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EP1835351B1 - Toner, Verfahren zu seiner Herstellung, Bilderzeugungsgerät, Prozesskartusche und Bilderzeugungsverfahren - Google Patents

Toner, Verfahren zu seiner Herstellung, Bilderzeugungsgerät, Prozesskartusche und Bilderzeugungsverfahren Download PDF

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Publication number
EP1835351B1
EP1835351B1 EP20070104302 EP07104302A EP1835351B1 EP 1835351 B1 EP1835351 B1 EP 1835351B1 EP 20070104302 EP20070104302 EP 20070104302 EP 07104302 A EP07104302 A EP 07104302A EP 1835351 B1 EP1835351 B1 EP 1835351B1
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EP
European Patent Office
Prior art keywords
toner
image
particle diameter
parts
bearing member
Prior art date
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EP20070104302
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English (en)
French (fr)
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EP1835351A1 (de
Inventor
Shigeru Emoto
Akinori Saitoh
Naohiro Watanabe
Masahide Yamada
Masahiro Ohki
Ryota Inoue
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Ricoh Co Ltd
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Ricoh Co Ltd
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Priority claimed from JP2006132990A external-priority patent/JP2007301855A/ja
Application filed by Ricoh Co Ltd filed Critical Ricoh Co Ltd
Publication of EP1835351A1 publication Critical patent/EP1835351A1/de
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    • 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
    • G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
    • G03G9/0806—Preparation methods whereby the components are brought together in a liquid dispersing medium whereby chemical synthesis of at least one of the toner components takes place
    • 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
    • G03G9/0827—Developers with toner particles characterised by their shape, e.g. degree of sphericity
    • 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
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08755—Polyesters
    • 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
    • G03G9/087—Binders for toner particles
    • G03G9/08775—Natural macromolecular compounds or derivatives thereof
    • G03G9/08782—Waxes
    • 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
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08793—Crosslinked polymers
    • 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
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
    • 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
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
    • 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 and a method of manufacturing the toner.
  • a toner image is fixed such that the surface of a heating roller having a releasing property to a toner is brought into contact with the toner image on a recording medium upon application of heat and pressure while the recording medium passes the heating roller.
  • This method is extremely thermally efficient so that a toner image is quickly fixed since the toner image is melted and fixed on a recording medium while the surface of the heating roller is contacted with the toner image under pressure.
  • a toner having a relatively low melting viscosity is used in comparison with the case of a low speed fixing.
  • the surface temperature of a heating roller is lowered and the fixing pressure is reduced to prevent high temperature offset and winding offset which occur during fixing of a toner image.
  • offset phenomena easily occur at a high temperature.
  • toner With regard to toner, toner has been reduced in size to improve image definition and vividness of images. However, the fixing property of such a toner in a halftone portion formed thereof deteriorates. These are significant phenomena in the case of high speed fixing. This is because the amount of toner is small in a half tone portion, the toner transferred to concave portions on a recording medium receives a small amount of heat from a hearing roller and the fixing pressure to the concave portions is restrained by convex portions. The toner transferred to concave portions in a half tone portion of a recording medium has a thin layer thickness and tends to receive a relatively large shearing force per toner particle in comparison with toner particles in a solid image portion at which a thick layer is formed. Thus, offset phenomenon easily occurs, resulting in poor quality of a resultant fixing image.
  • Toner is desired to have a small particle diameter with a narrow particle size distribution in terms of a good combination of fixing performance, anti-hot offset property and quality images. Furthermore, to improve transferability, toner form is desired to be spherical but toner having an irregular form has a wide applicability to an apparatus taking a blade cleaning method. Not only fixing property, image performance and cleaning performance but also preservability and a charging property are desired to be satisfied simultaneously at a high level. Variety of intensive studies have been made with a main focus on binder resins to meet these requirements.
  • JOP H11-149180 and 2000-292981 describe a toner containing a toner binder and a colorant, which is prepared by an elongation reaction and/or cross-linking reaction of a polyester prepolymer having isocyanatge groups in an aqueous medium by amines and the manufacturing method of the toner as a method of obtaining toner having a good combination of performance and economical production system.
  • JOPs H11-149180 and 2000-292981 describe toner manufacturing methods relating to granulation in aqueous medium.
  • toner When toner is granulated in an aqueous medium, pigments in oil phase having a small droplet form agglomerate at the interface between the oil phase and the aqueous phase, which causes decrease in volume resistance and non-uniform dispersion of the pigments.
  • the obtained toner has basic performance problems. Without targeted forms and characteristics, it is difficult to obtain oilless toner having a small particle diameter with suitably controlled forms and apply the toner to an apparatus.
  • Each JOP does not include descriptions of methods of making irregular formed toner, which leaves the problems about blade cleaning unsolved.
  • Pigments in toner particles granulated in an aqueous medium tend to be located on the surface of the toner particles and in addition the oleophilic component in an aqueous medium is easily attracted to the surface of the toner particle.
  • the specific surface area of the toner particle tends to be large.
  • polymer design and particle surface design are key to obtain desired charging characteristics and fixing characteristics but there is no specific method of achieving a good fixing performance.
  • JOP 2004-054204 describes a chemical toner using a prepolymer containing isocyanate groups which is good at improving technology on fixing property and hot offset property.
  • a charge controlling agent is fixed on the surface of the toner particle to secure the charging performance, which has an adverse impact on fixing property.
  • shearing force due to stirring is provided in addition to the adjustment time of removing a solvent.
  • particles manufactured from oil phase containing a solvent tend to be spherical so that it is extremely difficult to form a particle having an irregular shape.
  • JOPs 2002-148863 , H05-313416 and H02-148046 describe a method of manufacturing a toner containing a binder resin and a colorant.
  • the method contains a process of dispersing mother toner particles in water or an aqueous medium containing a dispersing agent to form a dispersion system, a process of making the mother toner particle absorbing a softening agent by pouring into the dispersion system a liquid mixture of the softening agent and an organic solvent which is soluble in the water or the aqueous medium and dissolves the softening agent, and a process of removing the softening agent from the mother toner particle.
  • the toner can have a spherical form regardless of the kind of resin component contained in the toner and without having an adverse impact on the particle size distribution of the mother toner particles.
  • JOPs 2002-148863 , H05-313416 and H02-148046 tends to roll on an image bearing member so that the toner easily slips into between the image bearing member and a cleaning blade when a blade cleaning system is adopted, resulting in poor cleaning performance.
  • this easily causes a problem that dust gathers around toner dots in the developing process and the transfer process.
  • the chemical toner which is prepared by granulating particles in an aqueous medium, tends to have a spherical form due to the interface tension of droplets produced during the dispersion process.
  • Spherical toner has a good fluidity even when the toner has a small particle diameter.
  • such a toner is advantageous to hopper design and developing unit design in that torque for rotating a developing roll can be reduced.
  • such a toner is selective in light of a cleaning system. Namely, the surface of an image bearing member after a toner image is transferred is cleaned by a blade, a fur brush, a magnetic brush, etc. Among these, blades are widely used because of their simple structure and good cleanability.
  • JOP H02-51164 describes a method of manufacturing a toner in which a resin solution containing a polyester resin and an organic solvent is emulsified in an aqueous medium, the organic solvent is removed to form resin particulates and the resin particulates are agglomerated to prepare toner particles.
  • JOP 2002-351139 describes a polymerized toner by suspension polymerization.
  • the polymerized toner is that irregular formed aggregates having a particle size of from 5 to 25 ⁇ m are formed by aggregating fine primary particles having a particle size not greater than 10 ⁇ m and pigments are dispersed in the primary particles.
  • this toner is made of styrene-acryl materials so that there is a limit to improving the fixing property of the toner.
  • the present inventors recognize that a need exists for a toner having an irregular shape and a good low temperature fixing property to produce quality images with high definition regardless of cleaning systems, including a blade cleaning system, while keeping advantageous points as a chemical toner, for example, a narrow particle size distribution, reduction in size and excellent fluidity and also for a method of manufacturing the toner.
  • an object of the present invention is to provide a toner having an irregular shape and a good low temperature fixing property to produce quality images with high definition regardless of cleaning systems, including a blade cleaning system, while keeping advantageous points as a chemical toner, for example, a narrow particle size distribution, reduction in size and excellent fluidity.
  • the toner is prepared by a method including dispersing or emulsifying a toner constituent liquid mixture containing the colorant, the binder resin and/or a precursor of the binder resin, the releasing agent and the laminar inorganic mineral, in an aqueous medium containing water to obtain a liquid dispersion or an emulsion, and removing the organic solvent and water from the liquid dispersion or the emulsion.
  • the toner particle has a structure such that when the particle is heated at a temperature ranging from 65 to 90 °C the releasing agent is melted on the outside of the toner particle to form a colored particle having a sea-island structure.
  • the volume average particle diameter of the toner is from 3 to 6 ⁇ m, the ratio (Dv/Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) it from 1.00 to 1.30, and the binder resin has a glass transition temperature (Tg) of from 40 to 55 °C and the weight average particle diameter (Mw) of from 3,000 to 6,500.
  • Tg glass transition temperature
  • Mw weight average particle diameter
  • the toner constituent liquid mixture further contains the binder resin further containing a polyester prepolymer containing at least one isocyanate group and a compound for conducting an elongation reaction or cross-linking reaction with the prepolymer and the method further includes conducting a cross-linking or elongation reaction in the toner constituent liquid mixture in the aqueous medium.
  • the ratio of the releasing agent having a dispersion particle diameter of from 0.3 to 1.0 ⁇ m is not greater than 70 % by number in the toner particle.
  • the toner constituent liquid mixture has a Casson yield value of from 1 to 10 Pa at 25°C and the toner has a form factor SF-1 of from 140 to 200.
  • a method of manufacturing a toner particle which includes dispersing or emulsifying a toner constituent liquid mixture containing an organic solvent, a colorant, the binder resin and/or a precursor thereof, a releasing agent having melting point of from 65°C to 80°C and a laminar inorganic mineral in which part or all ions present between layers therein are modified by organic ions, in an aqueous medium comprising water to obtain a liquid dispersion or an emulsion; and removing the organic solvent and water from the liquid dispersion or the emulsion.
  • the method produces a toner particle having a structure such that when the particle is heated at a temperature ranging from 65 to 90 °C the releasing agent is melted on the outside of the toner particle to form a colored particle having a sea-island structure.
  • the toner constituent liquid mixture has a Casson yield value of from 1 to 10 Pa at 25°C and the toner particle has a form factor SF-1 of from 140 to 200.
  • a developing agent which contains the toner mentioned above and a carrier.
  • an image forming apparatus which includes an image bearing member for bearing a latent image thereon, a charging device for charging the image bearing member, a developing device for developing the latent image comprising the toner mentioned above, a transfer device for transferring the latent image to a transfer body, a discharging device for dischargnig the image bearing member and a cleaning device for cleaning the surface of the image bearing member.
  • an image forming apparatus which includes charging an image bearing member by a charging device, irradiating the image bearing member by an irradiating device to form a latent electrostatic image thereon, developing the latent electrostatic image on the image bearing member with the toner mentioned above, removing residual toner remaining on the image bearing member by a cleaning device and transferring the toner image to a transfer body.
  • a toner container which includes a container and the toner mentioned above therein.
  • a process cartridge which includes an image bearing member for bearing a latent electrostatic image, a developing device for developing the latent electrostatic image containing the toner mentioned above and optionally at least one of a cleaning device, a transfer device, an irradiating device and a charging device.
  • the present invention provides a toner which is prepared by dispersing and/or emulsifying an oil phase (toner constituent liquid mixture containing an organic solvent containing a binder resin, a colorant (e.g., pigment), a releasing agent (e.g., wax) and a modified laminar inorganic mineral in an aqueous medium and removing the solvent from the obtained liquid dispersion and liquid emulsion.
  • the toner particle contains a dispersion body containing the wax, the binder resin, the pigment and the laminar inorganic mineral.
  • the wax is dispersed existing relatively near the surface of the toner particle and melts outside to form a sea-island structure of a colored particle in a heating test having a heating and cooling unit in the range of 65 to 90 °C.
  • the toner of the present invention is excellent in the releasing property and the low temperature fixing property due to oozing of a releasing agent (wax) and a binder resin and has a good cleanability, for example, in a blade cleaning system, with a small amount of transfer remaining toner due to its irregular form so that quality images can be obtained. Furthermore, the laminar inorganic mineral dispersing in the toner imparts the toner particle with a good charging ability and a good agglomeration property of the oil phase during emulsification to assist forming an irregular form of the toner particle.
