US20120115079A1 - Toner - Google Patents

Toner Download PDF

Info

Publication number
US20120115079A1
US20120115079A1 US13/288,653 US201113288653A US2012115079A1 US 20120115079 A1 US20120115079 A1 US 20120115079A1 US 201113288653 A US201113288653 A US 201113288653A US 2012115079 A1 US2012115079 A1 US 2012115079A1
Authority
US
United States
Prior art keywords
silica particles
toner
particles
mass
silica
Prior art date
Legal status (The legal status 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 status listed.)
Abandoned
Application number
US13/288,653
Other languages
English (en)
Inventor
Naotaka Ikeda
Emi Watanabe
Yuhei Terui
Taiji Katsura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Canon Inc
Original Assignee
Canon Inc
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 Canon Inc filed Critical Canon Inc
Assigned to CANON KABUSHIKI KAISHA reassignment CANON KABUSHIKI KAISHA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IKEDA, NAOTAKA, KATSURA, TAIJI, TERUI, YUHEI, WATANABE, EMI
Publication of US20120115079A1 publication Critical patent/US20120115079A1/en
Priority to US14/180,708 priority Critical patent/US9005865B2/en
Abandoned legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • G03G9/0802—Preparation methods
    • G03G9/0812—Pretreatment of components
    • 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
    • G03G9/0819—Developers with toner particles characterised by the dimensions of the 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
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09708—Inorganic compounds
    • G03G9/09716—Inorganic compounds treated with organic compounds
    • 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
    • G03G9/097—Plasticisers; Charge controlling agents
    • G03G9/09708—Inorganic compounds
    • G03G9/09725—Silicon-oxides; Silicates

