and metals such as iron, nickel, and cobalt; Alloys or mixtures of these metals with metals such as copper, zinc, antimony, aluminum, lead, tin, bismuth, beryllium, manganese, magnesium, selenium, tungsten, di / recombium, and vanadium; A mixture of the ferrite or the like, a metal oxide such as iron oxide, titanium oxide, or magnesium oxide; a nitride such as chromium nitride or vanadium nitride; or a carbide such as silicon carbide or tungsten carbide; , And (1) a mixture thereof.
  • ferrite, magnetite, and metals such as iron, nickel, and cobalt
  • Alloys or mixtures of these metals with metals such as copper, zinc, antimony, aluminum, lead, tin
  • the shape is not particularly limited, and may be spherical or irregular. Although there is no particular limitation on the particle size, for example, those having a particle size of 20 to 100 / m can be suitably used. If it is less than 20 // m, the carrier may adhere (scatter) to the electrostatic latent image carrier (generally the photoreceptor). If it exceeds 1 OO / zm, carrier streaks etc. will occur, May decrease. (3) Composition ratio
  • the composition ratio of the carrier core material is set to 90% by weight or more, preferably 95% by weight or more of the entire carrier. This composition ratio indirectly defines the thickness of the resin coating layer of the carrier. If the composition ratio is less than 90% by weight, the coating layer becomes too thick, and even if the coating layer is actually applied to the developer, the coating layer peels off, the charge amount increases, and the durability required for the developer is reduced. Charging stability cannot be satisfied. In addition, fine line reproducibility is inferior in image quality, and problems such as a decrease in image density occur. There is no particular upper limit, but the upper limit is such that the coating resin layer completely covers the surface of the carrier core material. This value varies depending on the physical properties of the carrier core material and the coating method.
  • a conductive layer may be provided on the carrier core particles, if necessary, prior to coating with a high molecular weight polyethylene resin.
  • the conductive layer formed on the carrier core particles for example, a layer in which conductive fine particles are dispersed in an appropriate binder resin can be used.
  • the formation of such a conductive layer is effective in enhancing the developability and obtaining a high-contrast clear image with high image density. This is probably because the presence of the conductive layer causes the electrical resistance of the carrier to be reduced appropriately, and the charge to be leaked and accumulated in a well-balanced manner.
  • the conductive fine particles to be added to the conductive layer include carbon black, the force one carbon black such Asechi Ren black, carbide such as S i C, magnetic powder such as Maguneta wells, the S N_ ⁇ 2, and titanium black be able to.
  • the binder resin for the conductive layer include a polystyrene resin, a poly (meth) acrylic resin, a polyolefin resin, a polyamide resin, a polycarbonate resin, a polyether resin, a polysulfonic acid resin, and a polyester resin.
  • Epoxy-based resins Epoxy-based resins, polybutyral-based resins, urea-based resins, urethane / urea-based resins, silicon-based resins, Teflon-based resins and other thermoplastic resins and thermosetting resins, and mixtures thereof.
  • Resin copolymers block polymers, graft polymers, polymer blends, and the like.
  • the conductive layer can be formed by applying a solution in which the conductive fine particles are dispersed in the above-described appropriate binder resin to the surface of the carrier core material particles by a spray coating method, a diving method, or the like. It can also be formed by melting, kneading and pulverizing core particles, conductive fine particles and binder resin. Further, it can also be formed by polymerizing a polymerizable monomer on the surface of the core particles in the presence of the conductive fine particles.
  • the size and amount of the conductive fine particles are not particularly limited as long as they satisfy various characteristics such as electric resistance of the finally obtained carrier of the present invention.
  • Particle size that can be uniformly dispersed in the resin solution specifically, average particle size of 2 to 0.01 // m, preferably:! ⁇ 0.01 ⁇ m is enough.
  • the amount of the conductive fine particles to be added cannot be specified strictly depending on the type or the like, the amount is 0.1% by weight to 60% by weight with respect to the binder resin of the conductive layer. / 0 , preferably from 0.1 to 40% by weight. / 0 is appropriate.
