WO2008056519A1 - Toner et procédé de production de toner - Google Patents

Toner et procédé de production de toner Download PDF

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Publication number
WO2008056519A1
WO2008056519A1 PCT/JP2007/070350 JP2007070350W WO2008056519A1 WO 2008056519 A1 WO2008056519 A1 WO 2008056519A1 JP 2007070350 W JP2007070350 W JP 2007070350W WO 2008056519 A1 WO2008056519 A1 WO 2008056519A1
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WO
WIPO (PCT)
Prior art keywords
particles
toner
wax
resin
resin particles
Prior art date
Application number
PCT/JP2007/070350
Other languages
English (en)
Japanese (ja)
Inventor
Yasuhito Yuasa
Hidekazu Arase
Kazuhiro Yanagi
Original Assignee
Panasonic Corporation
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Filing date
Publication date
Application filed by Panasonic Corporation filed Critical Panasonic Corporation
Priority to JP2008543023A priority Critical patent/JPWO2008056519A1/ja
Publication of WO2008056519A1 publication Critical patent/WO2008056519A1/fr

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—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
    • G03G9/0827—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
    • G03G9/08784—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
    • G03G9/093—Encapsulated toner particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/093—Encapsulated toner particles
    • G03G9/09392—Preparation thereof

Definitions

  • the present invention relates to a copying machine, a laser printer, plain paper FAX, a color PPC, a color laser printer, a color FAX, and a toner and a toner manufacturing method.
  • the problem with such a toner is that the toner has a high cohesive property, so that the toner image during transfer and the tendency of transfer failure are more prominent, making it difficult to achieve both transfer and fixing.
  • the low melting point component of the toner adheres to the carrier surface due to collisions between particles, friction, or mechanical collisions such as collision between particles and developer, friction, etc., and heat generated by friction.
  • the charging ability of the carrier which is prone to scavenging, is reduced, which hinders the extension of the developer life.
  • the toner for developing electrostatic charge used in the electrophotographic method is generally a resin component which is a binder resin, a coloring component consisting of a pigment or a dye, a plasticizer, a charge control agent, and if necessary. Consists of added components such as mold release agents! Resins containing natural or synthetic resins alone as resin components are used in a timely mixture.
  • the additive is premixed at an appropriate ratio, heated and kneaded by heat melting, finely pulverized by a gas impingement plate method, and finely classified to complete a toner base.
  • a toner base is prepared by a chemical polymerization method.
  • an external additive such as hydrophobic silica, for example, is added to the toner base to complete the toner.
  • a two-component developer can be obtained by mixing a force toner composed only of toner and a carrier composed of magnetic particles.
  • the particle size can be reduced to about 8 m in actuality from the viewpoint of reducing the particle size!
  • various methods for producing small particle size toners are being studied!
  • a method for realizing oil-less fixing by blending a release agent such as wax in a low softening resin at the time of toner kneading is being studied.
  • a release agent such as wax in a low softening resin
  • adverse effects such as a decrease in toner fluidity, an increase in voids during transfer, and filming on the photoreceptor occur.
  • the surface state of the pulverized particles is uneven, and it is difficult to control the surface smoothness.
  • a method for preparing a toner using an emulsion polymerization method is to form an aggregated particle dispersion by forming aggregated particles in a dispersion obtained by dispersing at least resin particles and colorant particles.
  • a resin fine particle dispersion obtained by dispersing resin fine particles in the dispersion is further added, and the resin fine particles are adhered to the aggregated particles, and heated and fused.
  • Patent Document 1 a toner comprising particles formed by polymerization and a coating layer composed of microparticles formed by emulsion polymerization on the particle surface, a water-soluble inorganic salt is added, It is disclosed that a coating layer made of microparticles is formed on the particle surface, and a coating layer made of microparticles is formed on the particle surface by changing the pH of the solution.
  • the release agent contains at least one ester comprising at least one of a higher alcohol having 12 to 30 carbon atoms and a higher fatty acid having 12 to 30 carbon atoms
  • the resin particles include
  • Patent Document 3 a resin layer (shell) formed by fusing resin particles by a salting-out / fusing method is formed on the surface of colored particles (core particles) containing a resin and a colorant.
  • core particles colored particles
  • toner particles are disclosed and subjected to long-term image formation in a high humidity environment where the amount of colorant present on the particle surface is small, changes in image density due to changes in chargeability and developability, capri The effect of not causing a change in color is described.
  • the toner particles include a core containing resin A and at least one layer covering the core.
  • Patent Document 5 discloses a toner having a shape factor of 100 to 137, forms an aggregate particle dispersion of resin fine particles and a colorant, and the obtained aggregate particle dispersion is used as a resin fine particle.
  • the temperature is raised to the glass transition temperature (Tg) of the particles or more, preferably Tg to Tg + 10 ° C, and the aggregate particles are grown until, for example, the desired toner particle diameter is obtained over 2 hours.
  • Tg glass transition temperature
  • Tg glass transition temperature
  • Tg + 10 ° C the aggregate particles are grown until, for example, the desired toner particle diameter is obtained over 2 hours.
  • the agglomeration is stopped and heated to the same temperature, and the surface of the agglomerated particles are fused and coalesced within 10 hours to form toner particles having a shape factor of 100 to 137. It is disclosed.
  • a toner of 50V ⁇ is disclosed, and at least one resin particle dispersion and at least one colorant dispersion are mixed, an aggregating agent is added to form aggregated particles, and then the resin particle glass is added.
  • a manufacturing method is disclosed in which toner particles are manufactured by fusing the agglomerated particles by heating to a temperature above the point.
  • Patent Document 1 JP-A 57-45558
  • Patent Document 2 JP-A-10-301332
  • Patent Document 3 Japanese Patent Laid-Open No. 2002-116574
  • Patent Document 4 Japanese Patent Laid-Open No. 2004-191618
  • Patent Document 5 Japanese Unexamined Patent Publication No. 2000-131876
  • Patent Document 6 Japanese Unexamined Patent Publication No. 2000-267331
  • the shape of the toner tends to be determined based on the relationship with the image forming process such as development, transfer, and cleaning process.
  • the shape of the toner is a shape index.
  • the toner shape is reduced to a shape factor that is close to a spherical shape to increase the transfer efficiency. Therefore, it is important to be able to arbitrarily control this shape index in order to ensure a design margin for the image forming process.
  • the shape is adjusted by adjusting the temperature and time when the aggregated particles are generated.
  • the adjustment of the temperature causes a change in the particle size distribution, and the shape adjustment and the particle size distribution can be immediately adjusted. It becomes difficult.
  • adjustments depending on the processing time may cause fluctuations in the particle size distribution, immediately affecting the surface smoothness of the particles, and also affecting productivity.
  • the shape factor within the set value the description of the specific method is not sufficient, and it cannot be said that the correlation between the condition of the method and the shape index is sufficiently obtained.
  • the present invention can appropriately control the particle shape without affecting the particle size distribution and the surface smoothness of the particle, and does not require a classification step for a small-sized toner having a narrow particle size distribution. It aims to be able to create.
  • the present invention provides an image forming apparatus capable of preventing hollowing out and scattering during transfer and obtaining high transfer efficiency.
  • the toner of the present invention is a toner containing toner base particles and an external additive, and the toner base particles are at least binder resin particles that are first resin particles in an aqueous medium, and second toner particles.
  • the coated resin particles, which are the second resin particles, are fused to the core particles formed by aggregating the shape-adjusting resin particles for adjusting the shape of the toner, which is the third resin particles, and the colorant particles and the wax particles.
  • the softening point of the shape-adjusting resin particles and the covering resin particles is higher than the softening point of the binder resin particles.
  • the toner production method of the present invention is a toner production method comprising toner base particles and an external additive, wherein the toner base particles have at least binder resin particles dispersed in an aqueous medium.
  • the first resin particle dispersion, the third resin particle dispersion in which resin particles for adjusting the shape of the toner are dispersed, the colorant particles in which the colorant particles are dispersed, and the dispersion and wax particles are dispersed.
  • FIG. 1 is a schematic cross-sectional view showing a configuration of an image forming apparatus used in an embodiment of the present invention.
  • FIG. 2 is a schematic sectional view showing the structure of the fixing unit used in the embodiment of the present invention.
  • FIG. 3 is a schematic perspective view of a stirring and dispersing apparatus used in an example of the present invention.
  • FIG. 4 is a schematic plan view of the stirring and dispersing apparatus used in the embodiment of the present invention.
  • FIG. 5 is a schematic sectional view of the stirring and dispersing apparatus used in the embodiment of the present invention.
  • FIG. 6 is a schematic plan view of the stirring and dispersing apparatus used in the embodiment of the present invention.
  • FIG. 7 is a schematic perspective view of a stirring and dispersing apparatus used in an example of the present invention.
  • FIG. 8 is a schematic plan view of the stirring and dispersing apparatus used in the example of the present invention.
  • FIG. 9 is a schematic perspective view of the stirring and dispersing apparatus used in the example of the present invention.
  • FIG. 10 is a schematic plan view of the stirring and dispersing apparatus used in the example of the present invention.
  • FIG. 11 is an explanatory diagram of a method for calculating the softening point (melting temperature in the 1/2 method) of the binder resin by the flow tester of the present invention.
  • FIG. 12 is a scanning electron microscope (SEM, magnification: 5000 times) observation image of the toner ctl prepared in the example of the present invention.
  • FIG. 13 is a SEM observation image (magnification 3000 times) of toner CT2 produced in the example of the present invention.
  • FIG. 14 is an SEM observation image (magnification 3000 times) of toner CT4 produced in an example of the present invention.
  • FIG. 15 is a SEM observation image (magnification 3000 times) of toner ct5 produced in the example of the present invention.
  • FIG. 16 is an SEM observation image (magnification 3000 times) of the toner CT7 produced in the example of the present invention.
  • FIG. 17 is an SEM observation image (magnification 3000 times) of toner CT8 produced in the example of the present invention.
  • FIG. 18 is an SEM observation image of the toner ctl 1 produced in the example of the present invention (magnification 3000 times)
  • FIG. 19 is an explanatory diagram for explaining the shape index of the present invention.
  • the present invention provides a core particle produced by aggregating at least the first resin particles, the third resin particles for adjusting the shape of the toner, the colorant particles, and the wax particles in an aqueous medium.
  • a core particle produced by aggregating at least the first resin particles, the third resin particles for adjusting the shape of the toner, the colorant particles, and the wax particles in an aqueous medium.
  • the resin particle dispersion is prepared by emulsion polymerization or seed polymerization of a bull monomer in a surfactant to obtain a resin particle of a homopolymer or copolymer (bull resin) of a bull monomer.
  • a dispersion is prepared in which is dispersed in a surfactant.
  • the means include high-speed rotary emulsifiers, high-pressure emulsifiers, colloidal emulsifiers, and dispersion devices known per se such as a ball mill, a sand mill, and a dyno mill having media.
  • the resin in the resin particles is a resin other than the homopolymer or copolymer of the bulle monomer
  • the resin has a relatively low solubility in water! If solubilized, the resin is dissolved in the oily solvent, and this solution is finely dispersed in water together with a surfactant and a polymer electrolyte using a disperser such as a homogenizer, and then heated or decompressed. By evaporating the oily solvent, a dispersion is prepared in which resin particles other than the bull resin are dispersed in a surfactant.
  • Polymerization initiators include 2,2'-azobis (2,4 dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1 carbonitryl). ), 2,2'-azobis-4-methoxy-2,4 azo- or diazo polymerization initiators such as dimethylvaleronitrile and azobisisobutyronitrile, and persulfates (potassium persulfate, ammonium persulfate) Etc.), azo compounds (4,4'-azobis 4 cyanovaleric acid and its salts, 2, 2, -Azobis (2-amidinopropane) salt, etc.), baroxide compounds and the like.
  • the colorant particle dispersion is prepared by adding colorant particles in water to which a surfactant has been added, and dispersing the particles using the above-described dispersion means.
  • the wax particle dispersion is prepared by adding wax particles in water to which a surfactant has been added, and dispersing the particles using the above-described means of dispersion.
  • the toner is required to have further low-temperature fixing, high-temperature non-offset property in oil-less fixing, releasability, high translucency of color images, and storage stability under a constant high temperature. Must be satisfied.
  • the toner of the present invention at least the first resin particle dispersion in which the first resin particles are dispersed and the third resin particles for adjusting the shape of the toner are dispersed in the aqueous medium.
  • a third resin particle dispersion, a colorant particle dispersion in which colorant particles are dispersed, and a wax particle dispersion in which wax particles are dispersed are mixed and aggregated to produce core particles.
  • the second resin particle dispersion in which the second resin particles are dispersed is added to the core particle dispersion containing the generated core particles, and the second resin particles are fused to the core particles. It is a toner.
  • the third resin particles are blended in the core particles for the purpose of controlling the shape of the particles.
  • the shape can be changed by changing the aggregation reactivity of the core particles.
  • the softening point in the melt viscosity characteristic of the third resin particle is Ts3 (° C)
  • the softening point in the melt viscosity characteristic of the first resin particle is Tsl ( ° C
  • the state of melting of the agglomerated particles is delayed due to the presence of resin particles having different melting states, By changing the effect of surface tension due to particle melting, the shape can be made into a spherical force potato shape or an indeterminate shape. If the difference between the softening points of the third resin particles and the first resin particles is less than 30 ° C, the state in which the melting of the core particles proceeds can be delayed, and the shape adjustment tends not to proceed well. is there.
  • the third tree If the difference in softening point between the fat particles and the first resin particles exceeds 80 ° C, the aggregation of the core particles is difficult to proceed, and the third resin particles are difficult to be taken into the core particles. May remain in the water system and leave cloudiness in the water system.
  • the weight average molecular weight in the gel permeation chromatogram of the third resin particles is Mwr3 and the weight average molecular weight of the first resin particles is Mwrl, Mwrl XI. 5 ⁇ Mwr3 ⁇ Mwrl X 12 is satisfied. Due to the presence of the third resin particles having a certain weight average molecular weight, the agglomeration reaction during the heat treatment process! /, The presence of the resin particles having different melting states causes the core particles to melt. By delaying, the shape can be changed from a spherical shape to a potato shape or an indeterminate shape.
  • the weight average molecular weight of the third resin particles is less than 1.5 times the weight average molecular weight of the first resin particles, it becomes difficult to delay the state in which the melting of the core particles proceeds, and the shape adjustment power increases. There is no tendency. Conversely, when the weight average molecular weight of the third resin particles exceeds 12 times the weight average molecular weight of the first resin particles, the aggregation of the core particles is difficult to proceed, and the third resin particles are taken into the core particles. The third resin particles are left in the aqueous system and white turbidity tends to remain in the aqueous system.
  • the mixing ratio of the third resin particles is preferably in the range of 2 to 30 parts by weight with respect to 100 parts by weight of the first resin particles. If it is less than 2 parts by weight, it is difficult to obtain the effect of shape adjustment. When the amount exceeds 30 parts by weight, the cohesiveness of the core particles deteriorates, and the third resin particles that are difficult to be incorporated into the core particles tend to remain in the aqueous system and remain cloudy in the aqueous system.
  • the blending ratio of the third resin particles is also related to the softening point or the weight average molecular weight of the third resin particles. The higher the softening point or the weight average molecular weight, the more effective the blending amount becomes. it can.
  • the mixing ratio of the third resin particles is 22 to 30 parts by weight with respect to 100 parts by weight of the first resin particles.