Definitions

  • the present invention relates to a toner for developing an electrostatic image used for image forming of an electrophotographic system typified by a copying machine and a printer.
  • Addition of an external additive having a large particle diameter has been proposed as a technique to improve the transferability of a toner (refer to Japanese Patent Laid-Open No. 2007-171666).
  • This proposal is directed to improve the transferability by adding silica particles having large particle diameters to toner particles and reducing physical adhesion between the toner and a photo conductor.
  • the silica particles, which are used in this proposal and which have large particle diameters are particles obtained by a deflagration method and, therefore, have a wide particle size distribution. Consequently, in the case where the toner is used over a long term, particles having large particle diameters are eliminated from the toner easily, and particles having small particle diameters are embedded in toner particles easily.
  • silica particles move to concave portions of toner particle surfaces, it is difficult to give stable chargeability, fluidity, and transferability to the toner.
  • Japanese Patent Laid-Open No. 2007-322919 discloses that silica particles which have large particle diameters with a sharp particle size distribution and which are produced by a sol-gel method are used, so as to improve long-term stable chargeability and improve transferability.
  • silica particles, which have large particle diameters and which are obtained by the sol-gel method, in the related art are hydrophilic particles having silanol groups to a large extent. Therefore, even when a hydrophobizing treatment is performed, there are large amounts of remaining silanol groups.
  • the property of the silica particles to give the chargeability to the toner is influenced by the temperature and the humidity easily, and it is difficult to give stable chargeability to the toner. Meanwhile, in the case where large amounts of hydrophobizing agent is used for silica particles in order to improve this harmful effect, a property to give fluidity to the toner is degraded. Consequently, in the case where a toner including such silica particles is used and images are output over a long term, it is difficult to maintain high image quality.
  • silica particles which have silanol groups to a relatively small extent and which have large particle diameters with a specific particle size distribution, to a toner has been proposed (refer to Japanese Patent Laid-Open No. 2008-262171).
  • silica particles which have large particle diameters and which are used in Japanese Patent Laid-Open No. 2008-262171, have a wide particle size distribution and there are problems in properties to give the fluidity and the chargeability to a toner.
  • silica particles which have large particle diameters and which can give stable chargeability and fluidity to a toner regardless of environment.
  • the present invention provides a toner having stable chargeability and fluidity regardless of environment. Furthermore, the present invention provides a toner which can produce a high-definition high-quality image over a long term stably in the case where the toner is used for image forming.
  • the present invention relates to a toner containing toner particles, each of which contains a binder resin and a colorant, and silica particles, wherein the above described silica particles have a volume average particle diameter (Dv) of 70 nm or more and 500 nm or less, the variation coefficient of diameters of the silica particles, based on volume distribution thereof, is 23% or less, and wherein when heating the silica particles to measure the mass variation, the ratio of mass decrease of the silica particles at the temperature in the range of 105° C. to 200° C. is 0.60% or less.
  • Dv volume average particle diameter
  • the toner according to the present invention has stable chargeability and fluidity regardless of environment. Furthermore, in the case where the toner according to the present invention is used for image forming, a high-definition high-quality image can be produced over a long term stably.
  • the present inventors performed intensive research on the properties of silica particles having large particle diameters with respect to a toner, to which silica particles having large particle diameters are added externally. As a result, it was found that the above described problems were able to be solved by adding the silica particles, which have large particle diameters and having the following properties, to the toner externally.
  • the silica particles used in the present invention are silica particles having large particle diameters and having a volume average particle diameter (Dv) of 70 nm or more and 500 nm or less.
  • Dv volume average particle diameter
  • the fluidity of the toner is hindered and, in addition, silica particles are eliminated from the toner surface easily. Therefore, such silica particles cannot give long-term stable chargeability and fluidity to the toner.
  • eliminated silica particles adhere to developing agent constituent materials and image forming system members or contaminate them. Consequently, degradation in charge characteristics and an occurrence of toner scattering may be caused.
  • the volume average particle diameter (Dv) of the silica particles is preferably 80 nm or more and 200 nm or less.
  • the variation coefficient of diameters of the silica particles, based on volume distribution thereof, is 23% or less.
  • the variation coefficient of diameters of the silica particles, based on volume distribution thereof is within the above described range, the silica particles exert a spacer effect on the toner surface more effectively. As a result, the toner transferability is improved. Furthermore, a toner having long-term stable chargeability and fluidity is obtained.
  • the variation coefficient of diameters of the silica particles is more than 23%, there are large variations in volume distribution of diameters of the silica particles.
  • the variation coefficient of diameters of the silica particles, based on volume distribution thereof, is preferably 15% or less, and further preferably 10% or less.
  • Measurements of the volume average particle diameter (Dv) of silica particles and the variation coefficient of diameters of silica particles, based on volume distribution thereof, are performed by using Zetasizer Nano ZS (produced by SYSMEX CORPORATION).
  • the variation coefficient is determined in a manner as described below. Initially, the volume distribution of the particle size is measured, so as to determine the half-width of the volume distribution thereof and the volume average particle diameter (Dv). Subsequently, the ratio (%) of the half-width to the volume average particle diameter is calculated and, thereby the variation coefficient is determined.
  • Sample preparation and the measurement condition are as described below.
  • About 1 mg of silica particles are added to 20 ml of pure water, and dispersion is performed for 3 minutes by using Homogenizer (produced by SMT).
  • Homogenizer produced by SMT
  • the volume average particle diameter (Dv) and the variation coefficient are measured just after the dispersion under the following condition.
  • the ratio of mass decrease at the temperature in the range of 105° C. to 200° C. (hereafter may be simply referred to as ratio of mass decrease) is 0.60% or less.
  • the ratio of mass decrease refers to the percentage of mass decrease of silica particles in the range of 105° C. to 200° C. when a thermogravimetric analyzer (TGA) is used and the silica particles are heated from 50° C. to 500° C. at normal pressure.
  • TGA thermogravimetric analyzer
  • silanol groups of the silica particles are dehydrated and condensed at about 130° C. and, thereby, the mass of silica particles decreases.
  • HMDS Hexamethyldisilazane
  • silicone oil silicone oil
  • the present inventors believe that the amount of silanol groups included in the silica particles is quantified by measuring the ratio of mass decrease of silica particles in the range of 105° C. to 200° C.
  • the silanol groups of the silica particles are water-adsorption sites and, therefore, the amount of silanol groups in the silica particles exerts a large effect on the hygroscopicity of the silica particles. Consequently, the amount of silanol groups included in the silica particles exerts a large effect on the properties to give the chargeability, the fluidity, and the transferability to the toner. In the case where the ratio of mass decrease of the silica particles is more than 0.60%, the amount of silanol groups in the silica particles is large.
  • silica particles adsorb a large amount of water, so that the toner is not provided with the chargeability and the fluidity sufficiently.
  • the ratio of mass decrease of the silica particles is preferably 0.10% or less, and further preferably 0.02% or less.
  • the ratio of mass decrease of silica particles is measured by using Hi-Res TGA 2950 Thermogravimetric Analyzer (produced by TA Instrument). About 0.03 g of silica particles serving as a sample are added to a pan for the above described analyzer, and the resulting pan is set into the analyzer. At that time, in consideration of the bulkiness of silica particles, the amount of sample is adjusted appropriately. After an equilibrium state is reached at normal pressure at 50° C., that state is held for 10 minutes, and the mass of the silica particles is measured. Subsequently, a nitrogen gas is supplied, the temperature is raised to 500° C. at 20° C./min at normal pressure, and the mass variation is measured. Then, the percentage of the amount of mass decrease of the silica particles in the range from 105° C. to 200° C. relative to the mass of the silica particles after being held at 50° C. for 10 minutes is taken as the ratio of mass decrease.
