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
  • G03G9/097—Plasticisers; Charge controlling agents
  • G03G9/09708—Inorganic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
  • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
• • 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
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/087—Binders for toner particles
  • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • G03G9/08773—Polymers having silicon in the main chain, with or without sulfur, oxygen, nitrogen or carbon only
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/097—Plasticisers; Charge controlling agents
  • G03G9/09708—Inorganic compounds
  • G03G9/09716—Inorganic compounds treated with organic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G9/00—Developers
  • G03G9/08—Developers with toner particles
  • G03G9/097—Plasticisers; Charge controlling agents
  • G03G9/09708—Inorganic compounds
  • G03G9/09725—Silicon-oxides; Silicates

Definitions

• the present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet method.
• toner As image forming apparatuses using toner, such as copiers and printers, are widely spread, the performance required of the toner is becoming more sophisticated. In order to obtain a high quality image even when outputting images at high speed and in a large amount over a long period of time, it is required that the characteristics of the toner be stable. Specifically, even when a strong stress is applied to the toner, a toner having a small change in chargeability and a small change in fluidity is required.
• JP-A-2012-149169 discloses a technique for maintaining the flowability of the main body of resin particles by adding atypical silica particles produced by a sol-gel method to the main body (toner particles) of resin particles. ing.
• the silica particles are atypical, the micro flowability of the silica particles on the surface of the toner particles is lowered, which causes a decrease in the chargeability of the toner, and changes in the density of the output image (image density).
• image density changes in the density of the output image (image density).
• An object of the present invention is to provide a toner with less change in chargeability and flowability.
• the present invention is a toner particle containing a binder resin, and a toner having an inorganic fine particle A,
• the shape factor SF-2 of the primary particles of the inorganic fine particles A is 116 or less
• the particle size at which the cumulative value from the small particle side is 16 volume% is D16
• the particle size at which the cumulative value is 50 volume% is D50.
• D84 the particle diameter at which the cumulative value is 84% by volume is D84
• D50 is 80 nm or more and 200 nm or less
• a toner having a particle size distribution index A represented by D84 / D16 is 1.70 or more and 2.60 or less.
• the toner of the present invention is a toner particle containing a binder resin and a toner having an inorganic fine particle A,
• the shape factor SF-2 of the primary particles of the inorganic fine particles A is 116 or less,
• the particle size at which the cumulative value from the small particle side is 16 volume% is D16
• the particle size at which the cumulative value is 50 volume% is D50.
• D84 the particle size distribution index A represented by D84 / D16 is characterized by being 1.70 or more and 2.60 or less.
• the particle size distribution index A in the present invention indicates the value of D84 / D16.
• the toner of the present invention is a highly durable toner with stable chargeability and little change in fluidity even when used for a long time, it is possible to output a high quality image stably.
• the inorganic fine particles A of the toner of the present invention have a broad particle size distribution on a volume basis as compared with conventional inorganic fine particles of large particle size.
• particle size distribution means particle size distribution on a volume basis unless otherwise noted.
• particles tend to be in a close-packed state.
• it is easy to roll on the surface of the toner particle may be unevenly distributed in the recess and may stay, and the spacer effect (effect as spacer particle) may be reduced.
• each of the large-diameter inorganic fine particles can be rotated on the surface of the toner particles, but the inorganic fine particles are closely arranged, so their mutual movement is limited to a certain extent. .
• the inorganic fine particles are easily present in the convex portions of the surface of the toner particles, and the spacer effect is maintained because the particles are not extremely unevenly distributed.
• the particle size distribution is sharp, the heights of the large-diameter inorganic fine particles from the surface of the toner particles are substantially the same. Therefore, when the toner continues to be stressed in the developing device or the like, the large-diameter inorganic fine particles on the surface of the toner particles are similarly loaded, and thus are similarly embedded in the toner particles.
• the particle size distribution is broad, the heights of the large-diameter inorganic fine particles on the surface of the toner particles are dispersed.
• the inorganic particle on the higher side larger particle size side
• the inorganic fine particles on the lower side small particle size side
• the spacer effect is maintained for a long time.
• the inorganic fine particles A of the toner of the present invention have high micro fluidity because the shape of the primary particles is approximately spherical to spherical. Therefore, as described above, even in the state of being limited to a certain extent on the surface of the toner particles, the large-diameter inorganic fine particles can move, and stable chargeability can be maintained.