  • Ts3 is Tsl + 45 ° C to Tsl + 65 ° C
  • the blending ratio of the third resin particles is 12-22 parts by weight with respect to 100 parts by weight of the first resin particles
  • Ts3 is Tsl + 65 ° C to Tsl + 80 ° C
  • the blending ratio of the third resin particles is 2 to 12 parts by weight with respect to 100 parts by weight of the first resin particles.
  • the amount of force S should be increased or decreased depending on the target force S and the target shape.
  • the mixing ratio of the third resin particles is in the range of 22 to 30 parts by weight with respect to 100 parts by weight of the first resin particles.
  • Mwrl X 4 to Mwrl X 8 the mixing ratio of the third resin particles is 12 to 22 parts by weight with respect to 100 parts by weight of the first resin particles, Mwr3 force Mwrl X 8 to Mwrl X
  • the ratio is 12
  • the mixing ratio of the third resin particles is 2 to 12 parts by weight with respect to 100 parts by weight of the first resin particles. The amount needs to be increased or decreased.
  • the toner production method of the present invention comprises, in an aqueous medium, at least a first resin particle dispersion in which first resin particles are dispersed, and a third resin particle for adjusting the shape of the toner.
  • a core particle containing core particles produced by mixing and aggregating a dispersed third resin particle dispersion, a colorant particle dispersion in which colorant particles are dispersed, and a wax particle dispersion in which wax particles are dispersed.
  • the second resin particle dispersion liquid in which the second resin particles are dispersed is added to the dispersion liquid, and the second resin particles are manufactured by a method of fusing the core resin particles.
  • the first resin particle dispersion in which the first resin particles are dispersed, and the third resin particles for adjusting the shape of the toner are dispersed. Adjusting the pH of the mixed dispersion of the third resin particle dispersion, the colorant particle dispersion in which the colorant particles are dispersed, and the wax particle dispersion in which the wax particles are dispersed to a certain condition, Add a certain amount of water-soluble inorganic salt. Thereafter, the first resin particles, the third resin particles, the colorant particles, and the wax particles are heated by heating the aqueous medium to the glass transition temperature (Tg) of the first resin particles or higher and / or the melting point of the wax or higher. Aggregated and at least partially melted core particles can be produced.
  • Tg glass transition temperature
  • the residue of the resin particle dispersion is decomposed by the heat during the heat aggregation process, resulting in a pH. May be fluctuated (decreased), so after emulsion polymerization, it will be at a certain temperature (preferably 80 ° C or more in order to sufficiently disperse the residue) for a certain time (about 1 to 5 hours). Preferable,) It is preferable to apply heat treatment.
  • the pH of the produced resin particle dispersion is preferably 4 or less, more preferably 1.8 or less.
  • the pH (hydrogen ion concentration) is measured by using a pipette to remove the liquid to be measured from the liquid tank. Collect 10 ml of the solution in a beaker of the same volume. Immerse this beaker in cold water and cool the sample to room temperature (30 ° C or below). Using a pH meter (Seven Multi: METTLER TOLEDO), immerse the measurement probe in the sample cooled to room temperature. When the meter display is stable, read the value and use it as the pH value.
  • the temperature of the mixed dispersion is raised while stirring the liquid.
  • the temperature rising rate is preferably 0.;! ⁇ 10 ° C / min. Slow productivity decreases. If it is too early, the shape of the particles tends to advance too spherically before the particle surface becomes smooth.
  • the pH of the above-mentioned mixed dispersion is preferably adjusted to a range of 9.5 to 12.2.
  • the pH is adjusted to 10.5-12.2, and more preferably the pH is adjusted to the range of 11.2-12.2.
  • the pH can be adjusted by adding 1N NaOH.
  • a water-soluble inorganic salt is added, and heat treatment is performed to form core particles having a predetermined volume average particle diameter, at least partially melted and aggregated.
  • the pH of the liquid is maintained in the range of 7 to 10; thus, a narrow particle size distribution in which wax containing less wax is contained is contained.
  • Core particles can be formed.
  • the pH is preferably in the range of 8 to 10, more preferably pH in the range of 8.4 to 10;
  • the amount of NaOH to be added, the type and amount of flocculant, the pH of the emulsion polymerization resin dispersion, the pH of the colorant dispersion, the pH of the wax dispersion, the heating temperature, and the time are appropriately selected. If the pH of the liquid when the particles are formed is less than 7, the core particles tend to become coarse. If the pH exceeds 10, there is a tendency for free wax to increase due to poor aggregation.
  • a wide blade shape flat plate blade
  • the Max Blend wing manufactured by Sumitomo Heavy Industries, Ltd. and the full zone wing manufactured by Shinko Pantech Co., Ltd. are effective.
  • Fig. 7 is a schematic diagram showing the configuration of the Max Blend wing
  • Fig. 8 is a plan view seen from above.
  • Fig. 9 shows a schematic diagram of the full zone blade configuration
  • 301 is a shaft connected to a stirring motor (not shown).
  • 302 is a stirring tank
  • 303 is a water surface of the liquid
  • 304 is a flat max blend blade
  • 305 holes are provided in the blade to adjust the stirring strength of the liquid.
  • Reference numeral 306 is a flat rectangular blade, and a stirring blade 307 is provided at the lower portion thereof, and is bent at about 130 degrees at the tip! 308 indicates the length of the stirring blade!
  • the rotational speed of the stirring blade varies depending on the particle concentration in the dispersion and the target particle size, but is preferably 0.5 to 2 ⁇ Om / s. More preferably, 0.7 to 1.8; 1.8 m / s, still more preferably 1.0 to 1.6 m / s. If the speed is too low, the particle size of the generated particles tends to be large and the particle size distribution tends to widen. If the speed is too high, the aggregation of the particles is hindered, and the shape becomes indefinite and the particles can be generated immediately.
  • the first resin particle dispersion, the third resin particle dispersion, the colorant particle dispersion, and the wax in an aqueous medium A mixed dispersion is produced by mixing the particle dispersion. Then, this mixed dispersion is heated, and after the liquid temperature of the mixed dispersion reaches a certain temperature, a water-soluble inorganic salt is added as a flocculant to the mixed dispersion.
  • the first resin particle dispersion, the third resin particle dispersion, and the coloring in an aqueous medium are used.
  • the agent particle dispersion is mixed and agglomerated to agglomerate the resin particles and the colorant particles to produce core particles.
  • the core particle dispersion in which the core particles are dispersed is added to the first resin particle dispersion and the wax particle dispersion. It is also preferable that the core particles are produced by mixing the core particles and aggregating the core particles with the first resin particles and the wax particles.
  • a resin particle dispersion in which resin particles are dispersed and a colorant particle dispersion in which colorant particles are dispersed are mixed to form a mixed solution.
  • a water-soluble inorganic salt is added to the mixed dispersion as an aggregating agent to aggregate the resin particles and the colorant particles, thereby forming the core particles. Is generated.
  • the resin particle dispersion and the nitrogen particle dispersion are added to the core particle dispersion in which the core particles are generated, and the core particles, the resin particles, and the wax are aggregated to form the core particles. Generate. By avoiding direct agglomeration with wax, the function of shape adjustment is more effective.
  • the aggregation reaction takes precedence over the reaction between the resin particles and the colorant particles and between the resin particles and the wax particles.
  • the particles and the wax particles are uniformly incorporated into the core particles, it is possible to form core particles with a small particle size and a narrow particle size distribution in which the wax and the colorant are uniformly encapsulated.
  • the core particle preferably has a structure in which a core particle portion obtained by aggregating resin particles and colorant particles and a mixed particle of resin particles and wax particles are fused to the surface of the core particle.
  • a core particle portion obtained by aggregating resin particles and colorant particles and a mixed particle of resin particles and wax particles are fused to the surface of the core particle.
  • the coagulant to be added is the ability to use an aqueous solution containing a water-soluble inorganic salt having a constant water concentration. After adjusting the pH value of the aqueous solution, at least the first resin in which the first resin particles are dispersed Color dispersion with particle dispersion, third resin particle dispersion, and colorant particles It is also preferable to add it to the mixed dispersion obtained by mixing the agent particle dispersion and the wax particle dispersion in which the wax particles are dispersed.
  • the aggregating action of the particles as the aggregating agent can be further enhanced by adjusting the pH value of the aqueous solution containing the aggregating agent to a constant value. It is preferable to have a certain relationship with the pH value of the mixed dispersion liquid. By adding an aqueous flocculant solution having a certain pH value to the mixed dispersion liquid, the core particles may become coarse. This is effective because it can suppress the phenomenon of uneven wax dispersion.
  • the mixed dispersion obtained by mixing the first resin particle dispersion, the third resin particle dispersion, the colorant particle dispersion, and the fox particle dispersion is subjected to heat treatment, and before the aqueous solution containing the flocculant is added.
  • the pH value of the mixed dispersion is HG
  • the pH value of the aqueous solution containing the flocculant is preferably adjusted to the range of HG + 2 to HG-4.
  • the range is preferably HG + 2 to HG-3, more preferably HG + l.5 to HG-2, and still more preferably HG +;! To HG-2.
  • the timing of adding the flocculant is the temperature of the mixed dispersion obtained by mixing the first resin particle dispersion, the third resin particle dispersion, the colorant particle dispersion, and the wax particle dispersion. It is preferable to add a flocculant after reaching the melting point of the wax measured by the DSC method described above. By adding a flocculant in the state in which the melting of the wax is started, the aggregation of the wax particles to be melted, the resin particles and the colorant particles proceeds at a stretch, and further, the heat treatment is continued, so that the wax particles and the resin particles It seems that melting progresses and particles are formed.
  • the particles hardly aggregate and no particles are formed.
  • the aggregation of the particles proceeds by adding a flocculant, and then 0.5 to 5 hours, preferably 0.5 to 3 hours, more preferably.
  • the core particles having a predetermined particle size distribution are produced by heating for 1 to 2 hours.
  • the heat treatment may be performed while keeping the specific temperature of the wax, but is preferably 80 to 95 ° C, more preferably 90 to 95 ° C. Aggregation reaction can be accelerated, leading to reduction of processing time.
  • the specific temperature of the wax having the lower melting point it is preferable to adjust the specific temperature of the wax having the lower melting point. More preferably, the temperature is adjusted to a specific temperature of a wax having a higher melting point. It is effective to add the flocculant at the temperature when the wax particles start to melt!
  • the total amount of the flocculant may be added all at once, but it is also preferable that the flocculant is dropped; taking a time of! -120 min. While it may be divided, continuous dripping is preferred.
  • the flocculant When the flocculant is dripped at a constant rate into the heated mixed dispersion, the flocculant gradually and uniformly mixes with the entire mixed dispersion in the reaction kettle, and the particle size distribution becomes broad due to uneven distribution. Or the generation of suspended particles of wax or colorant.
  • the rapid fall of the liquid temperature of a mixed dispersion liquid can be suppressed.
  • it is 5 to 60 min, more preferably 10 to 40 min, and further preferably 15 to 35 min.
  • the shape of the core particles does not progress to an indefinite shape, and a stable shape can be obtained. 1 By setting it to 20 min or less, the effect of suppressing the presence of particles floating alone due to poor aggregation of the colorant and wax particles is obtained.
  • the flocculant it is preferable to add 1 to 50 parts by weight of the flocculant with respect to 100 parts by weight of the total of the first resin particles, the third resin particles, the pigment fine particles, and the wax fine particles.
  • the mixed dispersion is ion-exchanged to adjust the solid concentration in the liquid. Adding water does not help.
  • the solid concentration in the liquid is preferably 5 to 40% by weight.
  • the flocculant it is also preferable to use a water-soluble inorganic salt adjusted to a constant concentration with ion-exchanged water or the like.
  • the concentration of the flocculant aqueous solution is preferably 5 to 50% by weight!
  • the first resin particle dispersion and the wax particle dispersion are added to the core particle dispersion in which the core particles are formed by aggregating the first resin particles, the third resin particles, and the colorant particles.
  • the core particles are produced by aggregating the core particles, the first resin particles, and the wax, the first resin particle dispersion, the third resin particle dispersion, and the It is also preferable to add the flocculant after the temperature of the mixed dispersion obtained by mixing the colorant particle dispersion is higher than the melting point of the wax measured by the DSC method described later.
  • the flocculant is added when the temperature of the mixed dispersion reaches the glass transition point of the first resin particles.
  • aggregation is difficult to proceed.
  • the temperature of the mixed dispersion reaches 80 ° C or higher, the particles grow and the particles tend to grow to a particle size of 1 to 3 Hm.
  • the specific temperature of the glass having the lower melting point it is preferable to adjust the specific temperature of the glass having the lower melting point. More preferably, the temperature is adjusted to a specific temperature of a wax having a higher melting point.
  • the flocculant is added to form the first resin particles, and the core particles formed by the aggregation of the third resin particles and the colorant particles, the first resin particle dispersion and the wax particle dispersion are dropped. Then, the core particles are aggregated with the first resin particles and the wax particles to generate core particles. At this time, the temperature of the aqueous medium is preferably continued without being changed.
  • First resin particles used as core particles, and then added together with wax particles to form core particles may be resins having different compositions and thermal properties! /, But preferably the same first resin particles! /.
  • the first resin particles used for the core particles are preferably 30 to 80 by weight. By setting it to 30 or more, it is possible to produce a core particle having a small particle size and a narrow particle size distribution by aggregation of the first resin particles and the colorant particles. If it is less than 30, the dispersibility of the colorant particles tends to decrease.
  • the first resin particles and the wax particle dispersion are preferably dropped separately, or it is preferable to drop a dispersion previously mixed at a constant rate at a constant dropping rate! If the total amount is added in large amounts, the temperature of the liquid may decrease, and aggregation may not progress uniformly.
  • the heat treatment is continued for a predetermined time.
  • the time is preferably 10 minutes to 2 hours.
  • the mixture is mixed to some extent and the temperature is kept stable, and then the pH of the mixed liquid in which the core particles, first resin particles and wax particles are mixed is adjusted to 7 or more and 10 or less. To do. Thereby, adhesion of the 1st resin particle and wax particle to a core particle can be advanced. If the pH of the mixed solution is less than 7 or greater than 10, it becomes difficult for the first resin particles and wax particles to adhere to the core particles, and the core particles become coarse or the floating particles increase. It will be a big deal.
  • the heating time is 0.5 to 5 hours, preferably 0.5 to 3 hours, more preferably 1 to 2 hours, to produce core particles having a predetermined particle size distribution.
  • the heat treatment may be performed while keeping the specific temperature of the wax, but it is preferably 80 to 95 ° C, more preferably 90 to 95 ° C. Aggregation reaction can be accelerated, leading to reduction of processing time.
  • the toner of the present invention is obtained by adding and mixing the second resin particle dispersion in which the second resin particles are dispersed in the core particle dispersion in which the core particles are dispersed, and heat-treating the core particles.
  • the second resin particles are fused to the core particles to produce toner base particles.
  • the second resin particles are formed into core particles with a fusion layer (sometimes referred to as a coating layer or a shell layer). It is desirable from the viewpoint of charging stability. In addition, since resin particles with different softening points exist in the core particle as shape adjustment, irregularities may occur on the particle surface, which may affect the chargeability and fluidity. It is valid.
  • resin particles having a high glass transition point are used to increase the high molecular weight from the viewpoint of ensuring high-temperature offset resistance during fixing. It is desirable to form the resin particles as a shell layer.
  • the second resin particle dispersion in which the second resin particles whose pH value has been adjusted to an alkaline state is dispersed is adjusted to a pH value of 7 described above. It is preferable to add to the core particle dispersion in which the core particles in a state of 10 to 10 are dispersed.