  • the silica particles used in the present invention have a small ratio of mass decrease of 0.60% or less and, therefore, the hygroscopicity is very small as compared with that of the large-diameter silica particles obtained by a sol-gel method in the related art. Consequently, the surfaces thereof are not necessarily subjected to a hydrophobizing treatment in contrast to the large-diameter silica particles obtained by the sol-gel method in the related art. However, in order to give long-term stable chargeability, fluidity, and transferability to the toner, the silica particles used in the present invention may be subjected to the hydrophobizing treatment.
  • the method for subjecting the silica particles to the hydrophobizing treatment is not specifically limited, and known methods may be used.
  • methods for subjecting the silica particles to the hydrophobizing treatment include a method in which the silica particles are treated with a hydrophobizing agent in a dry condition and a method in which the silica particles are treated with a hydrophobizing agent in a wet condition.
  • dry hydrophobizing treatment method can be employed because the toner is provided with excellent fluidity while aggregation of the silica particles is prevented.
  • dry hydrophobizing treatment methods include a method in which the silica particles are treated by spraying of a hydrophobizing agent under agitation and a method in which a vapor of hydrophobizing agent is introduced to the silica particles in a fluidized bed or under agitation.
  • hydrophobizing agents include the following: chlorosilanes, e.g., methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, t-butyldimethylchlorosilane, and vinyltrichlorosilane; alkoxysilanes, e.g., tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysi
  • alkoxysilanes, silazanes, and straight silicone oils can be used because a hydrophobizing treatment is performed easily.
  • Such hydrophobizing agents may be used alone or in combination.
  • the above described hydrophobizing agents may be used stepwise sequentially to surface-treat silica particles.
  • the amount of carbon derived from a hydrophobizing agent in the silica particles is preferably 0.01% by mass or more and 4.5% by mass or less.
  • the usage of the hydrophobizing agent is appropriate and degradation in fluidity of the silica particles is prevented.
  • the silica particles before being subjected to the hydrophobizing treatment have low hygroscopicity as compared with those in the related art. Therefore, in order to exert this effect sufficiently, the usage of the hydrophobizing agent is minimized. Consequently, good chargeability and fluidity of the toner is enhanced.
  • the above described amount of carbon is further preferably 0.02% by mass or more and 1.0% by mass or less, and particularly preferably 0.03% by mass or more and 0.08% by mass or less.
  • the amount of carbon of the silica particles is measured by using a carbon and sulfur analyzer (EMIA-320 produced by HORIBA, Ltd.). About 0.3 g of sample is precisely weighed into a crucible for the above described measurement apparatus, and 0.3 g ⁇ 0.05 g of tin (Spare No. 9052012500) and 1.5 g ⁇ 0.1 g of tungsten (Spare No. 9051104100) are added as fuel oil additives. Then, the silica particles are heated to 1,100° C. in an oxygen atmosphere following the description of the instruction manual attached to the measurement apparatus. Consequently, hydrophobic groups derived from the hydrophobizing agent on the silica particle surfaces are thermally decomposed to CO 2 . Thereafter, the amount of carbon contained in the silica particles is determined from the amount of the resulting CO 2 and this is taken as the amount of carbon derived from the hydrophobizing agent.
  • EMIA-320 produced by HORIBA, Ltd.
  • the fixing ratio of the hydrophobizing agent to the silica particles is preferably 90% or more.
  • the silica particles give good chargeability, fluidity, and transferability to the toner regardless of the environment.
  • the fixing ratio of the hydrophobizing agent to the silica particles is measured by the following method.
  • An Erlenmeyer flask is charged with 0.50 g of silica fine particles and 40 ml of chloroform and is covered with a lid, followed by agitation for 2 hours. Subsequently, agitation is stopped. Standing for 12 hours and centrifugal separation are performed and a supernatant liquid is removed completely.
  • the centrifugal separation is performed with Centrifuge H-9R (produced by KOKUSAN) by using Bn1 rotor and a plastic centrifuge tube for Bn1 rotor under the condition of 20° C., 10,000 rpm, and 5 minutes.
  • the centrifugally separated silica particles are put into the Erlenmeyer flask again, 40 ml of chloroform is added, the lid is set, and agitation is performed for 2 hours. Subsequently, agitation is stopped. Standing for 12 hours and centrifugal separation are performed and a supernatant liquid is removed completely. This operation is further repeated two times.
  • the resulting sample is dried by using a constant temperature bath at 50° C. for 2 hours. Furthermore, decompression to 0.07 MPa is performed, followed by drying at 50° C. for 24 hours, so as to volatilize chloroform sufficiently.
  • the amount of carbon of the silica particles treated with chloroform, as described above, and the amount of carbon of the silica particles before the treatment with chloroform are measured following the above described “Method for measuring amount of carbon of silica particles”.
  • the fixing ratio is calculated by using a formula described below.
  • the method for producing the silica particles used in the present invention will be described below.
  • the method for producing the silica particles used in the present invention is not specifically limited. Examples thereof include the following methods: a combustion method in which silica particles are obtained by combustion of a silane compound (that is, a method for producing fumed silica); a deflagration method in which silica particles are obtained by explosive combustion of a metal silicon powder; wet methods in which silica particles are obtained by a neutralization reaction between sodium silicate and a mineral acid (among them, synthesis under an alkaline condition is referred to as a sedimentation method, and synthesis under an acid condition is referred to as a gel method); and a sol-gel method in which silica particles are obtained by hydrolysis of alkoxysilanes, e.g., hydrocarbyloxysilane (a so-called Stoeber method).
  • the sol-gel method can be employed as a method for producing large-diameter silica particles because a
  • silica particles by the sol-gel method The method for producing silica particles by the sol-gel method will be described below. Initially, in an organic solvent in which water is present, an alkoxysilane is subjected to hydrolysis and condensation reactions in the presence of a catalyst, so as to obtain a silica sol suspension liquid. The catalyst is removed from the silica sol suspension liquid, and drying is performed, so that silica particles are obtained.
  • the silica particles obtained at this stage have silanol groups to a large extent and are hydrophilic. Therefore, the ratio of mass decrease takes on a value larger than 2%.
  • the silica particles are heat-treated at 300° C. to 500° C. Consequently, the silanol groups of the silica particles are dehydrated and condensed, so that the amount of silanol groups is reduced and it is possible to reduce the value of the ratio of mass decrease of the silica particles.
  • the timing of the heat treatment at 300° C. to 500° C. may be before, after, or at the same time with the hydrophobizing treatment.
  • the heat treatment is performed after the hydrophobizing treatment, the hydrophobizing agent is thermally decomposed, and the above described fixing ratio of the hydrophobizing agent may not be obtained. Therefore, the heat treatment can be performed before the hydrophobizing treatment.
  • the silica particles can be subjected to a disintegration treatment after being heat-treated.
  • the disintegration treatment can be performed before the surface treatment is performed with the hydrophobizing agent because the silica particle surfaces can be uniformly treated with the hydrophobizing agent.
  • the amount of addition (amount of external addition) of the silica particles used in the present invention to the toner is preferably 0.01 parts by mass or more and 2.50 parts by mass or less relative to 100 parts by mass of the toner particles. In the case where the amount of addition of the silica particles is within the above described range, the above described effects of the silica particles are exerted favorably.
  • the amount of addition of the silica particles to the toner is more preferably 0.10 parts by mass or more and 2.00 parts by mass or less relative to 100 parts by mass of toner particles.
  • the weight average particle diameter (D4) of the toner according to the present invention is preferably 4.0 ⁇ m or more and 9.0 ⁇ m or less, and more preferably 5.0 ⁇ m or more and 7.5 ⁇ m or less. In the case where the weight average particle diameter (D4) of the toner is within the above described range, an occurrence of charge up is suppressed and fogging, toner scattering, and reduction in image density are prevented.
  • the weight average particle diameter (D4) and the number average particle diameter (D1) of the toner are calculated in a manner described below.
  • a precise particle size distribution measurement apparatus “Coulter Counter Multisizer 3” (registered trademark, produced by Beckman Coulter, Inc.) equipped with a 100 ⁇ m aperture tube on the basis of a pore electrical resistance method is used.
  • an attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (produced by Beckman Coulter, Inc.) is used. In this regard, the measurement is performed with the number of effective measurement channels of 25,000 channels.
  • a solution prepared by dissolving special grade sodium chloride into ion-exchanged water in such a way as to have a concentration of about 1% by mass for example, “ISOTON II” (produced by Beckman Coulter, Inc.), may be used.
  • the above-described dedicated software is set as described below.