  • the releasing agent is present on the utmost surface, and organic resin particulates are present outside the utmost surface.
  • the toner can have a spindle form and/or a dimple form with a preferred volume average particle diameter of from 4.0 to 6.0 ⁇ m and form factor SF-1 of the toner preferably ranging from 140 to 200.
  • Fig. 1 illustrates the structure of a toner particle.
  • the structure is that pigments are dispersed in a resin, which is a main component, and wax is dispersed in all over the toner particle and significantly localized near the surface of the toner particle.
  • the toner particle is covered with organic particulates and modified laminar inorganic minerals (e.g., organically modified montmorillonite) are existent on the surface layer. Further, additives are fixedly attached to the uppermost layer of the toner particle.
  • Fig. 2 is a conceptual diagram illustrating a status (i.e., the sea-island structure) of a colored particle in the heating test mentioned above. Toner Structure, Toner Characteristics and Toner Quality
  • the inventors of the present invention made an intensive study on the fixing property, the hot offset property, the image quality, the high temperature preservation property, the charging property and the cleaning property and have thus obtained a toner having a particle structure achieving a good combination of these properties.
  • the toner contains particles formed by an elongation reaction and/or a cross-linking reaction of amines in an aqueous medium.
  • pigments and modified laminar inorganic minerals dispersed by a non-modified and/or modified polyester having a low glass transition temperature and a low molecular weight are contained and a wax having a high releasing property is present around the surface layer.
  • the toner particle By covering the surface of the toner particle with the releasing agent (wax) and organic particulates, the toner particle can have a high charging ability desired during development and transfer of toner. Furthermore, a low temperature softening polymer inside the particle rapidly oozes during fixing by a heating roller system so that the toner can have a good fixing property. In addition, the wax having a high releasing property which is dispersed near the surface of the toner particle oozes sooner than the binder does to secure the releasing property of the heating roller.
  • the binder having a low softening point prevents blocking caused by heat, a good combination of preservability and charging property can be obtained by forming a thin layer of organic particulates on the surface of toner particles and dispersing the modified laminar inorganic mineral functioning as a charge controlling agent material in the particle.
  • the status, i.e., dissolution and dispersion status of pigment, binder resin and wax component, exhibiting the function of such a particle, can be clearly seen by the following method in which the heating and cooling state of the particle is observed with a cooling and heating unit (manufactured by JAPAN HIGH TECH CO., LTD.) for a microscope. Observing Method of Heating and Cooling Unit for Microscope
  • Optical microscope (or another kind of microscope), manufactured by Olympus Corporation: magnification power: 20x and 40x.
  • Heating and cooling unit for microscope manufactured by JAPAN HIGH TECH CO., LTD.: rising rate of toner temperature: 5 °C/min.
  • the heating and cooling unit is connected to the microscope so that the melting status of toner particles can be observed.
  • Toner sample is set on a glass and a glass cover is placed on the sample.
  • the sample is heated at the rate mentioned above.
  • the temperature at which the wax melted out to form a sea-island structure and the temperature at which the toner particle is melted out are measured.
  • a laminar inorganic mineral is preferred which can be dissolved and/or dispersed in an organic solvent and can impart oil phase rheology effect when the laminar inorganic mineral is dispersed in a binder pigment liquid dispersion.
  • laminar inorganic mineral examples include montmorillonite, bentonite, hectorite, attapulgite, sepiolite and mixtures thereof.
  • montmorillonite and bentonite are preferred since these do not affect toner characteristics, it is easy to adjust the viscosity, and the addition amount thereof can be small.
  • Quaternium 18 Bentonites e.g., BENTONE 3, BENTONE 38, BENTONE 38V (manufactured by Elementis Specialties, Inc.), TIXOGEL VP (manufactured by United Catalyst Corporation), CLAYTONE 34, CLAYTONE 40, and CLAYTONE XL (manufactured by Southern Clay Inc.); Stearal conium BENTONITE, e.g., BENTONITE 27 (manufactured by Elementis Specialties, Inc.), TIXOGEL LG (manufactured by United Catalyst Corporation ), and CLAYTONE A and CLAYTONE APA(manufactured by Southern Clay Inc.); and QUATANIUM 18/BENZACONIUM BENZONITE.
  • toner forms can be easily made irregular by using a laminar inorganic mineral at least some of which is modified by organic ions.
  • the laminar inorganic mineral has a high hydrophilic property due to its layered structure.
  • a laminar inorganic mineral is used without modification for a toner which is granulated by dispersion in an aqueous medium, the laminar inorganic mineral is transferred into the aqueous medium so that it is difficult to make the toner have an irregular form.
  • the laminar inorganic mineral can have a suitable hydrophobic property.
  • the oil phase containing a toner component and/or a precursor thereof can have a non-Newtonian viscosity and the toner particles can have an irregular form.
  • the content of a laminar inorganic mineral at least partially modified by an organic anion is preferably from 0. 05 to 5 % by weight based on the toner material.
  • laminar inorganic mineral at least some of which is modified by an organic ion examples include montmorillonite, bentonite, hectorite, attapulgite, sepiolite and mixtures thereof.
  • montmorillonite and bentonite are preferred since these do not affect toner characteristics, it is easy to adjust the viscosity, and the addition amount thereof can be small.
  • Marketed products of laminar inorganic minerals at least some of which is modified by an organic ion include, for example, Quaternium 18 Bentonites, e.g., BENTONE 3, BENTONE 38, BENTONE 38V (manufactured by Elementis Specialties, Inc.), TIXOGEL VP (manufactured by United Catalyst Corporation), CLAYTONE 34, CLAYTONE 40, and CLAYTONE XL (manufactured by Southern Clay Inc.); Stearal conium BENTONITE, e.g., BENTONITE 27 (manufactured by Elementis Specialties, Inc.), TIXOGEL LG(manufactured by United Catalyst Corporation ), and CLAYTONE A and CLAYTONE APA(manufactured by Southern Clay Inc.); and QUATANIUM 18/BENZACONIUM BENZONITE. Among these, CLAYTONE AF and CLAYTONE APA are preferred.
  • a modified laminar inorganic mineral can be finely dispersed in a binder resin beforehand to make the modified laminar inorganic mineral finely disperse on the surface of toner particle.
  • the modified laminar inorganic mineral is finely dispersed in a toner and is fixed around the uppermost surface of toner particles during emulsification. This is considered to be because the modified laminar inorganic mineral in an oil phase has a hydrophilic tendency during emulsification.
  • a pigment master batch method is used to make a modified laminar inorganic mineral finely disperse in a binder resin.
  • Master batch pigments which are prepared by combining a colorant with a resin, can be used as the colorant of the toner composition of the present invention.
  • the resins for use in the master batch pigments or for use in combination with master batch pigments include the modified and unmodified polyester resins mentioned above; styrene polymers and substituted styrene polymers such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene; styrene copolymers such as styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-methyl acrylate copolymers, styrene-ethyl acrylate copolymers, styrene-butyl
  • the master batch mentioned above is typically prepared by mixing and kneading a resin and a colorant upon application of high shear stress thereto.
  • an organic solvent can be used to boost the interaction of the colorant with the resin.
  • flushing methods in which an aqueous paste including a colorant is mixed with a resin solution of an organic solvent to transfer the colorant to the resin solution and then the aqueous liquid and organic solvent are separated to be removed can be preferably used because the resultant wet cake of the colorant can be used as it is.
  • three-roll mills can be preferably used for kneading the mixture upon application of high shear stress thereto.
  • a toner that has a small volume average particle diameter (DV) can improve the fine line reproduction property.
  • the volume average particle diameter is not greater than 6 ⁇ m.
  • a toner that has an excessively small volume average particle diameter may cause deterioration of cleaning property so that the volume average particle diameter is preferably not smaller than 3 ⁇ m.
  • the ratio of toner particles having a volume average particle diameter less than 3 ⁇ m is greater than, for example, 20 %, the number of toner particles having a fine particle diameter, which is not easy to be developed on magnetic carriers or the surface of a developing roller, increases so that abrasive contact between the toner particles, magnetic carriers and/or the developing roller are not sufficient. As a result, the number of reversely charged toner particles increases, which may cause background fouling and lead to deterioration of image quality.
  • the particle diameter distribution represented by the ratio (Dv/Dn) of the volume average particle diameter (DV) to the number average particle diameter (Dn) is preferably from 1.00 to 1.30.
  • the particle diameter of a toner can be measured by using Coulter Counter Multisizer (manufactured by Beckman Coulter Inc.). The average particle diameter is obtained by measuring 50,000 toner particles with 50 ⁇ m aperture corresponding to the particle diameter of the toner.
  • the toner of the present invention can produce high definition and high quality images with an excellent low temperature fixing property and an excellent hot offset property to minimize the power consumption. Namely, to address to the demand for improving a releasing property of a toner, the toner is made to have an irregular form, for example, a spindle form and a dimple form, and wax is controlled to be present near the surface of the toner particle. Thus, the toner can satisfy both of the production of high definition and high quality images and an excellent fixing property.
  • the amount of wax present near the surface of the toner measured by FTATR-IR (Fourier Transform Attenuated Total Reflection - Infrared Spectroscopy) is from 2 to 10 % by weight based on all the component in the toner.
  • the volume average particle diameter (DV) of the toner is from 3.0 to 6.0 ⁇ m.
  • the form factor SF-1 of the toner is from 140 to 200. These contributes to improvement on cleaning property.
  • An SF-1 of from 140 to 160 is particularly preferred. When SF-1 is too large, a toner particle tends to crack, which leads to quality deterioration due to fine particles. When SF-1 is too small, the cleaning property tends to deteriorate.
  • MXLG, AREA and PERI represent the maximum particle diameter (major axis) of the projected image of a measured toner particle, the area thereof, and the circumstance thereof, respectively, as shown in Fig. 1 .
  • the form factor SF-1 is obtained by: multiplying the maximum particle diameter of a toner particle to the power of 2; dividing the resultant by the projected area of the toner particle; multiply n/4 with the resultant; and multiply 100 with the resultant.
  • a toner particle having an SF-1 that is close to 100 has a form close to a spherical form.
  • a toner particle having a spindle form, i.e., away from a spherical form has a large value, away from 100.
  • the form factor SF-1 represents the degree of roundness of a toner particle and is related to transfer efficiency in the transfer process and the amount of toner remaining on an image bearing member.
  • the amount of wax present near the surface of a toner particle based on all the components in the toner particle is dependent on the average dispersion particle diameter of the wax and is suitably from 2 to 10 % by weight.
  • this amount is too small, a desired anti-hot offset property is not obtained.
  • the amount is too large, the developing property and the transfer property may deteriorate and the filming on an image bearing member and a charge imparting member is significant, which are not preferred.
  • Near the surface represents the range between the surface and 0.3 ⁇ m therefrom in depth, which can be measured by a wavelength of 2,850 cm -1 of Attenuated Total Reflection - Infrared Spectroscopy (ATR-IR).
  • ATR-IR Attenuated Total Reflection - Infrared Spectroscopy
  • the maximum particle diameter of wax is determined as wax dispersion particle diameter.
  • toner is embedded in an epoxy resin and sliced to obtain super thin pieces (about 100 nm thickness).
  • the dyed sliced pieces are observed by a transmission electron microscope (TEM) at a magnification power of from 10,000 to 50,000 and photographed. The photographs are image-evaluated to observe the dispersion status of the wax, and the dispersion particle diameter is measured.
  • TEM transmission electron microscope
  • the existing ratio of wax exposed to the surface of a toner particle can be measured by Fourier Transform Attenuated Total Reflection - Infrared Spectroscopy
  • FTATR-IR method is; to irradiate a sample attached to ATR crystal with infrared to detect all the reflection component (the amount of wax contained in the range of from about 0.2 to about 0. 5 ⁇ m in depth from the surface of a toner particle can be detected) ; to make analytical curve of the amount of wax in the toner particle by FTIR in advance; to make relative analytical curve by ATR method; and to calculate the amount of wax from the relative analytical curve of the absorption wavelength of the wax and the absorption wavelength of a resin.
  • Wax for use in the toner of the present invention has a melting point of from 65 to 80 °C, to effectively function as a releasing agent for the toner. It is found that the wax in the toner starts melting at around 65 °C and oozes to form a sea-island status in which the wax is sea and pigment particles are islands when the toner is observed with a heating and cooling device (manufactured by Japan High Tech Co., Ltd.). High temperature offset can be prevented by using a toner in this status without applying a releasing agent, for example, oil. Wax in such a toner oozes relatively quickly in comparison with the case of a typical toner.