• the inorganic fine particles having a large particle diameter are hardly embedded in the surface of the toner particles, and the spacer effect is maintained. As a result, chargeability and fluidity can be maintained.
• the shape factor SF-2 of primary particles is 116 or less, preferably 113 or less, and more preferably 110 or less.
• the inorganic fine particles A of the toner of the present invention are approximately spherical or spherical. Therefore, the fluidity on the surface of the toner particles is excellent.
• the shape factor SF-2 is larger than 116, the micro fluidity is reduced, so that the chargeability of the toner tends to be reduced, or the toner particles are difficult to disperse uniformly on the surface of the toner particles. It becomes easy to fall.
• the inorganic fine particles A of the toner of the present invention have a particle diameter D50 of 80 nm or more and 200 nm or less in which the cumulative value from the small particle side is 50 volume% in the particle size distribution based on volume on the surface of toner particles.
• D50 is 80 nm or more and 180 nm or less, more preferably 80 nm or more and 150 nm or less.
• D50 is smaller than 80 nm, the fluidity of the toner can be secured at the initial stage of use, but the spacer effect can not be sufficiently obtained, so that the inorganic fine particles as the external additive are easily embedded in the toner particles when used for a long time.
• the flowability of the toner is likely to change significantly, making it difficult to obtain uniform charging, and making it difficult to obtain a stable image density.
• D50 is larger than 200 nm, the particle diameter becomes too large, and it becomes difficult to uniformly adhere to the surface of toner particles. As a result, it becomes difficult to obtain sufficient fluidity of the toner.
• the inorganic fine particles A of the toner particles of the present invention have a particle size distribution index A of 1.70 to 2.60, preferably 1.80 to 2.50, and more preferably 1.90 to 2.40. It is below.
• the particle size distribution index A is in the above-mentioned range, the inorganic fine particles can be densely present on the surface of the toner particles, so that their movements are restricted to a certain extent. As a result, the inorganic fine particles are easily present in the convex portions of the surface of the toner particles and are not extremely unevenly distributed, so that the spacer effect is maintained.
• the particle size distribution index A is smaller than 1.70, the particle size distribution is sharp, and thus the inorganic fine particles may easily roll on the surface of the toner particles, and may be unevenly distributed and retained in the concave portion. As a result, the spacer effect (effect as a spacer particle) may be reduced.
• the particle size distribution index A is larger than 2.60, coarse particles in the inorganic fine particles increase, it becomes difficult to disperse uniformly on the surface of the toner particles, and the spacer effect tends to be reduced.
• the particle size distribution index B represented by D84 / D50 is preferably 1.20 or more and 1.60 or less, and more preferably 1.25 or more and 1.50 or less. And more preferably 1.30 or more and 1.40 or less.
• the particle size distribution index B in the present invention indicates the value of D84 / D50. As the particle size distribution index B becomes larger, it is shown that the larger particle size side is broader than the smaller particle size side. When the particle size distribution index B is in the above range, the micro flowability of the inorganic fine particles is enhanced, and the flowability of the toner can be maintained higher.
• Inorganic particles A of the toner of the present invention preferably has a compaction degree is 1.05 g / cm 3 or more, more preferably 1.20 g / cm 3 or more, more preferably at 1.30 g / cm 3 or more is there.
• the pressure density in the present invention is a density measured by applying 10 MPa. Detailed measurement methods will be described later.
• the pressure density is in the above-mentioned range, the inorganic fine particles become denser, and the inorganic fine particles are arranged more firmly on the surface of the toner particles. Therefore, even when a strong stress is applied to the toner, the stress is dispersed in the surface (dispersed in the surface direction), so that it is difficult for the inorganic fine particles to be embedded in the surface of the toner particles.
• binder resin examples include the following polymers. Monomers of styrene and substituted compounds thereof, such as polystyrene, poly-p-chlorostyrene, polyvinyl toluene and the like; Styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinyl naphthalene copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene- ⁇ -chloromethacrylate Acid methyl ester copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl ethyl ether copolymer, st
• Styrenic copolymer Polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester, polyurethane, polyamide, furan resin, epoxy resin, xylene resin, polyvinyl butyral, Terpene resin, coumarone-indene resin, petroleum resin.
• polyester from the viewpoint of low temperature fixability and chargeability of the toner.
• the toner particles of the toner of the present invention may contain a wax.