  • the pH of the second resin particle dispersion in which the second resin particles adjusted to the alkaline state are dispersed is preferably in the range of 7.5 to 105.5. Preferably 8.5 to 10.5, more preferably 8.9 to 10.5.
  • the pH value of the second resin particle dispersion in which the second resin particles are dispersed is higher than the pH value of the core particle dispersion in which the core particles are dispersed, that is, adjusted to a more alkaline state. Is preferably added.
  • the pH value of the second resin particle dispersion in which the second resin particles are dispersed is preferably 0.5 or more higher than the pH value of the core particle dispersion in which the core particles are dispersed. More preferably, it is 1 or more.
  • the ratio is smaller than 0.5, the generation of floating second resin particles that do not participate in fusion tends to increase.
  • the difference exceeds 3.5 the second resin particles that float and do not participate in fusion are generated, and secondary aggregation occurs between the core particles, and the generated particles tend to be coarse. is there.
  • the pH value of the core particle dispersion is in the range of 7 to 10; and the pH value of the second resin particle dispersion is Is added after adjusting to 7.5 to 10.5, the adhesion of the second resin particles to the core particles is promoted, and the generation of floating second resin particles not added to the fusion is suppressed, and the core is suppressed. It is possible to form a narrow particle size distribution with a small particle size while suppressing the occurrence of secondary aggregation between particles.
  • the pH value of the core particle dispersion is less than 7 and the pH value of the second resin particle dispersion is less than 7.5, the adhesion of the second resin particles to the core particles does not proceed and the second resin particle dispersion does not proceed.
  • the resin particles tend to remain floating without being fused to the core particles.
  • the pH value of the core particle dispersion is greater than 10 and the pH value of the second resin particle dispersion is greater than 10.5, the second resin particle does not adhere to the core particles and is generated. The tendency of the particles to be coarsened ⁇ ⁇ .
  • the pH value can be adjusted by adding sodium hydroxide or hydrochloric acid solution.
  • the amount of the generated core particles is set as a dropping condition of the second resin particle dispersion in the core particle dispersion in which the generated core particles are dispersed. It is preferable that the dropping rate of the second resin particles is dropped at a dropping condition of 0.14 parts by weight / min to 2 parts by weight / min with respect to 100 parts by weight. Preferably 0.15 parts by weight / min to 1 parts by weight / min, more preferably 0.2 parts by weight / mil! ⁇ 0.8 parts by weight / min.
  • the second resin particle dispersion is added as it is when the core particles reach a predetermined particle size.
  • the addition is preferably performed by dropping sequentially.
  • a predetermined total amount is added all at once or exceeds 2 parts by weight / min, only the second resin particles are aggregated, and the particle size distribution tends to be broad.
  • the liquid temperature rapidly decreases and the agglomeration reaction stops, and a part of the second resin particles are suspended in the aqueous system without being attached to the core particles. It may remain.
  • the thickness of the resin layer fused with the second resin particles is preferably 0.5 m to 2 m. If it is thinner than this, the effects of storage stability and high temperature non-offset property will not be exhibited, and if it is thicker, low temperature fixability will be hindered.
  • the first resin particles are obtained by emulsion polymerization of a monomer in a water-based medium using a polymerization initiator.
  • the polymerization initiator is a persulfate having a solubility of 4 g or more in 100 g of water at a water temperature of 20 ° C
  • the monomer is a styrene-based monomer Body, including a (meth) acrylic acid ester monomer and a bull monomer having an acid group, and the amount of the bull compound having an acid group is 0.;! To 5.0% by weight in the monomer
  • the polymerization initiator is a persulfate having a solubility of 4 g or more in 100 g of water at a water temperature of 20 ° C
  • the monomer is a styrene-based monomer Body, including a (meth) acrylic acid ester monomer and a bull monomer having an acid group, and the amount of the bull compound having an acid group is 0.;! To 5.0% by
  • the amount of the polymerization initiator added tends to affect the aggregation of the first resin particles, the third resin particles, the colorant particles, and the wax particles depending on the amount of hydrophilic groups derived from the polymerization initiator. . In other words, if the amount of polymerization initiator added is large, the agglomeration reaction tends to proceed slowly, and if the amount of polymerization initiator added is small, the agglomeration reaction tends to proceed quickly.
  • the amount of polymerization initiator added is a single amount. 0.5 to 2.5 parts by weight per 100 parts by weight of body. The amount is preferably 0.7 to 2.0 parts by weight, more preferably 1.0 to 1.5 parts by weight.
  • the addition amount of the polymerization initiator is less than 0.5 parts by weight, the aggregation of the first resin particles proceeds rapidly, and the core particles are not aggregated with the wax and pigment, and the first resin particles are aggregated. Coarse particles of the resin are produced. 2. If the amount is more than 5 parts by weight, the aggregation of the core particles tends to be delayed, which takes time for productivity. Also high temperature non-off As a result, the setability deteriorates and the fixable temperature range is narrowed. This is thought to affect the dispersibility of the wax because the agglomeration reaction proceeds slowly due to the amount of hydrophilic groups derived from the polymerization initiator.
  • the polymerization initiator it is preferable to use persulfates having a solubility of 4 g or more in 10 g of water at a water temperature of 20 ° C.
  • the cohesiveness and fixability of the core particles can be made appropriate by optimizing the amount of hydrophilic groups derived from the polymerization initiator. If the solubility is low, it takes time to dissolve the persulfate during the emulsion polymerization reaction, resulting in slow productivity. When the dispersion state of persulfates during emulsification changes, the cohesiveness during the coagulation reaction may become unstable.
  • the amount of the bur compound having an acid group is from 0.;! To 5.0% by weight in the monomer. Preferably, it is 0.2 to 4.5% by weight, more preferably 0.5 to 2.0% by weight. This is a range in which the first resin particles, the third resin particles, the colorant particles, and the wax particles can be properly aggregated. When the amount is less than 1% by weight, the aggregation of the first resin particles is accelerated, and the core particles aggregated with the wax and the pigment are not generated. The core particles tend to be coarse. 5. If the amount is more than 0% by weight, the aggregation of the core particles tends to be delayed.
  • the main component of the surfactant used in preparing the colorant particle or wax particle dispersion is preferably a nonionic surfactant.
  • the main component means 50% by weight or more.
  • the first resin particle dispersion in which the first resin particles are dispersed the third resin particle dispersion in which the third resin particles are dispersed, or the second resin particle in which the second resin particles are dispersed.
  • the main component of the surfactant used in preparing the resin particle dispersion is a nonionic surfactant
  • the main component of the surfactant used in the colorant particle and wax particle dispersion is a nonionic surfactant. It ’s better to be an agent!
  • the first resin particle dispersion in which the first resin particles are dispersed the third tree Of the surfactants used in preparing the third resin particle dispersion in which the fat particles are dispersed or the second resin particle dispersion in which the second resin particles are dispersed, the nonionic surfactant is the surface active agent. It is preferable to have 50 to 95% by weight based on the whole agent. More preferred is 55 to 90% by weight, still more preferred is 60 to 85% by weight.
  • the nonionic surfactant preferably has 50 to 100% by weight based on the entire surfactant. More preferably 60-; 100% by weight, more preferably 60-90% by weight.
  • the blending ratio of the ionic surfactant (preferably a cationic surfactant) to the whole surfactant is such that the wax particles, the colorant particles, the first It is preferable to increase in the order of resin particles and third resin particles.
  • the first resin particles using a large amount of anionic surfactant start to aggregate to form nuclei, and then the amount of anionic surfactant is higher than that of wax particles!
  • the colorant particles used in the process start to aggregate around the core of the resin particles.
  • the nonionic surfactant is used in the most abundant ratio! /,
  • the wax particles are aggregated, and the colorant particles are aggregated so as to be wrapped together with the resin particles to form core particles.
  • the first resin particles start to aggregate to form nuclei, but the colorant particles and wax particles are not taken into the core particles, and the colorant particles and wax particles that do not participate in aggregation in the core particle dispersion liquid. This is considered to be a point to avoid the remaining phenomenon.
  • the surfactant used in preparing the first resin particle dispersion in which the first resin particles are dispersed and the third resin particle dispersion in which the third resin particles are dispersed is nonionic. It is also preferable that the surfactant is a mixture of an ionic surfactant and that the main component of the surfactant used in the wax particle dispersion and the colorant particle dispersion is only a nonionic surfactant.
  • a mixed system of a nonionic surfactant and an ionic surfactant is used, and the surfactant of the first resin particle dispersion and the third resin particle dispersion is! /, And a nonionic interface.
  • the activator is preferably 50 to 95% by weight based on the total surfactant. More preferably, it is 55 to 90% by weight, and still more preferably 60 to 85% by weight. By making it 50% by weight or more, it becomes easy to suppress the phenomenon that the particle size distribution of the core particles to be generated is widened. By controlling the amount to 95% by weight or less, the dispersion of the resin particles themselves in the resin particle dispersion can be easily stabilized.
  • the ionic surfactant an anionic surfactant is preferable.
  • the average ethylene oxide addition mole number of the nonionic surfactant used for dispersing the wax particles is dispersed in the colorant particles and the wax particle dispersion liquid dispersed only with the nonionic surfactant. It is preferable that the average number of moles of added ethylene oxide of the noionic surfactant used for dispersing the colorant particles is larger. This is because a nonionic surfactant having a smaller average number of moles of added ethylene oxide tends to have a higher cohesiveness to the coagulant.
  • the average number of moles of ethylene oxide added to the nonionic surfactant used for dispersing the pigment particles is preferably 18 to 33. More preferably, it is 20-30, More preferably, it is 20-26.
  • Nonionic surfactant used for dispersion of pigment particles has multiple nonionic surfactants It is also preferable to contain an agent. By itself, even if the average ethylene oxide addition mole number of the nonionic surfactant is not in the range of 20-30, the weight average ethylene oxide addition mole number of the plurality of nonionic surfactants should be in the range of 20-30. That's fine.
  • the aggregating property of each particle with respect to the aggregating agent is determined by dropping the particle dispersion into an aggregating agent aqueous solution of various concentrations (for example, magnesium sulfate aqueous solution) and aggregating the particles to a certain size.
  • concentrations for example, magnesium sulfate aqueous solution
  • the amount of the nonionic surfactant with respect to the pigment particles is preferably 10 to 20 parts by weight with respect to 100 parts by weight of carbon black from the viewpoint of dispersion stability.
  • the main component of the surfactant used in the second resin dispersion is preferably a nonionic surfactant.
  • the surfactant used for the second resin particle dispersion is a mixture of a nonionic surfactant and an ionic surfactant.
  • the nonionic surfactant is preferably 50 to 95% by weight based on the whole surfactant. More preferably, it is 55 to 90% by weight, and still more preferably 60 to 85% by weight. By setting it to 50% by weight or more, adhesion of the second resin particle fine particles to the core particles can be promoted. By controlling the content to 95% by weight or less, there is an effect of stabilizing the dispersion of the resin particles themselves in the resin particle dispersion.
  • the toner base particles can be obtained through any washing step, solid-liquid separation step, and drying step. In this cleaning process, the chargeability is improved. In view of the above, it is preferable to carry out substitution washing with ion-exchanged water sufficiently.
  • the separation method in the solid-liquid separation step is preferably a known filtration method such as a suction filtration method or a pressure filtration method from the viewpoint of productivity that is not particularly limited.
  • the drying method in the drying step publicly known drying methods such as a flash jet drying method, a fluidized drying method, and a vibration type fluidized drying method are preferably mentioned from the viewpoint of productivity that is not particularly limited.
  • persulfates such as potassium persulfate, ammonium persulfate, sodium persulfate and the like are preferable materials.
  • a water-soluble inorganic salt examples thereof include an alkali metal salt and an alkaline earth metal salt.
  • the alkali metal include lithium, potassium, sodium, and the like
  • examples of the alkaline earth metal include magnesium, calcium, strontium, and sodium. Of these, potassium, sodium, magnesium, calcium, and barium are preferable.
  • counter ions (anions constituting the salt) of the Al-strength metal or al-strength earth metal include chloride ions, bromide ions, iodide ions, carbonate ions, sulfate ions, and the like. It is also preferable to adjust the concentration with ion-exchanged water.
  • nonionic surfactants include higher alcohol ethylene oxide adducts, alkylphenol ethylene oxide adducts, fatty acid ethylene oxide adducts, polyhydric alcohol fatty acid ester ethylene oxide adducts, and fatty acid amide ethylene oxide adducts.
  • Polyethylene glycol-type nonionic surfactants such as ethylene oxide adducts of fats and oils, polypropylene glycol ethylene oxide adducts, fatty acid esters of glycerol, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and carebitan, sucrose And polyhydric alcohol type nonionic surfactants such as alkyl esters of other alcohols, fatty acid amides of alkanolamines, and the like.
  • Polyethylene glycol-type nonionic surfactants such as higher alcohol ethylene oxide adducts and alkylphenol ethylene oxide adducts can be particularly preferably used.
  • examples of the aqueous medium include water such as distilled water and ion-exchanged water, and alcohols. These may be used alone or in combination of two or more.
  • the content of the polar surfactant in the dispersant having the polarity cannot be generally defined and can be appropriately selected according to the purpose.
  • examples of the polar surfactant include sulfate ester salt, sulfonate salt, phosphate ester salt, and salting agent.
  • anionic surfactants such as amines
  • cationic surfactants such as amine salt types and quaternary ammonium salt types.
  • anionic surfactant examples include sodium dodecylbenzenesulfonate, sodium dodecylsulfate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate and the like.
  • cationic surfactant examples include alkylbenzene dimethyl ammonium chloride, alkyl trimethyl ammonium chloride, distearyl ammonium chloride and the like. These may be used alone or in combination of two or more.
  • thermoplastic binder resins examples include thermoplastic binder resins. Specifically, styrenes such as styrene, norchlorochlorostyrene, a -methylstyrene, methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, 2-ethyl hexyl acrylate, etc.
  • Acrylic monomers such as methyl methacrylate, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, and other methacrylic monomers, acrylic acid, methacrylic acid, maleic acid, fumar
  • a homopolymer such as an unsaturated polycarboxylic acid monomer having a carboxyl group of an acid group such as an acid as a releasing group, a copolymer obtained by combining two or more of these monomers, or a mixture thereof. Can be mentioned.
  • the solid content of the resin particles in the resin particle dispersion is usually 5 to 50% by weight, preferably 10 to 40% by weight.
  • the softening point (Tsl) of the first resin particles constituting the core particles is preferably in the range of 80 ° C to 130 ° C. Preferably from 80 ° C; 125 ° C, more preferably from 80 ° C; 120 ° C, more preferably 85 ° C ⁇ ; 110 ° C.
  • the softening point is less than 80 ° C, the agglomeration proceeds rapidly and it tends to be difficult to form particles with a small particle size and a narrow particle size distribution. Also, the shape is close to a true sphere, and it tends to be difficult to control the shape.
  • the softening point exceeds 130 ° C, the low-temperature fixability tends to deteriorate.
  • the glass transition point of the first resin particles constituting the core particles is preferably 45 ° C to 60 ° C. More preferably, it is 45 degreeC-55 degreeC, More preferably, it is 45 degreeC-52 degreeC. If the glass transition point of the resin particles is less than 45 ° C, the core particles become coarse and the storage stability tends to decrease. If it exceeds 60 ° C, the low-temperature fixability tends to deteriorate.