  • the carrier filling rate is 90 weight. / 0, and the thickness of the coating layer is relatively thick, the continuous reproducibility of fine lines using such a carrier causes a problem of reduced reproducibility. The problem is solved by the addition of the conductive fine particles.
  • carrier core particles those in which a functional layer such as a conductive layer is formed on the carrier core particles will be simply referred to as carrier core particles without misunderstanding.
  • the high-molecular-weight polyethylene resin is usually simply referred to as polyethylene.
  • a resin having a number-average molecular weight of 10,000 or more or a weight-average molecular weight of 50,000 or more is particularly preferable. In general, the number average molecular weight is less than 10,000.
  • polyethylene wax (Mitsui High Wax (Mitsui Petrochemical), Dialen 30 (Mitsubishi Chemical), Stone Rexpol (manufactured by Nippon Oil Co., Ltd.), Sunwax (manufactured by Sanyo Chemical Co., Ltd.), Poly Let's (manufactured by Chusei Wax Polymer Co., Ltd.), Neowax (manufactured by Yasuhara Chemical Co., Ltd.), AC Polyethylene (manufactured by Allied Chemical Co., Ltd.) ), Epolen (Eastman's Kodak), Hex Wax (Hexto), A-Wax (BASF), Polywax (Petrolite), Escoma (Exon) Chemical Co., Ltd.) is distinguished from the high molecular weight polyethylene resin used in the present invention. Polyethylene wax can be coated by ordinary dipping or spraying by dissolving it in hot toluene or the like.However, due to the low mechanical strength of the resin,
  • one or more kinds of functional fine particles such as the conductive fine particles and the fine particles having charge control ability described later may be added to the coating layer made of the high molecular weight polyethylene resin.
  • the method for forming the coating layer used in the present invention is not particularly limited, and known methods such as dipping method, fluidized bed, dry method, spray drying, polymerization method, etc. S, polyethylene resin
  • the following polymerization method is preferred for the coating of (1) because the resin coating strength is high and the resin is hardly peeled off.
  • the polymerization method refers to a method in which the surface of a carrier core material is treated with an ethylene polymerization catalyst to produce a polyethylene resin-coated carrier while polymerizing (generating) ethylene directly on the surface.
  • Examples of the method include the methods described in Japanese Patent Application Laid-Open No. 10-68080 and Japanese Patent Application Laid-Open No. 2-187770. That is, the polyethylene resin coating layer is prepared by pre-contacting a carrier core material with a highly active catalyst component containing titanium and / or zirconium and soluble in a hydrocarbon solvent (eg, hexane, heptane, etc.).
  • an organoaluminum compound It can be formed by suspending in a hydride solvent, supplying an ethylene monomer, and polymerizing on the surface of the carrier core material. Further, when the fine particles having the charge imparting function or the conductive fine particles are added, they may be added and present at the time of forming the high molecular weight polyethylene resin coating layer.
  • the polyethylene coating layer is formed directly on the surface of the carrier core material, so that the resulting coating has excellent strength and durability.
  • one or more kinds of functional fine particles such as conductive fine particles and fine particles having charge control ability can be added and supported as described above to modify the high molecular weight polyethylene resin coating.
  • conductive fine particles to be added and supported in the high molecular weight polyethylene resin coating all conventionally known conductive fine particles can be used, for example, the above-mentioned conductive materials such as carbon black, carbide such as SiC, and magnetite. magnetic powder, S n 0 2, it is possible to use a titanium black.
  • the average particle size of the conductive fine particles is preferably from 0.01 to 5.0 ⁇ m.
  • the coating layer is a layer containing a magnetic powder which is a convex polyhedron surrounded by a plane or curved surface having a three-dimensional shape of at least 6 as its outermost shell layer, or a layer containing the magnetic powder and silica and And / or a layer containing fine particle resin.
  • Examples of the material of the magnetic powder used in the present invention include magnetite, ferrite, iron powder and the like.
  • the three-dimensional shape of the magnetic powder is a convex polyhedron surrounded by six or more planes and / or curved surfaces.