  • protective materials i.e., resin particulates present at outer side protect the binder resin having a low melting point and wax having a low softening point located on the inner side of the toner particle in summer time (temperature from about 30 to 50 °C).
  • the temperature observation range of from 65 to 90 °C in which the sea-island structure of wax and resin dispersion particulate is formed by a heating and cooling device is an optimal range for having a good combination of low temperature fixing property and anti-hot offset property.
  • wax tends to melt soon so that the fixing property deteriorates to the contrary.
  • wax tends to start melting late so that the anti-hot offset property deteriorates.
  • the melting point of wax for use in the present invention is determined as the maximum endotherm peak by a differential scanning calorimeter (DSC).
  • the melting point ranging from 65 to 80 °C of wax components functioning as the releasing agent for use in the present invention is a temperature range for a good anti-hot offset property by the heating and cooling device.
  • waxes include vegetable waxes, for example, candelilla wax (melting point: 78 °C), rice wax (melting point: 80 °C), mineral waxes, for example, ozocerite (melting point: 72 °C), paraffin wax (melting point: 65 to 75 °C), and microcrystalline wax.
  • Synthesized waxes can be also used. Specific examples thereof include synthesized hydrocarbon waxes, ester waxes, ketone waxes, and ether waxes having a melting point of from 65 to 80 °C with a high releasing property.
  • crystalline polymer materials can be used. Among these, paraffin wax is preferred.
  • a wax dispersing agent is used such that wax is made to be present near the surface of a toner particle.
  • the wax dispersing agent there can be used a monomer for a toner binder resin which is hardly affiliatve with water during emulsification of a toner and the polymerization reaction product of which is non-compatible or hardly compatible with wax.
  • Such a wax dispersing agent is added in an amount of from 20 to 100 % based on a wax and dispersed and polymerized so that the wax can be controlled to be positioned near the surface of a toner particle.
  • wax dispersing agent When the content of such a wax dispersing agent is too small, wax may not be contained in a toner particle.
  • wax dispersion is not sufficient or wax tends to be positioned on the inner side of a toner particle so that the wax may ooze late and the effect of the wax is reduced.
  • Monomers for use in a typical toner binder resin can be used as the binder resin which hardly affiliates with water.
  • styrene based monomers e.g., styrene, ⁇ -methyl styrene, p-methyl styrene, m-methyl styrene, p-methoxy styrene, p-hydroxy styrene, p-acetoxy styrene, vinyl toluene, ethyl styrene, phenyl styrene and benzyl styrene), unsaturated carboxyl acid alkyl ester (having 1 to 18 carbon atoms) (e.g., methyl(meth)acrylate, ethyl(meth)acrylate, buthyl(meth)acrylate, and 2-ethylhexyl(meth)acrylate), vinyl ester based monomers (e.g., vinyl acetate), vinyl ether based monomer (e.g., vinyl methyl ether), hal
  • styrene based monomers unsaturated carboxylic acid alkyl esters, (meth)acylic acid alkyl esters and mixtures thereof are preferred.
  • the glass transition temperature (Tg) of the toner is not higher than 50 °C.
  • the glass transition temperature of such a polymer depends on its molecular weight.
  • the fixing property tends to be improved but the preservability may deteriorate.
  • Tg of the toner is designed by a binder having an extremely low Tg of from 40 to 55 °C and polymer particulates having a glass transition temperature of from 50 to 110 °C are present on the surface layer of the toner particle in an amount of from 0.3 to 2. 5 % based on the toner particle.
  • the particles uniformly covering the toner particle protect the binder resin having a low softening point from heat such that the particles function as an encapsulating particle.
  • the reason of having a good combination of the anti-hot offset, the low temperature fixing property and the high temperature presevability is that the binder resin on the surface of a toner particle has a large molecular weight through urea linkage formed as the reaction result of prepolymers and amines and part of the surface is mesh-structured to form a three dimension structure relatively strong for stress. Furthermore, while a material having the same thermal characteristics as a typical toner is used on the surface of a toner particle, a polyester resin, which has a low glass transition temperature, is used in the inner side of the toner particle.
  • such a toner has a particle structure advantageous for having a good low temperature fixing property in comparison with a homogeneous toner particle prepared by kneading and pulverization.
  • Polymer particulates covering the surface of a toner particle are desired to quickly react to the heat from a heating roller during fixing to ooze toner particle binder resins outside of the surface layer.
  • the balance between the high temperature preservability and oozing can be controlled by the content of the polymer particulate covering a toner particle.
  • Polymer particulates remaining on a toner particle have a particle diameter of from 10 to 200 nm and the amount of the polymer particulates covering the toner particle is from 0. 3 to 2 % by weight.
  • Tg of a toner the temperature range of from 40 to 55 °C is preferred in consideration of a good low temperature fixing property. When the glass transition temperature is too low, it is difficult to granulate toner. A glass transition temperature that is excessively high is not preferred to have a good low temperature fixing property.
  • a toner having a spherical form made by a wet polymerization has a low cleanability. Even a toner having an average particle diameter of about 10 ⁇ m is subject to poor cleaning performance for a blade cleaning system. This is because such a toner has a smooth surface so that the toner particle tends to roll on an image bearing member and easily slips into between a cleaning blade and the image bearing member. Since a spherical toner does not have a rough surface, all the external additives attached thereto contact the surface of an image bearing member.
  • toner having an irregular form has a rough surface and does not roll on an image bearing member before a cleaning blade. Therefore, it is easy to remove remaining toner.
  • a toner having a spindle form has a limited number of rotation axes around which toner easily rolls on an image bearing member in comparison with a spherical toner. In the case of a toner having a flat form, such rotation can be further limited.
  • a toner having a spherical form on an image bearing member has a smooth surface and a good powder fluidity. Furthermore, since the attraction force between toner particles or toner particles and an image bearing member is small, such toner particles are easily subject to electric force line and are transferred truly along the electric force line so that the transfer rate is high. However, when a recording medium is detached from an image bearing member, a high electric field is generated (i.e., burst phenomenon) between the image bearing member and the recording medium, which makes toner dust gather on the recording medium. A toner having a spherical form, which is easily affected by electric force line, produces a large amount of toner dust, resulting in degradation of image quality.
  • a toner having an irregular form or a flat form is hardly affected by the electric force line and hardly transferred therealong. Namely, the transfer rate is low.
  • the attachment force between toner particles is large and toner dots transferred onto a recording medium are not easily cracked by an external force so that the generation of toner dust caused by burst phenomenon can be restrained.
  • a toner having a spindle form has a smooth surface with a suitable fluidity, is succumbed to the electric force line and truly transferred therealong so that the transfer rate is high. Further, a toner particle having a spindle form has a limited number of rotation axes around which the toner particle easily rolls. Therefore, toner particles do not easily scatter from toner dots on a recording medium by the burst phenomenon, resulting in quality images.
  • toner particles having a spherical form on a developing roller are easily influenced by the electric force line and truly developed along the electric force line of a latent electrostatic image.
  • fine line reproducibility is improved because such toner particles are easily positioned in a dense and uniform manner.
  • toner particles developed on an image bearing member are easily moved by abrasion against a magnetic brush or a developing roller, which may cause image quality deterioration due to dust.
  • Toner particles having an irregular form on a magnetic carrier or a developing roller do not have a good powder fluidity and the electric force line does not work on each toner particle smoothly. Thus, toner dots are not orderly positioned during development, which makes true development difficult, resulting in low fine line representation. This applies to toner particles having a flat form.
  • Toner particles having a spindle form have a suitable adjusted powder fluidity. Therefore, fine line reproducibility is good because the development is performed true to the electric force line of a latent electrostatic image. Toner particles developed on an image bearing member are not easily moved by abrasion against a magnetic brush or a developing roller, resulting in a visualized image without significant image deterioration caused by toner dust, etc.
  • viscous fluidity of a toner oil phase to be emulsified is desired to be restricted.
  • a desired form of toner particles is obtained in a toner oil phase, when the viscous fluidity of the toner oil phase is that Casson yield value is from 1 to 25 Pa.
  • the toner oil phase is a solution or a liquid dispersion in which at least a prepolymer formed of a binder resin and modified polyester resin, a compound to conduct an elongation or cross-linking reaction with the prepolymer, a colorant, and a release agent are dissolved and/or dispersed in an organic solvent or an liquid emulsified dispersion in which only a non-modified polyester resin is used as a binder resin.
  • a modified laminar inorganic mineral in an amount of from 0.05 to 5 % in the solid portion of the solution or liquid dispersion.
  • a modified laminar inorganic mineral is too small, it is difficult to obtain a desired Casson yield value. An excessive content thereof may cause an adverse impact on the fixing property because the modified laminar inorganic mineral is fixed on the surface of a toner particle in an excessive amount.
  • Casson yield value can be measured by using a high shear viscosity meter under the following conditions:
  • the toner of the present invention preferably contains a material (hereinafter referred to as fixing material) which is fixed on the surface of the toner particle and makes the surface hydrophobic.
  • a material hereinafter referred to as fixing material
  • a mixture of silica and titanium oxide is preferred in terms of the charging ability and the fixing property.
  • the toner particle has a small particle diameter and does not have a good fluidity and in addition, polymer particulates cover the surface of the toner particle.
  • the toner particle tends to combine with moisture in air so that the charging ability greatly fluctuates.
  • an inorganic material functioning as a fluidizing agent is added and mixed on the surface of a toner particle. The material covering the surface tends to reduce the fixing ability.
  • These surface protective materials are fixed on the surface of a toner particle so that the materials are prevented from being detached from the surface.
  • the materials are not attached to or damage carriers, a developing roller, an image bearing member, a contact type charging device, etc.
  • These materials are fixed on the surface of a toner particle by using an external additive mixing device (or condition) having relatively a large mechanical stress in comparison with the case of a typical device.
  • a charge controlling agent can be fixed on the surface of a toner particle as a material to protect the surface before silica and titanium oxide are used.
  • the surface of the toner can be abrasively charged and friction charging can be secured.
  • a toner and a protective material are mixed in a container by using a rotation body.
  • a rotation body is rotated at a high speed to mix a toner and a protective material so that a toner on which the protective material is fixed can be obtained.
  • a toner and a protective material are mixed beforehand.
  • the mixture is sprayed with a hot air in a container by, for example, an atomizer to make the surface of the toner melted followed by rapid cooling.
  • a toner to which the protective layer is attached is obtained.
  • a protective material can be fixed by absorbing the protective material on the surface of a toner particle.
  • the content of silica which is attached to and fixed on the surface of the toner of the present invention is from 0.3 to 1.5 %.
  • the content of titanium oxide which is attached and fixed on the surface of the toner of the present invention is from 0.1 to 1.0 %. When the content of both in total is too large, the fixing property tends to sharply deteriorate.
  • binder resin a non-modified or modified polyester resin can be preferably used but the usable binder resins are not limited thereto.
  • the modified polyester represents a status in which a linking group other than ester linkage is existing in a polyester resin or a resin component having a different structure is bonded by, for example, ion-binding or covalent binding, in a polyester resin.
  • a functional group for example, isocyanate group reactive with an acid group or a hydroxyl group, is introduced at the end of a polymer and the polymer conducts a reaction with a compound having an active hydrogen to modify the end.
  • modified polyesters (i) include a compound obtained from the reaction between polyester prepolymer (A) having an isocyanate group and amines (B).
  • polyester prepolymers (A) having an isocyanate group include a resultant of the reaction between polyisocyanate (3) and a polyester, i.e., a polycondensation compound having an active hydrogen group which is prepared by polyol (1) and polycarboxylic acid (2).
  • the active hydrogen group contained in the polyesters mentioned above include hydroxyl groups (alcohol hydroxyl groups and phenol hydroxyl groups), amino groups, carboxylic groups, and mercarpto groups. Among these, alcohol hydroxyl groups are preferred.
  • Suitable polyols (1) include diols (1-1) and polyols (1-2) having three or more hydroxyl groups. It is preferred to use a (1-1) alone or mixtures in which a small amount of a (1-2) is mixed with a (1-1).