• the wax include the following. Hydrocarbon-based waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; Oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; Waxes based on fatty acid esters such as carnauba wax; Deoxidized some or all of fatty acid esters such as deoxidized carnauba wax.
• Hydrocarbon-based waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, Fischer-Tropsch wax
• Oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof
• Waxes based on fatty acid esters such as carnauba wax
• Deoxidized some or all of fatty acid esters such as
• hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax
• fatty acid ester waxes such as carnauba wax
• hydrocarbon-based waxes are more preferable from the viewpoint of the hot offset resistance of the toner.
• the content of the wax in the toner particles is preferably 1.0 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin in the toner particles.
• the hot offset resistance at high temperature is further improved.
• the peak temperature of the maximum endothermic peak of the toner it is preferable to satisfy the following regarding the peak temperature of the maximum endothermic peak of the toner.
• the peak temperature of the maximum endothermic peak existing in the temperature range of 30 ° C. or more and 200 ° C. or less is 50 ° C. or more and 110 ° C. or less in the endothermic curve at the time of temperature rise measured by differential scanning calorimetry (DSC) Is preferred.
• the toner particles of the toner of the present invention may contain a colorant.
• a colorant known yellow colorants, magenta colorants, cyan colorants and black colorants can be used.
• black colorant examples include carbon black, and those toned in black using a yellow colorant, a magenta colorant and a cyan colorant.
• a coloring agent a pigment or a dye may be used alone, or a combination of a dye and a pigment may be used.
• the content of the colorant in the toner particles is preferably 0.1 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the binder resin in the toner particles.
• the toner of the present invention may be magnetic toner or nonmagnetic toner.
• magnetic iron oxide As a magnetic toner, it is preferable to use magnetic iron oxide as a magnetic substance to be contained in toner particles.
• magnetic iron oxide include magnetite, maghematite and ferrite.
• the content of the magnetic substance in the toner particles is preferably 25 parts by mass or more and 95 parts by mass or less, and more preferably 30 parts by mass or more and 45 parts by mass or less with respect to 100 parts by mass of the binder resin in the toner particles. It is.
• the toner particles of the toner of the present invention may contain a charge control agent.
• charge control agents include negative charge control agents and positive charge control agents.
• negative charge control agents examples include Salicylic acid metal compound, Naphthoate metal compound, Metal compounds of dicarboxylic acid, Polymer type compounds having a sulfonic acid or carboxylic acid in the side chain, Polymer type compounds having a sulfonate or sulfonate ester in the side chain, Polymer type compounds having carboxylic acid salt or carboxylic acid ester in the side chain, Boron compounds, Urea compounds, Silicon compounds, Calixarene etc. are mentioned.
• the charge control agent may be internally or externally added to the toner particles.
• the content of the charge control agent in the toner particles is preferably 0.2 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the binder resin in the toner particles.
• the toner of the present invention has inorganic fine particles A.
• the inorganic fine particles A for example, silicon oxide (silica), aluminum oxide (alumina), titanium oxide (titania), magnesium oxide, zirconium oxide, chromium oxide, chromium oxide, cerium oxide, tin oxide, zinc oxide and the like metal oxides There are fine particles. Further, as the inorganic fine particles A, for example, amorphous carbon (such as carbon black), nitride (such as silicon nitride), carbide (such as silicon carbide), metal salt (such as strontium titanate, calcium sulfate, barium sulfate or calcium carbonate) And the like.
• amorphous carbon such as carbon black
• nitride such as silicon nitride
• carbide such as silicon carbide
• metal salt such as strontium titanate, calcium sulfate, barium sulfate or calcium carbonate
• the inorganic fine particles as described above may be used alone as the inorganic fine particles A, or plural kinds thereof may be used in combination. Further, the inorganic fine particles A of the toner of the present invention may be fine particles of a composite of a plurality of metal oxides.
• the inorganic fine particles A are preferably silica fine particles. Since the silica fine particles have high resistance, resistance as a toner is increased, charge relaxation in a high temperature and high humidity (H / H) environment is suppressed, and the charge rising property of the toner is excellent.
• Examples of the method for producing silica fine particles include the following methods.
• a flame melting method in which silicon compounds are made gaseous and decomposed and melted in a flame.
• a gas phase process (dry process silica, fumed silica) in which silicon tetrachloride is burned at a high temperature with a mixed gas of oxygen, hydrogen and a diluent gas (eg, nitrogen, argon, carbon dioxide, etc.).