  • a polyhedron means a solid surrounded only by a plane, but the present invention also includes a solid body in which all or some of the surfaces are curved. It is important that ridges and vertices formed by such a plane or a curved surface exist.
  • the conductive efficiency is improved by changing from a conductive mechanism at the surface to a conductive mechanism at a point at the convex portion of the polyhedron.
  • the polyhedron may be a single kind or a combination of plural kinds.
  • the average particle size is preferably from 0.1 to 1 / m, more preferably from 0.2 to 0.7 // m. If it is less than 0. 1 m, the effect as a spacer is lost, and if it exceeds l / m, it may not be possible to add it to the outermost shell layer.
  • the resistance is preferably 1E + 7 to: IE + 10 ⁇ ⁇ cm, and more preferably 1E + 7 to: 1 ⁇ + 9 ⁇ ⁇ c. If it is less than 1 E + 7 ⁇ .cm, the chargeability may be impaired. If it exceeds 1 E + 10 ⁇ ⁇ cm, the resistance cannot be adjusted, and the function as a magnetic powder may not be achieved.
  • Magnetite MG-1306 octahedron
  • Magnetite MG-9300 polyhedron manufactured by Mitsui Kinzoku Co., Ltd. 2Silica
  • Examples of the silica used in the present invention include those obtained by subjecting silica to a surface beading treatment so as to be positively or negatively chargeable.
  • the primary particle size is preferably 40 nm or less, more preferably 10 to 30 nm. If it exceeds 40 nm, the gap between the silica particles becomes large and irregularities occur on the carrier surface.
  • RA 200 HS manufactured by Nippon Aerosil and 2015 EP and 2050 EP manufactured by Pecker Chemicals as positively chargeable silica
  • Nippon Aerosil Co., Ltd. as negatively chargeable silica
  • Examples of the fine particle resin used in the present invention include the following negatively chargeable resin (A) and positively chargeable resin (B).
  • Fluorine-based resins eg, vinylidene fluoride resin, tetrafluoroethylene resin, ethylene trifluoride ethylene resin, tetrafluoroethylene-hexylene propylene copolymer resin, etc.
  • vinyl chloride resin eg, celluloid
  • Acrylic resin polyamide resin (eg, nylon-6, nylon-6, nylon-11, etc.), styrene resin (polystyrene, ABS, AS, AAS, etc.), vinylidene chloride resin, polyester resin (Eg, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyatalylate, polyoxybenzoyl, polycarbonate, etc.), polyether-based resin (polyacetal, polyphenylene) Ethylene resin (EVE, E EA, EAA, EMA A, EA AM, EMMA, etc.)
  • a negatively chargeable resin be added to the positively charged toner, and a positively chargeable resin be added to the negatively charged toner.
  • both the silica and the fine particle resin may be contained, or only one of them may be contained. Further, the silica and the fine particle resin may each be a single kind or a plurality of kinds.
  • the layer thickness of the outermost shell is preferably 0.1 to 6 tm. If it is less than 0. 1 ⁇ ⁇ ⁇ , the coating is incomplete, when it exceeds 6 Myuiotaita, there is a risk that peeling of the outermost layer by mechanical impact such as friction from the outside occurs.
  • the method of forming and fixing the outermost shell layer used in the present invention is based on the particle size and shape of the magnetic powder to be used and the physical properties of the silica type and silica or resin (particle size, solubility in organic solvents, melting point, hardness, etc.). ), Can be selected from the following two types and used alone or in combination.
  • a crusher such as a Henschel mixer (Mitsui Miike Koki Co., Ltd., FM10L type)
  • a core material coated with a high molecular weight polyethylene resin and an appropriate amount of magnetic powder, or magnetic powder and silica and / or fine particle resin The outermost layer is formed by a mixture of the above.
  • the amount of the magnetic powder or the mixture of the magnetic powder and the silica or Z or fine particle resin is determined by the resistance value to be changed, the absolute value of the charge amount, and the stability of the density of the actual printed image.
  • 0.1 to 50 phr (% by weight of the additive to the coating resin) based on the coated polyethylene amount of the high molecular weight polyethylene coated carrier is used. Usually, it is added in a ratio, but considering durability, resistance change due to formation of the outermost layer, and production stability, an appropriate amount is about 20 to 30 phr.
  • the treatment with the Henschel mixer is performed in a treatment amount of 1 to 5 kg at a low rotation speed at which the added magnetic powder, silica, and particulate resin are not scattered.
  • the treatment time varies depending on the amount of the magnetic powder to be added, the amount of silica and / or fine particle resin, the amount of the coated high molecular weight polyethylene, and the like, but should be about 0.5 to 5 hours.