  • diols (1-1) include alkylene glycol (e.g., ethylene glycol, 1,2-propylene glycol, 1, 3-propylene glycol, 1,4-butanediol and 1, 6-hexanediol) ; alkylene ether glycols (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol); alicyclic diols (e.g., 1,4-cyclohexane dimethanol and hydrogenated bisphenol A); bisphenols (e.g., bisphenol A, bisphenol F and bisphenol S); adducts of the alicyclic diols mentioned above with an alkylene oxide (e.g., ethylene oxide, propylene oxide and butylene oxide) ; and adducts of the bisphenols mentioned above with an alkylene oxide (e.g., ethylene oxide, propylene oxide and butylene oxide
  • alkylene glycols having from 2 to 12 carbon atoms and adducts of a bisphenol with an alkylene oxide are preferable. More preferably, adducts of a bisphenol with an alkylene oxide, or mixtures of an adduct of a bisphenol with an alkylene oxide and an alkylene glycol having from 2 to 12 carbon atoms are used.
  • polyols (1-2) include aliphatic alcohols having three or more hydroxyl groups (e.g., glycerin, trimethylol ethane, trimethylol propane, pentaerythritol and sorbitol); polyphenols having three or more hydroxyl groups (trisphenol PA, phenol novolak and cresol novolak); adducts of the polyphenols mentioned above with an alkylene oxide; etc.
  • aliphatic alcohols having three or more hydroxyl groups e.g., glycerin, trimethylol ethane, trimethylol propane, pentaerythritol and sorbitol
  • polyphenols having three or more hydroxyl groups trisphenol PA, phenol novolak and cresol novolak
  • adducts of the polyphenols mentioned above with an alkylene oxide etc.
  • Suitable polycarboxylic acids (2) include dicarboxylic acids (2-1) and polycarboxylic acids (2-2) having three or more carboxyl groups. It is preferred to use dicarboxylic acids (2-1) alone or mixtures in which a small amount of a (2-2) is mixed with a (2-1) .
  • dicarboxylic acids (2-1) include alkylene dicarboxylic acids (e.g., succinic acid, adipic acid and sebacic acid); alkenylene dicarboxylic acids (e.g., maleic acid and fumaric acid) ; aromatic dicarboxylic acids (e.g., phthalic acid, isophthalic acid, terephthalic acid and naphthalene dicarboxylic acids; etc.
  • alkenylene dicarboxylic acids having from 4 to 20 carbon atoms and aromatic dicarboxylic acids having from 8 to 20 carbon atoms are preferably used.
  • polycarboxylic acids (2-2) having three or more hydroxyl groups include aromatic polycarboxylic acids having from 9 to 20 carbon atoms (e.g., trimellitic acid and pyromellitic acid).
  • anhydrides or lower alkyl esters e.g., methyl esters, ethyl esters or isopropyl esters
  • anhydrides or lower alkyl esters e.g., methyl esters, ethyl esters or isopropyl esters
  • Suitable mixing ratio i.e., an equivalence ratio [OH]/[COOH]
  • a polyol (1) to a polycarboxylic acid (2) is from 2/1 to 1/1, preferably from 1.5/1 to 1/1 and more preferably from 1.3/1 to 1.02/1.
  • polyisocyanates (3) include aliphatic polyisocyanates (e.g., tetramethylene diisocyanate, hexamethylene diisocyanate and 2,6-diisocyanate methylcaproate) ; alicyclic polyisocyanates (e.g., isophorone diisocyanate and cyclohexylmethane diisocyanate); aromatic diisosycantes (e.g., tolylene diisocyanate and diphenylmethane diisocyanate) ; aromatic aliphatic diisocyanates (e.g., ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl xylylene diisocyanate) ; isocyanurates; blocked polyisocyanates in which the polyisocyanates mentioned above are blocked with phenol derivatives thereof, oximes or caprolactams; etc. These compounds can be used alone or in combination.
  • aliphatic polyisocyanates e
  • Suitable mixing ratio (i.e., [NCO]/[OH]) of a polyisocyanate (3) to a polyester having a hydroxyl group is from 5/1 to 1/1, preferably from 4/1 to 1.2/1 and more preferably from 2.5/1 to 1. 5/1.
  • [NCO]/[OH] ratio is too large, the low temperature fixability of the toner deteriorates.
  • the molar ratio of [NCO] is too small, the urea content of a modified polyester tends to be small and the anti hot offset property easily deteriorates.
  • the content of the constitutional component of a polyisocyanate (PIC) in the polyester prepolymer (A) having a polyisocyanate group at its end portion is from 0.5 to 40 % by weight, preferably from 1 to 30 % by weight and more preferably from 2 to 20 % by weight.
  • PIC polyisocyanate
  • the number of isocyanate groups included in the prepolymer (A) per molecule is normally not less than 1, preferably from 1.5 to 3, and more preferably from 1.8 to 2.5. When the number of isocyanate groups is too small, the molecular weight of urea-modified polyester tends to be small and the anti-hot offset property easily deteriorates.
  • amines (B) include diamines (B1), polyamines (B2) having three or more amino groups, amino alcohols (B3), amino mercaptans (B4), amino acids (B5), and blocked amines (B6), in which the amines (B1-B5) mentioned above are blocked.
  • diamines (B1) include aromatic diamines (e.g., phenylene diamine, diethyltoluene diamine and 4,4'-diaminodiphenyl methane); alicyclic diamines (e.g., 4,4'-diamino-3,3'-dimethyldicyclohexyl methane, diaminocyclohexane and isophoron diamine); aliphatic diamines (e.g., ethylene diamine, tetramethylene diamine and hexamethylene diamine); etc.
  • polyamines (B2) having three or more amino groups include diethylene triamine, and triethylene tetramine.
  • amino alcohols (B3) include ethanol amine and hydroxyethyl aniline.
  • amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
  • amino acids (B5) include amino propionic acid and amino caproic acid.
  • Specific examples of the blocked amines (B6) include ketimine compounds which are prepared by reacting one of the amines B1-B5 mentioned above with a ketone such as acetone, methyl ethyl ketone and methyl isobutyl ketone; oxazoline compounds, etc.
  • diamines (B1) and mixtures in which a diamine (B1) is mixed with a small amount of a polyamine (B2) are preferred.
  • the molecular weight of the urea-modified polyesters can be controlled using a molecular-weight control agent, if desired.
  • a molecular-weight control agent include monoamines (e.g., diethyl amine, dibutyl amine, butyl amine and lauryl amine), and blocked amines (i.e., ketimine compounds) prepared by blocking the monoamines mentioned above.
  • the mixing ratio of the amines (B) to the prepolymer (A), i.e., the equivalent ratio ([NCO]/[NHx]) of the isocyanate group [NCO] contained in the prepolymer (A) to the amino group [NHx] contained in the amines (B), is normally from 1/2 to 2/1, preferably from 1.5/1 to 1/1.5 and more preferably from 1.2/1 to 1/1.2.
  • the modified polyesters can include a urethane linkage as well as a urea linkage.
  • the molar ratio (urea/urethane) of the urea linkage to the urethane linkage may vary from 100/0 to 10/90, preferably from 80/20 to 20/80 and more preferably from 60/40 to 30/70.
  • the hot offset resistance of the resultant toner deteriorates.
  • the urea-modified polyesters (i) of the present invention can be prepared in different ways, including, for example, one-shot methods and prepolymer methods.
  • the weight average molecular weight of the urea-modified polyesters is not less than 10,000, preferably from 20,000 to 10,000,000 and more preferably from 30,000 to 1,000,000.
  • the peak molecular weight is from 1,000 to 10,000. When the peak molecular weight is too small, elongation reaction tends to be not sufficiently conducted and the elasticity of the toner tends to be insufficient. Thus, the anti-hot offset easily deteriorates. When the peak molecular weight is too large, the fixing property may deteriorate and manufacturing cost tends to be high in terms of pulverization of toner.
  • the number average molecular weight of the urea-modified polyesters is not particularly limited when the unmodified polyester resin described below is used in combination. Namely, controlling of the weight average molecular weight of the modified polyester resins has priority over controlling of the number average molecular weight thereof.
  • the number average molecular weight thereof is not greater than 20,000, preferably from 1,000 to 10,000 and more preferably from 2,000 to 8,000.
  • the number average molecular weight is too large, the low temperature fixability of the resultant toner deteriorates, and in addition the gloss of full color images decreases when the toner is used in a full color image forming apparatus.
  • the low temperature fixability of the toner improves and in addition the toner can produce color images having high gloss when the toner is used in the full-color image forming apparatus.
  • polyester (ii) a polycondensation product of the polyol (1) and the polycalboxylic acid (2) as in the polyester (i) and preferred examples are the same as those for the polyester (i) .
  • the polyester (ii) can be modified by a chemical bond, for example, urethane linkage, other than urea linkage, in addition to the non-modified polyesters.
  • the polyester (i) at least partially mix with the polyester (ii) in terms of the low temperature fixability and hot offset resistance of the resultant toner.
  • the polyester (i) has a structure similar to that of the polyester (ii).
  • the mixing ratio of the polyester (i) to the polyester (ii) varies from 5/95 to 80/20, preferably from 5/95 to 30/70, more preferably from 5/95 to 25/75, and even more preferably from 7/93 to 20/80.
  • the hot offset resistance of the resultant toner deteriorates and, in addition, it is difficult to impart a good combination of high temperature preservability and low temperature fixability to the resultant toner.
  • the peak weight average molecular weight of the polyester (ii) is normally from 1,000 to 10,000, preferably from 2,000 to 8,000, and more preferably from 2,000 to 5,000. When the peak molecular weight is too small, the high temperature preservability tends to deteriorate. When the peak molecular weight is too large, the low temperature fixability tends to deteriorate.
  • the hydroxyl group value of the polyester (ii) is preferably not less than 5 mgKOH/g, more preferably from 10 to 120 mgKOH/g and even more preferably 20 to 80 mgKOH/g. When the hydroxyl group value of the unmodified polyester (PE) is too low, it is disadvantageous to achieve a good combination of high temperature preservability and low temperature fixability.
  • the acid value of the polyester (ii) is normally from 1 to 5 mgKOH/g, preferably from 2 to 4 mgKOH/g.
  • the toner of the present invention has a glass transition temperature (Tg) of the toner binder resin is from 40 to 55 °C.
  • Tg glass transition temperature
  • a glass transition temperature that is too low causes deterioration of high temperature preservability of the toner.
  • wax does not easily ooze (by the observation of a heating and cooling device) so that the anti-hot offset property deteriorates.
  • the toner of the present invention which has a low glass transition point, can have a relatively excellent combination of high temperature preservability and anti-hot offset property in comparison with a known polyester based toner. This is because material functions are desirably arranged in the toner particle structure of the toner of the present invention.
  • Hydrophobic silica and/or hydrophobic titanium oxide for use in the toner of the present invention preferably have a primary particle diameter between 5 nm and 2 ⁇ m, and more preferably between 5 nm and 500 nm.
  • the specific surface area of such particulate inorganic materials measured by a BET method be from 20 to 500 m 2 /g.
  • Suitable colorants for use in the toner of the present invention include known dyes and pigments.
  • specific examples of the colorants include carbon black, Nigrosine dyes, black iron oxide, Naphthol Yellow S, Hansa Yellow (10G, 5G and G), Cadmium Yellow, yellow iron oxide, loess, chrome yellow, Titan Yellow, polyazo yellow, Oil Yellow, Hansa Yellow (GR, A, RN and R), Pigment Yellow L, Benzidine Yellow (G and GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G and R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazane Yellow BGL, isoindolinone yellow, red iron oxide, red lead, orange lead, cadmium red, cadmium mercury red, antimony orange, Permanent Red 4R, Para Red, Fire Red, p-chloro-o-nitroaniline red, Lithol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL and F4
  • Master batch pigments which are prepared by combining a colorant with a resin, can be used as the colorant of the toner composition of the present invention.
  • the resins for use in the master batch pigments or for use in combination with master batch pigments include the modified polyester resins and the unmodified polyester resins mentioned above; styrene polymers and substituted styrene polymers such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene; styrene copolymers such as styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-methyl acrylate copolymers, styrene-ethyl acrylate copolymers, styrene-
  • Suitable aqueous media for use in the present invention include water, and mixtures of water with a solvent which can be mixed with water.
  • a solvent which can be mixed with water.
  • Specific examples of such a solvent include alcohols (e.g., methanol, isopropanol and ethylene glycol), dimethylformamide, tetrahydrofuran, cellosolves (e.g., methyl cellosolve), lower ketones (e. g., acetone and methyl ethyl ketone), etc.
  • urea-modified polyester can be obtained by conducting the reaction between polyester prepolymer (A) having an isocyanate group and amine (B) in an aqueous medium.