  • the first resin particles have a weight average molecular weight (Mwrl) of 10,000 to 60,000, and the ratio of the weight average molecular weight (Mwrl) to the number average molecular weight (Mnrl) is Mwrl / Mnrl of 1.5 to 6 It is preferable that More preferably, the weight average molecular weight (Mwrl) is 10,000 to 50,000, and the ratio of the weight average molecular weight (M wrl) to the number average molecular weight (Mnrl) Mwrl / Mnrl is preferably 1.5 to 3.9. .
  • the weight average molecular weight (Mwlr) is 10,000 to 30,000, and the ratio of the weight average molecular weight (Mwr 1) to the number average molecular weight (Mnlr) Mwlr / Mnrl is preferably 1.5 to 3.
  • the resin particles are preferably 60% by weight or more, more preferably 70% by weight or more, and still more preferably 80% by weight or more, based on the total toner resin.
  • Mwrl is less than 10,000, the core particles are coarsened, and the storage stability and heat resistance tend to decrease. If it exceeds 60,000, the low-temperature fixability tends to deteriorate.
  • Mwrl / Mnrl exceeds 6, the shape of the core particle is not stable, becomes irregular, and irregularities remain on the particle surface immediately, resulting in a tendency to deteriorate surface smoothness.
  • the first resin particles want to lower the softening point or molecular weight for improving the low-temperature fixability.
  • the first resin particles become spherical during the aggregation process. It tends to progress and tends to become ⁇ when adjusting the shape. Therefore, it is possible to achieve both low-temperature fixing and shape control by blending resin particles having a certain thermal characteristic relationship with the first resin particles having a low softening point or low molecular weight.
  • the second resin particles have a glass transition point of 55 ° C to 75 ° C and a softening point of 140 ° C to
  • weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 50,000 to 500,000, ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) Mw / Mn is 2 ⁇ ; 10 is preferred.
  • the glass transition point is 60 ° C to 70 ° C
  • the softening point is 145 ° C to 180 ° C
  • the Mw is 80,000 to 500,000
  • the Mw / Mn is 2 to 7.
  • the glass transition point is 65 ° C to 70 ° C
  • the softening point is 150 ° C to 180 ° C
  • Mw is 120,000 to 500,000
  • Mw / Mn is 2 to 5.
  • the core particles have different portions such as softening points.
  • it is effective to have a certain glass transition point, softening point or molecular weight characteristic as described above.
  • the second resin particles having the above-mentioned characteristics in order to prevent the adhesion of the second resin particles to be uneven. It is.
  • the glass transition point of the second resin particles is less than 55 ° C, secondary aggregation in which aggregation of core particles proceeds tends to occur. In addition, the storage stability tends to deteriorate. If it exceeds 75 ° C, the heat-fusibility to the core particle surface will deteriorate and the uniform adhesion will tend to decrease.
  • the Mw of the second resin particles is smaller than 50,000! /, And the durability, high-temperature non-offset property, and paper separation property tend to decrease. If it exceeds 500,000, the low-temperature fixability, glossiness, and translucency tend to decrease.
  • the molecular weights of the resin, wax, and toner are values measured by gel permeation chromatography (GPC) using several types of monodisperse polystyrene as standard samples.
  • the instrument is Tosoh's HLC8120GPC series, the column is TSKgel superHM—H H4000 / H300 0 / H2000 (6. Omml. D. — 150mm X 3), eluent THF (tetrahydrofuran), flow rate 0.6 mL / min, sample concentration 0.1% by weight, injection volume 20 L, detector RI, measurement temperature 40 ° C,
  • the measurement conditions are conditions in which the molecular weight distribution of the target sample is included in a range in which the logarithm of the molecular weight and the count number are linear in a calibration curve obtained with several types of monodisperse polystyrene standard samples.
  • the softening point of the non-resin resin (first resin) particles is in the range of 80 to 130 ° C, and the shape-adjusted resin particles (third resin) and the coating resin (second resin) particles
  • the softening point of each is 140 to; preferably 180 ° C.
  • the same resin can be used for the shape-adjusting resin particles (third resin) and the coating resin (second resin) particles.
  • the softening point of the binder resin is measured with a constant-load extrusion type capillary rheometer flow tester (CFT500) manufactured by Shimadzu Corporation.
  • CFT500 constant-load extrusion type capillary rheometer flow tester
  • a sample is filled in a cylinder, heated from the surroundings to melt, and a certain pressure is applied from above by a piston.
  • the molten sample is extruded through a die with a thin hole (diameter lmm, length lmm), and the flowability of the sample, ie, melt viscosity, is determined from the flow rate (cm 3 / g).
  • a heating furnace surrounding the cylinder and die is provided and set to 50 ° C. Fill cylinder with lg sample. Hold at 50 ° C for 2.5 min without applying load. Apply a load to remove air from the sample. At this time, the length of the piston coming out of the heating furnace should be about 12 to 15 mm. Start heating when the total holding time reaches 5 min.
  • the viscosity at each temperature can be measured from the relationship between the temperature rise characteristic and the relationship between the moving amount of the descending piston and the temperature.
  • Figure 11 shows the flow curve.
  • the horizontal axis shows the temperature
  • the vertical axis shows the piston movement.
  • A it is a solid state region of the sample.
  • a to B are transition regions where the sample is deformed by a compressive load and the internal voids gradually decrease.
  • B has uniform internal appearance with internal voids disappearing and non-uniform stress distribution This is the temperature at which one transparent body is formed.
  • C is defined as the temperature at which the sample begins to flow, and the temperature at which the sample begins to flow (outflow start temperature (Tfb)).
  • the region from C to D through E is the flow region where the sample clearly flows out of the die, where E is the end of the sample outflow.
  • the softening point of the binder resin is defined by the melting temperature in the 1/2 method (softening point Ts ° C). Specifically, the softening point is defined as the temperature at which the piston moves 50% from the outflow start temperature with respect to the total travel distance of the piston from the outflow start temperature to the outflow end temperature.
  • the glass transition point of the resin was raised to 100 ° C using a differential scanning calorimeter (Shimadzu DSC-50), left at that temperature for 3 minutes, and then cooled down to 10 ° C /
  • the sample was cooled to room temperature in min and heated at a heating rate of 10 ° C / min and the thermal history was measured, the peak line peaked from the base line extension and the peak rise point below the glass transition point. This is the temperature at the point of intersection with the tangent that indicates the maximum slope until.
  • the wax particle dispersion is prepared by heating, melting, and dispersing the wax in ion-exchanged water in an aqueous medium to which a surfactant is added.
  • the wax contains at least the first wax and the second wax, and the endothermic peak temperature (melting point Tswl (° C )) Force 3 ⁇ 40 ⁇ 90 ° C, and endothermic peak temperature (melting point Tsw2 (° C)) of the second wax by DSC method is 80 ⁇ ; 120 ° C. If Tswl is less than 50 ° C, storage stability deteriorates. If it exceeds 90 ° C, low-temperature fixability and color gloss will not improve. Tswl is preferably 55 to 85 ° C, more preferably 60 to 85 ° C, still more preferably 65 to 75 ° C.
  • Tsw2 is less than 80 ° C, high temperature non-offset property and paper separation tend to be weak. When the temperature exceeds 120 ° C, the cohesiveness of the wax decreases, and free particles that do not aggregate in the aqueous system tend to increase. Tsw2 is more preferably 85 to 100 ° C, further preferably 90 to 100 ° C.
  • the wax contains at least a first wax and a second wax, and the first wax is a higher alcohol having 16 to 24 carbon atoms and a higher alcohol having 16 to 24 carbon atoms. It is preferable to include an ester wax composed of at least one of fatty acids and to include a second wax power aliphatic hydrocarbon wax.
  • the wax includes at least a first wax and a second wax, and includes a wax having a first wax power of an iodine value of 25 or less and a saponification value of 30 to 300.
  • the second wax preferably contains an aliphatic hydrocarbon wax.
  • the endothermic peak temperature (melting point Tswl (° C)) of the first wax by DSC method is 50 to 90 ° C, preferably 55 ⁇ 85 ° C and more Preferably it is 60-85 degreeC, More preferably, it is 65-75 degreeC. If it is less than 50 ° C, the storage stability and heat resistance of toner will tend to deteriorate. When the temperature exceeds 90 ° C, the cohesiveness of the wax decreases, and free particles that do not aggregate in the aqueous system increase. It is also suitable when low-temperature fixability and glossiness are not improved.
  • the endothermic peak temperature (melting point Tsw2 (° C)) of the second wax by DSC method is 80 to 120 ° C, preferably Is preferably 85 to 100 ° C, more preferably 90 to 100 ° C. If it is less than 80 ° C, the storage stability tends to deteriorate, and the high temperature non-offset property and the paper separation property tend to be weakened. When the temperature exceeds 120 ° C, the cohesiveness of the wax decreases, and free particles that do not aggregate in the aqueous system tend to increase. In addition, low-temperature fixability and color translucency tend to be hindered.
  • the aliphatic hydrocarbon based wax when the core particles are formed together with the resin particles, the colorant and the aliphatic hydrocarbon wax in the aqueous system, the aliphatic hydrocarbon based wax is not mixed with the resin. Due to the compatibility, there is a tendency that aggregation with the resin does not easily occur, and the presence of particles floating without wax being incorporated into the core particles, or the particle size distribution tends to be broad without aggregation of the core particles.
  • the first wax becomes more compatible with the resin, which promotes the agglomeration with the aliphatic hydrocarbon-based resin and prevents the generation of suspended particles.
  • This force S is possible.
  • the first wax tends to improve the low-temperature fixability by partially compatibilizing with the resin.
  • these waxes have a function of improving high temperature offset and separability from paper. The ability to demonstrate S That is, the first wax has a function as a dispersion aid during the emulsification dispersion treatment of the aliphatic hydrocarbon wax, and further has a function as a low-temperature fixing aid.
  • the wax having a different melting point is aggregated with the resin and the colorant in the aqueous system to form toner particles.
  • the wax is uniformly incorporated into the toner to form particles with a small particle size and a narrow particle size distribution, and to promote the formation of a shell that melts and adheres the second resin to the core particles.
  • the first wax and the second wax are preferably prepared by mixing and dispersing the first wax and the second wax separately. That is, the first wax and the second wax are heated and emulsified and dispersed in a constant blending ratio in the emulsifying and dispersing apparatus. It is recommended that the final dispersion contains a mixture of the first wax and the second wax!
  • ES1 is the weight ratio of the first wax with respect to 100 parts by weight of the wax in the wax particle dispersion
  • FT2 is the weight ratio of the second wax.
  • the relationship of FT2 / ES1 is preferably 0.2 to 10; More preferably, it is in the range of 1 to 9, more preferably 1.5 to 3. If it is less than 0.2, that is, if the proportion of the first nitrogen is too high, the effect of high temperature non-offset property cannot be obtained, and the storage stability tends to deteriorate.
  • dispersion stability is improved by treating the wax, particularly an aliphatic hydrocarbon wax, with an anionic surfactant. Aggregation of 1S core particles At this time, the core particles become coarse and it is difficult to obtain particles having a sharp particle size distribution.
  • the wax particle dispersion is changed to a surfactant mainly composed of a nonionic surfactant. More preferably, the first wax and the second wax are mixed and emulsified and dispersed.
  • the total amount of added wax is preferably 5 to 30 parts by weight with respect to 100 parts by weight of the binder resin.
  • the amount is preferably 8 to 25 parts by weight, more preferably 10 to 20 parts by weight. If the amount is less than 5 parts by weight, the effects of low temperature fixing property, high temperature non-offset property, and paper separation property tend not to be exhibited. If it exceeds 30 parts by weight, it tends to be difficult to control particles with a small particle size.
  • Tsw2 is higher than Tswl by 5 ° C or higher, and preferably 50 ° C or lower. More preferably, the temperature is 10 ° C or higher, 40 ° C or lower, more preferably 15 ° C or higher, and preferably 35 ° C or lower.
  • the function of the wax can be separated efficiently, and there is an effect of achieving both low-temperature fixability, high-temperature non-offset property and paper separation property.
  • the temperature is lower than 5 ° C, the effects of achieving both low-temperature fixability, high-temperature non-offset property and poor paper separation tend to be exhibited.
  • the temperature is higher than 50 ° C., the first wax and the second wax are easily phase-separated and tend not to be uniformly incorporated in the toner particles.
  • the preferred first wax includes at least one ester composed of at least one of a higher alcohol having 16 to 24 carbon atoms and a higher fatty acid having 16 to 24 carbon atoms.
  • Examples of the alcohol component include monoalcohols such as methyl, ethyl, propyl, and butyl.
  • glycols such as ethylene glycol or propylene glycol or multimers thereof, triols such as glycerin or multimers thereof, polyhydric alcohols such as pentaerythritol, sorbitan, or cholesterol are preferable.
  • these alcohol components are polyhydric alcohols, the higher fatty acid may be a mono-substituted product or a poly-substituted product.
  • it comprises (1) higher alcohols having 16 to 24 carbon atoms and higher fatty acids having 16 to 24 carbon atoms such as stearyl stearate, palmityl palmitate, behenyl behenate or stearyl montanate.
  • Esters (2) Esters consisting of higher fatty acids having 16 to 24 carbon atoms and lower monoalcohols such as pityl stearate, isobutyl behenate, propyl montanate or 2-ethylhexyl oleate, (3) Montanic acid monoethylene glycol ester, ethylene glycol distearate, monostearic acid glyceride, monobehenic acid glyceride, trino-rumitic acid glyceride, pentaerythritol monobehenate, pentaerythritol resilinolate, pentaerythritol trioleate or Pentaerythritol tetrastearate, etc.
  • Esters of higher fatty acids having 16 to 24 carbon atoms and polyhydric alcohols or (4) diethylene glycol monobehenate, diethylene glycol dibehenate, dipropylene glycol monostearate, diglyceride distearate, tetrastearate
  • esters composed of higher fatty acids having 16 to 24 carbon atoms and polyhydric alcohol multimers such as acid triglyceride, hexabehenic acid tetraglyceride or decastearic acid decaglyceride. These waxes may be used alone or in combination of two or more.
  • the preferred first wax includes a wax having an iodine value of 25 or less and a saponification value of 30 to 300.
  • a wax having an iodine value of 25 or less and a saponification value of 30 to 300 When used in combination with the second wax, coarsening of the particle size can be prevented and core particles having a small particle size and a narrow particle size distribution can be produced.
  • the iodine value By defining the iodine value, the effect of improving the dispersion stability of the wax can be obtained, the core particles can be uniformly formed with the resin and the colorant particles, and the core particles with a small particle size and a narrow particle size distribution can be formed. To do.
  • the iodine number is 2 0 or less, saponification value 0 to 200, more preferably, iodine value is 10 or less, and saponification value is 30 to 150.
  • the iodine value exceeds 25, the dispersion stability becomes too good, core particles cannot be formed uniformly with the resin and colorant particles, and there is a tendency for the floating particles of the wax to increase, resulting in coarse particles and broad particles. It tends to be a particle size distribution.
  • the saponification value is less than 30, the presence of unsaponifiable matter and hydrocarbons increases, and it tends to be difficult to form a uniform core particle having a small particle size.
  • the saponification value exceeds 300, suspended matter in the water system tends to increase.
  • the loss of heat at 220 ° C of the wax having a defined iodine value and saponification value is preferably 8% by weight or less.
  • the loss on heating is more than 8% by weight, the glass transition point of the toner is lowered and the storage stability of the toner tends to be impaired.
  • the particle size distribution of the generated toner tends to be broad.
  • Molecular weight characteristics in gel permeation chromatography (GPC) of wax with prescribed iodine value and saponification value number average molecular weight 100-5000, weight average molecular weight 200-; 10000, weight average molecular weight and number average molecular weight Ratio (weight average molecular weight / number average molecular weight) is 1.01 to 8, ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 10, molecular weight 5 X 10 2 -1 it force S preferably has at least one molecular weight maximum peak in the region of X 10 4.