  • silica, Z or fine particle resin by mechanical shock, dust (various fine powder, etc.) is generated, so classification must be performed sufficiently.
  • a heat-sphering machine Hosokawa Micron Co., Ltd., thermo-sphering machine
  • a high-molecular-weight polyethylene resin-coated carrier and an appropriate amount of magnetic powder, or a magnetic powder and silica and / or fine particles are used.
  • the outermost shell layer is formed by the mixture.
  • the amount of the magnetic powder, silica, Z or fine particle resin added at this time is determined by the absolute value of the charge amount to be changed and the stability of the actual printed image.
  • the conductive properties of Canon rear optimum for the system developer using Kiyaria is vary, generally, the resistance measurement is an indication of the value of 1 0 2 ⁇ 1 0 14 ( ⁇ ⁇ cm) preferable.
  • the resistance value was determined by applying a voltage of 1 to 500 V to the upper and lower electrodes by providing a carrier layer with a thickness of 0.5 cm under a load of 1 kg with an electrode area of 5 cm, and applying the current to the bottom. was measured and converted.
  • the electrophotographic developer of the present invention can be obtained by mixing the carrier with various toners. 1. Toner
  • a toner produced by a known method for example, a toner produced by a suspension polymerization method, a pulverization method, a microcapsule method, a spray drying method, or a mechanochemical method can be used.
  • a binder resin, a colorant, and, if necessary, other additives such as a charge controlling agent, a lubricant, an offset preventing agent, and a fixing improving auxiliary can be blended.
  • a magnetic material can be added to form a magnetic toner, which is effective for improving development characteristics and preventing toner from scattering inside the machine.
  • a fluidizing agent may be externally mixed to improve the fluidity.
  • binder resin examples include polystyrene resins such as polystyrene, styrene / butadiene copolymer, and styrene / acrylic copolymer, polyethylene, ethylene / butyl acetate copolymer, and ethylene / butyl alcohol copolymer.
  • Ethylene copolymer, epoxy resin, phenolic resin, acrylic phthalate resin, polyamide resin Fats, polyester resins, maleic resins, and the like can be used.
  • colorant known dyes and pigments such as carbon black, Futaroshia Ninbunore, Indasurenpuru one, Peacock pull one, Nono 0 - Manentoretsu de, red iron oxide, Arizari Nreki, chrome green, Maracay Toguri Nreki, methylcarbamoyl Honoré bio Re' Toreki, Nono Nzai Yellow, no- zero —mant yellow, titanium oxide; positive charge control agents such as egrosin, nigrosine base, triphenylmethane compound, polybierpyridine, and quaternary ammonium salt as charge control agents
  • a metal complex salt of an alkyl-substituted salicylic acid for example, a chromium complex salt or a zinc complex salt of di-tert-butylsalicylic acid
  • lubricant such as Teflon, zinc stearate, and polyvinylidene fluoride
  • the average particle size of the toner is preferably 20 // m or less, more preferably 5 to 15 zm.
  • the mixing ratio of the toner in the present invention is 2 to 40% by weight of the total amount of the carrier and the toner. / 0 , preferably 3 to 30% by weight, more preferably 4 to 25% by weight. If the mixing ratio of the toner is less than 2% by weight, the toner charge becomes too high to obtain a sufficient image density, and if it exceeds 40% by weight, a sufficient charge cannot be obtained. Scattered from the developing machine, contaminating the inside of the copier and toner capri on the image.
  • the developer of the present invention is a two-component or 1.5-component developing electrophotographic system such as a copier (analog, digital, monochrome, color), Used for linters (monochrome, color), fax, etc. Particularly, it is optimally used in high-speed / ultra-high-speed copiers and printers in which the stress applied to the developer in the developing machine is large.
  • a copier analog, digital, monochrome, color
  • Used for linters used for linters (monochrome, color)
  • fax etc.
  • it is optimally used in high-speed / ultra-high-speed copiers and printers in which the stress applied to the developer in the developing machine is large.
  • image forming method exposure method, developing method (apparatus), and various control methods (for example, toner concentration control method in the developing machine).
  • the optimum carrier and toner resistance, particle size, and particle size depend on the system. The diameter distribution, magnetic force, charge amount, etc. may be adjusted.