• a mixed gas of oxygen, hydrogen and a diluent gas eg, nitrogen, argon, carbon dioxide, etc.
• a wet method in which an alkoxysilane is hydrolyzed with a catalyst in an organic solvent in the presence of water, condensation reaction is carried out, then the solvent is removed from the obtained silica sol suspension and the solvent is dried.
• a method of forming silica fine particles having a desired volume average particle diameter by classification treatment and / or crushing treatment may be employed by using silica fine particles obtained by the above-described manufacturing method.
• the volume average particle size is an average particle size on a volume basis.
• the fine inorganic particles A of the toner of the present invention are more resistant and less susceptible to humidity, and therefore, fine silica particles produced by a gas phase method or a flame melting method are more preferable.
• the volume average particle diameter or volume standard of primary particles of silica fine particles depending on the feed rate of the source gas, the supply amount of combustible gas and / or the oxygen ratio. It is possible to control the particle size distribution at
• the flame melting method is particularly preferable as the method for producing silica fine particles.
• the produced silica fine particles can be present as relatively independent particles.
• the fine silica particles produced by the sol-gel method tend to have a sharp particle size distribution on a volume basis.
• the surface of the inorganic fine particles A of the toner of the present invention be hydrophobized by surface treatment. Since the surface is hydrophobized, the moisture absorption of the silica fine particles is suppressed, the chargeability of the toner is increased, the toner is easily charged even during the endurance, and a stable image density is easily obtained.
• Examples of the surface treatment include silane coupling treatment, oil treatment, fluorine treatment, and surface treatment for forming an alumina coating. It is also possible to use a plurality of surface treatments in combination, and the order of those treatments can be arbitrarily selected.
• the inorganic fine particles A of the toner of the present invention is more preferably surface-treated using hexamethyldisilazane as a surface-treating agent.
• oils for oil treatment of inorganic fine particles examples include silicone oil, fluorine oil, various modified oils and the like. More specifically, dimethyl silicone oil, alkyl modified silicone oil, ⁇ -methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil and the like can be mentioned.
• the silicone oil one having a viscosity of 50 to 500 mm 2 / s at 25 ° C. is preferable.
• the oil processing amount is preferably 1 part by mass or more and 35 parts by mass or less with respect to 100 parts by mass of a raw material of inorganic fine particles (inorganic fine particles before treatment).
• the content of the inorganic fine particles A in the toner of the present invention is preferably 0.5 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the binder resin contained in the toner particles.
• the amount is more preferably 0.8 parts by mass or more and 10.0 parts by mass or less, and still more preferably 1.0 parts by mass or more and 8.0 parts by mass or less.
• the true density of the inorganic fine particles A of the toner of the present invention is preferably 2.0 g / cm 3 or more, more preferably 2.2 g / cm 3 or more.
• the coverage of the surface of the toner particles with the inorganic fine particles A is preferably 15% or more and 45% or less, and more preferably 20% or more and 35% or less.
• the coverage can be adjusted by controlling the addition amount of the inorganic fine particles A or the mixing time of the toner particles and the inorganic fine particles A.
• the inorganic fine particles A of the toner of the present invention preferably have one peak in the particle size distribution on a volume basis.
• inorganic fine particles A in which a plurality of types of inorganic fine particles having different average particle diameters are used in combination are used as the inorganic fine particles A, the chargeability and aggregation property of the respective inorganic fine particles constituting the inorganic fine particles A often differ. Therefore, the inorganic fine particles A may not be uniformly attached to the surface of the toner particles, or may be unevenly distributed for each of the inorganic fine particles constituting the inorganic fine particles A.
• small particle size inorganic fine particles have strong electrostatic and non-electrostatic adhesion to toner particles.
• the inorganic fine particles having a small particle size constituting the inorganic fine particles A tend to adhere to the surface of the toner particles more quickly than the inorganic fine particles having a large particle size.
• the large particle size inorganic fine particles having a strong spacer effect must be attached onto the small particle size inorganic fine particles attached to the surface of the toner particles.
• the inorganic fine particles having a large particle size tend to be unevenly distributed on the surface of the toner particles, and the spacer effect (the effect as a spacer particle) tends to be reduced by using for a long time.
• an external additive other than the inorganic fine particles A may be added in order to improve the flowability of the toner and to adjust the amount of frictional charge.
• inorganic fine particles such as silicon oxide (silica), aluminum oxide (alumina), titanium oxide (titania), strontium titanate, calcium carbonate and the like are preferable.