  • the number average molecular weight is 500 to 4500, the weight average molecular weight is 600 to 9000, and the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight) is 1.0;! To 7, Z average The ratio of molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.02 to 9, more preferably, the number average molecular weight is 700 to 4000, the weight average molecular weight is 800 to 8000, the weight average molecular weight and the number average molecular weight The ratio (weight average molecular weight / number average molecular weight) is 1.0;! To 6, and the ratio of Z average molecular weight to number average molecular weight (Z average molecular weight / number average molecular weight) is 1.0 2 to 8.
  • the number the average molecular weight is located in the range smaller than the small tool weight average molecular weight than 100 small instrument molecular weight maximum peak is 5 X 10 2 than 200, particle size distribution blow over of particles produced Tend to be Storage stability tends to deteriorate.
  • the first wax is a material such as a meadow foam oil derivative, carnauba wax derivative, jojoba oil derivative, wood wax, beeswax, ozokerite, carnauba wax, canderia wax, ceresin wax or rice wax. These derivatives are also preferably used. One type or a combination of two or more types can be used.
  • Meadowfoam oil fatty acid, metal salt of meadowfoam oil fatty acid, meadowfoam oil fatty acid ester, hydrogenated meadowfoam oil or meadowfoam oil triester can be preferably used as the meadowfoam oil derivative.
  • An emulsified dispersion having a small particle size and a uniform particle size distribution can be prepared. This is a preferred material that is effective for low-temperature fixability in oilless fixing, prolonging the life of the developer, and improving transferability. These can be used alone or in combination.
  • the metal salt may be a metal salt such as sodium, potassium, strength, magnesium, norlium, zinc, lead, manganese, iron, nickel, cobalt, or ano-remium. High temperature non-offset property is good.
  • Northfoam oil fatty acid esters include, for example, esters such as methyl, ethyl, butyl glycerin, pentaerythritol, polypropylene glycol, or trimethylolpropane, and in particular, meadowfoam oil fatty acid pentaerythritol monoester, medold Ufoform oil fatty acid pentaerythritol triester or Meadowfoam oil fatty acid trimethylolpropane ester is preferred. Effective for low-temperature fixability.
  • Hydrogenated Meadowfoam oil is obtained by hydrogenating Meadowfoam oil to form unsaturated bonds as saturated bonds. Low temperature fixability and glossiness can be improved.
  • an esterification reaction product of Meadowfoam oil fatty acid and a polyhydric alcohol such as glycerin, pentaerythritol, and trimethylolpropane is converted into tolylene diisocyanate (TD 1), diphenylmethane 1, 4, 4 ' Isocyanate polymer of Meadowfoam fatty acid polyhydric alcohol ester obtained by crosslinking with isocyanate such as isocyanate (MDI) Can also be preferably used. It is possible to extend the life of a two-component developer with less spent to the carrier.
  • TD 1 tolylene diisocyanate
  • MDI isocyanate
  • Jojoba oil derivatives include jojoba oil fatty acids, metal salts of jojoba oil fatty acids, jojoba oil fatty acid esters, hydrogenated jojoba oil, jojoba oil triester, maleic acid derivatives of epoxidized jojoba oil,
  • An isocyanate polymer of a monohydric alcohol ester, a rosinized modified jojoba oil can also be preferably used.
  • An emulsified dispersion having a uniform particle size distribution with a small particle size can be prepared. Easy mixing and dispersion of resin and wax. This is a preferable material that is effective for low-temperature fixability in oil-less fixing, long life of the developer, and improved transferability. These can be used alone or in combination of two or more.
  • Jojoba oil fatty acid obtained by saponification of jojoba oil consists of fatty acids having 4 to 30 carbon atoms.
  • the metal salt can be used with metal salts such as sodium, potassium, calcium, magnesium, barium, zinc, lead, manganese, iron, nickel, cobalt, and aluminum. High temperature non-offset property is good.
  • Examples of jojoba oil fatty acid esters include esters such as methyl, ethyl, butyl, glycerin, pentaerythritol, polypropylene glycol, and trimethylolpropane, and in particular, jojoba oil fatty acid pentaerythritol monoester and jojoba oil fatty acid pentaester. Erythritol triester, jojoba oil fatty acid trimethylolpropane ester and the like are preferable. Effective for low-temperature fixability.
  • Hydrogenated jojoba oil is obtained by hydrogenating jojoba oil to make unsaturated bonds saturated bonds. Low temperature fixability and glossiness can be improved.
  • esterification reaction products of jojoba oil fatty acid and polyhydric alcohols such as glycerin, pentaerythritol, and trimethylolpropane are converted into tolylene diisocyanate (TDI), diphenylmethane 4, 4, and diisocyanate.
  • TDI tolylene diisocyanate
  • An isocyanate polymer of jojoba oil fatty acid polyhydric alcohol ester obtained by crosslinking with isocyanate such as sulfonate (MDI) can also be preferably used. Longer life of two-component developer with less spent to carrier
  • the saponification value refers to the number of milligrams of potassium hydroxide required to saponify the sample lg.
  • the iodine value refers to the amount of halogen absorbed when a halogen is allowed to act on a sample, expressed in terms of g per 100 g of the sample. This is the number of grams of iodine absorbed. The larger this value, the higher the degree of unsaturation of fatty acids in the sample.
  • Add iodine and mercury (II) chloride alcoholic solution or chloroacetic acid glacial acetic acid solution to the chloroform or carbon tetrachloride solution of the sample. The amount of iodine absorbed is calculated by titration with a semi-liquid.
  • the sample cell weight is precisely weighed to 0.1 mg (Wlmg), and 10 to 15 mg of the sample is put therein, and then precisely weighed to 0.1 mg (W2 mg).
  • Endothermic peak temperature (melting point Tsw ° C), onset temperature and endothermic amount of DSC method (differential scanning calorimetry measurement method) of wax are manufactured by TA Instruments, Q 100 (genuine for cooling) Use an electric refrigerator), set the measurement mode to “standard”, purge gas (N2) flow rate to 50 ml / min, set the temperature in the measurement cell to 30 ° C after turning on the power, and then 1 hour After standing for a while, 10 mg ⁇ 2 mg of the sample to be measured was placed in a pure aluminum pan, and the aluminum pan containing the sample was placed in the measuring instrument.
  • the horizontal axis shows the temperature of an empty aluminum crimp pan
  • the vertical axis shows the heat flow
  • the temperature at which the endothermic curve starts to rise from the baseline is the onset temperature
  • the peak value of the endothermic curve was used.
  • a material of hydroxy stearic acid derivative, glycerin fatty acid ester, glycol fatty acid ester or sorbitan fatty acid ester is also preferably used. Use in combination of more than one type is also effective. Uniform emulsification-dispersed small particle size core particles can be prepared, and when used in combination with the second wax, coarsening of the particle size can be prevented, and toner base particles having a small particle size and a narrow particle size distribution can be generated.
  • Oilless fixing having low-temperature fixing, high glossiness, and translucency can be realized.
  • the life of the developer is extended with oilless fixing.
  • hydroxystearic acid examples include methyl 12-hydroxystearate, butyl 12-hydroxystearate, propylene glycol mono 12-hydroxy stearate, glycerin mono 12-hydroxy stearate or ethylene glycol mono 12-hydroxy stearate Etc. are suitable materials. It has low-temperature fixability, oil separation improvement effect, and photoconductor filming prevention effect in oilless fixing.
  • glycerin fatty acid esters include glycerin stearate, glycerin distearate, glycerin tristearate, glycerin monopalmitate, glycerin dipalmitate, glycerin lintrino normitate, glycerin behenate, glycerin dibenate, and glycerin tribenate.
  • Glycerin monomyristate, glycerin dimyristate, glycerin trimyristate, etc. are suitable materials. It has the effect of alleviating cold offset at low temperatures and preventing transfer deterioration in oilless fixing.
  • Suitable glycol fatty acid esters include propylene glycol fatty acid esters such as propylene glycol monopalmitate and propylene glycol monostearate, and ethylene glycolenole fatty acid esters such as ethylene glycol monomonoesterate and ethylene glycol monomonoremitate. Material. Low temperature fixability, good slippage in development and prevention of carrier spent.
  • sorbitan fatty acid esters sorbitan monopalmitate, sorbitan monostearate, sorbitan tripalmitate, and sorbitan tristearate are suitable materials. Furthermore, pentaerythritol stearate, adipic acid and stearic acid or It is also possible to use one kind or a combination of two or more kinds of materials such as mixed esters of oleic acid. It has the effect of improving paper separation in oilless fixing and the effect of preventing photoconductor filming.
  • fatty acid hydrocarbon waxes such as polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystalline wax, paraffin wax, and wet push push wax can be suitably used.
  • the wax particle dispersion is prepared by heating, melting, and dispersing wax in ion-exchanged water in an aqueous medium to which a surfactant is added.
  • PR16 16 0/0 diameter (PR16) force 20 ⁇ ; 100nm 50 ⁇ / ⁇ diameter (PR50) force 40 to; 160 nm 8 4 0/0 size (PR 84) force 260nm or less, PR 84 / PR16 force 1.
  • particles of 150 nm or less are 65% by volume or more and particles exceeding 400 nm are 10% by volume or less.
  • PR 84 0/0 size (PR 84) force 220nm or less PR 84 / PR16 force 1. 2-1. 8. It is preferable that particles of 130 nm or less are 65% by volume or more and particles exceeding 300 nm are 10% by volume or less.
  • the 50% diameter (PR50) is reduced to 40 300 nm to obtain a fine dispersion.
  • PR50 50% diameter
  • the molten resin particles surround and include the melted wax particles due to the surface tension.
  • the release agent is easily included in the fat.
  • PR 6 force 200nmJ Redirecting a fence
  • 50 0/0 diameter (PR_50) force 300nmj Redirecting a fence
  • PR_84 force 400nm Yorichi large PI ⁇ 84 / PI ⁇ 16 power 2 ⁇ 0 Rimodai fence
  • 65 vol 0/0 Ri Sukunagu 500 nm 200 nm is more than 10 vol%, the wax aggregation of only "wax itself between the been written Ri taken between the resin particles tends to frequently .
  • particles that are not taken into the resin particles and float in water tend to increase.
  • agglomerated particles When agglomerated particles are obtained by heating the agglomerated particles in an aqueous system, the wax is encapsulated in the resin, in which the melted resin particles do not include the melted wax particles.
  • the amount of wax that is exposed and released on the surface of the toner base increases, filming on the photoconductor, increasing the amount of scavenging on the carrier, handling properties in development, and developing memory. Tends to occur.
  • PR16 force 20nm / J, 50% diameter (PR50) force 40nm / J, drill, PR84 / PR16 force. If you try to make it smaller than 2, the dispersion of the wax will be difficult to maintain Reagglomeration occurs and the stability of the particle size distribution tends to decrease. In addition, the load increases during dispersion, heat generation increases, and productivity tends to decrease.
  • the wax particles can be finely dispersed by emulsifying and dispersing by the action of a high shear force generated by a rotating body rotating at high speed.
  • a gap of about 0.1 mm to 10 mm is provided on the wall of the fixed capacity tank shown in Figs. 3 and 4, and the rotating body is 30 m / s or more, preferably 40 m / s or more, more preferably 50 m.
  • the rotating body is 30 m / s or more, preferably 40 m / s or more, more preferably 50 m.
  • a gap of about 1 to 100 m is provided and is 30 m / s or more, preferably 40 m / s or more, more preferably 50 m / s or more.
  • a fine dispersion can be created by applying a strong shearing force action with the rotating rotating body.
  • the particle size distribution of fine particles is narrower than that of a disperser such as a homogenizer. Can be formed. Further, even when left for a long time, the fine particles forming the dispersion can be kept in a stable dispersion state without reaggregating, and the standing stability of the particle size distribution is improved.
  • a molten liquid is prepared by heating in a high pressure state. Also, the wax is dissolved in an oily solvent. This solution is obtained by dispersing fine particles in water together with a surfactant using a disperser shown in FIGS. 3, 4, 5 and 6, and then evaporating the oily solvent by heating or decompressing.
  • the particle size can be measured using a Horiba laser diffraction particle size measuring device (LA920), a Shimadzu laser diffraction particle size measuring device (SALD2100), or the like.
  • LA920 Horiba laser diffraction particle size measuring device
  • SALD2100 Shimadzu laser diffraction particle size measuring device
  • a colorant (pigment) used in the present embodiment as a colorant (pigment) used in the present embodiment, as a cyan pigment, a blue dyed pigment of phthalocyanine and its derivatives such as CI bignent'blue 15: 3 can be preferably used.
  • Pigment Blue 15: 3 KETBLUE111 manufactured by Dainippon Ink, FASTOGEN BLUE CT-BX130, SANDYESUPERBLUE1809 manufactured by Sanyo Dye Co., and the like can be preferably used.
  • Yellow pigments are CI pigments. Yellow 1, 3, 74, 97 or 98 acetoacetate arylamide monoazo yellow pigments, CI pigments' Yello 12, 13, 14, 17 etc. A yellow pigment, CI sorben yellow 19, 77, 79 or CI disperse yellow 164 is blended, and a CI pigment yellow 93, 180, 185 benzimidazolone pigment is particularly preferred.
  • magenta pigments examples include CI pigment red 48, 49: 1, 53: 1, 57, 57: 1, 81, 1 22, 5 etc. CI solvent. Red 49, 52, 58, 8 Red dyes such as can be preferably used.
  • carbon black can be suitably used.
  • carbon black having a DBP oil absorption (ml / 100g) of 45 to 70 is preferred. That's right. Preferably it is 45-63, More preferably, it is 45-60, More preferably, it is 45-53.
  • the particle size of carbon black is preferably 20 to 40 nm. Preferred particle size is 20 ⁇
  • the particle diameter is an arithmetic average diameter measured by an electron microscope. When the particle size is large, the coloring power tends to decrease. When the particle size is small, dispersion in the liquid tends to be difficult.
  • # 52 particle size 27nm, DBP oil absorption 63ml / 100g
  • # 50 (same 28 belly, 65ml / 100g)
  • # 47 (same 23, 64ml / 100g) manufactured by Mitsubishi Chemical Corporation
  • # 45 (24 and 53 ml / 100 g)
  • # 45 L (24 and 45 ml / 100 g)
  • Cabot REGAL 250R 35 and 46 ml / 100 g
  • REGAL330R 25 and 25 ml) 65ml / 100g
  • MOGULL 24nm, 60ml / 100g
  • More preferred are # 4 5, # 45 and LREGAL250R.
  • the median diameter of each particle is usually 1 ⁇ m or less, preferably 0.01 to 1 m.
  • the median diameter exceeds, the particle size distribution of the finally obtained electrostatic image developing toner becomes wide, or free particles are generated, which tends to deteriorate performance and reliability.
  • the median diameter is within the above range, there is no such disadvantage, and uneven distribution between toners is present. This is advantageous in that it decreases, disperses in the toner better, and reduces variations in performance and reliability.
  • the median diameter can be measured, for example, using a Horiba laser diffraction particle size measuring instrument (LA 920).
  • inorganic fine powder is mixed and added as an external additive.
  • external additives include silica, alumina, titanium oxide, zirconium oxide, magnesia, ferrite, magnetite and other metal oxide fine powders, barium titanate, calcium titanate, titanates such as strontium titanate, barium zirconate, A zirconate salt such as calcium zirconate or strontium zirconate or a mixture thereof is used.