  • a method of securely forming a dispersion body formed of a modified polyester for example, urea-modified polyester, or prepolymer (A) in an aqueous medium
  • a composition of toner materials containing a modified polyester, for example, urea-modified polyester, or prepolymer (A) in an aqueous medium is added to an aqueous medium followed by shearing for dispersion.
  • Prepolymer (A) and other toner compositions for example, a colorant, a colorant master batch, a releasing agent, a charge controlling agent and an unmodified polyester resin can be mixed when forming a dispersion body in an aqueous medium. It is preferred to mix the toner materials in advance and add the mixture to an aqueous medium for dispersion.
  • toner materials for example, a colorant, a releasing agent and a charge controlling agent are not necessarily mixed during formation of particles in an aqueous medium but can be added after particles are formed. For example, particles not containing a colorant are formed first and a colorant can be added to the particles by a known dying method.
  • oil phase for emulsification can be formed by using a non-modified polyester binder resin as an only binder resins.
  • Liquid dispersion for emulsification using a modified laminar inorganic mineral can be used to form toner particles.
  • the dispersion method There is no particular restriction for the dispersion method. Low speed shearing methods, high speed shearing methods, friction methods, high pressure jet methods, ultrasonic methods, etc., can preferably be used. Among these methods, high speed shearing methods are more preferred because particles having a particle diameter of from 2 to 20 ⁇ m can be easily prepared.
  • a high speed shearing type dispersion machine there is no particular limit to the rotation speed thereof, but the rotation speed is typically from 1,000 to 30,000 rpm, and preferably from 5,000 to 20,000 rpm.
  • the dispersion time is also not particularly limited, but is typically from 0.1 to 5 minutes for a batch production method.
  • the temperature in the dispersion process is typically from 0 to 150 °C (under pressure), and preferably from 40 to 98 °C.
  • the dispersion process is preferably performed at a high temperature because the dispersion body containing a urea-modified polyester and a prepolymer (A) has a low viscosity at a high temperature so that dispersion can be easily performed.
  • the content of the aqueous medium is normally from 50 to 2,000 parts by weight and preferably from 100 to 1,000 parts by weight per 100 parts by weight of a toner component containing urea-modified polyester and prepolymer (A).
  • a toner component containing urea-modified polyester and prepolymer (A) When the content of the aqueous medium is too small, the toner constituent liquid mixture tends not to disperse well and thereby toner particles having a desired particle diameter are difficult to obtain. When the content is too large, the manufacturing cost increases. It is also possible to add a dispersing agent to an aqueous medium, which makes it possible to have a narrow particle size distribution of a dispersion body and improve the dispersion stability.
  • dispersing agents are used for dispersing a toner component in an oil phase and emulsifying an oil phase in an aqueous medium.
  • dispersing agents include a surface active agent, an inorganic particulate and a polymer particulate dispersing agent.
  • the surface active agents include anionic dispersing agents, for example, alkylbenzene sulfonic acid salts, ⁇ -olefin sulfonic acid salts, and phosphoric acid salts; cationic dispersing agents, for example, amine salts (e.g., alkyl amine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives and imidazoline), and quaternary ammonium salts (e.g., alkyltrimethyl ammonium salts, dialkyldimethyl ammonium salts, alkyldimethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts and benzethonium chloride); nonionic dispersing agents, for example, fatty acid amide derivatives, polyhydric alcohol derivatives; and ampholytic dispersing agents, for example, alanine, dodecyldi(aminoethyl)glycin
  • a good dispersion can be prepared with an extremely small amount of a surface active agent having a fluoroalkyl group.
  • the anionic surface active agents having a fluoroalkyl group include fluoroalkyl carboxylic acids having from 2 to 10 carbon atoms and their metal salts, disodium perfluorooctanesulfonylglutamate, sodium 3- ⁇ omega-fluoroalkyl(C6-C11)oxy ⁇ -1-alkyl(C3-C4) sulfonate, sodium 3- ⁇ omega-fluoroalkanoyl(C6-C8)-N-ethylamino ⁇ -1-propanesulfonate, fluoroalkyl(C11-C20) carboxylic acids and their metal salts, perfluoroalkylcarboxylic acids and their metal salts, perfluoroalkyl(C4-C12)sulfonate and their metal salts, perfluorooctanesulfonic
  • Specific examples of the marketed products of such surface active agents having a fluoroalkyl group include SURFLON® S-111, S-112 and S-113, which are manufactured by Asahi Glass Co., Ltd.; FRORARD® FC-93, FC-95, FC-98 and FC-129, which are manufactured by Sumitomo 3M Ltd.; UNIDYNE® DS-101 and DS-102, which are manufactured by Daikin Industries, Ltd.; MEGAFACE® F-110, F-120, F-113, F-191, F-812 and F-833 which are manufactured by Dainippon Ink and Chemicals, Inc.; ECTOP® EF-102, 103, 104, 105, 112, 123A, 306A, 501, 201 and 204, which are manufactured by Tohchem Products Co., Ltd.; FUTARGENT® F-100 and F150 manufactured by Neos; etc.
  • cationic surface active agents having a fluoroalkyl group include primary, secondary and tertiary aliphatic amino acids, aliphatic quaternary ammonium salts (for example, perfluoroalkyl(C6-C10)sulfoneamidepropyltrimethyl ammonium salts), benzalkonium salts, benzetonium chloride, pyridinium salts, and imidazolinium salts.
  • SURFLON® S-121 from Asahi Glass Co., Ltd.
  • FRORARD® FC-135 from Sumitomo 3M Ltd.
  • UNIDYNE® DS-202 from Daikin Industries, Ltd.
  • MEGAFACE® F-150 and F-824 from Dainippon Ink and Chemicals, Inc.
  • ECTOP® EF-132 from Tohchem Products Co., Ltd.
  • FUTARGENT® F-300 from Neos
  • a water hardly soluble inorganic dispersing agents can be used.
  • a water hardly soluble inorganic dispersing agents include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica and hydroxyapatite.
  • Polymer particulates have been confirmed to have the same effect as an inorganic compound.
  • particulate polymers include particulate polymethyl methacylate having a particle diameter of from 1 to 3 ⁇ m, particulate polystyrene having a particle diameter of from 0.5 to 2 ⁇ m, particulate styrene-acrylonitrile copolymers having a particle diameter of 1 ⁇ m, etc.
  • marketed particulate polymers include PB-200H (from Kao Corp.), SGP (Soken Chemical & Engineering Co., Ltd.), TECHNOPOLYMER® SB (Sekisui Plastics Co., Ltd.), SPG-3G (Soken Chemical & Engineering Co., Ltd.), MICROPEARL® (Sekisui Fine Chemical Co., Ltd.), etc.
  • protection colloids include polymers and copolymers prepared using monomers, for example, acids (e.g., acrylic acid, methacrylic acid, ⁇ -cyanoacrylic acid, ⁇ -cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid and maleic anhydride), acrylic monomers having a hydroxyl group (e.g., ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate, ⁇ -hydroxypropyl acrylate, ⁇ -hydroxypropyl methacrylate, ⁇ -hydroxypropyl acrylate, ⁇ -hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethyleneglycolmonoacrylic acid esters, diethyleneglycolmonomethacrylic
  • polymers for example, polyoxyethylene compounds (e.g., polyoxyethylene, polyoxypropylene, polyoxyethylenealkyl amines, polyoxypropylenealkyl amines, polyoxyethylenealkyl amides, polyoxypropylenealkyl amides, polyoxyethylene nonylphenyl ethers, polyoxyethylene laurylphenyl ethers, polyoxyethylene stearylphenyl esters, and polyoxyethylene nonylphenyl esters), and cellulose compounds, for example, methyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, can also be used as the polymeric protective colloid.
  • polyoxyethylene compounds e.g., polyoxyethylene, polyoxypropylene, polyoxyethylenealkyl amines, polyoxypropylenealkyl amines, polyoxyethylenealkyl amides, polyoxypropylenealkyl amides, polyoxyethylene nonylphenyl ethers, polyoxyethylene laurylphenyl ethers
  • the entire system is gradually heated while stirring in a layer streaming manner. After violent stirring in a certain temperature range and desolvent, toner particles having a spindle form or dimpled toner can be manufactured.
  • a dispersing agent When a dispersing agent is used, it is possible to allow the dispersing agent remain on the surface of toner particles.
  • a dispersing agent When a solvent is used, a dispersing agent can be removed from the resultant obtained after elongation and/or cross-linking reaction by amine of modified polyester (prepolymer) under normal or reduced pressure.
  • polyester for example, urea-modified polyester and prepolymer (A)
  • A urea-modified polyester and prepolymer
  • the organic solvent is preferred to be volatile and have a boiling point lower than 100 ° since it is easy to get removed.
  • Specific examples thereof include non-water soluble solvents, for example, aqueous toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, methyl acetate and ethyl acetate, methylethyl ketone and methylisobuthyl ketone. These can be used alone or in combination.
  • aromatic hydrocarbons for example, toluene and xylene
  • halogenated hydrocarbons for example, methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride
  • the content of the organic solvent is from 0 to 300 parts by weight, preferably from 0 to 100 parts by weight and more preferably from 25 to 70 parts by weight based on 100 parts by weight of prepolymer (A).
  • a method in which the entire system is gradually heated to completely evaporate and remove the organic solvent in droplets there can be used a method in which the entire system is gradually heated to completely evaporate and remove the organic solvent in droplets.
  • a drying method can be used in which the dispersing body is sprayed in a dry atmosphere to completely evaporate and remove not only the non-water soluble organic solvent in droplets to form toner mother particles but also the remaining dispersing agent.
  • the dry atmosphere can be prepared by heating gases, for example, air, nitrogen, carbon dioxide and combustion gases.
  • the temperature of the heated gases is preferred to be higher than the boiling point of the solvent having the highest boiling point among the solvents used in the dispersion.
  • a drying apparatus for example, a spray dryer, a belt dryer, a rotary kiln, the drying treatment can be completed in a short period of time.
  • the volume average particle diameter Dv, the number average particle diameter Dn, the ratio (Dv/Dn) thereof, and the ratio of spindle form can be controlled by adjusting, for example, aqueous phase viscosity, oil phase viscosity, characteristics of resin particulates and the content of addition.
  • the toner of the present invention can be used for a two-component developer in which the toner is mixed with a carrier.
  • the weight ratio (T/C) of the toner (T) to the carrier (C) is preferably from 1/100 to 10/100.
  • Suitable carriers for use in a two component developer include known carrier materials, for example, iron powders, ferrite powders and magnetite powders which have a particle diameter of from about 20 to about 200 ⁇ m.
  • the surface of the carriers can be coated by a resin.
  • resins to be coated on the carriers include amino resins, for example, urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, and polyamide resins, and epoxy resins.
  • vinyl or vinylidene resins for example, acrylic resins, polymethylmethacrylate resins, polyacrylonitirile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins, styrene-acrylic copolymers, halogenated olefin resins, for example, polyvinyl chloride resins, polyester resins, for example, polyethyleneterephthalate resins and polybutyleneterephthalate resins, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoropropylene resins, vinylidenefluoride-acrylate copolymers, vinylidenefluoride-vinylfluoride copolymers, fluoroterpolymers, for example, a copolymer of tetrafluor
  • the electroconductive powder can be optionally included in the resin.
  • specific examples of such electroconductive powders include metal powders, carbon blacks, titanium oxide, tin oxide, and zinc oxide.
  • the average particle diameter of such electroconductive powders is preferably not greater than 1 ⁇ m. When the particle diameter is too large, it is hard to control the resistance of the resultant toner.
  • the toner of the present invention can also be used as a one-component magnetic developer or a one-component non-magnetic developer.
  • the volume average particle diameter of a toner contained in a two-component developing agent When the volume average particle diameter of a toner contained in a two-component developing agent is too small, the toner tends to be attached to the surface of a carrier during stirring in a developing device over an extended period of time. Thus, the charging ability of the carrier may deteriorate.
  • filming of the toner on a developing roller and attachment thereof to a member, for example, a blade for regulating the layer of the toner easily occur.
  • the volume average particle diameter of a toner is too large, it is difficult to obtain quality images with high definition.
  • the particle diameter of the toner significantly varies in most cases.
  • the ratio of the weight average particle diameter to the number average particle diameter of a toner is greater than, for example, 1.20, it is found that the same applies to the toner.
  • the average particle diameter and size distribution of a toner can be measured by Coulter Counter method.