  • Dehydrated hexane is added to a 1-liter autoclave with an inner volume replaced with argon.
  • the internal pressure was 3.0 kg / cm 2 G.
  • hydrogen was supplied and the pressure was increased to 3.2 kg / cm 2 G.
  • Triethylaluminum 5.0 mmol was added and polymerization was started.
  • the system pressure was 2.3 kg / cm 2 in about 5 minutes. It decreased to G and stabilized.
  • 5.5 g of carbon black (manufactured by Mitsubishi Chemical Corporation; MA-100) was slurried with 100 ml of dehydrated hexane, and then the internal pressure was increased to 4.3 kg / cm 2 G.
  • the intermediate stage carrier obtained through this step is called a carrier.
  • the weight average molecular weight of the coated polyethylene was measured by GPC and found to be 206,000.
  • the carrier was classified with a 125 ⁇ m sieve to remove particles having a large particle size of 125 / m or more.
  • the fluidized bed The carrier was placed in a flow classifier, and air (115 ° C) heated so that the airflow linear velocity of the classifier body became 20 (cmZs), and the carrier was allowed to flow for 10 hours.
  • the resulting carrier and the carrier A 2 The resulting carrier and the carrier A 2.
  • Example 1 was the same as Example 1 except that the amount of magnetic powder mixed was changed from 8 g to 20 g. As a result, carrier C was obtained.
  • Carrier A 2 1 OOO g is placed in a 10 liter Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd .: FM10L type), and stirred for 1 hour to give a mechanical shock to carrier A 2 . The surface was smoothed. Then the magnetic powder
  • Carrier A 2 1 OOO g is placed in a 10 liter Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd .: FM10 L type), and magnetic powder (Mitsui Metals: magnetite MG 13 06 ( octahedron)) to 8 g and particulate resin (Soken chemical Co., Ltd.: MP 2 7 0 1) of 8 g were mixed and stirred to adhere electrostatically or mechanically on the carrier a 2 surface 1 minute.
  • a 10 liter Henschel mixer manufactured by Mitsui Miike Kakoki Co., Ltd .: FM10 L type
  • magnetic powder Mitsubishi Chemical Co., Ltd.: magnetite MG 13 06 ( octahedron)
  • particulate resin Soken chemical Co., Ltd.: MP 2 7 0 1
  • heat treatment with hot air of 200 ° C was performed by a heat sphering machine (Hosokawa Mikuguchi Co., Ltd .: heat sphering machine) to melt and fix the magnetic powder and fine particle resin in the coated polyethylene resin.
  • the outermost layer of the resin mixture was formed.
  • a large particle size carrier, agglomerated magnetic powder, and agglomerated resin were removed by sieving.
  • treatment was performed at a linear velocity of 20 cm for 2 hours using a fluidized bed type air flow classifier. As a result, carrier E was obtained.
  • Example 1 was the same as Example 1 except that the magnetic powder type was changed from Mitsui Kinzoku's magnetite MG 13 06 to Magnetite MG 9300 (polyhedron). As a result, carrier F was obtained.
  • Example 1 the magnetic powder (manufactured by Mitsui Kinzoku Co., Ltd .: magnetite MG130) 6 (octahedron)) was replaced by magnetic powder (DFC450, 25 ⁇ m, manufactured by Dowa Iron Powder Co., Ltd.). The particle size of this magnetic powder was too large to be fixed.
  • Example 2 was the same as Example 1 except that the magnetic powder was changed from a magnet MG1306 manufactured by Mitsui Kinzoku Co., Ltd. to a ferrite MG8200 (spherical) manufactured by Mitsui Kinzoku. As a result, carrier G was obtained.
  • Toner A Styrene-n-butyl methacrylate copolymer resin
  • Toner B Bisphenol A polyester resin 00 parts by weight carbon black (Cabot, BPL)
  • Carrier type obi (C / g)
  • Toner-A Toner-B ( ⁇ cm) 150V 200V 250V 300V 350V Carrier A 2 + 11.2 1 13.5 3.1E + 11 1.17 1.23 1.30 1.32 1.33 Carrier B + 10.9 -13.1 1. 1E + 10 1.19 1.27 1.35 1.44 1.53
  • Figure 1 shows the dependence of the image density on magnet roller bias potential in Application Example 1.
  • the shape of the magnetic powder added to the outermost layer of the electrophotographic carrier used in the electrophotographic developer into an octahedron or the like, the image density with respect to the bias potential is reduced. There is a proportional relationship, and even in a high bias potential region, the increase rate of the image density increases without lowering, so that a clear print density and a stable image can be obtained.
  • the present invention not only the durability and the chargeability are excellent, but also the print density in actual printing is clarified as compared with the conventional one, and the delicate static resistance adjustment and the adjustment of the charge amount are performed. It is possible to provide an electrophotographic carrier and an electrophotographic developer using the same, which can be freely performed.