  • External additives are hydrophobized as necessary.
  • silicone oil-based material to be treated as the external additive examples include dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, and methacryl-modified silicone.
  • External additives that are treated with at least one of the following: oil oil, alkyl-modified silicone oil, fluorine-modified silicone oil, amino-modified silicone oil, and chlorophenyl-modified silicone oil are preferably used.
  • Treatment is a method of mixing external additives and materials such as silicone oil with a mixer such as a Henschel mixer (FM 20B manufactured by Mitsui Mining Co., Ltd.), or a method of spraying silicone oil-based materials onto the external additives
  • a mixer such as a Henschel mixer (FM 20B manufactured by Mitsui Mining Co., Ltd.)
  • a method of spraying silicone oil-based materials onto the external additives There is a method in which a silicone oil-based material is dissolved or dispersed in a solvent, mixed with an external additive, and then removed to remove the solvent. It is preferable that 1 to 20 parts by weight of the silicone oil-based material is blended with respect to 100 parts by weight of the external additive.
  • silane coupling agent examples include dimethyldichlorosilane, trimethylchlorosilane, alcohol dimethylchlorosilane, hexamethyldisilazane, arylphenyldichlorosilane, methoxysilane, butyltriethoxysilane, dioxysilane. Bullchlorosilane or dimethylvinylchlorosilane can be preferably used. Silane coupling agent treatment, stirring external additives, etc.
  • the external additive having positive electrode chargeability is treated with aminosilane, amino-modified silicone oil or epoxy-modified silicone oil.
  • Hexamethyldisilazane dimethyldichlorosilane is also used to enhance hydrophobic treatment.
  • silicone oil treatments are preferable.
  • fatty acids it is also preferable to treat the surface of the external additive with one or more types (hereinafter referred to as fatty acids).
  • Surface-treated silica or fine titanium oxide powder is more preferable.
  • Fatty acids or fatty acid metal salts include strong prillic acid, strong puric acid, undecylic acid, lauric acid, myristylic acid, parimitic acid, stearic acid, behenic acid, montanic acid, rataceric acid, oleic acid, erucic acid , Sorbic acid or linoleic acid. Among them, carbon number 12
  • ⁇ 22 fatty acids are preferred.
  • Examples of the metal constituting the fatty acid metal salt include aluminum, zinc, calcium, magnesium, lithium, sodium, lead, and barium. Of these, aluminum, zinc, and sodium are preferable. Particularly preferred is aluminum distearate (Al (OH) (C
  • Fatty acid aluminum and mono fatty acid aluminum are preferable. Having an OH group prevents overcharging and suppresses transfer failure. In addition, it is considered that processing with external additives is improved during processing.
  • Examples of the aliphatic amide include carbons such as normitic acid amide, palmitoleic acid amide, stearic acid amide, oleic acid amide, arachidic acid amide, eicosenoic acid amide, behenic acid amide, erucic acid amide, and ligrinoselic acid amide. Saturated or monovalent unsaturated with the number 16-24 Japanese aliphatic amides are preferably used.
  • fatty acid esters include esters comprising higher alcohols having 16 to 24 carbon atoms and higher fatty acids having 16 to 24 carbon atoms such as stearyl stearate, palmityl normitate, behenyl behenate or stearyl montanate.
  • Esters of higher fatty acids having 16 to 24 carbon atoms and lower monoalcohols such as butyl stearate, isobutyl behenate, propyl montanate or 2-ethylhexyl oleate, or fatty acid pentaerythritol monoester, fatty acid Pentaerythritol triester or fatty acid trimethylolpropane ester is preferably used.
  • One or a combination of two or more types of materials such as polyhydroxy alcohol fatty acid esters such as hydroxystearic acid derivatives, glycerin fatty acid esters, glycol fatty acid esters or sorbitan fatty acid esters may be used.
  • polyhydroxy alcohol fatty acid esters such as hydroxystearic acid derivatives, glycerin fatty acid esters, glycol fatty acid esters or sorbitan fatty acid esters may be used.
  • the surface of the external additive to be treated is treated with a coupling agent and / or polysiloxane such as silicone oil and then treated with a fatty acid or the like.
  • a coupling agent and / or polysiloxane such as silicone oil
  • the toner can be highly charged, and the fluidity when added to the toner is improved.
  • the above effect can also be achieved by treating a fatty acid or the like with a coupling agent and / or silicone oil.
  • Fatty acids and the like are dissolved in a hydrocarbon-based organic solvent such as toluene, xylene, or hexane, and this is mixed with an external additive such as silica, titanium oxide, and alumina by wet mixing and externally added by a processing agent. It is produced by adhering to the surface of the agent, subjecting it to a surface treatment, and then performing a drying treatment by distilling off the solvent.
  • a hydrocarbon-based organic solvent such as toluene, xylene, or hexane
  • the mixing ratio of the polysiloxane and the fatty acid or the like is preferably 1: 2 to 20: 1.
  • the amount of fatty acid and the like is larger than the ratio force S1: 2
  • the charge amount of the external additive increases, and the image density tends to decrease, and charge-up tends to occur in two-component development.
  • the amount of fatty acid or the like is less than 20: 1, the effect on transfer loss and reverse transcription tends to decrease.
  • the loss on ignition of the external additive whose surface is treated with a fatty acid or the like is preferably 1.5 to 25% by weight. More preferably, it is 5-25 weight%, More preferably, it is 8-20 weight%. 1. 5 When the content is less than% by weight, the function of the treating agent is not fully exhibited, and the effect of improving the chargeability and transferability does not appear. If it exceeds 25% by weight, untreated agent is present, which adversely affects developability and durability.
  • the surface of the toner base particles produced according to the present invention is formed of only a resin, so that it is advantageous in terms of charge uniformity. This is because compatibility with the external additive used is important with respect to charge retention.
  • an external additive having an average particle diameter of 6 nm to 200 nm with respect to 100 parts by weight of the toner base particles.
  • the average particle size is smaller than 6 nm, the floating particles and the filming to the photoconductor tend to occur easily. Reverse transfer during transfer tends to occur easily. When it exceeds 200 nm, the fluidity of the toner tends to deteriorate. If the amount is less than 1 part by weight, the fluidity of the toner tends to deteriorate. Reverse transfer during transfer tends to occur. When the amount is more than 6 parts by weight, the floating particles and the filming on the photosensitive member tend to occur.
  • the external additive having an average particle diameter of 6 nm to 20 nm is 0.5 to 2.5 parts by weight with respect to 100 parts by weight of the toner base particles, and the external additive having an average particle diameter of 20 nm to 200 nm is the toner base particles. It is also preferable to add at least 0.5 to 3.5 parts by weight with respect to 100 parts by weight.
  • the ignition loss of the external additive having an average particle size of 6 nm to 20 nm is preferably 0.5 to 20% by weight, and the ignition loss of the average particle size of 0.3 to 200 nm is preferably 1.5 to 25% by weight. .
  • ignition loss is 1.5-1 7% by weight, more preferably 4 to 10% by weight.
  • the loss on ignition with an average particle size of 20 nm to 200 nm is less than 1.5% by weight, the transfer margin for reverse transfer and voids tends to be narrow. If it exceeds 25% by weight, the surface treatment becomes uneven, and there is a tendency for variation in charging.
  • the ignition loss is preferably 2.5 to 20% by weight, more preferably 5 to 15% by weight.
  • an external additive having an average particle diameter of 6 nm to 20 nm and an ignition loss of 0.5 to 20% by weight is 0.5 to 2 parts by weight with respect to 100 parts by weight of the toner base particles.
  • An external additive having a diameter of 20 nm to 100 nm and an ignition loss of 1.5 to 25% by weight is 0.5 to 3.5 parts by weight with respect to 100 parts by weight of the toner base particles, and the average particle diameter is 100 nm to 200 nm.
  • the functionally separated external additive composition that specifies the average particle size and loss on ignition increases the charge imparting and charge retention, reverse transfer during transfer, and improvements in voids, as well as deposits on the carrier surface. The effect is obtained in removing.
  • an external additive having a positive charging property with an average particle diameter of 6 nm to 200 nm and an ignition loss of 0.5 to 25% by weight is further added to 0.2 to 100 parts by weight of the toner base particles. It is also preferable to externally treat 5 parts by weight.
  • the effect of adding an external additive having a positive charging property can prevent the toner from being overcharged during long-term continuous use, and can further extend the life of the developer. Furthermore, the effect of suppressing scattering during transfer due to overcharging can also be obtained. In addition, the spent on the carrier can be prevented. If the amount is less than 0.2 parts by weight, it is difficult to obtain the effect. 1. If the amount exceeds 5 parts by weight, fogging during development increases.
  • the loss on ignition is preferably 1.5 to 20% by weight, more preferably 5 to 19% by weight.
  • the average particle size is a straight line obtained by taking an enlarged photograph with SEM and calculating the average value of the major and minor axes of about 100 particles.
  • Loss on drying (% by weight) is obtained by weighing approximately 1 lg of sample in a container that has been dried, allowed to cool, and precisely weighed in advance. Dry in a hot air drier (105 ° C ⁇ 1 ° C) for 2 hours. Allow it to cool in a desiccator for 30 minutes, then weigh it precisely and calculate it using the following formula.
  • Loss on drying (wt%) [Loss on drying (g) / Sample (g)] X 100 For loss on ignition, take approximately 1 lg of sample in a magnetic crucible that has been dried, allowed to cool, and precisely weighed in advance, and weigh it accurately.
  • Loss on ignition (wt%) [Loss on ignition (g) / Sample amount (g)] X 100
  • the moisture absorption amount of the treated external additive is preferably 1% by weight or less. Preferably, it is 0.5% by weight or less, more preferably 0.1% by weight or less, and further preferably 0.05% by weight or less. If the amount is more than 1% by weight, the chargeability is lowered and filming on the photoconductor during durability is caused.
  • the water adsorption amount was measured with a continuous vapor adsorption device (BELS ORP18: Nippon Bell Co., Ltd.) for the water adsorption device.
  • the degree of hydrophobicity is measured by methanol titration, and 0.2 g of the product to be tested is weighed into 50 ml of distilled water placed in a 250 ml beaker. At the tip, add methanol from the burette infiltrated in the liquid until the total amount of the external additive is wet. In that case, slowly stir slowly with an electromagnetic stirrer. The degree of hydrophobicity is calculated from the amount of methanol a (ml) essential for complete wetting by the following formula.
  • the toner base particles containing a binder resin, a colorant and a wax have a volume average particle diameter of 3 to 6111, a volume-based variation coefficient of 10 to 25%, and 2.0 to 3 in a number-based distribution.
  • the content of toner particles having a particle size of 111 is 10 to 85% by number, and the toner particles having a particle size of 3.5 to 4 ⁇ 53 m in the volume-based distribution is 25 to 75% by volume.
  • the toner particles having a particle size of 6.06 m or more in the distribution are contained in 5% by volume or less, and the volume percent of the toner particles having a particle size of 3.5 to 4.53 111 in the volume-based distribution is V 34,
  • the number of toner particles having a particle size of 3.5 to 4.53 m in the number-based distribution,% P34 is preferably in the range of P34 / V34 force SO. 4 to 2.2.
  • the volume average particle size of the toner base particles is 3 to 511 m, and the volume-based coefficient of variation is
  • the content of toner particles having a particle size of 2.0 to 3.63 m in the number-based distribution of 10 to 20% is 15 to 85% by number, and the particle size of 3.5 to 4.53 111 in the volume-based distribution.
  • the toner particles have a particle size of 30-65% by volume and a volume-based distribution of 6.06 m or more. Toner particles are contained in an amount of 2% by volume or less, and P34 / V34 force SO.
  • the toner base particles have a volume average particle size of 3 to 5 m, a volume-based variation coefficient of 10 to 16%, and a particle size distribution of 2.0 to 3.63 m in the number-based distribution.
  • the toner particle content is 25 to 85% by number, and the toner particle having a particle size of 3.5 to 4.53 111 in the volume-based distribution is 40 to 60% by volume, and the particle size of 6.06 m or more in the volume-based distribution. In the range of 0.5 to 0.9% by volume, and P34 / V34 force SO. 5 to 0.9.
  • the toner particle size distribution affects toner fluidity, image quality, storage stability, filming on the photoconductor, developing roller, and transfer body, aging characteristics, transferability, especially multi-layer transfer in the tandem system. In addition, it affects the high temperature non-offset property and glossiness of oilless fixing.
  • the amount of fine powder has an effect on the compatibility with tandem transferability in toners containing tuss to achieve oilless fixing.
  • volume average particle size exceeds 6 m, it is impossible to achieve both image quality and transfer!
  • volume average particle size is less than 3 m, the handling of toner particles during development tends to be difficult.
  • toner particles having a particle size of 2.0 to 3.63 m in the number-based distribution is less than 10% by number, it tends to be impossible to achieve both image quality and transfer. If it exceeds 85% by number, handling of the toner base particles during development tends to be difficult. In addition, filming may occur on the photosensitive member, the developing roller, and the transfer member. In addition, the fine powder has a high adhesion to the heat roller, so it tends to be hot offset! In addition, as compared with the tandem system, toner aggregation becomes stronger, and the second-color transfer failure tends to easily occur during multi-layer transfer. An appropriate range is required.
  • toner particles having a particle size of 3.5 to 4.53 111 in the volume-based distribution are less than 25% by volume, the image quality tends to deteriorate. If it exceeds 75% by volume, it tends to be impossible to achieve both image quality and transfer.
  • toner particles having a particle size of 6.06 111 or more in the volume-based distribution are contained in an amount exceeding 5% by volume, the image quality is deteriorated and tends to cause transfer defects.
  • P34 / V34 is smaller than 0.4, the amount of fine powder present becomes excessive, and the fluidity tends to decrease, the transferability deteriorates, and the ground strength prevails. 2. When larger than 2, there are many large particles and the particle size distribution becomes broad, and it tends to be impossible to achieve high image quality.
  • P34 / V34 can be used as an index for making toner particles small and narrowing the particle size distribution.
  • the coefficient of variation is obtained by dividing the standard deviation of the toner particle diameter by the average particle diameter. This is based on the particle size measured using a corner letter counter (Coulter).
  • the standard deviation is expressed as the square root of the value obtained by dividing the square of the difference from the average value of each measured value by dividing (n-1) when measuring n particle systems.
  • the variation coefficient represents the extent of the particle size distribution. If the variation coefficient of the volume particle size distribution is less than 10% or the variation coefficient of the number particle size distribution is less than 10%, it is difficult to produce. This is difficult and causes cost increase. If the coefficient of variation of volume particle size distribution is greater than 25%, or the coefficient of variation of number particle size distribution is greater than 28%, the particle size distribution becomes broad, toner cohesion becomes stronger, and filming and transfer to the photoconductor are performed. It tends to cause defects.
  • the shape index of the toner is preferably 1.25 to; 1.55, more preferably 1.33 to 1.46, and still more preferably 1.35-1.42.
  • the sagging property due to the rubber blade that progresses in a spherical shape decreases, and when the irregular shape progresses, the transferability tends to decrease.
  • the shape index of the toner base particles is SC and the volume average particle diameter is d50 (am)
  • the product of SC and d50 is a force of 3.9-7.3. . It is preferably 4.0 to 6.6, more preferably ⁇ to 4. 1 to 5.7.
  • the cleaning performance with the rubber blade tends to deteriorate when the spheroidization of the shape proceeds when the particle is shifted to a small particle size.
  • the particle shifts to a large particle size if the shape progresses to an irregular shape, it may tend to cause a decrease in transferability and a decrease in image quality.