• external additives other than inorganic fine particles include resin fine particles such as vinyl resins, polyesters, silicone resins, and the like.
• These inorganic fine particles and resin fine particles function as toner charging control, flowability and cleaning aids.
• toner particles and external additive including inorganic fine particles A
• a mixer can be used.
• the toner of the present invention is preferably mixed with a magnetic carrier and used as a two-component developer from the viewpoint of obtaining a stable image over a long period of time.
• Magnetic carrier for example, Iron powder with oxidized surface or unoxidized iron powder, Metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, rare earths or alloy particles thereof Oxide particles, Magnetic particles such as ferrite, Magnetic substance dispersed resin carrier (so-called resin carrier) containing magnetic substance particles and binder resin for holding the magnetic substance particles in a dispersed state
• resin carrier Magnetic substance dispersed resin carrier
• the toner particles of the present invention can be produced by a known method for producing toner particles, such as a melt-kneading method, an emulsion aggregation method, or a dissolution suspension method.
• the shape factor SF-2 of the inorganic fine particles A on the surface of the toner particles and the particle size based on the volume of the inorganic fine particles A were calculated as follows. First, a surface image of toner particles was photographed at 30,000 times using an ultra-high resolution field emission scanning electron microscope (trade name: S-4800) manufactured by Hitachi High-Technologies Corporation.
• the shape factor SF-2 of the inorganic fine particles A, the inorganic fine particles A is analyzed by analyzing the photographed surface image with an image analysis software (trade name: Image-Pro Plus ver. 5.0) manufactured by Nippon Roper. The particle size on a volume basis was calculated.
• the particle size of the inorganic fine particles A on a volume basis is D16, where the cumulative value from the small particle side is 16% by volume, and the cumulative value is 50% by volume, in the cumulative frequency of equivalent circle diameters from the obtained image.
• D50 be the particle diameter that results
• D84 be the particle diameter at which the cumulative value is 84% by volume.
• the same operation was performed on the inorganic fine particles A on the surface of ten toner particles, and the average value of each was determined.
• the particle size distribution index A: D84 / D16 and the particle size distribution index B: D84 / D50 were respectively calculated from the determined values.
• a sample left for 24 hours in an environment of 23 ° C./50% RH was precisely weighed, placed in a measuring cell (10 cm 3 ), and inserted into a main body sample chamber.
• the measurement can be automatically measured by inputting the mass (weight) of the sample into the body and starting the measurement.
• the measurement conditions of automatic measurement used helium gas adjusted at 20.000 psig (2.392 ⁇ 10 2 kPa). After purging the sample chamber ten times, equilibrate the pressure change in the sample chamber to 0.005 psig / min (3.447 ⁇ 10 -2 kPa / min), and repeatedly purge helium gas until the equilibrium state is reached. did. The pressure in the main sample chamber at equilibrium was measured.
• sample volume was calculated by the pressure change when it reached its equilibrium state.
• the sample volume was calculated and the true density of the sample was calculated by the following equation.
• Sample true density (g / cm 3 ) sample mass (g) / sample volume (cm 3 )
• the average value of the values obtained by repeating this automatic measurement five times was taken as the true density (g / cm 3 ) of the inorganic fine particles A.
• the coverage is the image of the surface of toner particles taken with a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corp.) as image analysis software Image-Pro Plus ver. It analyzed and computed with 5.0 (Nippon Roper Co., Ltd.). Image shooting conditions of S-4800 are as follows.
• the sample stage was set in the sample holder, and the sample stage height was adjusted to 36 mm by a sample height gauge.
• the anticontamination trap attached to the S-4800's case was flushed with liquid nitrogen and left for 30 minutes.
• the "PC-SEM" of S-4800 was activated to perform flushing (cleaning of the FE chip as an electron source).
• the acceleration voltage display portion of the control panel on the screen was clicked, and the [Flushing] button was pressed to open the flushing execution dialog.
• the flushing intensity was confirmed to be 2 and executed. It was confirmed that the emission current by flushing was 20 to 40 ⁇ A.
• the sample holder was inserted into the sample chamber of the S-4800 housing.
• the [Origin] on the control panel was pressed to move the sample holder to the observation position.
• the acceleration voltage display unit was clicked to open the HV setting dialog, and the acceleration voltage was set to [0.8 kV], and the emission current was set to [20 ⁇ A].