  • the total count number in the control mode is set at 50,000 particles
  • the number of measurements is set at 1 time
  • the Kd value is set at a value obtained by using “Standard particles 10.0 ⁇ m” (produced by Beckman Coulter, Inc.).
  • the threshold value and the noise level are automatically set by pressing “Threshold value/noise level measurement button”.
  • the current is set at 1,600 ⁇ A
  • the gain is set at 2
  • the electrolytic solution is set at ISOTON II
  • a check is entered in “Post-measurement aperture tube flush”.
  • the bin interval is set at logarithmic particle diameter
  • the particle diameter bin is set at 256 particle diameter bins
  • the particle diameter range is set at 2 ⁇ m to 60 ⁇ m.
  • a 250 ml round-bottom glass beaker dedicated to Multisizer 3 is charged with about 200 ml of the above-described electrolytic aqueous solution, the beaker is set in a sample stand, and counterclockwise agitation is performed with a stirrer rod at 24 revolutions/sec. Then, contamination and air bubbles in the aperture tube are removed by “Aperture flush” function of the dedicated software.
  • a 100 ml flat-bottom glass beaker is charged with about 30 ml of the above-described electrolytic aqueous solution.
  • a diluted solution is prepared by diluting “Contaminon N” (a 10% by mass aqueous solution of neutral detergent for washing a precision measuring device, including a nonionic surfactant, an anionic surfactant, and an organic builder and having a pH of 7, produced by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water by a factor of about 3 on a mass basis and about 0.3 ml of the diluted solution serving as a dispersing agent is added to the inside of the beaker.
  • Consaminon N a 10% by mass aqueous solution of neutral detergent for washing a precision measuring device, including a nonionic surfactant, an anionic surfactant, and an organic builder and having a pH of 7, produced by Wako Pure Chemical Industries, Ltd.
  • the height position of the beaker is adjusted in such a way that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker is maximized.
  • Ultrasonic waves are applied to the electrolytic aqueous solution in the beaker of the above-described item (4). In this state, about 10 mg of toner is added to the above-described electrolytic aqueous solution little by little and is dispersed. Subsequently, an ultrasonic dispersion treatment is further continued for 60 seconds.
  • the water temperature of the water tank is controlled at 10° C. or higher and 40° C. or lower appropriately.
  • “Average diameter” on the screen of “Analysis/statistical value on volume (arithmetic average)” is the weight average particle diameter (D4)
  • “Average diameter” on the screen of “Analysis/statistical value on the number (arithmetic average)” is the number average particle diameter (D1).
  • the toner according to the present invention can contain at least one type of wax.
  • the total amount of waxes contained in the toner is preferably 2.5 parts by mass or more and 25.0 parts by mass or less relative to 100 parts by mass of the toner particles.
  • the total amount of waxes contained in the toner particles is preferably 4.0 parts by mass or more and 20 parts by mass or less, and further preferably 6.0 parts by mass or more and 18.0 parts by mass or less.
  • the amount of wax is 2.5 parts by mass or more and 25.0 parts by mass or less, an appropriate bleeding property of wax is ensured during heating and pressurizing of the toner, so that winding resistance is improved.
  • waxes include the following: aliphatic hydrocarbon based waxes, e.g., low-molecular weight polyethylene, low-molecular weight polypropylene, microcrystalline waxes, Fischer-Tropsch waxes, and paraffin waxes; oxides of aliphatic hydrocarbon based waxes, e.g., oxidized polyethylene wax, or block copolymers thereof; waxes containing a fatty acid ester as a primary component, e.g., carnauba wax and montanic acid ester wax, and waxes produced by partly or wholly deacidifying fatty acid esters, e.g., deacidified carnauba wax; saturated straight chain fatty acids, e.g., palmitic acid, stearic acid, and montanic
  • binder resins of the toner include the following: polystyrenes; homopolymers of styrene substitution products, e.g., poly-p-chlorostyrene and polyvinyltoluene; styrene based copolymers, e.g., styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-methyl ⁇ -chloromethacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers,
  • the toner particles used in the present invention may be produced by using a known pulverization method or polymerization method.
  • the polymerization method can be employed because toner particles which are close to a sphere and which have surfaces with a low level of unevenness are obtained as compared with the pulverization method and, thereby the effect of giving the transferability is exerted by the silica particles synergetically.
  • toner particles can be obtained by a suspension polymerization method.
  • a polymerizable monomer composition containing a polymerizable monomer, a colorant, a wax, other additives as necessary, and the like is dissolved or dispersed with a dispersing machine, e.g., a homogenizer, a ball mill, a colloid mill, or an ultrasonic dispersing machine, so as to be suspended in an aqueous medium containing a dispersion stabilizer.
  • a dispersing machine e.g., a homogenizer, a ball mill, a colloid mill, or an ultrasonic dispersing machine, so as to be suspended in an aqueous medium containing a dispersion stabilizer.
  • a polymerization initiator is used and the polymerizable monomer in the polymerizable monomer composition is polymerized, so as to produce toner particles.
  • the polymerization initiator may be added at the same time as addition of the other additives to the polymerizable monomer, or be mixed just before the polymerizable monomer composition is suspended in the aqueous medium.
  • the polymerization initiator dissolved into the polymerizable monomer or the solvent may be added just after granulation is completed and before the polymerization reaction is initiated.
  • a vinyl based polymerizable monomer capable of being radically polymerized is used.
  • a monofunctional monomer or a polyfunctional monomer may be used.
  • monofunctional polymerizable monomers include the following: styrene; styrene derivatives, e.g., ⁇ -methyl styrene, ⁇ -methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, p-n-butyl styrene, p-tert-butyl styrene, p-n-hexyl styrene, p-n-octyl styrene, p-n-nonyl styrene, p-n-decyl
  • polyfunctional polymerizable monomers include the following: diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexane diol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2′-bis(4-(acryloxy•diethoxy)phenyl)propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexane diol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimeth
  • the monofunctional polymerizable monomers are used alone, in combination of at least two types, or in combination with the polyfunctional polymerizable monomers.
  • the polyfunctional polymerizable monomer may also be used as a cross-linking agent.
  • oil-soluble initiators As for the polymerization initiator used in polymerization of the polymerizable monomer, oil-soluble initiators and/or water-soluble initiators are used.
  • oil-soluble initiators include the following: azo compounds, e.g., 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis(cyclohexane-1-carbonitrile), and 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile; and peroxide based initiators, e.g., acetylcyclohexylsulfonyl peroxide, diisopropyl peroxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t-butyl peroxy-2-ethylhexanoate, benzoy
  • water-soluble initiators include the following: ammonium persulfate, potassium persulfate, 2,2′-azobis(N,N′-dimethylene isobutyl amidine) hydrochloride, 2,2′-azobis(2-aminodinopropane) hydrochloride, azobis(isobutyl amidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, ferrous sulfate, and hydrogen peroxide.
  • a chain transfer agent, a polymerization inhibitor, and the like may be used in order to control the degree of polymerization of the polymerizable monomer.
  • a compound having at least two polymerizable double bonds is used.
  • aromatic divinyl compounds e.g., divinylbenzene and divinylnaphthalene
  • carboxylic acid esters having two double bonds e.g., ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butane diol dimethacrylate
  • divinyl compounds e.g., divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone
  • compounds having at least three vinyl groups are used alone or as a mixture.
  • black, yellow, magenta, and cyan colorants may be used.
  • black colorant carbon black and magnetic substances may be used. Furthermore, a color and a toner resistance may be adjusted by mixing the following coloring materials.
  • pigment based yellow colorants compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used. Specific examples include C. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110, 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 155, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191:1, 191, 192, 193, and 199.
  • die based yellow colorants include C. I. solvent Yellow 33, 56, 79, 82, 93, 112, 162, and 163, and C. I. disperse Yellow 42, 64, 201, and 211.
  • magenta colorants condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specific examples include C. I. Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, and 269 and C. I. Pigment Violet 19.
  • cyan colorants phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds are used. Specific examples include C. I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.
  • colorants may be used alone or in combination. Furthermore, the colorant may be used in the state of solid solution.
  • the colorant is selected from the viewpoint of the hue angle, the saturation, the brightness, the weather resistance, the OHP transparency, and dispersibility into the toner.
  • the amount of addition of the colorant is preferably 1 part by mass or more and 20 parts by mass or less relative to 100 parts by mass of binder resin.