  • the shape is shifted to an irregular shape.
  • the product of SC and d50 is set within a certain range. 3. If it is smaller than 9, the cleaning property tends to deteriorate. 7.
  • the particle size distribution is measured using a Coulter Counter TA-II (Coulter Counter), connected to an interface (manufactured by Nikkiki) that outputs the number distribution and volume distribution, and a personal computer.
  • Electrolyte solution with a surfactant sodium lauryl sulfate
  • Add about 2 mg of the toner to be measured to about 50 ml, and the electrolyte solution in which the sample is suspended is about 3 with an ultrasonic disperser. Dispersed for minutes! /, Coulter counter TA-II aperture 70 m aperture was used.
  • the particle size distribution measurement range is 1. 26 ⁇ 111-50.8 m, the force is less than 2.0 m.
  • the area below 2.0 m is affected by external noise, etc. Is low! /, Not practical for! / ,. Therefore, the measurement area was set to 2 ⁇ 0 ⁇ to 50 ⁇ 8 ⁇ m.
  • the shape index was determined by measuring the maximum length and projected area of 100 toner base particles magnified 1000 times, and using the following formula ( d: maximum length of toner particles, A: projected area of toner particles, ⁇ is the circumference).
  • ⁇ is a perfect circle whose diameter is the maximum length d of toner particles
  • the area of perfect circle B is ⁇ ⁇ (d / 2) 2
  • oil is not used as a means for fixing toner! /, And it is preferably used for an electrophotographic apparatus having a fixing process of an oil-less fixing configuration.
  • the heating means electromagnetic induction heating is preferable from the viewpoint of shortening the warm-up time and saving energy.
  • a transfer medium such as copy paper on which toner is transferred is passed between the rotary heating member and the rotary pressurizing member and fixed.
  • the feature is that the warm-up time of the rotary heating member is much faster than when using a conventional halogen lamp! Therefore, the temperature of the rotary pressurizing member is sufficiently raised! / ,! In order to enter the copying operation, low temperature fixing and a wide range of offset resistance are required.
  • a configuration using a fixing belt in which a heating member and a fixing member are separated is also preferably used.
  • a nickel electric belt having heat resistance and deformability, or a polyimide heat resistant belt is preferably used.
  • silicone rubber, fluororubber or fluororesin is preferable to use as the surface layer.
  • the toner With the toner having releasability without using oil, it is no longer necessary to apply release oil. However, if the release oil is not applied, the toner may jump due to the effect of charging when the toner image is immediately charged and the unfixed toner image comes close to the heating member or the fixing member. Especially at low temperatures and low humidity!
  • the toner of this embodiment low temperature fixing and a wide range of offset resistance can be realized without using oil, and high color translucency can be obtained. Further, the toner can be prevented from being overcharged, and toner flying due to the charging action with the heating member or the fixing member can be suppressed.
  • this embodiment has a plurality of toner image forming stations including a photosensitive member, a charging unit, and a toner carrier, and visualizes an electrostatic latent image formed on the image carrier.
  • a primary transfer process in which an endless transfer member is brought into contact with the image bearing member and transferred to the transfer member is sequentially executed in order to form a multilayer transfer toner image on the transfer member.
  • the transfer process configured to execute a secondary transfer process in which the multilayer toner images formed on the transfer body are collectively transferred to a transfer medium such as paper or OHP
  • the first primary When the distance from the transfer position to the second primary transfer position is dl (mm), and the peripheral speed of the photoconductor is v (mm / s), the transfer position is dl / v ⁇ 0.65. It is intended to achieve both the miniaturization of the machine and the printing speed. It is essential to shorten the distance between multiple toner image forming stations and increase the process speed in order to realize a miniaturization that can process 20 sheets per minute (A4) or more and the machine can be used for SOHO applications. It is.
  • the above value is 0.6 or less.
  • the time from the primary transfer of the first color yellow toner to the primary transfer of the next second color magenta toner is extremely short.
  • the magenta toner is repelled by the charge action of the yellow toner, resulting in a decrease in transfer efficiency.
  • cyan toner splatters, transfer defects, and transfer loss occur significantly when transferred onto the previous yellow and magenta toners.
  • the toner of a specific particle size is selectively developed during repeated use, and if the flowability of each toner particle is significantly different, the chance of tribocharging is different, resulting in variations in charge amount and more transferability. It will cause deterioration.
  • the toner of the present embodiment the charge distribution is stabilized, toner overcharge can be suppressed, and fluidity fluctuation can be suppressed. For this reason, it is possible to prevent a decrease in transfer efficiency without sacrificing the fixing characteristics, character dropout during transfer, and reverse transfer.
  • the R SiO unit represented by (Chemical Formula 1) is 15 ⁇ 4mo.
  • R is a methyl group, ie (CH 3)
  • R represented by (Chemical Formula 2) is a methyl group, that is, CH SiO unit is 84.6 mol% 250 g of polyonoreganosiloxane was reacted with 21 g of CF 2 CH 2 CH 3 Si (OCH 3) to obtain a fluorine-modified silicone resin. Further, 100 g of the fluorine-modified silicone resin and 10 g of aminosilane coupling agent ( ⁇ -aminopropyltriethoxysilane) in terms of solid content were weighed and dissolved in 3 OOcc toluene solvent.
  • R ′, R 2 , R 3 and R 4 are methyl groups, and m is the average degree of polymerization and is 100.
  • R ′, R 2 , R 3 , R 4 , R 5 , R s are methyl groups, and n is the average degree of polymerization, which is 80.
  • Table 1 shows the characteristics of the resin particles obtained in the prepared resin particle dispersions (RL1, RL2, RL3, RH1, RH2, RH3, RH4, RH5, RH6).
  • Mn is the number average molecular weight
  • Mw is the weight average molecular weight
  • Mz is the Z average molecular weight
  • Mw / Mn is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) Mw / Mn
  • Mz / Mn is the ratio of Z average molecular weight (Mz) to number average molecular weight (Mn) Mz / Mn
  • Mp is the peak molecular weight
  • Tg (° C) is the glass transition point
  • Ts ( ° C) represents the softening point.
  • Non-ionic surfactant manufactured by Sanyo Kasei Co., Ltd.
  • styrene 240 ⁇ lg n-butylene taleate 59 ⁇ 9 g
  • clinoleic acid 8 g Nonipol 400
  • Anionic surfactant (Daiichi Kogyo Seiyaku, Neogen S20-F (20% by weight aqueous solution concentration)) 24g (Real anion amount 4 ⁇ 8g)
  • Dodecanethiol 8g After dispersing, 4.5 g of potassium persulfate was added thereto, and emulsion polymerization was performed at 78 ° C.
  • Table 2 shows the nonionic amount (g) and the anionic amount (g) of the surfactant used in each resin particle dispersion, and the ratio (wt%) of the nonionic amount to the total surfactant amount.
  • a liquid using an anionic surfactant (Daiichi Kogyo Seiyaku, Neogen S20-F (solid content 20% by weight))
  • ion-exchanged water was adjusted so that the concentration would be about 20% by weight.
  • the weight ratios in Table 2 indicate the actual anion content ratio!
  • Tables 3 and 4 show the blending amounts of acrylic acid and potassium persulfate used for each resin particle dispersion based on the preparation of resin particle dispersion RL1 in the emulsion polymerization of each resin particle dispersion.
  • Potassium persulfate indicates parts by weight based on 100 parts by weight of the monomer component.
  • Table 5 and Table 6 show the pigments that are colorants and the surfactants used.
  • Table 8 Table 9 and Table 10 show the wax materials used and their characteristics, respectively, in preparation of the wax particle dispersion according to this example formed as an example of the preparation of the wax particle dispersion.
  • Fig. 3 shows a schematic diagram of a stirrer / disperser (T-K Film Mix manufactured by Tokushu Kika Co., Ltd.), and Fig. 4 shows a top view.
  • 801 is an outer tank, in which cooling water is injected from 808 and discharged from 807.
  • 802 is a dam plate that stops the liquid to be treated, and a hole is formed in the central portion. The treated liquid is sequentially taken out through 805 to the outside.
  • 803 is a rotating body that rotates at a high speed and is fixed to the shaft 806 and can rotate at a high speed. On the side of the rotating body, a hole of about 1 to 5 mm is drilled to allow the liquid to be treated to move.
  • the tank is 120 ml, and about half of the liquid to be treated is charged.
  • the speed MAX of the rotating body can be up to 50m / s.
  • the diameter of the rotating body is 52 mm, and the inner diameter of the tank is 56 mm.
  • Reference numeral 804 denotes a raw material inlet for continuous processing. Seal for high pressure treatment or batch type!
  • Table 13 shows the respective configurations of the toner bases (CT2, CT3, CT4) and toner bases (ctl, ct5) for comparison according to the examples of the present invention, which were prepared as toner base preparation examples.
  • the temperature was raised from 20 ° C to 90 ° C at a rate of / min, and then heat-treated for 3 hours to obtain core particles.
  • the resulting core particle dispersion had a pH of 9.1.
  • the second resin particle dispersion RH4 adjusted to pH 10.5, 120g was continuously added dropwise over the required time of 30min. 1. Heat treated for 5 hours to obtain particles in which the second resin particles were fused.
  • toner base material was filtered and washed seven times with ion-exchanged water.
  • the toner base thus obtained was dried at 35 ° C. for 8 hours with a fluid dryer to obtain toner base CT2.
  • Table 14 shows the characteristics obtained in the toner base prepared.
  • the difference in Ts is the difference in softening point Ts3 between the first resin Tsl and the third resin
  • the difference in Mw is the Mwr3 of the third resin divided by Mwr3 of the first resin.
  • d50 m represents the volume average particle size of the toner base particles
  • the volume variation coefficient represents the spread of the particle size distribution on the volume basis of the toner base particles in the obtained toner base. 2.
  • 0-3.63 ( ⁇ %) is the content of toner particles having a particle size of 2.0-3.63 H m in the number-based distribution, and over 6.06 m (v%) is 6 in the volume-based distribution.
  • the SEM observation image of the ctl toner shape is shown in Fig. 12, the SEM observation image of CT2 is shown in Fig. 13, the SEM observation image of CT4 toner is shown in Fig. 14, and the SEM observation image of ct5 toner is shown in Fig. 15.
  • CT2, CT3, and CT4 toners exhibited good cohesiveness and obtained toner bases with small particle size and narrow particle size distribution. In Sampnore, where the softening point of the third resin is increased, the shape tends to shift from spherical to potato.
  • Table 15 shows the compositions of the toner bases (CT7, CT8, CT9, CT10) according to the examples of the present invention prepared as examples of toner bases and the toner bases (ct6, ctl l) for comparison. Show.
  • Table 16 shows the characteristics obtained in the toner base prepared.
  • Fig. 16 shows the SEM image of CT7
  • Fig. 17 shows the SEM image of CT8 toner
  • Fig. 18 shows the SEM image of ctl l toner.
  • CT7, CT8, CT9, and CT10 toners showed good cohesiveness and obtained toner bases with small particle size and narrow particle size distribution.
  • the spherical force tends to shift to a potato shape.
  • Table 17 shows the respective compositions of the toner bases (CT13, CT14, CT15) and toner bases for comparison (ctl2) prepared as examples of toner bases according to the present invention.
  • Table 18 shows the characteristics obtained in the toner base prepared.
  • the pH of the mixed dispersion was set to 11 because the aggregation of the core particles progressed quickly.
  • CT13, CT14, and CT15 toners showed good aggregation properties.
  • the shape tends to shift from spherical to potato.
  • Table 19 shows toner bases (C
  • T17, CT18) and comparative toner bases show the respective compositions.
  • Table 20 shows the characteristics obtained in the toner base prepared.
  • the toners of CT17 and CT18 showed good cohesiveness and a toner base having a small particle size and a narrow particle size distribution.
  • the shape tends to shift from spherical to potato as the amount increases.
  • the blending amount is increased too much, the ctl9 toner does not progress completely until the core particles agglomerate. Even after 6 hours, the liquid is not completely transparent.
  • the toner bases CTw20, CTw21, CTw22, CTw23, CTw24, CTw25, and CTw26 were observed based on the conditions of CT17 by changing the wax dispersion to be added and observing the cohesiveness of the particles.
  • Table 21 shows toner bases (CTw20, CTw21, CTw22, CTw23, CTw24, CTw25, CTw26) prepared as examples of toner bases according to the embodiments of the present invention. Indicates.
  • Table 22 shows the characteristics obtained in the toner matrix prepared.
  • Table 23 shows the materials and characteristics of the external additives (Sl, S2, S3, S4, S5, S6, S7, S8, S9) used in this example.
  • the 5-minute value is preferably ⁇ 100 ⁇ 800 C / g, and the 30-minute value is preferably ⁇ 50 to ⁇ 600 ° C./g. Highly charged silica can exhibit these characteristics with a small amount.
  • Table 24 shows toners (TCT2 to TCT4, TCT7 to TCT10, TCT12 to TCT14, TCT17 to TCT18, TCT20 to TCT26) prepared as examples of toner preparation and toners for comparison (t ctl).
  • Tct5, tct6, tctlO, tctll, tctl5, tctl6, tctl9 Show the material composition of each. Unblended indicates no addition.
  • the value in parentheses at the end of the symbol indicating the external additive in the external additive column indicates the value of the external additive relative to 100 parts by weight of the toner base. Represents the amount (parts by weight).
  • stirring blade Z0S0 type stirring blade Z0S0 type, rotation speed 2000min—treatment time 5min, input lkg
  • FIG. 1 is a cross-sectional view showing a configuration of an image forming apparatus for full color image formation used in this example.
  • the transfer belt unit 17 includes a transfer belt 12, a first color (yellow) transfer roller 10Y made of an elastic material, a second color (magenta) transfer roller 10mm, a third color (cyan) transfer roller 10C, and a fourth color ( Black) Transfer roller 10K, drive roller 11 made of aluminum roller, second transfer roller 14 made of elastic, second transfer driven roller 13, belt cleaner blade 16 for cleaning the toner image remaining on the transfer belt 12, cleaner A roller 15 is provided at a position facing the blade.
  • the distance from the first color ( ⁇ ) transfer position to the second color ( ⁇ ) transfer position is 70mm.
  • (2nd color (M) transfer position to 3rd color (C) transfer position, 3rd color (C) transfer position to 4th color (K) transfer position is also the same distance
  • peripheral speed of photoconductor is 125mm / s It is.
  • the transfer belt 12 is used by kneading a conductive filler in an insulating polycarbonate resin and forming a film with an extruder.
  • polycarbonate resin for example, Iupilon Z300 manufactured by Mitsubishi Gas Chemical Co., Ltd.
  • conductive carbon for example, ketjen black
  • the surface is coated with a fluororesin, the thickness is about 100 m, the volume resistance is 10 7 to 10 12 ⁇ 'cm, and the surface resistance is 10 7 to 10 12 ⁇ / mouth. This is also for improving dot reproducibility.
  • the first transfer roller is a carbon conductive urethane foam roller having an outer diameter of 8 mm, and the resistance value is 10 2 to 10 6 ⁇ .
  • the first transfer roller 10 is pressed against the photosensitive member 1 via the transfer belt 12 with a pressing force of 1.0 to 9.8 ( ⁇ ), and the toner on the photosensitive member is transferred onto the belt. Is done.
  • the resistance value is smaller than 10 2 ⁇ , retransfer is likely to occur. Larger than 10 6 ⁇ , transfer failure tends to occur. If it is less than 1.0 ( ⁇ ), transfer defects will occur, and if it is greater than 9.8 ( ⁇ ), transfer characters will be lost.