  • COULTER COUNTER TA-II COULTER MULTI-SIZER IIe (both are manufactured by Beckman Coulter Inc.).
  • COULTER COUNTER MULTI-SIZER TA-II is connected to an interface (manufactured by the institute of Japanese Union of Science and Engineers) and a PC9801 personal computer (manufactured by NEC Corporation) to measure the number distribution and the volume distribution.
  • the measuring method is described below.
  • the whole range is a particle diameter of from 2.00 to not greater than 40.30 ⁇ m and the number of the channels is 13.
  • These channels are: from 2.00 to not greater than 2.52 ⁇ m; from 2.52 to not greater than 3.17 ⁇ m; from 3.17 to not greater than 4.00 ⁇ m; from 4.00 to not greater than 5.04 ⁇ m; from 5.04 to not greater than 6.35 ⁇ m; from 6.35 to not greater than 8.00 ⁇ m; from 8.00 to not greater than 10.08 ⁇ m; from 10.08 to not greater than 12.70 ⁇ m; from 12.70 to not greater than 16.00 ⁇ m, from 16.00 to not greater than 20.20 ⁇ m; from 20.20 to not greater than 25.40 ⁇ m; from 25. 40 to not greater than 32.00 ⁇ m; and from 32.00 to not greater than 40.30 ⁇ m.
  • the volume average particle diameter (Dv) obtained by the volume distribution, the number average particle diameter (Dv) obtained by the number distribution and the ratio (Dv/Dn) are obtained.
  • the toner of the present invention when used in a two-component developing agent, the toner can be mixed with a magnetic carrier for use.
  • the content ratio of toner to carrier in a developing agent is preferably from 1 to 10 parts by weight based on 100 parts by weight of the carrier.
  • Suitable magnetic carriers for use in a two component developer include known carrier materials, for example, iron powders, ferrite powders, magnetite powders, magnetic resin carriers, which have a particle diameter of from about 20 to about 200 ⁇ m.
  • carrier materials for example, iron powders, ferrite powders, magnetite powders, magnetic resin carriers, which have a particle diameter of from about 20 to about 200 ⁇ m.
  • the surface of the carriers may be coated by a resin.
  • Such resins to be coated on the carriers include amino resins such as urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins, and epoxy resins.
  • vinyl or vinylidene resins for example, acrylic resins, polymethylmethacrylate resins, polyacrylonitirile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins, styrene-acrylic copolymers, halogenated olefin resins, for example, polyvinyl chloride resins, polyester resins, for example, polyethyleneterephthalate resins and polybutyleneterephthalate resins, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoropropylene resins,
  • an electroconductive powder may be included in the toner.
  • electroconductive powders include metal powders, carbon blacks, titanium oxide, tin oxide, and zinc oxide.
  • the average particle diameter of such electroconductive powders is preferably not greater than 1 ⁇ m. When the particle diameter is too large, it is hard to control the resistance of the resultant toner.
  • the toner of the present invention can also be used as a one-component magnetic developer or a one-component non-magnetic developer.
  • the status how wax particles are dispersed in a toner particle and on the surface thereof can be found by observing a slice of the toner particle with a transmission electron microscope (TEM). According to this observation, it is found that wax particles having a diameter from 0.2 to 1.0 ⁇ m are dispersed near the surface of a toner particle. Portion near the surface is quantity-analyzed.
  • ATR-IR when the relative strength of wax particles is measured using a wavelength of 2, 850 cm -1 , C-H vibration of the wax can be measured. The depth of measurement is about 0.3 ⁇ m and is from 0.2 to 1.2 ⁇ m considering the accuracy of absorption wavelength.
  • the content of wax is quantified by X ray irradiation analysis, for example, ESCA but the analysis depth is not less than 2 ⁇ m, almost all of the put-in content of wax is the value obtained.
  • a wax dispersing agent is used for dispersing wax near the surface of a toner particle.
  • the status of dispersion can be controlled by the amount of a wax dispersing agent.
  • the dispersing agent for use in the present invention has typically, for example, a grafted polymer (C) the structure of which is that at least some of a polyolefin resin (A) is grafted by a vinyl based resin (B).
  • a releasing agent is encapsulated in the graft polymer (C).
  • Encapsulation represents "since the portion of polyolefin resin (A) in a graft polymer (C) is compatible with a releasing agent, the releasing agent is selectively taken in or attached to the portion of the polyolefin resin (A) in the graft polymer (C)".
  • a toner When a toner is made as follows: (1) a toner component containing a polyester resin is dissolved and/or dispersed in an organic medium; (2) the resultant solution or dispersion body is dispersed in an aqueous medium under the presence of an inorganic dispersing agent or polymer particulates to conduct polyaddition reaction of the resultant solution or dispersion body; and (3) the solvent of the obtained emulsified dispersion body is removed, graft polymer (C) in which at least some of a polyolefin resin (A) is modified by a vinyl based resin (B) is positioned between a releasing agent and a toner binder.
  • graft polymer (C) in which at least some of a polyolefin resin (A) is modified by a vinyl based resin (B) is positioned between a releasing agent and a toner binder.
  • Poor dispersion means that the release agent having a high polar linkage portion is negatively attached to a modified polyester as a toner binder at the interface therebwtween so that the releasing agent selectively moves to the surface of the toner particle and the release agent having a few high polar linkage portion moves to the center of the toner particle. Also the releasing agent can quickly have an effect when the releasing agent passes through a fixing device since the toner securely has a releasing agent having a suitable dispersion particle diameter near the surface thereof.
  • a graft polymer (C) when a graft polymer (C) has a large dispersion particle diameter in the resin, the graft polymer (C) easily takes in or attracts a releasing agent so that the releasing agent easily oozes or detaches from the toner.
  • a releasing agent encapsulated therein tends to have a large dispersion particle diameter.
  • the content of a releasing agent contained in a graft polymer (C) is from 33 to 1,000 parts by weight, preferably from 50 to 300 parts by weight based on 100 parts of the graft polymer (C). It is preferred that at least 80 %, preferably 90 %, of all wax contained in a toner is contained in a graft polymer (C).
  • a process cartridge can be detachably attached to the main body of an image forming apparatus, for example, a photocopier and a printer, which integrally includes an image bearing member (e.g., a photoreceptor) and a developing device with optional devices, for example, a charging device, a cleaning device and a transfer device.
  • an image bearing member e.g., a photoreceptor
  • a developing device with optional devices, for example, a charging device, a cleaning device and a transfer device.
  • Fig. 3 is a conceptual diagram illustrating an example of a process cartridge 10 containing the toner of the present invention:
  • This process cartridge 10 has a drum form photoreceptor 1 as a latent image bearing member around which a non-contact closely positioned roller type charging device 3, a developing device 2 and a cleaning device 4 are arranged.
  • the developing device 2 includes a developing agent accommodation portion, a toner accommodation portion connected thereto via a toner replenishing path, a magnet roller, a developing agent supply regulating device and a developing agent accommodation case.
  • the developing agent accommodation portion magnetically scoops a developing agent formed of a toner and a magnetic carrier and charges the developing agent by stirring with a developing agent stirring device.
  • the charged developing agent is supplied to a development sleeve.
  • the developing agent supply regulating device regulates the amount of a developing agent supplied to the development sleeve.
  • the toner accommodation portion has a toner stirring device.
  • the cleaning device 4 has a collected toner accommodation tank to accommodate toner scraped down by a cleaning blade from the development surface.
  • the invention also relates to a method of manufacturing a toner particle comprising dispersing or emulsifying a toner constituent liquid mixture comprising an organic solvent, a colorant, the binder resin and/or a precursor of the binder resin, a releasing agent having a melting point of from 65 °C to 80 °C and a laminar inorganic mineral in which part or all ions present between layers therein are modified by organic ions, in an aqueous medium comprising water to obtain a liquid dispersion or an emulsion; and removing the organic solvent and water from the liquid dispersion or the emulsion, the method preferably producing a toner particle having a structure such that when the particle is heated at a temperature ranging from 65 to 90 °C the releasing agent is melted on the outside of the toner particle to form a colored particle having a sea-island structure.
  • the invention method preferably uses a constituent liquid mixture having a Casson yield value of from 1 to 10 Pa at 25 °C
  • Particulate liquid dispersion 1 an aqueous liquid dispersion (Particulate liquid dispersion 1) of a vinyl based cross-linking resin (i.e., a copolymer of styrene, methacrylic acid, and butyl acrylate) is obtained.
  • the volume average particle diameter of Particulate liquid dispersion 1 is 50 nm when measured by LA-920.
  • Particulate liquid dispersion 2 is prepared in the same manse as in Particulate liquid dispersion 1 except that
  • Particulate liquid dispersion 2 of a vinyl based cross-linking resin (i.e., a copolymer of styrene, methacrylic acid, and butyl acrylate) is obtained.
  • the volume average particle diameter of Particulate liquid dispersion 1 is 20 nm when measured by LA-920.
  • Particulate liquid dispersion 2 of a vinyl based cross-linking resin (i.e., a copolymer of styrene, methacrylic acid, and butyl acrylate) is obtained.
  • the volume average particle diameter of Particulate liquid dispersion 1 is 20 nm when measured by LA-920.
  • a binder resin (polyester resin: formed of adduct of Bisphenol A with propylene oxide succinic acid derivative, manufactured by Sanyo Chemical Industries Ltd., acid value: 10, Tg: 52 °C) is mixed and kneaded for 15 minutes by a two-roll with a setting of the roll surface temperature of 110 °C and the roll gap of 2 mm. Then, 10 parts of modified montmorillonite (Clayton HY, manufactured by Wilbur-Ellis Co., Ltd.) are placed into the polyester resin, kneaded for 30 minutes and cooled down to room temperature. The resultant is pulverized by a pulverizer to a size of 2 mm ⁇ to obtain Modified laminar inorganic mineral dispersion body 1.
  • a binder resin (polyester resin: formed of adduct of Bisphenol A with propylene oxide succinic acid derivative, manufactured by Sanyo Chemical Industries Ltd., acid value: 10, Tg: 52 °C) is mixed and kneaded for 15 minutes by a two-roll with a setting of the roll surface temperature of 110 °C and the roll gap of 2 mm. Then, 10 parts of modified montmorillonite (Clayton APA, manufactured by Wilbur-Ellis Co., Ltd.) are placed into the polyester resin, kneaded for 30 minutes and cooled down to room temperature. The resultant is pulverized by a pulverizer to a size of 2 mm ⁇ to obtain Modified laminar inorganic mineral dispersion body 2.
  • a binder resin polyester resin: formed of adduct of Bisphenol A with propylene oxide succinic acid derivative, manufactured by Sanyo Chemical Industries Ltd., acid value: 10, Tg: 52 °C
  • Particle liquid dispersion 1 Eighty (80) parts of Particle liquid dispersion 1 are mixed with 990 parts of water, 40 parts of a 48.5 % aqueous solution of sodium dodecyldiphenyletherdisulfonate (EREMINOR MON-7 manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate and a milk white liquid (Aqueous phase 1) is obtained.
  • EREMINOR MON-7 sodium dodecyldiphenyletherdisulfonate
  • Particle liquid dispersion 2 Eighty (80) parts of Particle liquid dispersion 2 are mixed with 990 parts of water, 40 parts of a 48.5 % aqueous solution of sodium dodecyldiphenyletherdisulfonate (EREMINOR MON-7 manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate and a milk white liquid (Aqueous phase 2) is obtained.
  • EREMINOR MON-7 sodium dodecyldiphenyletherdisulfonate
  • Particle liquid dispersion 3 Eighty (80) parts of Particle liquid dispersion 3 are mixed with 990 parts of water, 40 parts of a 48.5 % aqueous solution of sodium dodecyldiphenyletherdisulfonate (EREMINOR MON-7 manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate and a milk white liquid (Aqueous phase 3) is obtained.
  • EREMINOR MON-7 sodium dodecyldiphenyletherdisulfonate
  • Low molecular weight polyester resin 1 Forty five (45) parts of trimellitic anhydride is added in the container to conduct a reaction at 180 °C under normal pressure for 2 hours and obtain Low molecular weight polyester resin 1.
  • the weight average molecular weight (Mw) of Low molecular weight polyester resin 1 is 4,500 and the acid value thereof is 28.