• the [Basic] tab of the operation panel set the signal selection to [SE], select [Up (U)] and [+ BSE] for the SE detector, select [+ BSE] in the selection box to the right L. A. 100] was selected, and the observation mode was set to a backscattered electron image.
• the probe current of the electron optical system condition block is set to [Normal]
• the focus mode is set to [UHR]
• WD is set to [3.0 mm].
• the acceleration voltage was applied by pressing the [ON] button on the acceleration voltage display section of the control panel.
• the magnification was set to 10,000 (10 k) times, focusing was performed using the focus knob and the STIGMA / ALIGNMENT knob in the same manner as described above, and focusing was performed again by autofocus. This operation was repeated again to focus.
• the inclination angle of the observation surface is large, the measurement accuracy of coverage tends to be low. Therefore, by selecting the one in which the entire observation surface is simultaneously in focus at the time of focus adjustment, the one with no surface inclination as much as possible is selected. And analyzed.
• toner (toner particles) to be photographed toner particles having a maximum length (Lt) of toner (toner particles) in the range of 0.8 ⁇ Dv ⁇ Lt ⁇ 1.2 ⁇ Dv were selected. This is intended to use an average toner close to the volume average particle size (Dv).
• Image storage Brightness adjustment was performed in the ABC mode, and a photo was taken with a size of 640 ⁇ 480 pixels and stored. The following analysis was performed using this image file. One photograph was taken for one toner particle, and an image was obtained for at least 100 toner particles.
• the surface coverage is calculated by performing image processing on the image obtained by the above-described method using the following analysis software.
• the analysis conditions of 5.0 are as follows. Soft Image-Pro Plus 5.1 J When the background which is not the surface of the toner (toner particles) is reflected, the following analysis is performed after only the surface portion of the toner (toner particles) is regarded as the area of interest (AOI).
• the free curve AOI button can be selected from the AOI tool, and the AOI can be defined by drawing a closed curve that traces the contour of the surface portion of the toner (toner particles). In the toolbar, "Measure”-"Count / Size” was selected in the order, and "Automatic extraction of bright objects” was selected in the "Selection of brightness range” column.
• the volume average particle diameter (Dv) of the toner is A precise particle size distribution measuring device by pore electric resistance method (trade name: Coulter Counter Multisizer 3, manufactured by Beckman Coulter, Inc.) equipped with a 100 ⁇ m aperture tube, Using dedicated software (product name: Beckman Coulter Multisizer 3 Version 3.51, Beckman Coulter made) for setting measurement conditions and analyzing measurement data, the number of effective measurement channels: 25,000 channels It measured on conditions and analyzed and measured measurement data.
• electrolytic aqueous solution used for the measurement a solution obtained by dissolving special grade sodium chloride in deionized water to a concentration of about 1% by mass (trade name: ISOTON II, manufactured by Beckman Coulter, Inc.) was used.
• binder resin ⁇ Production example of polyester resin>
• the above monomer material was charged into a reaction vessel equipped with a cooling pipe, a stirrer, a nitrogen introducing pipe and a thermocouple.
• the pressure in the reaction vessel is lowered to 8.3 kPa, maintained for 1 hour, cooled to 180, allowed to react as it is, and it is confirmed that the softening point measured according to ASTM D36-86 has reached 122 ° C. The temperature was lowered to stop the reaction.
• the softening point (Tm) of the obtained polyester resin was 112 ° C., and the glass transition temperature (Tg) was 63 ° C.
• silica fine particle 1 In the production of the silica fine particle 1, a double-pipe hydrocarbon-oxygen mixed burner capable of forming an inner flame and an outer flame was used as a combustion furnace.
• the burner is configured such that a two-fluid nozzle for slurry injection is grounded at the center of the burner and a silicon compound of the raw material is introduced. Further, a combustible gas of hydrocarbon and oxygen is injected from the periphery of the two-fluid nozzle, and it is configured to form an inner flame and an outer flame which are reducing atmospheres.
• the atmosphere, temperature and flame length can be adjusted.
• silica fine particles are generated from the silicon compound of the raw material, and further, the silica fine particles can be fused until the desired particle size is obtained. Thereafter, the resultant is cooled, and the generated silica fine particles are collected by a bag filter or the like to obtain silica fine particles having a desired particle diameter.
• silica fine particles As a raw material silicon compound, hexamethyl cyclotrisiloxane was used to manufacture silica fine particles. Next, with respect to 100 parts by mass of the obtained silica fine particles, surface treatment was performed with 4% by mass of hexamethyldisilazane to obtain a silica fine particle 1.