  • a charge control agent can be applied to the toner.
  • negative charge control agents include the following: monoazo metal compounds; acetylacetone metal compounds; aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, dicarboxylic acids, and metal compounds, anhydrides, and ester compounds of these acids; phenol derivatives, e.g., bisphenol; urea derivatives; metal-containing salicylic acid based compounds; metal-containing naphthoic acid based compounds; boron compounds; quaternary ammonium salts; calixarenes; and resin based charge control agents.
  • positive charge control agents include the following: nigrosine-modified compounds on the basis of nigrosine, fatty acid metal salts, and the like; guanidine compounds, imidazole compounds, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, quaternary ammonium salts, e.g., tetrabutylammonium tetrafluoroborate, onium salts which are analogues thereof, e.g., phosphonium salts, and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (examples of laking agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanides, and ferrocyanides); metal salts of higher fatty acids; diorganotin oxides, e.g., dibutyltin oxide, dioctylt
  • salicylic acid based metal compounds can be used as the charge control agent, and furthermore, aluminum or zirconium can be employed as the metal thereof.
  • aluminum salicylate compounds can be used as the charge control agent.
  • the content of the charge control agent is preferably 0.01 parts by mass or more and 20.00 parts by mass or less relative to 100 parts by mass of binder resin, and more preferably 0.50 parts by mass or more and 10.00 parts by mass or less.
  • silica particles can be externally added in order to improve the charge stability, developability, the fluidity, the transferability, and the like.
  • examples of other fine particles include metal oxides, e.g., silica, alumina, and titania, and compound oxides thereof and fluorocarbon. At least two types of them may be used in combination.
  • silica, alumina, titania, and compound oxides thereof can be used because the fluidity and the chargeability of the toner are maintained favorably and adsorption performance with respect to toner particles is high.
  • the inorganic fine powder used besides the above described silica particles has an average primary particle diameter of preferably 5 nm or more and 70 nm or less. In the case where the average primary particle diameter of the inorganic fine powder is within the above described range, good fluidity and chargeability of the toner can be maintained over a long term.
  • the inorganic fine powder is observed with a transmission electron microscope, and in a field of view magnified by 30,000 to 50,000 times, an average value of major axes of 300 primary particles having major axes of 1 nm or more is calculated.
  • the photograph is further magnified in such a way that the primary diameters become 5 mm or more, and the measurement is performed.
  • the inorganic fine powder can be subjected to a hydrophobizing treatment.
  • the hydrophobizing treatment method and the hydrophobizing agent are the same as those in the case where the above described silica particles are subjected to the hydrophobizing treatment.
  • the total amount of the silica particles and the inorganic fine powder added to the toner is preferably 0.5 parts by mass or more and 4.5 parts by mass or less, and more preferably 0.8 parts by mass or more and 3.5 parts by mass or less relative to 100 parts by mass of toner particles.
  • the fluidity of the toner is obtained sufficiently, degradation in fogging and toner scattering associated with reduction in chargeability of the toner can be prevented.
  • charge control particles include metal oxides (tin oxide, titania, zinc oxide, alumina, antimony oxide, and the like) and carbon black.
  • abrasives include metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, and the like), nitrides (silicon nitride and the like), carbides (silicon carbide and the like), and meal salts (calcium sulfate, barium sulfate, calcium carbonate, and the like).
  • a lubricant may also be used in order to reduce contamination of the members.
  • lubricants include fluorine based resin powders (polyvinylidene fluoride, polytetrafluoroethylene, and the like) and fatty acid metal salts (zinc stearate, calcium stearate, and the like). Among those described above, zinc stearate can be used.
  • the amount of addition of these charge control particles, abrasive, caking inhibitor, and the like is preferably 0.01 parts by mass or more and 2.50 parts by mass or less, and more preferably 0.10 parts by mass or more and 2.00 parts by mass or less relative to 100 parts by mass of toner particles.
  • the toner according to the present invention may be used for any one of a high-speed system, oilless fixing, a cleaner-less system, and a developing system in which carriers degraded through a long term of use in a developing device are recovered sequentially and fresh carriers are supplied.
  • the toner can be applied to known image forming methods by using a one-component developing system or a two-component developing system.
  • the toner according to the present invention has very good transferability and, therefore, can be used in an image forming method including an intermediate transfer body and an image forming method including a cleaner-less system regardless of the one-component developing system or the two-component developing system.
  • the toner according to the present invention may be used as a two-component system developing agent with respect to either full color or monochrome.
  • a 3-liter glass reactor provided with an agitator, a dropping funnel, and a thermometer was charged with 589.6 g of methanol, 42.0 g of water, and 47.1 g of 28% by mass ammonia water, followed by mixing.
  • the resulting solution was adjusted to become 35° C., and addition of 1,100.0 g (7.23 mol) of tetramethoxysilane and 395.2 g of 5.4% by mass ammonia water was started at the same time under agitation. Tetramethoxysilane was dropped over 6 hours and ammonia water was dropped over 5 hours.
  • the above described step was performed several tens of times, and the resulting silica particles were subjected to a disintegration treatment with Pulverizer (produced by Hosokawa Micron Corporation).
  • silica particles were charged into a polytetrafluoroethylene internal cylinder type stainless steel autoclave having an internal volume of 1,000 ml.
  • the inside of the autoclave was substituted with nitrogen and, then, 0.5 g of hexamethyldisilazane (HMDS) and 0.1 g of water made into a fog with a two-fluid nozzle were blown on the silica particles uniformly while an agitation blade attached to the autoclave was rotated at 400 rpm.
  • HMDS hexamethyldisilazane
  • water made into a fog with a two-fluid nozzle
  • the amount of methanol used at an initial stage was changed to 530.6 g, 634.0 g, and 737.3 g, respectively. Furthermore, the dropping time of tetramethoxysilane was changed to 7 hours, 6 hours, and 5 hours, respectively, and the dropping time of the 5.4% by mass ammonia water was changed to 6 hours, 5 hours, and 4 hours, respectively.
  • the amount of methanol used at an initial stage was changed to 491.3 g, 360.1 g, and 294.8 g, respectively. Furthermore, the dropping time of tetramethoxysilane was changed to 7 hours, 5.5 hours, and 5 hours, respectively, and the dropping time of the 5.4% by mass ammonia water was changed to 6 hours, 4.5 hours, and 4 hours, respectively.
  • the dropping time of tetramethoxysilane was changed to 6 hours, 5 hours, 3.5 hours, and 2 hours, respectively, and the dropping time of the 5.4% by mass ammonia water was changed to 5 hours, 4 hours, 3 hours, and 2 hours, respectively.
  • the volume average particle diameter (Dv) of the silica particles and the variation coefficient of diameters of the silica particles, based on volume distribution thereof, were adjusted by the above described operation.
  • the amounts of HMDS and water were adjusted in such a way that the amount of carbon became the same as the amount of Silica particles 1 and, thereby, Silica particles 8 to 11 were obtained.
  • the properties of Silica particles 8 to 11 are shown in Table 1.
  • Silica particles (fumed silica) having a volume average particle diameter (Dv) of 92 nm were produced by a combustion method.
  • the particles were classified and, thereby, silica particles having a volume average particle diameter (Dv) of 85 nm and a variation coefficient of diameters of particles, based on volume distribution thereof, of 21% were obtained.
  • the particles were surface-treated with HMDS in the same manner as that for Silica particles 1, so as to obtain Silica particles 16.
  • the properties of Silica particles 16 are shown in Table 1.
  • the particles were classified and, thereby, silica particles having a volume average particle diameter (Dv) of 120 nm and a variation coefficient of diameters of particles, based on volume distribution thereof, of 21% were obtained.
  • the particles were surface-treated with HMDS in the same manner as that for Silica particles 1, so as to obtain Silica particles 17.
  • the properties of Silica particles 17 are shown in Table 1.
  • Silica particles 24 were obtained as in the production example of Silica particles 1 except those described above. The properties of Silica particles 24 are shown in Table 1.
  • a pressurizable reaction container provided with a reflux tube, an agitator, a thermometer, a nitrogen introduction tube, a dropping device, and a decompression device is charged with 250 parts by mass of methanol, 150 parts by mass of 2-butanone, and 100 parts by mass of 2-propanol, which are solvents, and 77 parts by mass of styrene, 15 parts by mass of 2-ethylhexyl acrylate, and 8 parts by mass of 2-acrylamide-2-methylpropane sulfonic acid, which are monomers, and was heated to a reflux temperature under agitation.
  • the resulting Charge control resin 1 containing a sulfur atom had Tg of 58° C., Mp of 13,000, and Mw of 30,000.