  • Intermediate body polyester 1 Adduct of bisphenol A with 2 mole of ethylene oxide 712 parts Adduct of bisphenol A with 2 mole of propylene oxide 84 parts Terephthalic acid 292 parts Trimellitic anhydrate 32 parts Dibutyl tin oxide 2 parts
  • the obtained Intermediate body polyester 1 has a number average molecular weight of 2,100, a weight average molecular weight of 10,500, a glass transition temperature of 55 °C, an acid value of 0.5 mgKOH/g and a hydroxyl value of 49 mgKOH/g.
  • Prepolymer 1 Intermediate body polyester 1 411 parts Isophorone diisocyanate 89 parts Ethyl acetate 500 parts
  • Prepolymer 1 has an isolated isocyanate weight % of 1.48 %.
  • Ketimine compound 1 In a reaction container equipped with a stirrer and a thermometer, 60 parts of isophoronediamine and 140 parts of methyl ethyl ketone are mixed to obtain Ketimine compound 1. The amine value of Ketimine compound 1 is 408.
  • the mixture is mixed and kneaded for 60 minutes by a two-roll with the surface temperature of the rolls of 130°C.
  • the resultant is pulverized to a size of 1 mm ⁇ to obtain Master batch 1.
  • the mixture is agitated, heated to 80 °C, and kept at 80 °C for 5 hours and then cooled down to 30°C in 1 hour. Then, 500 parts of Master batch 1 and 500 parts of ethyl acetate are added to the reaction container and mixed for 1 hour to obtain Liquid material 1.
  • Liquid material 1, 110 parts of Laminar inorganic mineral 1 are transferred to a reaction container and dispersed using a bead mill (ULTRAVISCOMILL from AIMEX) under the following conditions to disperse the laminar inorganic mineral, carbon black and the wax:
  • the following components are contained in a container to be mixed for 1 minute using a TK HOMOMIXER (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotation of 5,000 rpm.
  • Pigment wax liquid dispersion 1 618 parts Prepolymer 1 115 parts Ketimine compound 1 6.6 parts
  • Emulsion slurry 1 is prepared.
  • Emulsion slurry 1 is added and heated at 30 °C for 8 hours to remove the solvents therefrom. Subsequent to aging at 45 °C for 4 hours, Slurry dispersion 1 is obtained.
  • Emulsion slurry 1 One hundred (100) parts of Emulsion slurry 1 are filtered by filtering under a reduced pressure. Then the following operations are performed.
  • Filtered cake 1 is dried for 48 hours at 45 °C using a circulating drier. The dried cake is sieved using a screen having openings of 75 ⁇ m.
  • One hundred (100) parts of the toner particles, 0.5 parts of hydrophobic silica and 0.5 parts of hydrophobic titan oxide are mixed in a HENSCHEL MIXER to prepare Toner 1 (volume average particle diameter: 5.85 ⁇ m, number average particle diameter: 4.33 ⁇ m, measured by MULTISIZER II).
  • Toner 2 is manufactured in the same manner as in Example 1 except that 110 parts of Laminar inorganic mineral dispersion body 1 of Manufacturing Example 2 is changed to 220 parts of Laminar inorganic mineral dispersion body 2 of Manufacturing Example 3 and Aqua phase 1 is changed to Aqua phase 2.
  • Toner 2 has a volume average particle diameter (Dv) of 5.65 ⁇ m, a number average particle diameter (Dn) of 5.09 ⁇ m and Dv/Dn is 1.11.
  • Low molecular weight polyester resin 1 A reaction is conducted at 180 °C under normal pressure for 2 hours to obtain Low molecular weight polyester resin 2.
  • the weight average molecular weight (Mw) of Low molecular weight polyester resin 1 is 3,900, Tg is 58 °C and the acid value thereof is 16.5.
  • the mixture is agitated, heated to 80 °C, and kept at 80 °C for 5 hours and then cooled down to 30 °C in 1 hour. Then, 500 parts of Master batch 1 and 500 parts of ethyl acetate are added to the reaction container and mixed for 1 hour to obtain Liquid material 2.
  • Liquid material 2 1,224 parts are transferred to a reaction container and dispersed using a bead mill (ULTRAVISCOMILL from AIMEX) under the following conditions to disperse carbon black and the wax:
  • Toner 3 is manufactured in the same manner as in Example 2 except that Pigment wax liquid dispersion 2 is used instead of Pigment wax liquid dispersion 1.
  • Toner 3 has a volume average particle diameter (Dv) of 4.95 ⁇ m, a number average particle diameter (Dn) of 4.19 ⁇ m and Dv/Dn is 1.18.
  • Toner 4 is manufactured in the same manner as in Example 2 except that 115 parts of Prepolymer 1 is changed to 50 parts. Toner 4 has a volume average particle diameter (Dv) of 5.60 ⁇ m, a number average particle diameter (Dn) of 4.96 ⁇ m and Dv/Dn is 1.13.
  • Dv volume average particle diameter
  • Dn number average particle diameter
  • Cyan pigment (ECB-301, manufactured by Dainichiseika Color & Chemicals Mfg.Co.,Ltd.) 40 parts
  • Binder resin Polyester resin (manufactured by SanyoKasei Co., Ltd., acid value: 10, Mw: 7,000, Tg: 52 °C) Water 20 parts
  • the mixture is mixed and kneaded for 60 minutes by a two-roll with the surface temperature of the rolls of 130 °C.
  • the resultant is pulverized to a size of 1 mm ⁇ to obtain Master batch 2.
  • Magenta pigment PR-F6B, manufactured by Clariant
  • Binder resin Polyester resin (manufactured by SanyoKasei Co., Ltd., acid value: 10, Mw: 7,000, Tg: 52 °C) Water 20 parts
  • the mixture is mixed and kneaded for 60 minutes by a two-roll with the surface temperature of the rolls of 130 °C.
  • the resultant is pulverized to a size of 1 mm ⁇ to obtain Master batch 4.
  • the mixture is agitated, heated to 80 °C, and kept at 80 °C for 5 hours and then cooled down to 30 °C in 1 hour. Then, 500 parts of Master batch 2 and 500 parts of ethyl acetate are added to the reaction container and mixed for 1 hour to obtain Liquid material 3.
  • Liquid material 2 1,324 parts are transferred to a reaction container and dispersed using a bead mill (ULTRAVISCOMILL from AIMEX) under the following conditions to disperse carbon black and the wax:
  • the following components are contained in a container to be mixed for 1 minute using a TK HOMOMIXER (manufactured by Tokushu Kika Kogyo Co., Ltd.) at a rotation of 5,000 rpm.
  • Pigment wax liquid dispersion 3 618 parts
  • Laminar inorganic mineral dispersion body 2 220 parts
  • Prepolymer 1 115 parts
  • Ketimine compound 1 6.6 parts
  • Emulsion slurry 2 is prepared.
  • This mixture is transferred to a beaker equipped with a thermometer having an oar type stirring stick.
  • the peripheral speed of stirring stick can be faster than 5 m/s.
  • Forty (40) parts of viscosity improver (CELLOGEN BS-H-3, manufactured by Dai-ichi Kogyo Seiyaku Kogyo Co., Ltd.) are added to the slurry and the mixture is rapidly stirred at 30 °C for 2 hours at the peripheral speed of 6 m/s to obtain mother toner particles having a spindle form.
  • the stirring time can be prolonged.
  • the solvent is removed with a reduced pressure at a temperature not higher than 50 °C in 1 hour.
  • Toner 5 volume average particle diameter: 5.32 ⁇ m, number average particle diameter: 4.25 ⁇ m, measured by
  • Emulsion slurry 3 is manufactured in the same manner as in Example 5 except that Master batch 2 is replaced with Master batch 3 to obtain Toner 6 (volume average particle diameter (Dv): 5.95 ⁇ m, number average particle diameter (Dn) : 5.04 ⁇ m, Dv/Dn: 1.18).
  • Emulsion slurry 4 is manufactured in the same manner as in Example 5 except that Master batch 2 is replaced with Master batch 4 to obtain Toner 7 (volume average particle diameter (Dv): 4.85 ⁇ m, number average particle diameter (Dn): 4.61 ⁇ m, Dv/Dn: 1.05).
  • Toner 8 is obtained in the same manner as in Example 1 except that 115 parts of Prepolymer 1 and 6.6 parts of Ketimine Compound 1 are removed. Toner 8 has a volume average particle diameter (Dv) of 3.65 ⁇ m, a number average particle diameter (Dn) of 3.11 ⁇ m and a ratio (Dv/Dn) of 1.17.
  • Dv volume average particle diameter
  • Dn number average particle diameter
  • Dv/Dn ratio
  • Toner 9 is obtained in the same manner as in Example 5 except that 115 parts of Prepolymer 1 and 6.6 parts of Ketimine Compound 1 are removed. Toner 9 has a volume average particle diameter (Dv) of 5.30 ⁇ m, a number average particle diameter (Dn) of 4.77 ⁇ m and a ratio (Dv/Dn) of 1.11.
  • Black toner which is manufactured in Example 4, cyan toner, which is manufactured in Example 5, magenta toner, which is manufactured in Example 6, and yellow toner, which is manufactured in Example 7, are used.
  • a covered carrier in which a ferrite core material having an average particle diameter of 50 ⁇ m is coated by 0.75 % by weight of a resin of a copolymer of 2 hydroxyethyl methacrylate, methyl methacrylate and styrene and a copolymer of vinylidene fluoride and tetrafloroethylen with a weight ratio of 75/25 covers around based on the weight of the core material.
  • a developing agent is manufactured such that the toner density is 5 % and the total weight of the toner and the carrier is measured to be 1,000 g.
  • Each color developing agent in each color developing unit is used.
  • a scorotron charger, a urethane cleaning blade and a fixing roller are used.
  • Initiator aqueous solution which 2.1 g of Potassium persulfate is dissolved in 120 ml of distilled water is added to the mixture followed by a 3-hour stirring in a nitrogen atmosphere at 70 °C to complete polymerization.
  • Polymer binder particulate liquid dispersion 1 is obtained after cooling down to room temperature.
  • Initiator aqueous solution which 11.2 g of Potassium persulfate is dissolved in 600 ml of distilled water is added to the mixture followed by a 3-hour stirring in a nitrogen atmosphere at 70 °C to complete polymerization.
  • Low molecular weight binder particulate liquid dispersion 2 is obtained after cooling down to room temperature.
  • an aqueous solution of sodium chloride in which 50 g of sodium chloride is dissolved in 600 ml of distilled water and an aqueous solution of surface active agent in which 77 ml of isopropanol and 10 mg of Fluorade FC-1700 (fluorine based nonion surface active agent, manufactured by 3 M ) in 10 ml are sequentially added to the mixture while stirring. After heating the resultant to an inner temperature of 85 °C and a 6-hour reaction, the resultant is cooled down to room temperature. An aqueous solution of 5N-sodium hydroxide is used to adjust PH of the reaction solution to be 13 and the resultant is filtered.
  • Comparative Toner 1 volume average particle diameter (Dv): 6.52 ⁇ m, number average particle diameter (Dn): 5.31 ⁇ m, the ratio (Dv/Dn): 1.23)
  • Comparative Toner 2 is manufactured in the same manner as in Example 1 except that the laminar inorganic mineral is not added.
  • Comparative Toner 2 has a volume average particle diameter (Dv) of 5.60 ⁇ m, a number average particle diameter (Dn) of 4.14 ⁇ m and Dv/Dn is 1.35.
  • Comparative Toner 3 is manufactured in the same manner as in Example 3 except that paraffin wax is replaced with ethylene wax (melting point: 110 °C, manufactured by Sanyo Chemical Industries Ltd.).
  • Comparative Toner 3 has a volume average particle diameter (Dv) of 5.65 um, a number average particle diameter (Dn) of 4.51 ⁇ m and Dv/Dn is 1.25.
  • a developing agent of a toner having 5 % by weight and a copper-zinc ferrite carrier having 95 % by weight the surface of which is covered with a silicone resin is prepared.
  • the toner has been subject to external additive treatment.
  • the carrier has an average particle diameter of 40 ⁇ m.
  • a high elevated flow tester (CFT 500D type, manufactured by Shimadzu Corporation) can be used as a flow tester.
  • Flow curve by this flow tester is as shown in Fig. 4 .
  • Each temperature can be read from the graph in Fig. 4 .
  • Ts represents a softening temperature
  • Tfb represents flow starting temperature
  • melting point is T1/2.
  • the amount of charge is obtained by setting 6 g of a developing agent in a sealable metal cylinder for blow.
  • the toner density is from 4.5 to 5.5 % by weight.