• silica fine particles 3 to 14 were obtained by adjusting the production conditions of the silica fine particle 1 described above.
• silica fine particles 1 and 3 to 14 Physical properties of the toner using the obtained silica fine particles 1 and 3 to 14 are shown in Table 1.
• Silica fine particles 1 and 3 to 14 correspond to inorganic fine particles A according to the present invention.
• silica fine particle 2 100 parts by mass of the silica fine particles produced by the sol-gel method was surface-treated with 4% by mass of hexamethyldisilazane to obtain a silica fine particle 2.
• the silica fine particles 2 do not correspond to the inorganic fine particles A according to the present invention.
• Polyester resin 1 100.0 parts by mass
• Aluminum 3,5-di-t-butylsalicylic acid 0.5 parts by mass Fischer-Tropsch wax (peak temperature of maximum endothermic peak: 90 ° C.) 5.0 parts by mass C.
• Pigment Blue 15 35.0 parts by mass
• a Henschel mixer (trade name: FM75J type, manufactured by Mitsui Miike Kako Co., Ltd.) under the conditions of 20 s -1 rotation speed and 5 minutes rotation time
• the mixture was kneaded with a twin-screw kneader (trade name: PCM-30 type, manufactured by Ikegai Co., Ltd.) set to a temperature of 125.degree.
• the obtained kneaded product was cooled and roughly crushed to 1 mm or less with a hammer mill to obtain a roughly crushed product.
• the obtained crude product was finely pulverized by a mechanical pulverizer (trade name: T-250, manufactured by Turbo Kogyo Co., Ltd.). Further, classification was performed using a rotary type classifier (trade name: 200 TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles.
• the operating condition of the rotary classifier (trade name: 200 TSP, manufactured by Hosokawa Micron Corporation) was such that the classification rotor rotational speed was 50.0 s ⁇ 1 .
• the volume average particle diameter (Dv) of the obtained toner particles was 6.2 ⁇ m.
• To 100.0 parts by mass of the obtained toner particles 1.0 parts by mass of hydrophobic silica fine particles having a primary average particle diameter of 15 nm surface-treated with 20.0% by mass of hexamethyldisilazane, and the above-mentioned silica fine particles 1 5.0 parts by mass was added, mixed with a Henschel mixer (trade name: FM75J type, manufactured by Mitsui Miike Koko Co., Ltd.), passed through an ultrasonic vibration sieve with a mesh size of 54 ⁇ m, and Toner 1 was obtained.
• a Henschel mixer trade name: FM75J type, manufactured by Mitsui Miike Koko Co., Ltd.
• the obtained toner 1 had an endothermic peak derived from a wax component at 90 ° C. in a DSC curve by differential scanning calorimetry.
• the magnetic carrier used is a magnetic ferrite carrier particle (number average particle diameter: 35 ⁇ m) obtained by surface coating with an acrylic resin.
• the two-component developer 1 was obtained as described above.
• Toners 2 to 15 were produced in the same manner as in Example 1 except that the silica fine particles 1 were changed as shown in Table 1, and further, two-component developers 2 to 15 were produced.
• Example 2 The same evaluation as in Example 1 was performed using the obtained two-component developers 2 to 15. The evaluation results are shown in Table 2.
• the image output endurance test of 300,000 sheets is carried out under normal temperature and humidity environment (23 ° C./50% RH) and high temperature and high humidity environment (30 ° C./80% RH), and then evaluated by the following method.
• Evaluation 1 Evaluation of image density Regarding the evaluation of the image density, after the endurance test, three solid images were outputted on the entire surface of A3 size paper, and the third image was used for the evaluation.
• the density of the output image was measured at 5 points using a spectrodensitometer (trade name: 500 series) manufactured by X-Rite Co., and the average value of the 5 points was taken to obtain an image density, which was judged by the following index. Since the change in the chargeability of the toner affects the image density, it is possible to evaluate the stability (the small amount of change) in the chargeability of the toner by this evaluation. The higher the image density maintenance rate described below, the higher the stability of the chargeability of the toner (the change of the chargeability is small).
• Dot reproducibility index (I) ⁇ / S ⁇ 100 A: I is less than 4.0 B: I is 4.0 or more and less than 6.0 C: I is 6.0 or more and less than 8.0 D: I is 8.0 or more

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