  • a polymerizable monomer composition was prepared by dissolving 7.1 parts by mass of 70% toluene solution of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate serving as a polymerization initiator into the dispersion liquid.
  • the above described polymerizable monomer composition was put into the above described aqueous medium, and agitation was performed at a temperature of 65° C. for 10 minutes in a N 2 atmosphere with TK type Homomixer at 10,000 rpm, so as to granulate the polymerizable monomer composition. Thereafter, the temperature was raised to 67° C. while agitation was performed with a paddle agitation blade, and when the degree of polymerization conversion of the polymerizable vinyl based monomer reached 90%, 0.1 mol/l sodium hydroxide aqueous solution was added to adjust the pH of the aqueous dispersion medium to 9. Furthermore, the temperature was raised to 80° C.
  • ultrafine powders and coarse powders were precisely classified and removed with a multi-division classifier (Elbow-Jet Classifier produced by Nittetsu Mining Co., Ltd.) at the same time, so that cyan Toner particles 1 having a weight average particle diameter (D4) of 6.3 ⁇ m was obtained.
  • a multi-division classifier Elbow-Jet Classifier produced by Nittetsu Mining Co., Ltd.
  • Toner 1 was obtained by dry-mixing 1.5 parts by mass of Silica particles 1 and 0.2 parts by mass of rutile-type titanium dioxide fine powder surface-treated with dimethyl silicone oil (average primary particle diameter: 30 nm) relative to 100 parts by mass of Toner particles 1 for 5 minutes with Henschel mixer (produced by MITSUI MINING COMPANY, LIMITED). Then, Toner 1 was evaluated as described below. The evaluation results are shown in Table 2.
  • LBP-7200C produced by CANON KABUSHIKI KAISHA was used, and images were evaluated in various environments.
  • LBP 7200C is a system which does not have a cleaning member in an intermediate transfer unit portion and which recovers remaining toners of primary and secondary transfer with a cleaning member in a photo conductor unit.
  • a cartridge filled with 70 g of Toner 1 was mounted on the cyan station of the above described printer, dummy cartridges were mounted on other stations, and an image output test was performed.
  • the degree of whiteness was measured with “REFLECTMETER MODEL TC-6DS” (produced by Tokyo Denshoku Co., Ltd.).
  • the filter the Amberlite filter was used.
  • the fogging concentrations were ranked as described below. A, B, and C are acceptable levels in the present invention.
  • the image density was measured with a color reflection densitometer (X-RITE 404 produced by X-Rite).
  • X-RITE 404 produced by X-Rite.
  • the difference between the maximum density and the minimum density was determined and was evaluated on the basis of the criteria described below.
  • A The image density difference is 0.1 or less.
  • B The image density difference is more than 0.1 and 0.3 or less.
  • C The image density difference is more than 0.3 and 0.5 or less.
  • D The image density difference is more than 0.5.
  • the thin line reproducibility was evaluated from the viewpoint of image quality.
  • image output test after 4,600 sheets of images were output, an image in which a lattice pattern with a line width of 3 pixels was drawn all over an A4 paper (coverage of 4% on a volume basis) was printed, and the thin line reproducibility was evaluated on the basis of the criteria described below.
  • the line width of 3 pixels are 127 ⁇ m theoretically.
  • the line width of the image was measured with Microscope VK-8500 (produced by KEYENCE CORPORATION).
  • the line widths at 5 points selected at random were measured, the maximum value and the minimum value were excluded, and when an average value of the remaining 3 points was represented by d ( ⁇ m), the thin line reproducibility index L was defined as described below.
  • the thin line reproducibility index L is defined as the difference between the theoretical line width of 127 ⁇ m and the line width d in the output image.
  • the absolute value of the difference is employed in the definition because d may be larger than 127 or be smaller than 127. Smaller L indicates that the thin line reproducibility is excellent.
  • Toners 2 to 4 were produced as in Example 1 except that Silica particles 1 was changed to Silica particles 2 to 4, respectively, in Example 1. Then, Toners 2 to 4 were evaluated as in Example 1. The results of evaluation are shown in Table 2. As is clear from the results, regarding Comparative example 1, the stability of image density and the thin line reproducibility (image quality) were degraded. The reason for this is estimated that the volume average particle diameter (Dv) of the silica particles was too small and, thereby, the silica particles were not able to exert the effect as the spacer particles on the toner surfaces, so as to degrade the transferability.
  • Dv volume average particle diameter
  • Toners 5 to 7 were produced as in Example 1 except that Silica particles 1 was changed to Silica particles 5 to 7, respectively, in Example 1. Then, Toners 5 to 7 were evaluated as in Example 1. The results of evaluation are shown in Table 2. As is clear from the results, regarding Comparative example 2, all items were degraded in evaluation. The reason for this is estimated that the volume average particle diameter (Dv) of the silica particles was too large and, thereby, the silica particles were eliminated from the toner particle surfaces easily in a long term of use, and stable chargeability and fluidity were not given to the toner continuously.
  • Dv volume average particle diameter
  • Toners 8 to 11 were produced as in Example 1 except that Silica particles 1 was changed to Silica particles 8 to 11, respectively, in Example 1. Then, Toners 8 to 11 were evaluated as in Example 1. The results of evaluation are shown in Table 2. As is clear from the results, regarding Comparative example 3, in particular the thin line reproducibility (image quality) was degraded. The reason for this is believed to be that there were large variations in size of the silica particles, the individual particles became difficult to function as spacer particles efficiently and, thereby, the transferability was degraded.
  • Toners 12 to 15 were produced as in Example 1 except that Silica particles 1 was changed to Silica particles 12 to 15, respectively, in Example 1. Then, Toners 12 to 15 were evaluated as in Example 1. The results of evaluation are shown in Table 2. As is clear from the results, regarding Comparative example 4, all items were degraded in evaluation with respect to high-temperature and high-humidity. The reason for this is estimated that the ratio of mass decrease of Silica particles 15 was large and, thereby the amount of silanol groups was large, a large amount of water was adsorbed, the degrees of giving of the chargeability and the fluidity to the toner were degraded significantly, and stable developability and transferability were not obtained.
  • Toners 16 and 17 were produced as in Example 1 except that Silica particles 1 was changed to Silica particles 16 and 17, respectively, in Example 1. Then, Toners 16 and 17 were evaluated as in Example 1. The results of evaluation are shown in Table 2. As is clear from the results, the thin line reproducibility (image quality) was degraded slightly. The reason for this is believed to be that the silica particles were obtained by a fuming method or a deflagration method, the variation coefficient of diameters of the silica particles, based on volume distribution thereof, is large as compared with the silica particles obtained by a sol-gel method and, thereby, the individual particles became difficult to function as spacer particles efficiently and the transferability was degraded slightly. Furthermore, the reason is estimated that differences among the individual particles occurred slightly in giving the chargeability and the fluidity to the toner and, thereby, distribution of charge was extended, so as to degrade fogging and the like slightly.
  • Toners 18 and 19 were produced as in Example 1 except that Silica particles 1 was changed to Silica particles 18 and 19, respectively, in Example 1. Then, Toners 18 and 19 were evaluated as in Example 1. The results of evaluation are shown in Table 2. As is clear from the results, regarding Example 15, fogging and the thin line reproducibility (image quality) were degraded slightly with respect to high-temperature and high-humidity. The reason for this is estimated that the fixing ratio of the hydrophobizing agent of Silica particles 19 was low and, thereby, in a long term of use, the hydrophobizing agent was isolated from the silica particles because of the stress in the developing device, and stable hydrophobicity and fluidity were not obtained.
  • Toners 20 to 23 were produced as in Example 1 except that Silica particles 1 was changed to Silica particles 20 to 23, respectively, in Example 1. Then, Toners 20 to 23 were evaluated as in Example 1. The results of evaluation are shown in Table 2. As is clear from the results, regarding Example 19, all items were degraded in evaluation with respect to high-temperature and high-humidity. The reason for this is estimated that the amount of surface treatment of the silica particles with the hydrophobizing agent was large, the degree of giving of the fluidity to the toner was reduced slightly, the start-up of charging of the toner was delayed slightly and, thereby, when the image was output after a long term of standing, fogging and the transferability were degraded slightly.
  • Toner 24 was produced as in Example 1 except that Silica particles 1 was changed to Silica particles 24 in Example 1. Then, Toner 24 was evaluated as in Example 1. The results of evaluation are shown in Table 2. As is clear from the results, good results were obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Developing Agents For Electrophotography (AREA)
US13/288,653 2010-11-10 2011-11-03 Toner Abandoned US20120115079A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/180,708 US9005865B2 (en) 2010-11-10 2014-02-14 Toner