  • the second transfer roller 14 is a carbon conductive urethane foam roller having an outer diameter of 10 mm, and the resistance value is 10 2 to 10 6 ⁇ .
  • the second transfer roller 14 is pressed against the transfer roller 13 via the transfer belt 12 and a transfer medium 19 such as paper or paper.
  • the transfer roller 13 is configured to be driven to rotate by the transfer belt 12.
  • the second transfer roller 14 and the counter transfer roller 13 in the second transfer are pressed against each other with a pressing force of 5.0 to 21.8 ( ⁇ ), and toner is transferred from the transfer belt onto the recording material 19 such as paper. Transcribed.
  • the resistance value is smaller than 10 2 ⁇ , retransfer is likely to occur. Transfer defects are more likely to occur than 10 6 ⁇ . If it is less than 5 ( ⁇ ), the transfer will be defective, and if it is more than 21.8 ( ⁇ ), the load will increase and jitter will be likely to occur.
  • Each image forming unit 18Y, 18M, 18C, 18K is made up of the same constituent members except for the developer contained therein. Therefore, in order to simplify the description, the image forming unit 18Y for a bag is described and others The description of the color unit is omitted.
  • the image forming unit is configured as follows. 1 is a photoconductor, 3 is a pixel laser signal light, 4 is a developing roller made of aluminum with a magnet having a magnetic force of 1200 gauss inside, and has a 10 mm outer diameter, facing the photoconductor with a gap of 0.3 mm, in the direction of the arrow Rotate to. 6 is a stirring roller that stirs the toner and carrier in the developing unit and supplies them to the developing roller. The mixing ratio of the carrier and the toner is read by a magnetic permeability sensor (not shown) and supplied from a toner hopper (not shown) in a timely manner. 5 is a metal magnetic blade that regulates the developer magnetic brush layer on the developing roller.
  • the developer amount is 150g.
  • the gap was 0.4 mm.
  • the power source is the omitted force s , and the developing roller 4 is applied with a DC voltage of 500 V and an AC voltage of 1.5 kV (pp) and a frequency of 6 kHz.
  • the peripheral speed ratio between the photoconductor and the developing roller was 1: 1.6.
  • the mixing ratio of toner and carrier was 93: 7, and the amount of developer in the developing unit was 150 g.
  • [0381] 2 is a charging roller made of epichlorohydrin rubber having an outer diameter of 10 mm, and a DC bias of 1.2 kV is applied. Charge the surface of photoconductor 1 to -600V. 8 is a cleaner, 9 is a waste toner bot, and 7 is a developer.
  • the paper is conveyed from below the transfer unit 17, and the paper 19 is fed by a paper feed roller (not shown) to the nip portion where the transfer belt 12 and the second transfer roller 14 are in pressure contact with each other. In addition, a paper conveyance path is formed.
  • the toner on the transfer belt 12 is transferred to the paper 19 by +1000 V applied to the second transfer roller 14, and the fixing roller 201, the caloric pressure roller 202, the fixing paper 203, the heating medium roller 204, and the induction heater section. It is conveyed to a fixing unit composed of 205 and fixed there.
  • Fig. 2 shows the fixing process diagram. Between the fixing roller 201 and the heat roller 204, there is a belt 203 force S force. A predetermined load is applied between the fixing roller 201 and the pressure roller 202, and an ep is formed between the belt 203 and the pressure roller 202.
  • An induction heater unit 205 consisting of a ferrite core 206 and a coil 207 is provided on the outer peripheral surface of the heat roller 204, and a temperature sensor 208 is disposed on the outer surface.
  • the belt is made of 30 mm of Ni as a base material, and silicone rubber is 150 mm on it. Overlay the 30 ⁇ m PFA tube.
  • the pressure roller 202 is pressed against the fixing roller 201 by a pressure spring 209.
  • the recording material 19 having the toner 210 moves along the guide plate 211.
  • the fixing roller 201 as a fixing member has a rubber hardness (JIS-A) of 20 according to the JIS standard on the surface of an aluminum hollow roller metal core 213 having a length of 250 mm, an outer diameter of 14 mm, and a thickness of 1 mm.
  • An elastic layer 214 having a thickness of 3 mm and made of silicone rubber is provided.
  • a silicone rubber layer 215 is formed with a thickness of 3 mm, and the outer diameter is about 26 mm. It receives a driving force from a drive motor (not shown) and rotates at 125mm / s.
  • the heat roller 204 is a hollow pipe having a wall thickness of lmm and an outer diameter of 20mm.
  • the surface temperature of the fixing belt was controlled at 170 ° C using a thermistor.
  • the pressure roller 202 as a pressure member has a length of 250 mm and an outer diameter of 20 mm.
  • This is a hollow roller cored bar 216 made of aluminum with an outer diameter of 16 mm and a thickness of 1 mm.
  • An elastic layer 217 with a thickness of 2 mm made of silicone rubber with a JIS standard rubber hardness (JIS-A) of 55 degrees is provided on the surface.
  • JIS-A JIS standard rubber hardness
  • the pressure roller 202 is rotatably installed, and a two-ply width of 5. Omm is formed between the pressure roller 202 and the fixing roller 201 by a spring-loaded spring 209 on one side 147N.
  • the operation will be described.
  • the first transfer rollers 10 of all of Y, M, C, and K are pushed up, and the photoreceptor 1 of the image forming unit is pressed through the transfer belt 12.
  • a DC bias of +800 V is applied to the first transfer roller.
  • An image signal is sent from the laser beam 3 and is incident on the photosensitive member 1 whose surface is charged by the charging roller 2 to form an electrostatic latent image.
  • the toner on the developing roller 4 that rotates in contact with the photoreceptor 1 visualizes the electrostatic latent image formed on the photoreceptor 1.
  • the image forming speed of the image forming unit 18Y (125 mm / s equal to the peripheral speed of the photoconductor) and the moving speed of the transfer belt 12 are 0.5 to 1. It is set to be 5% slower.
  • Y signal light 3Y is input to image forming unit 18Y, and image formation with Y toner is performed. Simultaneously with the image formation, the first transfer roller 10Y causes the Y toner image to be transferred from the photosensitive member 1Y to the transfer belt 12. At this time, the first transfer roller 10Y has + 800V A DC voltage was applied.
  • 3M is input to the image forming unit 18M to form an image with M toner.
  • the first transfer roller 10M causes the M toner image to be transferred from the photoreceptor 1M to the transfer belt 12.
  • the first color (Y) toner is formed and the M toner is transferred.
  • image formation with C (cyan) and K (black) toners is performed, and simultaneously with image formation, a YMCK toner image is formed on the transfer belt 12 by the action of the first transfer rollers 10C and 10B. This is a so-called tandem system.
  • the transfer belt 12 On the transfer belt 12, four color toner images were positioned and overlapped to form a color image. After the final transfer of the B toner image, the four color toner images are collectively transferred to the paper 19 fed from a paper feed cassette (not shown) at the same time by the action of the second transfer roller 14. At this time, the transfer roller 13 was grounded, and a + lkV DC voltage was applied to the second transfer roller 14. The toner image transferred to the paper was fixed by a fixing roller pair 201 ⁇ 202. The paper was then discharged out of the apparatus through a pair of discharge rollers (not shown). The toner remaining on the intermediate transfer belt 12 is cleaned by the action of the cleaning blade 16 and is prepared for the next image formation.
  • the two-component developers DCT2 to DCT4, DCT7 to DCT9, DCT12 to DCT14, DCT17 to DCT18, and DCT20 to DCT26 according to the examples of the present invention were subjected to a 100,000-sheet run-ung durability test on A4 size paper.
  • the toner filming on the photoconductors was at a level with no practical problem.
  • the toner filming on the transfer belt was also at a level where there was no practical problem.
  • no poor cleaning of the photoreceptor and transfer belt occurred. Even in a full-color image in which the three colors overlapped, no paper wrapping around the fixing belt occurred.
  • the two-component developers according to the examples of the present invention both obtained high-density images having an image density of 1.3 or more. Even after the endurance test of 100,000 sheets of A4 stencil, the flowability of the two-component developer was stable, and the image density showed stable characteristics with little change of 1.3 or more.
  • the two-component developers according to the embodiments of the present invention are both high-image density, toner scattering that causes non-image area fogging, etc. It was high resolution. The uniformity was also good when a solid image was taken at the time of development.
  • the two-component developers according to the examples of the present invention were at a level where there was no practical problem such as blanking. . Also, even in a full-color image in which the three colors overlapped, no transfer failure occurred. The transfer efficiency was about 95%.
  • the two-component developer according to the embodiment of the present invention has a toner concentration with little change in image quality such as image density and background fog. A wide degree of control!
  • the two-component developer (dct5, dctlO, dctl 5, dctl9) for comparison causes toner filming on the photoreceptor in the running durability test.
  • the image density before and after the running test tends to be low, the image density will decrease after long-term use, or the fog in the non-image area will increase.
  • the charge decreased and the fog increased.
  • the phenomenon worsened in a wet environment. This may be due to the effects of wax, resin particles and particles that are not added to the aggregation during the aggregation reaction.
  • Table 26 shows the evaluation results on the fixing property, non-offset property, high-temperature storage stability, and paper wrapping property around the fixing lentore in a full-color image.
  • “G” indicates that the evaluation result is good
  • “F” indicates that there is a problem.
  • a solid image with an adhesion amount of 1.2 mg / cm 2 was processed at a process speed of 125 mm / s, a fixing device using a belt not coated with oil, OHP film transmittance (fixing temperature 160 ° C), and at least The fixing temperature and the temperature at which the offset phenomenon occurred at high temperatures were measured.
  • the storage stability test at high temperature evaluated the toner state after standing at 50 ° C for 24 hours.
  • the film transmittance for OHP was measured using a spectrophotometer U-3200 (Hitachi) to measure the light transmittance at 700 nm.
  • Toners TCT2 to TCT4, TCT7 to TCT9, TCT12 to TCT1, 4, TCT17 to TCT18, and TCT20 to TCT21 all have a film transmittance for OHP of 70% or more. It was good.
  • non-offset properties can be obtained over a wide range of 140 to 200 ° C or more in the non-offset temperature range for fixing rollers that do not use oil, and the fixing temperature range (minimum fixing temperature to high temperature offset phenomenon occurrence temperature) Wide). The offset phenomenon did not occur even with 200,000 full-color images of plain paper.
  • the surface deterioration phenomenon of the belt was not observed even when the oil was not applied to the fixing belt made of a silicone resin or a fluororesin.
  • the agglomeration was a force hardly observed even in the storage stability at 50 ° C for 24 hours.
  • the paper jam around the fixing belt did not cause jamming of the OHP film at the fixing nip.
  • Toners for comparison, tct5, tctlO, tbtl5, and tbtl9 toners had weak high-temperature non-offset properties, and the margin of the fixable area was narrow. This seems to be the effect of wax particles and resin particles that do not participate in the aggregation reaction.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

Le toner selon l'invention comprend des particules à base de toner et un additif externe, dans lequel les particules à base de toner sont des particules obtenues en fusionnant des particules de résine d'enrobage sous la forme de deuxièmes particules de résine avec des particules noyaux produites par l'agrégation d'au moins des particules de résine liante en tant que premières particules de résine, des particules de résine ajustant la forme pour ajuster la forme du toner sous la forme de troisièmes particules de résine, des particules de colorant, et des particules de cire dans un milieu aqueux, les particules de résine ajustant la forme et les particules de résine d'enrobage ayant des points de ramollissement supérieurs à celui des particules de résine liante. Par conséquent, un toner ayant une distribution granulométrique étroite avec un petit diamètre de particule et ayant une forme convenablement ajustée peut être produit sans avoir besoin d'une étape de séparation granulométrique. Ce toner est efficace pour empêcher l'apparition d'endroits non imprimés ou des pertes pendant le transfert. L'invention concerne également un procédé de production du toner.
PCT/JP2007/070350 2006-11-07 2007-10-18 Toner et procédé de production de toner WO2008056519A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140107519A (ko) * 2011-12-28 2014-09-04 캐논 가부시끼가이샤 토너
US20210302851A1 (en) * 2020-03-24 2021-09-30 Canon Kabushiki Kaisha Toner and method for producing toner

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003066639A (ja) * 2001-08-30 2003-03-05 Konica Corp 電子写真画像形成装置、画像形成方法及びプロセスカートリッジ
JP2004354411A (ja) * 2003-05-26 2004-12-16 Kao Corp トナーの製造方法
JP2005134605A (ja) * 2003-10-30 2005-05-26 Konica Minolta Business Technologies Inc 静電荷像現像用トナー及び静電荷像現像用トナーの製造方法
JP2005221933A (ja) * 2004-02-09 2005-08-18 Konica Minolta Business Technologies Inc 静電荷像現像用トナー
JP2006011385A (ja) * 2004-05-26 2006-01-12 Matsushita Electric Ind Co Ltd トナーの製造方法、これを用いた二成分現像剤及び画像形成装置
JP2006084923A (ja) * 2004-09-17 2006-03-30 Matsushita Electric Ind Co Ltd トナー、トナーの製造方法、二成分現像剤及び画像形成装置
JP2006221207A (ja) * 2006-05-29 2006-08-24 Konica Minolta Holdings Inc 静電荷像現像用トナー及び画像形成方法
JP2006267301A (ja) * 2005-03-22 2006-10-05 Fuji Xerox Co Ltd 静電荷像現像用トナー及びその製造方法、静電荷像現像剤並びに画像形成方法
JP2006301606A (ja) * 2005-03-23 2006-11-02 Konica Minolta Business Technologies Inc 電子写真用トナー及びその製造方法

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003066639A (ja) * 2001-08-30 2003-03-05 Konica Corp 電子写真画像形成装置、画像形成方法及びプロセスカートリッジ
JP2004354411A (ja) * 2003-05-26 2004-12-16 Kao Corp トナーの製造方法
JP2005134605A (ja) * 2003-10-30 2005-05-26 Konica Minolta Business Technologies Inc 静電荷像現像用トナー及び静電荷像現像用トナーの製造方法
JP2005221933A (ja) * 2004-02-09 2005-08-18 Konica Minolta Business Technologies Inc 静電荷像現像用トナー
JP2006011385A (ja) * 2004-05-26 2006-01-12 Matsushita Electric Ind Co Ltd トナーの製造方法、これを用いた二成分現像剤及び画像形成装置
JP2006084923A (ja) * 2004-09-17 2006-03-30 Matsushita Electric Ind Co Ltd トナー、トナーの製造方法、二成分現像剤及び画像形成装置
JP2006267301A (ja) * 2005-03-22 2006-10-05 Fuji Xerox Co Ltd 静電荷像現像用トナー及びその製造方法、静電荷像現像剤並びに画像形成方法
JP2006301606A (ja) * 2005-03-23 2006-11-02 Konica Minolta Business Technologies Inc 電子写真用トナー及びその製造方法
JP2006221207A (ja) * 2006-05-29 2006-08-24 Konica Minolta Holdings Inc 静電荷像現像用トナー及び画像形成方法

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140107519A (ko) * 2011-12-28 2014-09-04 캐논 가부시끼가이샤 토너
KR101582063B1 (ko) 2011-12-28 2015-12-31 캐논 가부시끼가이샤 토너
US20210302851A1 (en) * 2020-03-24 2021-09-30 Canon Kabushiki Kaisha Toner and method for producing toner
US11966196B2 (en) * 2020-03-24 2024-04-23 Canon Kabushiki Kaisha Toner and method for producing toner

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