Abstract

Cette invention concerne un support pour électrophotographie tirant partie des caractéristiques excellentes d'un support comportant un revêtement de résine polyoléfinique, dont il est possible d'ajuster facilement la charge et la résistance statique, qu'il est possible d'obtenir d'une image dotée d'une densité stable et qui permet d'éviter efficacement l'utilisation d'additifs externes en raison de l'adhésion des additifs externes. L'invention concerne également un révélateur pour électrophotographie utilisant ce support. Dans un support pour électrophotographie comportant un noyau magnétique et une couche de revêtement constituée d'un polyéthylène de poids moléculaire élevé recouvrant la surface du noyau du support, ladite couche de revêtement, qui est constituée du polyéthylène à poids moléculaire élevé, comporte, au moins en tant que couche la plus externe, une couche contenant une poudre magnétique dont la forme cubique est un corps polyédrique convexe entouré par au moins six couches plates et/ou courbes, ou une couche contenant cette poudre magnétique, de la silice et/ou une résine en fines particules.
PCT/JP1997/004563 1996-12-11 1997-12-11 Support pour electrophotographie et revelateur utilisant un tel support WO1998026332A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP97947898A EP0883035B1 (fr) 1996-12-11 1997-12-11 Particules porteuses pour l'electrophotographie et developpeur les contenant
DE69724592T DE69724592T2 (de) 1996-12-11 1997-12-11 Carrierteilchen für die elektrophotographie und entwickler

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP8/330757 1996-12-11
JP33075796A JPH10171168A (ja) 1996-12-11 1996-12-11 電子写真用キャリアおよびそれを用いた電子写真用現像剤

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US09/426,647 Continuation-In-Part US6197465B1 (en) 1996-12-11 1999-10-25 Carrier for electrophotography and developer for electrophotography using the carrier

Publications (1)

Publication Number Publication Date
WO1998026332A1 true WO1998026332A1 (fr) 1998-06-18

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1997/004563 WO1998026332A1 (fr) 1996-12-11 1997-12-11 Support pour electrophotographie et revelateur utilisant un tel support

Country Status (4)

Country Link
JP (1) JPH10171168A (fr)
DE (1) DE69724592T2 (fr)
TW (1) TW384418B (fr)
WO (1) WO1998026332A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100469177B1 (ko) * 1996-09-12 2005-12-21 교세라 가부시키가이샤 전자사진용캐리어및이를사용하는전자사진용현상제

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0883035B1 (fr) 1996-12-11 2003-09-03 Idemitsu Kosan Company Limited Particules porteuses pour l'electrophotographie et developpeur les contenant
JP5467016B2 (ja) * 2010-08-30 2014-04-09 シャープ株式会社 樹脂被覆キャリアおよび樹脂被覆キャリアの製造方法
JP5935424B2 (ja) * 2012-03-19 2016-06-15 富士ゼロックス株式会社 静電荷像現像用キャリア、静電荷像現像用現像剤、トナーカートリッジ、プロセスカートリッジ、画像形成装置、及び画像形成方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02187771A (ja) * 1989-01-13 1990-07-23 Minolta Camera Co Ltd ポリオレフィン系樹脂被覆キャリア
JPH08211658A (ja) * 1995-02-02 1996-08-20 Idemitsu Kosan Co Ltd 電子写真現像剤用キャリア
JPH08234500A (ja) * 1995-02-24 1996-09-13 Kyocera Corp 静電潜像現像剤用キャリアおよびその製造方法
JPH08248718A (ja) * 1995-03-13 1996-09-27 Konica Corp カラー画像形成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02187771A (ja) * 1989-01-13 1990-07-23 Minolta Camera Co Ltd ポリオレフィン系樹脂被覆キャリア
JPH08211658A (ja) * 1995-02-02 1996-08-20 Idemitsu Kosan Co Ltd 電子写真現像剤用キャリア
JPH08234500A (ja) * 1995-02-24 1996-09-13 Kyocera Corp 静電潜像現像剤用キャリアおよびその製造方法
JPH08248718A (ja) * 1995-03-13 1996-09-27 Konica Corp カラー画像形成方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100469177B1 (ko) * 1996-09-12 2005-12-21 교세라 가부시키가이샤 전자사진용캐리어및이를사용하는전자사진용현상제

Also Published As

Publication number Publication date
TW384418B (en) 2000-03-11
DE69724592T2 (de) 2004-07-01
DE69724592D1 (de) 2003-10-09
JPH10171168A (ja) 1998-06-26

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