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-251905 2010-11-10
JP2010251905 2010-11-10

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/180,708 Continuation US9005865B2 (en) 2010-11-10 2014-02-14 Toner

Publications (1)

Publication Number Publication Date
US20120115079A1 true US20120115079A1 (en) 2012-05-10

Family

ID=46019951

Family Applications (2)

Application Number Title Priority Date Filing Date
US13/288,653 Abandoned US20120115079A1 (en) 2010-11-10 2011-11-03 Toner
US14/180,708 Expired - Fee Related US9005865B2 (en) 2010-11-10 2014-02-14 Toner

Family Applications After (1)

Application Number Title Priority Date Filing Date
US14/180,708 Expired - Fee Related US9005865B2 (en) 2010-11-10 2014-02-14 Toner

Country Status (2)

Country Link
US (2) US20120115079A1 (enrdf_load_stackoverflow)
JP (1) JP5984356B2 (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140220485A1 (en) * 2013-02-05 2014-08-07 Satoshi Kojima Toner, developer and image forming apparatus
US20140308608A1 (en) * 2013-04-15 2014-10-16 Xerox Corporation Sol-Gel Silica Additives
US20160139521A1 (en) * 2014-11-14 2016-05-19 Canon Kabushiki Kaisha Toner
US10501568B1 (en) * 2017-05-16 2019-12-10 Southwest Petroleum University Sulfonate lycine type hydrophobic associated polymer and preparation method thereof