  • Toner is tested using imagio Neo 450 (manufactured by Ricoh, Co., Ltd.) for solid image on plain (Type 6200, manufactured by Ricoh, Co., Ltd.) and thick (Photocopying paper ⁇ 135>, manufactured by Ricoh, Co., Ltd.) transfer paper with a toner density of from 0.9 to 1.1 mg/cm 2 .
  • the temperature of a fixing belt can be variably adjusted. The temperature below which offset occurs is measured for the plain paper. The lowest fixing temperature is measured for the thick paper. The lower limit fixing temperature is determined as the fixing roll temperature below which the remaining ratio of the image density is less than 70 % after the fixed image is rubbed by a pad.
  • 10.6 g of the toner is set in a 50 ml sample bottle followed by tapping for 35 seconds.
  • the bottle is preserved in a constant temperature bath at 50 °C for 24 hours and the toner is measured by a penetrometer.
  • the melting point and the glass transition temperature (Tg) of the releasing agent for use in the present invention can be measured by a Differential Scanning Calorimeter (DSC).
  • the melting point of the wax can be determined by the peak top which indicates the maximum endothermic amount.
  • the measuring is performed by TA-60WS (manufactured by Shimadzu Corporation) and DSC-60 under the following conditions:
  • the measurement results are analyzed by data analysis software (TA-60, version 1.52, manufactured by Shimadzu Corporation) .
  • the peak temperature is obtained by the analysis method in which the peak analysis function of the analysis software is used with a range setting of from a temperature - 5 °C lower than the maximum peak point of DrDSC curve which is DSC differential curve on the second temperature rise to + 5 °C higher than the point.
  • the obtained temperature corresponds to the melting point.
  • Tg of the resin is measured by the following method.
  • a sample is set in an aluminum sample container.
  • the container is set on a holder unit and the holder unit is set in an electric furnace.
  • the sample is heated from room temperature to 150 °C at a temperature rising rate of 10 °C/min and held at 150 °C for 10 minutes.
  • After cooled down to room temperature the sample is left for 10 minutes and heated again in a nitrogen atmosphere to 150 °C at a temperature rising rate of 10 °C/min for DSC measurement.
  • TG is analyzed by using TA-60 (version 1.52) and calculated by the intersectional point of the tangent of endothermic curve near Tg and the base line.
  • Toner is tested using imagio Neo 450 (manufactured by Ricoh, Co., Ltd.) for solid image on plain (Type 6200, manufactured by Ricoh, Co., Ltd.) and thick (Photocopying paper ⁇ 135>, manufactured by Ricoh, Co., Ltd.) transfer paper.
  • imagio Neo 450 manufactured by Ricoh, Co., Ltd.
  • plain Type 6200, manufactured by Ricoh, Co., Ltd.
  • thick Photocopying paper ⁇ 135>, manufactured by Ricoh, Co., Ltd.
  • a white image is suspended in the middle of development and the developing agent on an image bearing member after development is transferred by a tape.
  • the difference between the image density of the tape and that of a non-transferred tape is measured by 938 spectrodensitometer (manufactured by X-Rite Incorporated).
  • Toner remaining after transfer on an image bearing member after cleaning process is transferred to white paper by a Scotch (manufactured by Sumitomo 3M).
  • the white paper is measured by Macbeth reflection densitometer RD514 type. A difference between blank paper and the white paper that is not greater than 0.01 is evaluated as G (good) and that is greater than 0.01 is determined as B (bad).
  • a 600 dpi image is printed using imagio Neo 450 (optical system laser: 600 dpi, manufactured by Ricoh Co., ltd.) and observed by an optical microscope with a magnification power of 20x for the following 3 rank rating against sample for each rank: G (good), F (fair), B (bad).
  • imagio Neo 450 optical system laser: 600 dpi, manufactured by Ricoh Co., ltd.
  • GPC Gel Permeation Chromatography measuring method is described below.
  • a column is stabilized in a heat chamber at 40 °C.
  • Tetrahydrofuran (THF) is used as a solvent and flown at a rate of 1 ml/min.
  • a resin THF solution which is adjusted such that the sample density is 0.05 to 0.6 % by weight is poured in an amount of 50 to 200 ⁇ l for measurement.
  • the molecular weight distribution of the sample is calculated by the relationship between the count number and the logarithm value of the analytical curve made based on several kinds of simple dispersion polystyrene standard sample.
  • polystyrene standard samples for making analytical curve for example, polystyrenes having a molecular weigh of 6 ⁇ 10 2 , 2.1 ⁇ 10 2 , 4 ⁇ 10 2 , 1.75 ⁇ 10 4 , 5.1 ⁇ 10 4 , 1.1 ⁇ 10 5 , 3.9 ⁇ 10 5 , 8.6 ⁇ 10 6 , 2 ⁇ 10 5 or 4.48 ⁇ 10 6 .
  • At least 10 polystyrene samples are desired to be used.
  • a refraction index (RI) detector is used as the detector.
  • Weight average molecular weight (Mw), Number average molecular weight (Mn) and the ratio (Mw/Mn) are automatically calculated from the obtained values.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Developing Agents For Electrophotography (AREA)

Claims (11)

  1. Toner, umfassend ein Tonerteilchen, wobei das Toner-Teilchen folgendes umfasst:
    ein Bindeharz;
    ein Farbmittel;
    ein Trennmittel mit einem Schmelzpunkt von 65 °C bis 80 °C; und
    ein anorganisches Schichtmineral, in dem ein Teil oder alle Ionen, die zwischen Schichten darin vorhanden sind, durch organische Ionen modifiziert sind,
    wobei das Tonerteilchen durch ein Verfahren hergestellt wird, umfassend Dispergieren oder Emulgieren eines flüssigen Toner-Bestandteilgemisches, umfassend ein organisches Lösungsmittel, ein Farbmittel, mindestens ein Element, ausgewählt aus der Gruppe, bestehend aus dem Bindeharz und einem Vorläufer des Bindeharzes, dem Trennmittel, und dem anorganischen Schichtmineral, in einem wässrigen Medium, umfassend Wasser, um eine flüssige Dispersion oder eine Emulsion zu erhalten, und Entfernen des organischen Lösungsmittels und des Wassers aus der flüssigen Dispersion oder Emulsion.
  2. Toner nach Anspruch 1, wobei ein volumenmittlerer Teilchendurchmesser (Dv) des Toners 3 bis 6 µm beträgt, ein Verhältnis (Dv/Dn) eines volumenmittleren Teilchendurchmessers (Dv) zu einem zahlenmittleren Teilchendurchmesser (Dn) 1,00 bis 1,30 beträgt und das Bindeharz eine Glasübergangstemperatur (Tg) 40 bis 55 °C beträgt und ein gewichtsmittleres Molekulargewicht (Mw) 3000 bis 6500 beträgt.
  3. Toner nach Anspruch 1 oder 2, wobei das flüssige Toner-Bestandteilgemisch ein Polyester-Prepolymer umfasst das mindestens eine Isocyanatgruppe und eine Verbindung umfasst, zur Durchführung einer Dehnungsreaktion in dem flüssigen Toner-Bestandteilgemisch in dem wässrigen Medium umfasst.
  4. Toner nach einem der Ansprüche 1 bis 3, wobei der Anteil des Trennmittels mit einem Dispersionsteilchendurchmesser von 0,3 bis 1,0 µm nicht größer als 70 Zahlen-% in dem Tonerteilchen ist.
  5. Verfahren zur Herstellung eines Tonerteilchens, umfassend:
    Dispergieren oder Emulgieren eines flüssigen Toner-Bestandteilgemisches, umfassend ein organisches Lösungsmittel, ein Farbmittel, mindestens ein Element, ausgewählt aus der Gruppe, bestehend aus dem Bindeharz und einem Vorläufer des Bindeharzes, einem Trennmittel mit einem Schmelzpunkt von 65 bis 80 °C und einem anorganischen Schichtmineral, in dem ein Teil oder alle Ionen, die zwischen Schichten darin vorhanden sind, durch organische Ionen modifiziert sind, in einem wässrigen Medium, umfassend Wasser, um eine flüssige Dispersion oder eine Emulsion zu erhalten, und
    Entfernen des organischen Lösungsmittels und des Wassers aus der flüssigen Dispersion oder Emulsion.
  6. Verfahren zur Herstellung eines Toners nach Anspruch 5,
    wobei das flüssige Toner-Bestandteilgemisch eine Casson-Fliessgrenze von 1 bis 10 Pa bei 25 °C besitzt.
  7. Entwicklungsmittel, umfassend:
    den Toner nach einem der Ansprüche 1 bis 4; und
    einen Träger.
  8. Bildformungsgerät umfassend:
    ein bildtragendes Element, das konfiguriert ist, um darauf ein latentes Bild zu tragen;
    eine Ladungsvorrichtung, die konfiguriert ist, um das bildtragend Element zu laden;
    eine Entwicklungsvorrichtung, die konfiguriert ist, um das latente Bild zu entwickeln;,
    wobei die Entwicklungsvorrichtung den Toner nach einem der Ansprüche 1 bis 4 umfasst;
    eine Übertragungsvorrichtung, die konfiguriert ist, um das latente Bild auf einen Übertragungskörper zu übertragen;
    eine Entladevorrichtung, die konfiguriert ist, um das bildtragend Element zu entladen; und
    eine Reinigungsvorrichtung, die konfiguriert ist, um die Oberfläche des bildtragenden Elements zu reinigen.
  9. Verfahren zum Bilden eines Bilds, umfassend:
    Laden eines bildtragenden Elements durch eine Ladungsvorrichtung;
    Bestrahlen des bildtragenden Elements durch eine Bestrahlungsvorrichtung, um ein latentes elektrostatisches s Bild darauf zu bilden;
    Entwickeln des latenten elektrostatischen Bildes auf dem bildtragenden Element mit dem Toner nach einem der Ansprüche 1 bis 4;
    Entfernen von auf dem bildtragenden Element verbleibendendem Resttoner durch eine Reinigungsvorrichtung
    und
    Übertragen des Tonerbildes auf einen Übertragungskörper.
  10. Tonerbehälter, umfassend einen Behälter und, darin, den Toner nach einem der Ansprüche 1 bis 4.
  11. Prozesspatrone, umfassend:
    ein bildtragendes Element, das konfiguriert ist, um ein latentes elektrostatisches Bild zu tragen;
    eine Entwicklungsvorrichtung, die konfiguriert ist, um ein elektrostatisches Bild zu entwickeln, wobei die Entwicklungsvorrichtung den Toner nach einem der Ansprüche 1 bis 4 umfasst; und
    mindestens eine fakultative Vorrichtung, die aus der Gruppe ausgewählt ist, bestehend aus einer Reinigungsvorrichtung, einer Übertragungsvorrichtung, einer Betrahlungsvorrichtung und einer Ladevorrichtung.
EP20070104302 2006-03-17 2007-03-16 Toner, Verfahren zu seiner Herstellung, Bilderzeugungsgerät, Prozesskartusche und Bilderzeugungsverfahren Active EP1835351B1 (de)

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EP1903403B1 (de) * 2006-09-19 2015-11-04 Ricoh Company, Ltd. Bilderzeugungsvorrichtung und Prozesskartusche mit Toner
US20080213682A1 (en) * 2007-03-02 2008-09-04 Akinori Saitoh Toner for developing electrostatic image, method for producing the toner, image forming method, image forming apparatus and process cartridge using the toner
JP4909182B2 (ja) * 2007-05-31 2012-04-04 株式会社リコー 静電荷像現像用トナーの製造方法
US7939237B2 (en) 2007-08-17 2011-05-10 Xerox Corporation Nano-sized composites containing polymer modified clays and method for making toner particles using same
US7892714B2 (en) 2007-08-17 2011-02-22 Xerox Corporation Toner particles having nano-sized composites containing polymer modified clays
JP2022117311A (ja) * 2021-01-29 2022-08-10 富士フイルムビジネスイノベーション株式会社 静電荷像現像用トナー、静電荷像現像剤、トナーカートリッジ、プロセスカートリッジ及び画像形成装置

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DE19957245A1 (de) * 1999-11-27 2001-05-31 Clariant Gmbh Verwendung von salzartigen Struktursilikaten als Ladungssteuermittel
DE60225103T2 (de) * 2001-11-02 2009-02-26 Ricoh Co., Ltd. Toner, Verfahren zu dessen Herstellung, sowie sein Bildherstellungsverfahren und Apparat, der den Toner enthält
JP2003202708A (ja) * 2002-01-08 2003-07-18 Kao Corp 電子写真トナー用電荷調整剤
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