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9023575B2 (en) * 2012-09-14 2015-05-05 Canon Kabushiki Kaisha Toner and method for producing toner
JP6497907B2 (ja) * 2014-11-28 2019-04-10 キヤノン株式会社 トナー
US9658546B2 (en) 2014-11-28 2017-05-23 Canon Kabushiki Kaisha Toner and method of producing toner
JP6666033B2 (ja) * 2015-12-21 2020-03-13 キヤノン株式会社 トナー
JP6910805B2 (ja) 2016-01-28 2021-07-28 キヤノン株式会社 トナー、画像形成装置及び画像形成方法
JP2018017785A (ja) * 2016-07-26 2018-02-01 キヤノン株式会社 画像形成方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020115008A1 (en) * 1999-08-24 2002-08-22 Fuji Xerox Co., Ltd. Toner for developing electrostatic latent image, process for producing the same, developer for developing electrostatic latent image, and process for forming image
JP2007099582A (ja) * 2005-10-07 2007-04-19 Shin Etsu Chem Co Ltd 高疎水性球状ゾルゲルシリカ微粒子、その製造方法、該微粒子からなる静電荷像現像用トナー外添剤および該トナー外添剤を用いた現像剤

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1059040C (zh) * 1989-09-19 2000-11-29 佳能株式会社 静电图像显影用有机调色剂的制法
JPH04340971A (ja) * 1991-05-17 1992-11-27 Minolta Camera Co Ltd 静電荷像現像用トナー
JPH04340972A (ja) * 1991-05-17 1992-11-27 Minolta Camera Co Ltd 静電荷像現像用トナー
JP3769968B2 (ja) * 1999-03-08 2006-04-26 富士ゼロックス株式会社 現像剤、シリカの製造方法及び画像形成方法
JP2001201888A (ja) * 2000-01-19 2001-07-27 Konica Corp 反転現像用トナーおよび画像形成方法
JP3942162B2 (ja) * 2001-03-23 2007-07-11 株式会社リコー 電子写真用トナーおよび現像方法
JP4578400B2 (ja) * 2005-12-26 2010-11-10 株式会社トクヤマ 電子写真用トナー外添剤
JP2007322919A (ja) * 2006-06-02 2007-12-13 Fuji Xerox Co Ltd 画像形成装置
JP2009015250A (ja) * 2007-07-09 2009-01-22 Seiko Epson Corp 一成分非磁性トナーおよび該トナーを使用した画像形成装置
JP5232494B2 (ja) * 2008-02-18 2013-07-10 株式会社日本触媒 シリカ粒子、およびその製造方法
JP5197148B2 (ja) * 2008-05-16 2013-05-15 キヤノン株式会社 トナー
JP2010107601A (ja) * 2008-10-28 2010-05-13 Sharp Corp トナー、現像剤、現像装置および画像形成装置

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020115008A1 (en) * 1999-08-24 2002-08-22 Fuji Xerox Co., Ltd. Toner for developing electrostatic latent image, process for producing the same, developer for developing electrostatic latent image, and process for forming image
JP2007099582A (ja) * 2005-10-07 2007-04-19 Shin Etsu Chem Co Ltd 高疎水性球状ゾルゲルシリカ微粒子、その製造方法、該微粒子からなる静電荷像現像用トナー外添剤および該トナー外添剤を用いた現像剤

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Machine translation of JP2007-099582 . *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140220485A1 (en) * 2013-02-05 2014-08-07 Satoshi Kojima Toner, developer and image forming apparatus
US9523931B2 (en) * 2013-02-05 2016-12-20 Ricoh Company, Ltd. Toner, developer and image forming apparatus
US20140308608A1 (en) * 2013-04-15 2014-10-16 Xerox Corporation Sol-Gel Silica Additives
US20160139521A1 (en) * 2014-11-14 2016-05-19 Canon Kabushiki Kaisha Toner
US9857707B2 (en) * 2014-11-14 2018-01-02 Canon Kabushiki Kaisha Toner
US10501568B1 (en) * 2017-05-16 2019-12-10 Southwest Petroleum University Sulfonate lycine type hydrophobic associated polymer and preparation method thereof

Also Published As

Publication number Publication date
US9005865B2 (en) 2015-04-14
JP2012118511A (ja) 2012-06-21
US20140162185A1 (en) 2014-06-12
JP5984356B2 (ja) 2016-09-06

Similar Documents

Publication Publication Date Title
US9005865B2 (en) Toner
US8426094B2 (en) Magnetic toner
US9239528B2 (en) Toner
CN107229196B (zh) 调色剂颗粒的生产方法
US7704661B2 (en) Toner and image forming method
JP2012150172A (ja) トナー
JP6478662B2 (ja) トナー及びトナーの製造方法
WO2012002278A1 (ja) 静電荷像現像用トナー
JP2015146037A (ja) 静電荷像現像用トナー
JP4985019B2 (ja) 静電荷像現像用正帯電性トナー
JP6115207B2 (ja) 画像形成方法
US12276938B2 (en) Toner
JP6478663B2 (ja) トナー、トナーの製造方法及び画像形成方法
JP4214613B2 (ja) 静電荷像現像用現像剤
WO2014132900A1 (ja) 静電荷像現像剤
JP5423385B2 (ja) 正帯電性静電荷像現像用トナー、及び、当該トナーを用いたカラー画像形成方法
US9023575B2 (en) Toner and method for producing toner
JP2023001872A (ja) トナー
JP2013235046A (ja) 静電荷像現像用トナー
JP2011137980A (ja) 静電荷像現像用トナー、静電荷像現像剤及び画像形成方法
JP5326526B2 (ja) 静電荷像現像用正帯電性トナー
JP2015041049A (ja) トナーおよび画像形成装置
JP5630198B2 (ja) 画像形成方法
JP2009109827A (ja) 磁性トナー
JP2020076790A (ja) トナー

Legal Events

Date Code Title Description
AS Assignment

Owner name: CANON KABUSHIKI KAISHA, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:IKEDA, NAOTAKA;WATANABE, EMI;TERUI, YUHEI;AND OTHERS;REEL/FRAME:027739/0683

Effective date: 20111024

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION