[go: up one dir, main page]

WO2005071493A1 - Toner et procede de fabrication de toner - Google Patents

Toner et procede de fabrication de toner Download PDF

Info

Publication number
WO2005071493A1
WO2005071493A1 PCT/JP2004/018438 JP2004018438W WO2005071493A1 WO 2005071493 A1 WO2005071493 A1 WO 2005071493A1 JP 2004018438 W JP2004018438 W JP 2004018438W WO 2005071493 A1 WO2005071493 A1 WO 2005071493A1
Authority
WO
WIPO (PCT)
Prior art keywords
toner
wax
measured
scan
particles
Prior art date
Application number
PCT/JP2004/018438
Other languages
English (en)
Japanese (ja)
Inventor
Yasukazu Ayaki
Koji Abe
Original Assignee
Canon Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Canon Kabushiki Kaisha filed Critical Canon Kabushiki Kaisha
Priority to EP20040801658 priority Critical patent/EP1693711B1/fr
Priority to JP2005517200A priority patent/JP4721429B2/ja
Priority to US11/122,031 priority patent/US7250241B2/en
Publication of WO2005071493A1 publication Critical patent/WO2005071493A1/fr
Priority to US11/688,704 priority patent/US7300737B2/en

Links

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
    • G03G9/0802—Preparation methods
    • G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0802—Preparation methods
    • G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
    • G03G9/0806—Preparation methods whereby the components are brought together in a liquid dispersing medium whereby chemical synthesis of at least one of the toner components takes place
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0821—Developers with toner particles characterised by physical parameters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature

Definitions

  • the present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, a magnetic recording method, and a toner jet method, and a method for producing the toner.
  • an electrostatic image is formed on a photoreceptor by various means, and then the electrostatic image is developed using toner to form a toner image on the photoreceptor.
  • the toner image is fixed to the transfer material by a fixing method such as heating, pressure, heating pressure, or solvent vapor to obtain an image (for example, Non-Patent Document 1).
  • toners used for these purposes are generally prepared by melt-mixing a colorant comprising a dye and / or a pigment in a thermoplastic resin, producing a uniformly dispersed colorant-dispersed resin composition, and then dispersing the colorant.
  • the resin composition has been manufactured to have a desired particle size by a fine milling device and a classifier.
  • the colorant-dispersed resin composition must be sufficiently brittle and capable of being pulverized in an economically feasible manufacturing equipment.
  • the particle size range of the particles formed when the material is actually pulverized at high speed tends to be widened, and in particular, there is a problem that relatively large particles are included.
  • the colorant-dispersed resin composition is made brittle, the particle size range of the particles formed when the material is actually pulverized at high speed tends to be widened, and in particular, there is a problem that relatively large particles are included. Sometimes.
  • a method for producing a toner by a suspension polymerization method has been proposed.
  • a polymerizable monomer, a colorant, a polymerization initiator, and, if necessary, a crosslinking agent, a charge control agent, and other additives are uniformly dissolved or dispersed, and the polymerizable monomer is dissolved.
  • the polymerizable monomer composition is dispersed in an aqueous dispersion medium containing a dispersion stabilizer using a suitable stirrer, and the polymerizable monomer is polymerized to obtain a desired particle size.
  • this method does not include a pulverizing step, the toner particles do not need to be brittle and a soft material can be used. It has excellent triboelectricity. Since the classifying process can be omitted, cost saving effects such as energy saving, shortening of manufacturing time, and improvement of process yield are great.
  • a pressure heating method using a heat roller hereinafter, referred to as a heat roller fixing method
  • a heat fixing method hereinafter, referred to as a heat roller fixing method
  • a fixing method such as a film fixing method has been developed.
  • fixing is performed by allowing a toner image on a sheet to be fixed to pass through the surface of a heat roller or a fixing film under pressure by a contacting pressure member.
  • the heat roller or the surface of the fixing film and the toner image of the sheet to be fixed come into contact with each other under pressure. Good fixation can be performed ,.
  • a toner containing a box having a high affinity for a binder resin shows good offset resistance performance and low-temperature fixing performance under specific fixing conditions (for example, Patent Documents 4 and 5).
  • the toner containing two or more types of waxes having different affinities with the binding resin can improve the anti-offset performance while exhibiting a good low-temperature fixing property under specific fixing conditions. (See, for example, Patent Documents 6, 7, 8, and 9).
  • the glass transition point of the toner decreases as the wax becomes compatible with the binder resin, so if the low-temperature fixing performance is to be further improved, the storage stability, fluidity, and chargeability Is easily damaged, and particularly when continuous printing is performed, a remarkable decrease in density and image defects are likely to occur. For this reason, a toner that satisfies storage stability performance and development stability performance and has further low-temperature fixing performance has been desired.
  • Patent Document 1 Japanese Patent Publication No. 36-10-023 1
  • Patent Document 2 Japanese Patent Publication No. Sho 42-10779
  • Patent Document 3 Japanese Patent Publication No. 51-148985
  • Patent Literature 4 Japanese Patent Application Laid-Open No. H8-503703
  • Patent Document 5 Japanese Patent Application Laid-Open No. 2001-318484
  • Patent Document 8 Japanese Patent Application Laid-Open No. 2001-324834 ''
  • Non-Patent Document 1 "The Basics and Applications of Electrophotographic Technology", edited by the Society of Electrophotography Koguchina Co., Ltd., June 15, 1988, p. 46-79.
  • An object of the present invention is to provide a toner that can solve the above-mentioned problems.
  • the object of the present invention is to provide an excellent offset resistance as well as low-temperature fixing performance, and excellent storage stability, fluidity, chargeability, and development durability in a developing device without impairing those performances. This is to provide a toner.
  • An object of the present invention is to provide a toner which is excellent in low-temperature fixing performance as well as in anti-offset performance, and is free from toner contamination and carrier contamination on the surface of a toner carrier or a photoreceptor in a developing machine due to durability.
  • Another object of the present invention is to provide a method for producing the toner suitably.
  • the glass transition point (T g1) measured in the first scan is from 50.0 to 70.0 ° C.
  • the temperature difference (Tg1-Tg2) between the glass transition point (Tgl) measured in the scan and the glass transition point (Tg2) measured in the second scan is 3.0 to 20.0 ° C Regarding a certain toner.
  • the present invention provides a method for dispersing a polymerizable monomer composition having at least a colorant, a wax, and a polymerizable monomer for synthesizing a binder resin in an aqueous dispersion medium.
  • a polymerizing step of polymerizing the polymerizable monomer in the polymerizable monomer composition to form toner particles, wherein the toner particles are formed at a temperature of 70.0 to 95.0 ° C to 0.01 ° C / min.
  • the glass transition point (Tg 1) measured in the first scan is 50.0 to 70.0 ° C.
  • the temperature difference (Tgl-Tg2) between the glass transition point (Tgl) measured in the scan and the glass transition point (Tg2) measured in the second scan is 3.0 to 20.0 ° C
  • the toner of the present invention has both low-temperature fixability and offset resistance, is excellent in storage stability and development durability, and forms a high-quality image for a long time without causing contamination in a developing machine. can do.
  • FIG. 1 is a graph of a heating mode of the DSC measuring device.
  • FIG. 2 is a DSC curve obtained by measuring the toner of Example 1 in the first scan.
  • FIG. 3 is a DSC curve obtained by measuring the value of Example 1 in the second scanning.
  • FIG. 4 is a chart showing the measured values of the deformation start point, the deformation end point, and the deformation coefficient defined in the present invention. This is an example.
  • FIGS. 5A, 5B, and 50 show the crystal state of the wax in the toner.
  • FIG. 6 and FIG. 6 are diagrams showing the dispersion state of the wax in the toner.
  • the glass transition point of the toner measured by the differential scanning calorimeter (DSC) is the glass transition point (Tgl) measured in the first scan and the glass transition point measured in the second scan.
  • the transition point (Tg 2) may be different, and the glass transition point (Tgl) measured in the first scan is in the range of 50.0 to 70.0 ° C and measured in the first scan
  • the difference (T g1-T g 2) between the measured glass transition point (Tg l) and the glass transition point (T g 2) measured in the second scan is 3.0 to 20.0 ° C. In some cases, they have found that the low-temperature fixing performance, the anti-offset performance, and the developing performance of the toner can be improved.
  • the toner performance before the fixing step such as the storage stability performance and the development stability performance of the toner depends on the glass transition point (Tgl) of the toner obtained by the measurement method of the present invention.
  • the low-temperature fixing performance in the process depends on the glass transition point (T g 2) of the toner.
  • Tg 2 glass transition point
  • the glass transition point of the toner is Tg1.
  • the fixing step when the toner on the transfer material is heated by contact with the fixing device, a part of the crystalline resin in the toner becomes compatible with the binder resin, and the apparent glass transition point of the toner is lowered.
  • the glass transition point of the toner becomes the value of Tg 2 as described above. This makes it possible to express low-temperature deposition ability, which could not be achieved in the past, without deteriorating storage stability performance and development stability ability.
  • the toner may contain a resin component having a molecular weight of 2,000 to 5,000 to 1.0 to 40.0% by mass based on the total mass of the toner. preferable.
  • a resin component having a molecular weight of 2,000 to 5,000 is within the above range, crystallization of a crystalline resin such as wax is promoted at the time of toner production, and most of the crystalline resin contained in the toner is crystallized.
  • the toner is heated to a high temperature such as the fixing temperature, It becomes possible to manufacture a toner in which the crystalline resin is compatible.
  • the ease of crystallization of the crystalline resin in the toner manufacturing process and the ease of compatibility of the crystalline resin with the binder resin in the fixing process depend on the content of the resin component having a molecular weight of 2,000 to 5,000 contained in the toner.
  • the degree of crystallization of the crystalline resin increases in the solid state as the molecular chain has more regular folded structures and overlapping structures. If the amount of the low-molecular-weight resin component having a molecular weight of 2,000 to 5,000 contained in the binder resin is too large, the crystalline resin and the low-molecular-weight component are easily mixed, and when the crystalline resin is solidified, a regular folding structure is formed. , The formation of the overlapping structure is easily inhibited. For this reason, the smaller the amount of the low molecular weight component, the higher the degree of crystallinity tends to be.
  • the content of the resin component having a molecular weight of 2,000 to 5,000 is less than 1.0% by mass, the crystal growth of the crystalline resin in the toner production process is promoted. The amount of compatible crystalline resin is reduced. For this reason, the crystalline resin does not exhibit the plasticizing effect due to its compatibility with the binding effect, and the fixing property of the toner may decrease.
  • the content of the resin component having a molecular weight of 2,000 to 5,000 exceeds 40.0% by mass, the amount of the crystalline resin compatible with the binder resin in the toner production process increases, and Tgl and Tg2 are reduced. Differences tend to be less than 3 ° C. In this case, the low-temperature fixing performance is good, but the storage stability performance and the development stability performance are likely to decrease.
  • the preferred content of the resin component having a molecular weight of 2,000 to 5,000 is 1.0 to 40.0% by mass relative to the total mass of the toner, and more preferably 1.5 to 20.0%. % By mass.
  • the temperature difference between Tg1 and Tg2 is 3.0
  • the temperature is from 20.0 ° C, preferably from 4.0 to 15.0 ° C, and more preferably from 5.0 to 12.0 ° C. If the temperature difference between Tg 1 and Tg 2 (Tg l—Tg 2) is less than 3.0 ° C, the storage stability and development stability will decrease if the low-temperature fixing performance is improved, and the storage If the stability performance and development stability performance are improved, sufficient storage stability performance cannot be obtained.
  • Tgl_Tg2 when the temperature difference (Tgl_Tg2) between Tg1 and Tg2 exceeds 20.0 ° C, low-temperature fixing performance and storage stability performance may be good, but in the fixing process, The melt viscosity of the toner decreases, and the toner penetrates into a transfer material such as plain paper, and a sufficient image density cannot be obtained.
  • Tgl_Tg2 values vary depending on the composition and molecular weight of the binder resin contained in the toner, the composition and amount of the crystalline resin, the production process of the toner, and the like. In the present invention, Tgl is from 50.0 to 70.0 ° C, preferably from 50.0 to 65.0 ° C, more preferably from 53.0 to 62.0 ° C. is there.
  • Tgl When the value of Tgl exceeds 70.0 ° C, the amount of the crystalline resin in the toner that becomes compatible with the binder resin during the production of the toner decreases, and the amount that the crystalline resin becomes compatible with the binder resin during fixing. Also tend to be small. For this reason, good low-temperature fixing performance cannot be obtained in order to exhibit sufficient storage stability performance.
  • Tgl is less than 50.0 ° C.
  • the amount of the crystalline resin compatible with the binder resin during the production of the toner increases, and the amount of the crystalline resin compatible with the binder resin during the fixing also increases. . As a result, good low-temperature fixing performance can be obtained, but sufficient storage stability and development stability cannot be obtained.
  • T g 2 is preferably 45.0 to 55.0 ° C.
  • Tg1 and Tg2 described above are measured using a differential scanning calorimeter (DSC) measuring device.
  • DSC differential scanning calorimeter
  • M-DSC manufactured by TA Instrument Co., Ltd. was used as the DSC measurement device.
  • the measurement method was as follows: 6 mg of the toner as a measurement sample was precisely weighed in an aluminum pan, and an empty aluminum pan was used as a reference pan. The measurement is performed at a modulation amplitude of 1.0 ° C and a frequency of 1 / min under an elementary atmosphere. After holding at 1 o ° c for 1 minute, the reversing heat flow curve obtained by scanning from 1 ⁇ ° C to 160 ° C at a heating rate of 1 ° C / min is defined as a DSC curve.
  • Tg1 is determined from the DSC curve by the midpoint method. After holding at 160 ° C for 10 minutes, cool from 160 ° C to 10 ° C at a cooling rate of 2 ° 0 minutes, and hold at 10 ° C for 10 minutes. After that, Tg2 is determined by the midpoint method from the repurging heat flow curve (DSC curve) obtained by running from 10 ° C to 160 ° C at a heating rate of 1 ° C / min.
  • Fig. 1 shows a graph of the temperature rise mode of the DSC measurement device at this time.
  • the glass transition point obtained by the midpoint method is defined as the glass transition having the intersection between the baseline before the endothermic peak and the baseline after the endothermic peak in the DSC curve at the time of temperature rise, and the rising curve. (See Figures 2 and 3).
  • the temperature at which the melting peak has a maximum value in the repurposing heat flow curve obtained by the same measurement as above is defined as the melting point.
  • the onset value and offset value of the melting point are defined as the temperature at the intersection of the tangent drawn at the point of maximum slope of the rising part of the peak and the outer base line before the peak, and the melting point onset.
  • the temperature at the intersection of the tangent drawn at the point of maximum slope before the end of the melting peak and the outer baseline after the peak shall be the melting point offset value.
  • the endothermic amount is a straight line connecting the point where the peak rises from the extrapolated baseline before the melting peak and the point where the peak comes into contact with the external baseline after the end of the melting peak in the reparsed heat flow curve obtained by the above measurement. Calculate from the area enclosed by the and the melting peak.
  • the molecular weight of the resin component contained in the toner and the content of the resin component having a molecular weight of 2,000 to 5,000 contained in the toner can be determined by using a gel permeation chromatography (GPC) apparatus (manufactured by Tosoh Corporation). It was measured.
  • GPC gel permeation chromatography
  • the GPC device will be described below.
  • THF tetrahydrofuran
  • 100 ⁇ l of a THF sample solution is injected to measure.
  • the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve created from several types of monodisperse polystyrene standard samples and the count number.
  • the standard polystyrene samples for preparing the calibration curve for example, Tosoh Co.
  • one company or the molecular weight of Showa Denko KK is used of about 10 2 to 10 7, using standard polystyrene emissions sample at least about 10 Is appropriate.
  • An RI (refractive index) detector is used as the detector.
  • the content of the resin component having a molecular weight of 2,000 to 5,000 is determined from the elution curve obtained by the above measurement.
  • the sample used for the GPC device is prepared as follows.
  • the toner sample is placed in tetrahydrofuran (THF), mixed well, and allowed to stand for 12-18 hours.
  • a sample processing filter pore size 0.45 to 0.5 ⁇ , for example, Myshori Disc ⁇ —25-5 manufactured by Tosoh I. Co., Ltd., and Exocolodisc 25 CR manufactured by Germanic Science Japan can be used.
  • the sample that has passed through is used as the GPC sample. Adjust the sample concentration so that the resin component concentration is 0.04 to 0.08% by mass.
  • any known binder resin can be used, for example, a styrene copolymer or a polyester resin such as a styrene-acrylate resin or a styrene-methacrylate resin.
  • a styrene copolymer or a polyester resin such as a styrene-acrylate resin or a styrene-methacrylate resin.
  • the toner of the present invention preferably has a tetrahydrofuran (THF) insoluble content of 5 to 90% by mass based on the total mass of the toner. More preferably, it is 5 to 70% by mass, and still more preferably 5 to 65% by mass. This is because the balance between storage stability, image stability and low-temperature fixing performance is further improved.
  • THF tetrahydrofuran
  • THF-insoluble component in the toner refers to the mass ratio of the ultrahigh molecular weight polymer component (substantially crosslinked polymer) that has become insoluble in the THF solvent.
  • the THF insoluble content of the toner is defined by a value measured as follows.
  • the toner lg is weighed (Wlg), placed in a thimble filter paper (for example, No. 86R manufactured by Toyo Roshi Kaisha), subjected to a Soxhlet extractor, extracted with 200 ml of THF as a solvent for 6 hours, and the soluble components extracted with the THF solvent are extracted After evaporation, vacuum-dry at 100 ° C for several hours and weigh the THF-soluble matter (W2 g).
  • the THF insoluble content of the toner is calculated from the following equation. .
  • THF-insoluble content of toner ⁇ (Wl-W2), / W1 ⁇ XI00
  • the toner of the present invention has a number average molecular weight (Mn) of 3000 to 100000, and a weight average It is preferable that the molecular weight (Mw) is 10,000 to 1,000,000 and the ratio of Mw to Mn (MwZMn) is 2.00 to 100: 00. This is because the balance between storage stability, development stability, and low-temperature fixing performance is improved.
  • the toner of the present invention preferably has a melting point (Tml) at 55.0 to 70.0 ° C in a DSC curve measured in the first scan.
  • Tml melting point
  • the ratio (Q 1 / Q2) of the heat absorption Q1 measured in the first scan to the heat absorption Q2 determined in the second scan is 2.00 to 50. 00 is preferred.
  • a toner having a melting point (Tml) at 55.0 to 70.0 ° C preferably has a balance between crystallization of a crystalline resin such as wax at the time of toner production and compatibility with a binder resin at the time of fixing. , Q 1 / Q 2 values between 2.00 and 50.00 It becomes.
  • the storage stability performance and the low-temperature fixing performance are further improved. If the value of Q1 / Q2 is more than 50.00, the melt viscosity of the toner may be too low and the fixing area on the high temperature side may be small. If the value of Q 1 / Q 2 is less than 2, the fixing area on the low temperature side may be small.
  • the toner of the present invention preferably has a melting point ( ⁇ 2) at 71.0 to 150.0 ° C. in a DSC curve measured in the second scan. Further, in the toner of the present invention, the ratio (Q3 / Q4) of the heat absorption Q3 determined in the first scan to the heat absorption Q4 measured in the second scan is 0.80 to 1.20. Is preferred. This is because when the value of Q 3 / Q 4 is within the above range, the fixing area on the high temperature side is further improved. Further, the above Q4 is preferably in the range of 1.5 to 20. O J / g. If Q4 is more than 20.0 JZg, toner may not be sufficiently transmitted from the fixing device, and the fixing area on the low temperature side may be reduced. If Q4 is less than 1.5 jZg, the fixing area on the high-temperature side may be small.
  • the toner according to the present invention has a deformation start point (pound 1) of 45.0 to 60.0 ° C., a deformation end point (T f 2) of 55.0 to 75.0 ° C., and a deformation coefficient (T—fr). ) Is preferably from 0.3 to 0.7.
  • the deformation start point (T f 1), deformation end point (T f 2), and deformation coefficient (T fr) in the present invention are indices indicating the thermodynamic properties of the toner, and are specifically measured by the following method. Value.
  • a load of 10 kgf was applied to the pressurized jig, and the temperature was raised at a rate of 1 ° CZ for 1 minute.
  • T ff 1 The temperature at the intersection (onset point) of the straight line that extends the low-temperature-side baseline to the high-temperature side and the tangent drawn at the point where the slope of the curve at the step change in deformation is maximized is defined as T ff 1
  • Hf1 the height of the pressurized jig at that time is Hf1
  • T fr the deformation coefficient
  • the above measurement can be performed, for example, by using a SUS — 316 plate with no holes in place of a die for placing a sample in a flow tester (CFT-500D, manufactured by Shimadzu Corporation).
  • Fig. 4 shows an example of the measurement chart.
  • T f r (H f 2-H f 1) / (T f f 2-T f f 1)
  • the deformation start point (T f1) obtained from the above measurement correlates with blocking resistance, low-temperature fixing performance and development stability performance, and the deformation end point (T f 2) is high-temperature offset resistance, deformation
  • the coefficient (T fr) correlates with the dalos performance.
  • T f 1 when the deformation starting point (T f 1) is less than 45.0 ° C., the low-temperature fixing performance is improved, but blocking occurs in the developing machine, and capri and image defects occur. On the other hand, if T f 1 exceeds 60.0 ° C., the development stability performance is improved. Sufficient low-temperature fixing performance cannot be obtained.
  • T f 2 If the deformation end point (T f 2) is less than 55.0 ° C, high-temperature offset is likely to occur, and the fixing area becomes extremely small. T f 2 is high-temperature offset performance in a range exceeding 75. 0 D C is improved, low-temperature fixing performance becomes low-temperature offset is liable to occur is reduced.
  • T fr deformation coefficient
  • the above physical properties of the toner are achieved by a balance between the glass transition point (T g) of the binder resin and the amount of the crystalline resin that plasticizes the binder resin such as wax to be compatible with the binder resin.
  • T g glass transition point
  • a toner having a low Tg determined by DSC tends to have small values of Tf1 and Tf2.
  • toner having a large amount of crystalline resin compatible with the binder resin, such as wax tends to have a T fr value exceeding 0.7, and toner having a small amount of crystalline resin compatibility has a T fr of fr is likely to be less than 0.3.
  • the amount of compatibility of these crystalline resins can be controlled by the composition and molecular weight distribution of the binder resin, the amount and amount of plasticizing component added, the method of producing the toner, and the like.
  • the smaller the Tg of the binder resin the larger the amount of compatibility of the crystalline resin becomes, and the smaller the molecular weight, the larger the amount of compatibility becomes.
  • the lower the melting point the greater the compatibility with the binder resin.
  • the smaller the carbon number of the alkyl group contained in the wax the greater the compatibility with the binder resin.
  • the greater the carbon number of the alkyl group contained in the wax the greater the crystallinity, and the greater the difference between the melting point and the offset value, the greater the crystallinity.
  • a polar wax such as an ester wax tends to have a higher compatibility with a binder resin
  • a low-polar wax such as a paraffin wax tends to have a lower compatibility.
  • these resins have an increased affinity for the binder resin at high temperatures, the toner produced by quenching from a high temperature state has a higher compatibility with the binder resin than the slowly cooled toner. It is easy to grow.
  • Examples of the crystalline resin such as wax used in the toner of the present invention include paraffin resin, polyolefin wax, microcrystalline wax, and fish.
  • Examples include polymethylene wax such as Jatrophish wax, amide wax, higher fatty acids, long-chain alcohols, ester waxes, ketone waxes and derivatives thereof such as graft compounds and block compounds, and these have a low molecular weight contained in the wax.
  • crystalline resin examples include waxes such as linear alkyl alcohols having 18 to 42 carbon atoms, fatty acids, fatty acid amides, fatty acid esters, and montan derivatives.
  • waxes such as linear alkyl alcohols having 18 to 42 carbon atoms, fatty acids, fatty acid amides, fatty acid esters, and montan derivatives.
  • crystals during toner production o such as linear alkyl alcohols having 18 to 42 carbon atoms, fatty acids, fatty acid amides, fatty acid esters, and montan derivatives.
  • an ester wax having an ester compound having 18 to 42 carbon atoms is preferable, and an ester compound having 30 to 42 carbon atoms is more preferable.
  • the ester wax used in the present invention preferably has a fatty acid ester conjugate having an alkyl group having 10 to 21 carbon atoms. Further, those from which impurities such as liquid fatty acids have been removed in advance from these waxes are also preferable.
  • ester wax examples include those formed from compounds represented by the following formulas (I) to (VI).
  • R 1 and R 2 are organic groups having 1 to 40 carbon atoms, and R 1 and R 2 are At least one has a carbon number of 10 to 21.
  • m and n are integers of 0 to 20, and m and n are not simultaneously 0.
  • R 1 and R 2 is an organic group having 1 to 40 carbon atoms, and at least one of R 1 and R 2 is an alkyl group having 10 to 21 carbon atoms.
  • R 3 is a hydrogen atom or an organic group having 1 to 20 or more carbon atoms.
  • m and n are integers from 0 to 20; m and n are never 0 at the same time.
  • R 1 and R 3 are organic groups having 1 to 40 carbon atoms, and at least one of R 1 and R 3 is an alkyl group having 10 to 21 carbon atoms.
  • R 2 represents an organic group having 1 to 20 carbon atoms.
  • R 1 and R 2 are organic groups having 1 to 40 carbon atoms, and at least one or more of R 1 and R 3 is an alkyl group having 10 to 21 carbon atoms.
  • N Represents an integer of 1 to 20.
  • a is an integer of 0 to 3
  • b is an integer of 1 to 4
  • a + b is 4.
  • R 1 is an alkyl group having 1 to 21 carbon atoms.
  • n is an integer from 0 to 20 and m and n cannot be 0 at the same time.
  • R 1 and R 2 are alkyl groups having 1 to 39 carbon atoms, and the total of the number of carbon atoms of R 1 and the number of carbon atoms of R 2 is 17 to 41.
  • polymethylene wax such as paraffin wax, polyolefin wax, microcrystalline wax, and fish tropic wax
  • polymethylene wax alkylene is Low molecular weight polymethylene wax polymerized by cal polymerization or low pressure using a Ziegler catalyst or other catalysts; a polymethylene wax obtained by subjecting a high molecular weight alkylene polymer to thermal decomposition.
  • Methylene wax polymethylene wax obtained by separating and purifying a low-molecular-weight alkylene polymer produced as a by-product when polymerizing alkylene; from the distillation residue of a hydrocarbon polymer obtained from a synthesis gas consisting of carbon monoxide and hydrogen by the Age method, Alternatively, a polymethylene wax obtained by extracting and separating a specific component from a synthetic hydrocarbon obtained by hydrogenating a distillation residue is included. These boxes may be supplemented with an antioxidant.
  • the crystalline resin such as wax used in the present invention has a melting point (temperature corresponding to the maximum endothermic peak of the DSC curve in the temperature range of 20.0 to 200.0 ° C) of 40.0 to 150.0 ° C.
  • the temperature is preferably 55.0 to 150.0 ° C, more preferably 55.0 to 110.0 ° C.
  • an ester wax as the crystalline resin in view of the relationship between the crystallinity during the production of the toner and the compatibility with the binder resin.
  • a wax in which the difference between the onset value of the melting point and the offset value is within 20.0 ° C is preferable, and more preferably, it is within 10. ° C.
  • the value of the difference between the onset value and the offset value of the melting point affects the compatibility of the wax with the binder resin. If the value exceeds 20 ° C., the developability may be reduced.
  • a wax having a difference between the melting point and the onset value within 10.0 ° C. is preferable, and more preferably within 5.0 ° C.
  • a wax having a difference between the melting point and the offset value within 10.0 ° C is preferable, and more preferably within 5.0 ° C.
  • the value of the difference between the melting point and the onset value and the value of the difference between the melting point and the offset value affect the compatibility of the wax with the binder resin, and if each value exceeds 10 ° C. Developability may decrease.
  • a solid wax which is solid at room temperature is preferable, and a low melting point wax having a melting point of 50.0 to 70.0 ° C and a low melting point wax having a melting point of 71.0 to 150.0 ° C. It is preferable to use a point wax in combination.
  • a wax having a difference between the onset value and the offset value of the melting point within 20.0 ° C is preferable, and more preferably within 10.0 ° C.
  • the high melting point wax preferably has a melting point of 71.0 to 150.0 ° C, more preferably 71.0 to 111.0 ° C! /.
  • the difference between the onset value and the offset value of the melting point of the high melting point wax is 5.0 to 80.0 ° C, preferably 8.0 to 50 ° C.
  • the temperature is preferably 0 ° C.
  • the ester wax has two or more ester compounds, and contains 50 to 95% by mass of the esterified compound having the same structure among the ester compounds, based on the total mass of the ester. Ester wax is preferred.
  • the content value as described above affects the onset value and offset value at the melting peak of the wax, and affects the compatibility of the wax with the binder resin.
  • the content of the ester compound having the same structure can be measured by a gas chromatography method (GC method) described below.
  • GC-17A (manufactured by Shimadzu Corporation) is used for the measurement of the content of the ester compound having the same structure by the GC method.
  • the column used is UltraAlloy-1 (HT) having a diameter of 0.511111 and a length of 1 Om.
  • the column is first heated from 40 ° C to 200 ° C at a rate of 40 ° C / min, then at 15 ° C / min to 350 ° C, then to 7 ° C / min. Raise the temperature to 450 ° C at the heating speed.
  • the carrier gas is The gas flows under the pressure condition of 501 ⁇ ? &.
  • the compound species is identified by separately injecting an alkane with a known carbon number and comparing the same effluent times, or by introducing gasification components into mass spectrometry.
  • the content of the ester compound is calculated by calculating the ratio of the peak area to the total peak area of the chromatogram.
  • a preferable content of the wax is 1 to 40 parts by mass (more preferably, 2 to 20 parts by mass) per 100 parts by mass of the binder resin.
  • the wax is preferably blended in an amount of 1 to 40 parts by mass (more preferably, 2 to 20 parts by mass) with respect to 100 parts by mass of the polymerizable monomer.
  • the wax may be contained in the toner in an amount of 1 to 10 parts by mass (more preferably 2 to 8 parts by mass) per 100 parts by mass of the binder resin. preferable.
  • the wax used in the present invention preferably has a solubility parameter (SP) value in the range of 7.6 to 10.5. Boxes having an SP value of less than 7.6 have poor compatibility with the polymerizable monomer or binder resin used, and as a result, it is difficult to obtain good dispersion in the binder resin. At the time of copying or printing a large number of sheets, the wax tends to adhere to the developing sleeve, and the charge amount of the toner changes and becomes more chewy. Furthermore, toner density fluctuations during pre-ground and toner replenishment are also likely to occur. When a wax having an SP value exceeding 10.5 is used, blocking between toners is likely to occur when the toner is stored for a long period of time. Furthermore, since the compatibility with the Pinda resin is too good, it is difficult to form a sufficient releasable layer between the fixing member and the toner at the time of fixing, thereby causing an offset phenomenon.
  • SP solubility parameter
  • the solubility parameter (SP) value can be calculated by using the method of Fedors using the additive nature of atomic groups (Polym. Eng. Sc14 (2) 147 (1974)).
  • the wax used in the present invention has a melt viscosity at 135 ° C of 1 to 300 c.
  • melt viscosity is lower than lc P s, sleep contamination is likely to occur due to mechanical slippage when a thin layer of a toner layer is coated on a developing sleeve by a coating blade using a non-magnetic one-component developing method.
  • the two-component developing method when developing an electrostatic charge image using carrier particles and toner, the toner is caused by the slip between toner particles and carrier particles. Toner is easily damaged, external additives are buried, and toner is easily crushed.
  • the viscosity of the polymerizable monomer composition increases when producing a toner using a polymerization method, and the particle size distribution has a sharp fine particle size. It is difficult to obtain toner.
  • the melt viscosity of the wax can be measured using a cone plate type rotor (PK-1) with VP-500 manufactured by HAAK E.
  • the penetration of the wax is desirably 14 or less, preferably 4 or less, and more preferably 3 or less. If the penetration exceeds 14, filming is likely to occur on the surface of the photosensitive drum.
  • the measurement of the penetration shall be in accordance with J13-22-3235. ⁇ If the wax needs to be extracted from the toner to obtain the above physical properties, the extraction method is not particularly limited, and any method can be used.
  • a predetermined amount of toner is subjected to Soxhlet extraction with toluene, the solvent is removed from the obtained toluene-soluble matter, and then a form-insoluble matter is obtained.
  • identification analysis is performed by the IR method or the like. .
  • the toner of the present invention may be added with a condensation resin in addition to the binder resin.
  • a condensation resin in the case of a polymerization toner, it is possible to improve the granulation property, the environmental stability of the charge amount, the developability and the transfer property.
  • the condensation resin preferably has a weight average molecular weight (Mw) of 6,000 to 100,000, more preferably 6,500 to 85,000, and still more preferably. Is from 6,500 to 45,000.
  • the weight average molecular weight of the condensation resin When the weight average molecular weight of the condensation resin is less than 6,000, the external additive on the toner surface is easily buried due to durability in continuous image output, and the transferability is likely to be lowered. Conversely, if the weight average molecular weight exceeds 100,000, It takes a lot of time to dissolve the condensation resin in the monomer. Further, the viscosity of the polymerizable monomer composition increases, and it is difficult to obtain a toner having a small particle size and a uniform particle size distribution.
  • the condensation resin preferably has a number average molecular weight (Mn) of from 3,000 to 80,000, more preferably from 3,500 to 60,000, even more preferably from 3,500 to 12,000. is there.
  • the condensation resin has a main peak value (Mp) of a molecular weight distribution in a gel permeation chromatogram (GPC), a region having a molecular weight of 4,500 to 40,000, and more preferably a region having a molecular weight of 6,000 to 30,000. Good to exist. More preferably, the molecular weight is in the range of 6,000 to 20,000. Outside the above range, the same tendency as in the case of the weight average molecular weight is exhibited.
  • the condensed resin preferably has MwZMn of 1.2 to 3.0, more preferably 1.5 to 2.5.
  • MwZMn 1.2 to 3.0
  • the durability of a large number of toner sheets and the offset resistance are deteriorated.
  • the MwZMn is more than 3.0, the low-temperature fixability is slightly higher than that in the range. Inferior.
  • the condensation resin has a glass transition point (Tg) force of 50.0 to 100.0 ° C, preferably 50.0 to 95.0 ° C. More preferably, the temperature is 55 to 90 ° C. When the glass transition point is less than 50 ° Q, the blocking resistance of the toner is reduced. C When the glass transition point exceeds 100 ° C, the low-temperature offset resistance of the toner is reduced.
  • Tg indicates a value obtained by the midpoint method.
  • the acid value (mgKOH / g) of the condensation resin is 0.1 to 35.0, preferably 3.0 to 35.0, more preferably 4.0 to 35.0, and further preferably 5.0 to 35.0. 30.0.
  • the acid value is less than 0.1, the rise of the charge amount of the toner is slow, and capri easily occurs.
  • the acid value exceeds 35.0 the frictional charging characteristics of the toner after being left under high temperature and humidity tend to fluctuate, and the image density tends to fluctuate in continuous image output.
  • the acid value of the condensation resin If it exceeds 35.0, the condensed resin has a high affinity between the polymers, so that the condensed resin is difficult to dissolve in the polymerizable monomer, and a uniform polymerizable monomer composition cannot be obtained. It takes time to prepare.
  • the condensation resin has a hydroxyl value (mgKOH / g) of 0.2 to 50.0, preferably 5.0 to 50.0, more preferably 7.0 to 45.0.
  • a hydroxyl value mgKOH / g
  • the extraction of the condensation resin is not particularly limited, and any method can be used.
  • the condensation resin is preferably used in an amount of 0.1 to 20.0 parts by mass, more preferably 1.0 to 15.0 parts by mass, based on 100 parts by mass of the binder resin.
  • the acid value of the luster is determined as follows. The basic operation is based on JIS-K00 7 (H.
  • the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of sample is called acid value and is measured by the following method.
  • the acid value is calculated according to the following equation.
  • the hydroxyl value of the resin is determined as follows.
  • the basic operation conforms to JIS-K0070.
  • the number of mg of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group is determined by the hydroxyl value, and the following method is used.
  • acetic anhydride put 25 ml of acetic anhydride in a 100 ml volumetric flask, add pyridine to make the total volume 100 ml, and shake thoroughly. (In some cases, pyridine may be added.) Keep the acetylating reagent away from moisture, carbon dioxide and acid vapors, and store in a brown bottle.
  • the flask was heated again in a glycerin bath for 10 minutes. Titrate with 1 liter of water-soluble alcohol. Perform a blank test in parallel with this test. In some cases, KOH-THF solution may be used as the indicator.
  • the hydroxyl value is calculated by the following equation.
  • A ⁇ (B— C) X f X 28. 05 / S ⁇ + D
  • condensation resin usable in the present invention resins such as polyester, polycarbonate, phenol resin, epoxy resin, polyamide, and cellulose can be used. More preferably, polyester is desired from the diversity of materials.
  • the method for producing the polyester used as the condensation resin and the ester wax used as the crystalline resin include, for example, a synthesis method by an oxidation reaction, a synthesis from cataphoric acid and its derivatives, and a reaction with Michael. It is produced by a method using an ester group introduction reaction, a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound, a reaction from an acid halide and an alcohol compound, and a transesterification reaction.
  • the catalyst may be a common acidic or alkaline catalyst used for the esterification reaction, for example, zinc oxide, a titanium compound, or the like. Thereafter, it may be highly purified by a recrystallization method, a distillation method, or the like.
  • a particularly preferred production method is a dehydration-condensation reaction between a carboxy compound and an alcohol compound because of the variety of raw materials and the speed of the reaction.
  • composition of the polyester when the polyester is used as the condensation resin will be described below.
  • polyester 45-55 m 0% of all components are alcohol components, and 5% It is preferable that 5 to 45 mol% is an acid component.
  • alcohol components ethyl alcohol, propylene glycol, 1,
  • R ′ represents one CH 2 CH 2 —, one CH 2 —0H— or one CH 2 —C one.
  • diols such as diols represented by CH 3 .
  • divalent carboxylic acids examples include phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, diphenyl-4,4'-dicarboxylic acid, naphthalene-1,2,7-dicarboxylic acid, naphthalene-1,2,6-dicarboxylic acid, Benzenedicarboxylic acids such as diphenylmethane 1,4'-dicarboxylic acid, benzophenone-1,4,4'-dicarboxylic acid, 1,2-diphenoxetane-1,4'-dicarboxylic acid or anhydrides; succinic acid, adipic acid, Alkyl dicarboxylic acids such as sebacic acid, azelaic acid, glutaric acid, cyclohexanedicanololeic acid, triethylene dicarboxylic acid and malonic acid or anhydrides thereof, and also alkyls having 6 to 18 carbon atoms And unsaturated anhydrides such as fuma
  • a particularly preferred alcohol component is a bisphenol derivative represented by the above formula (VII), and an acidic component is phthalic acid, terephthalic acid, isophthalic acid or an anhydride thereof, succinic acid, n-dodecyl-succinic acid, or a mixture thereof.
  • Examples include dicarboxylic acids such as anhydride, fumaric acid, maleic acid, and maleic anhydride.
  • the condensation resin can be obtained by synthesizing from a divalent dicarboxylic acid and a divalent diol.However, in some cases, a polycarboxylic acid or polyol having a valency of 3 or more does not adversely affect the present invention. It is good to use a small amount in the range.
  • Trivalent or higher polycarboxylic acids include trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acids, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-mononaphthalenetricarboxylic acid, 1,2,4 1-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylene lipoxylpropane, 1,3-dicarboxyl-2-methyl-methylenecarboxylpropane, tetra (methylene Carboxyl) methane, 1,2,7,8-octanetetracarboxylic acid and their anhydrides.
  • Trihydric or higher polyols include sulitol, 1,2,3,61-hexanexetol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4 Monomethantriol, glycerin, 2-methylpropanetriol, 2-methyl1-1,2,4-butanetriol, trimethyloloneethane, trimethylolpropane, 1,3,5-trimethyloxymethylbenzene .
  • the toner of the present invention may use a charge control agent.
  • Examples of the charge control agent for controlling the toner to be negatively charged include the following substances.
  • organometallic compounds, chelate compounds, monoazo metal compounds, acetyla examples include seton metal compounds, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, quaternary ammonium salts, calixarene, silicon compounds, non-metal carboxylic acid compounds, and derivatives thereof.
  • the following charge control agents are used to control the toner to be positively charged.
  • quaternary ammonium salts such as -denatured products of glycine and fatty acid metal salts, triptylbenzylammonium 1-hydroxy-14-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like
  • Phosphorum salts such as phospho-pam salts, which are analogs thereof, their lake pigments, triphenyl methane dyes and their lakes (the lakes are made of phosphotungstic acid, phosphomolybdic acid, phosphotungsten) Molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids; diorganotinos such as dibuty / resuzuoxide, dioctyltin oxide, dicyclohexynolesse Oxide: dibutylt
  • the charge control agent is preferably contained in an amount of 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin in the toner.
  • the toner of the present invention contains a colorant.
  • the black colorant carbon black, a magnetic substance, or a black color tone using the following yellow magenta / cyan colorant is used.
  • the yellow colorant as a pigment, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and arylamide compounds are used.
  • C.I. pigmentation yellow 3,7,10,12 to 15,17,23,24,60,62,74, 75, 83, 93-95, 99, L 00, 101, 104 108-: L 1] 117, 123, 128, 129 138, 1 39, 147 148, 150 166, 168-177, 179 180, 181, 183 185, 191 1, 191, 192, 193, 199 are preferably used.
  • Examples of the dye system include C. 1. Solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163 and C. I. Disperse Yellow 42, 64, 201, 211.
  • magenta colorant examples include a condensed azo compound, a diketovirolopyrroylium compound, anthraquinone, a quinatalidone compound, a basic dye lake compound, a naphthol compound, a benzimidazolone compound, a thioindigo compound, and a perylene compound.
  • C.I. Pigment Red 2, 3, 5-7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169 , 177, 184, 185, 202, 206, 220, 221, 254, CI Pigment Violet 19 are particularly preferred.
  • cyan coloring agent a copper phthalocyanine compound and its derivatives, an anthraquinone compound, a basic dye lake compound and the like can be used. Specifically, CI Pigment Blue 1, 7, 15, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 is particularly preferably used.
  • colorants can be used alone or as a mixture or in the form of a solid solution.
  • the colorant of the present invention is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, transparency of OHP, and dispersibility in toner.
  • the coloring agent is used in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the binder resin.
  • the toner of the present invention may contain a magnetic substance and be used as a magnetic toner.
  • the magnetic material can also serve as a colorant.
  • the magnetic substance contained in the magnetic toner may be oxidized iron such as magnetite, hematite, or ferrite; a metal such as iron, cobalt, or nickel; Alloys with metals such as aluminum / cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, force cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof.
  • the magnetic material used in the present invention is more preferably a surface-modified magnetic material.
  • the magnetic material When used in a polymerization method toner, it is subjected to a hydrophobic treatment with a surface modifier which is a substance having no polymerization inhibition. Is preferred.
  • a surface modifier include a silane coupling agent and a titanium coupling agent. .
  • These magnetic materials preferably have an average particle size of 2 ⁇ or less, preferably about 0.1 to 0.5 ⁇ .
  • the amount to be contained in the toner is preferably from 20 to 200 parts by mass, particularly preferably from 40 to 150 parts by mass, per 100 parts by mass of the binder resin.
  • the magnetic properties when applying 796 kA / m (10 k oersted) are coercive force (He) 1.59 ⁇ 23.9 k AZm (20 ⁇ 300 Oersted), Saturation magnetism ( ⁇ s) 50 ⁇ 200 emu / g
  • the magnetic material has a residual magnetism ( ⁇ ⁇ ) of 2 to 20 emu / g.
  • an external additive for improving various characteristics of the toner is used.
  • the external additive preferably has a particle diameter of 1 to 5 or less of the volume average diameter of the toner.
  • the particle size of the additive means the average particle size obtained by observing the surface of the toner with an electron microscope.
  • the external additives for imparting these properties for example, the following are used.
  • Examples thereof include silicon oxide, silicon oxide, aluminum oxide, titanium oxide, metal oxides such as hydrotalcite, carbon black, and carbon fluoride. It is more preferable that each is subjected to a water-phobic treatment.
  • abrasive examples include metal oxides such as strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, and chromium oxide, and nitrides such as silicon nitride. And carbides such as silicon carbide, and metal salts such as calcium sulfate, barium sulfate, and calcium carbonate.
  • metal oxides such as strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, and chromium oxide
  • nitrides such as silicon nitride.
  • carbides such as silicon carbide, and metal salts such as calcium sulfate, barium sulfate, and calcium carbonate.
  • lubricant examples include fluorine resin powders such as vinylidene fluoride and polytetrafluoroethylene, and fatty acid metal salts such as zinc stearate and calcium stearate.
  • Examples of the charge control particles include tin oxide, titanium oxide, zinc oxide, silicon oxide, metal oxides such as aluminum oxide, and carbon black.
  • These external additives are used in an amount of 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the toner particles. These external additives may be used alone or in combination of two or more.
  • the toner of the present invention preferably has a cohesion of 1 to 50%, more preferably 1 to 30%, furthermore preferably 4 to 30%, and particularly preferably 4 to 20% from the viewpoint of development.
  • the degree of aggregation of the toner is measured by the following method.
  • a vibrating sieve of a powder tester (manufactured by Hosokawa Micron), open a sieve of 33 ⁇ (400 ⁇ 63 ⁇ ), 77 ⁇ (20 Ome sh) and 154 ⁇ m (10 Ome sh) on the shaking table. From the bottom, a sieve with a mesh of 33 m, a sieve with a mesh of 77 ⁇ , and a sieve with a mesh of 1 54 ⁇ um are set in this order so that the sieve with an opening of 154 m is at the highest level. I do. Place the sample on the set sieve with the opening of 1 54 m, adjust the input voltage to the shaking table to 15 V, and adjust the amplitude of the shaking table to be in the range of 60 to 90 m.
  • Vibration is applied for about 25 seconds, then the weight of the sample remaining on each sieve is measured, and the degree of cohesion is obtained based on the following equation.
  • the sample size is 5 g, and the sample is allowed to stand in a normal temperature and normal humidity environment (20 ° C / 60% RH) for 7 days before measurement.
  • Cohesion (%) (Mass of sample on sieve with opening of 1 54 ⁇ 111 (g) / 5 g)
  • the toner according to the present invention has a circle-equivalent number average diameter D 1 ( ⁇ ) of 2 in a circle-equivalent-diameter circularity scattergram based on the number of toners measured by a flow-type particle image measuring apparatus described later.
  • the average circularity of the toner is preferably from 0.920 to 0.995, and the standard deviation of the circularity is preferably less than 0.040. More preferably, the average circularity is 0.950 to 0.995, and the circularity standard deviation value is less than 0.035. More preferably, the average circularity is from 0.970 to 0.995, and the standard deviation of the circularity is from 0.015 to less than 0.035.
  • the content of the toner having a circularity of less than 0.950 is preferably 15% by number or less. Further, the number variation coefficient obtained by dividing the standard deviation of the circle-equivalent number average diameter by the circle-equivalent number average diameter is preferably 0.35 or less, particularly preferably 0.30 or less.
  • Toner having an average number of equivalent circles of 2 to 7 ⁇ has excellent reproducibility in the development of the outline portion of an image, especially a character image or a line pattern.
  • reducing the particle size of the toner necessarily increases the abundance of the fine particle toner, making it difficult to uniformly charge the toner.
  • Adhesion to the surface of the image carrier and the developer carrier increases, resulting in a decrease in development characteristics.
  • the average circularity of the circularity frequency distribution of the toner is 0.920 to 0.995, preferably 0.950 to 0.995, more preferably 0.970 to 0.9.
  • the toner of the present invention has a circularity standard deviation of less than 0.040, preferably less than 0.035, so that the problem relating to developability can be significantly improved.
  • the toner having the above-mentioned shape is very effective for developing a digital minute spot latent image or for forming a full-color image in which an intermediate transfer member is used for multiple transfer operations. It will be good.
  • the average circularity is used as a simple method for quantitatively expressing the shape of a particle.
  • the average circularity is 1.0000, and the toner shape is complicated. Indeed, the circularity has a small value. Specifically, for example, it can be measured using a flow-type particle image analyzer FPI-210 (manufactured by Toa Medical Electronics Co., Ltd.).
  • the circularity is determined by the following equation, and the value obtained by dividing the total circularity of all the particles measured by the following equation by the total number of particles is defined as the average circularity.
  • the average circularity of the toner is measured using a flow-type particle image measurement system "FPIA-210"
  • particle projection area is the area of the binarized toner particle image
  • perimeter of the particle projection image is the outline of the contour line obtained by connecting the edge points of the toner particle image. Defined as length.
  • the measurement uses the perimeter of a particle image when image processing is performed at an image processing resolution of 512 ⁇ 512 (pixels of 0.3 ⁇ m ⁇ 0.3 ⁇ ).
  • the circularity in the present invention is an index indicating the degree of unevenness of the toner.
  • the circularity is 1.0000.
  • the average circularity c which means the average value of the circularity frequency distribution, is calculated from the following equation, where ci is the circularity (center value) at the dividing point i of the particle size distribution and m is the number of particles measured. .
  • Average circularity C ⁇ ci / m
  • the circularity standard deviation SD is calculated from the following equation, where the average circularity C, the circularity c i of each particle, and the number of measured particles are m.
  • the measuring device used in the present invention calculates the circularity of each particle, and then calculates the average circularity and the standard deviation of the circularity. Based on the obtained circularity, the particles are divided into classes in which the circularity of 0.4 to 1.0 is equally divided every 0.01, and the average circularity and the number of measured particles are calculated using the center value of the division point and the number of measured particles. Calculate the circularity standard deviation.
  • 1 Oml of ion-exchanged water from which impurity solids and the like have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzenesulfonate, is added as a dispersant thereto. Add 0.02 g of the measurement sample and disperse it evenly.
  • Dispersion treatment is performed for 2 minutes using an ultrasonic disperser “Tetora 150 type” (manufactured by Nikkaki Bios) to obtain a dispersion for measurement. At this time, the dispersion is appropriately cooled so that the temperature of the dispersion does not exceed 40 ° C.
  • the installation environment of the flow type particle image analyzer FP IA-2100 was controlled to 23 ° 0 ° C and 0.5 ° C so that the temperature inside the device was 26 to 27 ° C. Automatic focusing is performed at regular intervals, preferably every 2 hours, using 2 ⁇ latex particles.
  • the dispersion liquid concentration was readjusted so that the toner concentration at the time of the measurement was 3 to 1 in 10,000 using the above-mentioned flow type particle image measuring apparatus, and the toner was measured. Measure 1000 or more. After measurement, use this data to cut data with a circle-equivalent diameter of less than 2 ⁇ to determine the average circularity of the toner.
  • the measuring device “FP IA-2100” used in the present invention has a smaller magnification of the processed particle image than “FP IA-1000” which has been conventionally used for calculating the shape of the toner.
  • the accuracy of toner shape measurement has been improved by improving the processing resolution of the captured image (256X256 ⁇ 512X512), thereby achieving a more reliable capture of fine particles. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPI A2100 which can obtain information on the shape more accurately is more useful.
  • a method for producing the toner of the present invention will be described.
  • a suspension polymerization method described in JP-B-36-10231, JP-A-59-53856, and JP-A-59-61842 is directly used.
  • Tonerization by a method of forming a toner Toner by an emulsion polymerization method represented by a soap-free polymerization method in which a monomer is soluble and is directly polymerized in the presence of a water-soluble polymerization initiator to form a toner; Tonerization by an interfacial polymerization method such as a production method or an insite polymerization method; Tonerization by a coacervation method; as disclosed in JP-A-62-106473 and JP-A-63-186253.
  • the toner is formed by an association polymerization method.
  • the toner is formed by a dispersion polymerization method characterized by monodispersion.
  • the necessary resins are dissolved in a water-insoluble organic solvent.
  • the toner components are kneaded using a pressure kneader extruder or a media disperser, and then uniformly dispersed. After cooling, the kneaded product is targeted mechanically or under a jet stream. And pulverize to the desired toner particle size. And a method in which the toner obtained by the pulverization method is subjected to spheroidizing treatment by heating or the like in a solvent to obtain a toner.
  • a preferred method for producing the toner of the present invention is to disperse a polymerizable monomer composition having at least a colorant, a wax, and a polymerizable monomer for synthesizing a binder resin in an aqueous dispersion medium. Granulating to form particles of the polymerizable monomer composition, wherein the particles of the polymerizable monomer composition in the aqueous dispersion medium at 70.0 to 95.0 ° C. A polymerization step of heating to polymerize the polymerizable monomer in the polymerizable monomer composition to form toner particles, and the toner particles are heated from 70 ° to 95.0 to 0.01 ° C.
  • a toner production method having at least a cooling step of cooling to 45.0 ° C or less at a cooling rate of 2.00 ° CZ or less, wherein the toner produced by the toner production method is a differential scanning calorimeter.
  • the glass transition point (Tgl) measured in the first scan 50.0 to 70.0 ° C
  • the temperature difference (Tg) between the glass transition point (Tgl) measured in the first scan and the glass transition point (Tg2) measured in the second scan This is a method for producing a toner having l—T g 2) of 3.0 to 20.0 ° C.
  • the cooling step reduces the toner particles from 70.0 to 95.0 ° C to 0.01 ° C.
  • the cooling step is a cooling step of cooling the toner particles to 45.0 ° C or less at a cooling rate of not less than 0.50 ° C / minute and more preferably not more than 70.
  • This is a cooling step of cooling from 0 ° C to 45.0 ° C or less at a cooling rate of 0.01 ° C / minute or more and less than 0.25 ° C / minute.
  • the cooling step includes cooling the toner particles in an aqueous dispersion medium, and the cooling step includes removing the toner particles from the aqueous dispersion medium and cooling the toner particles. Any of the cooling steps may be used.
  • the heating step at a temperature of 70.0 ° C. or higher includes a suspension polymerization method, an associative polymerization method, an emulsion dispersion method, and a dispersion polymerization method.
  • toner particles prepared by a known method may be redispersed in an aqueous dispersion medium and heated to 70.0 ° C. or more.
  • aqueous dispersion medium a medium that does not substantially dissolve the toner, such as water and alcohol, can be suitably used.
  • a suspension polymerization method in which a toner having a small particle size can be easily obtained is desired.
  • a seed polymerization method in which a monomer is further adsorbed on the obtained polymer particles, and then a polymerization initiator is used and polymerization is performed can also be suitably used in the present invention. At this time, it is also possible to disperse or dissolve a polar compound in the monomer to be adsorbed before use.
  • the toner can be directly produced by the following production method.
  • a polymerizable monomer composition in which at least a polymerizable monomer for synthesizing a binder resin, a wax, and a colorant are uniformly dissolved or dispersed with a homogenizer and a stirrer such as an ultrasonic disperser is formed. I do.
  • a crosslinking agent and other additives may be contained in the polymerizable monomer composition. It is dispersed in an aqueous dispersion medium having a dispersion stabilizer containing magnesium, calcium, barium, zinc, aluminum or phosphorus by using a conventional stirrer, homomixer, or homogenizer.
  • the polymerization initiator may be contained in at least one of the polymerizable monomer composition and the aqueous dispersion medium.
  • the stirring speed and time are adjusted so that the droplets of the polymerizable monomer composition have a desired toner size, and granulation is performed. Thereafter, stirring may be performed to such an extent that the particle state is maintained and the precipitation of the particles is prevented by the action of the dispersion stabilizer.
  • the polymerization is carried out at a polymerization temperature of 40.0 ° C or higher, usually 50.0 to 95.0 ° C (preferably 55.0 to 85.0 ° C). The temperature may be raised in the latter half of the polymerization reaction, and the pH may be changed if necessary.
  • the polymerizable monomer composition includes a step of forming a colorant composition having a polymerizable monomer and a colorant, and a step of dispersing the colorant composition. It is preferably formed by adding an additive. For the purpose of improving the dispersibility of the colorant, a charge control agent, a known pigment dispersant, and other resins may be added.
  • the polymerizable monomer composition is prepared by preparing a dispersion A in which at least polymethylene wax is dispersed, and then mixing the dispersion A with a dispersion B containing at least an ester wax.
  • a dispersion A in which at least polymethylene wax is dispersed
  • a dispersion B containing at least an ester wax.
  • it is a monomer composition.
  • the wax dispersion state in the toner tends to be polynuclear and needle-like. This further improves development stability and high-temperature offset resistance.
  • the pH in the aqueous dispersion medium during granulation is not particularly limited, but is preferably pH 4.5 to 13.0, more preferably 4.5 to 12.0, and particularly preferably 4.5 to 15.0. 11.0, most preferably 4.5-7.5. If the pH is less than 4.5, dissolution may occur in a part of the dispersion stabilizer, making it difficult to stabilize the dispersion and making granulation impossible. If the pH exceeds 13.0, components added to the toner may be decomposed, and sufficient charging ability may not be exhibited. When the granulation is performed in the acidic region, the content of the metal derived from the dispersion stabilizer in the toner can be suppressed from being excessive, and a toner satisfying the requirements of the present invention can be easily obtained. Become.
  • the toner particles it is preferable to wash the toner particles with an acid having a pH of 3.0 or less, more preferably an acid of pH 1.5 or less.
  • an acid having a pH of 3.0 or less, more preferably an acid of pH 1.5 or less.
  • the acid used for washing is not particularly limited, and an inorganic acid such as hydrochloric acid or sulfuric acid is used. be able to.
  • Examples of the dispersion stabilizer used in the present invention include magnesium phosphate, triphosphate calcium, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, and metal hydroxide.
  • Examples include calcium silicate, calcium sulfate, barium sulfate, and hydroxypatide.
  • one containing at least one of magnesium, calcium, parium, zinc, aluminum, and phosphorus is used, and preferably, one of magnesium, calcium, aluminum, and phosphorus is used. It is hoped that it is rare.
  • An organic compound such as polyvinyl alcohol, gelatin, methinoresenorelose, methinolehydroxypropinoresenorelose, etinoresenorelose, a sodium salt of carboxymethylcellulose, and starch may be used in combination with the dispersion stabilizer. It is preferable to use 0.01 to 2.0 parts by mass of these dispersion stabilizers with respect to 100 parts by mass of the polymerizable monomer.
  • a surfactant may be used in combination for making these dispersion stabilizers finer.
  • commercially available nonionic, ionic and cationic surfactants can be used.
  • a vinyl polymerizable monomer capable of radical polymerization may be used as the polymerizable monomer used for producing the toner of the present invention by a polymerization method.
  • Monofunctional polymerizable monomers include styrene ⁇ -methylstyrene, ⁇ -methinolestyrene, ⁇ -methylstyrene, m-methynolestyrene, p-methylstyrene, 2,4-dimethylstyrene, p-n-butylinolestyrene, p-tert-butylstyrene , P-n-hexynolestyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecinolestyrene, p-methoxystyrene, p-pheny / restile Styrene derivatives such as
  • Polyfunctional biopolymerizable monomers include diethylene glycol diacrylate, Polyethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diatalylate, 1, 6-hexanediol diatalylate, neopentyl glycol diatalylate, tripropylene glycol cornoresialate, polypropylene Glyconoresacrylate, 2,2,1-bis [4-1 (ataryloxy 'diethoxy) phenyl] propane, trimethylolpropanetriatalylate, tetramethylolmethanetetraacrylate ethylene glycol dimethacrylate, diethyleneglyconoresimethacrylate Relay, triethyleneglyconoresin methacrylate, tetraethyleneglyconoresin methacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycoldi Methacrylate, 1,6-hexanediol dimethacrylate, neopentyl
  • the above-mentioned monofunctional polymerizable monomers are used alone or in combination of two or more kinds, or the above-mentioned monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. I do.
  • the polyfunctional polymerizable monomer can be used as a crosslinking agent.
  • oil-soluble initiator and / or a water-soluble initiator are used as the polymerization initiator used in the polymerization of the polymerizable monomer.
  • oil-soluble initiators include 2,2, azobisisobutyronitrile, 2,2'azobis-1,2,4-dimethylvaleronitrile, 1,1'azobis (cyclohexane-11- Azo compounds such as 2,2,1-azobis-1-methoxy-1,2,4-dimethylpaleronitrile; acetylsilyl hexylsulfonyl-peroxyside.
  • Disopropyl peroxycarbonate decanoyl peroxide, lauperyl peroxide, stearoyl peroxide, propionyl peroxide, aceti'norepoxide, tert-butyl peroxy 2- Ethylhexanox: p-to-, benzoylperoxide, tert-butylperoxyisobutylate, cyclohexanone peroxide, methylethylketone peroxide, dicumyl peroxide, tert —Peroxide-based opening agents such as butyl hydroperoxide, g-tert-butyl peroxide and cumene hydroperoxide.
  • water-soluble initiator examples include ammonium persulfate, potassium persulfate, 2,2'-azobis ( ⁇ , ⁇ , dimethyleneisobutyroamidine) hydrochloride, 2,2, -azobis (2- Aminodinopropane) hydrochloride, azobis (isobutylamidine) hydrochloride, sodium 2,2'-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.
  • a chain transfer agent, a polymerization inhibitor and the like in order to control the degree of polymerization of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor and the like can be further added and used.
  • a resin having cross-linking can be obtained by using a cross-linking agent.
  • a cross-linking agent a compound having two or more polymerizable double bonds can be used.
  • aromatic divinyl compounds such as dibutylbenzene and diburnaphthalene; a force having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate.
  • Nolevonic acid esters divinyl compounds such as divininorea diphosphine, divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups. These are used alone or as a mixture.
  • the toner of the present invention can be used as a toner for a one-component developer, and can also be used as a toner for a two-component developer having carrier particles.
  • a magnetic toner When a magnetic toner is used as a one-component developer and a magnetic material is contained in the toner, there is a method in which the magnetic toner is transported and charged using a magnet built in a developing sleeve.
  • a non-magnetic toner containing no magnetic material there is a method in which a blade or a roller is used to forcibly triboelectrically charge the toner with a developing sleeve and adhere the toner onto the sleeve to convey the toner.
  • the magnetic carrier is composed of iron, copper, zinc, nickel, cobalt, manganese, and chromium elements alone or in a composite ferrite state.
  • the shape of the magnetic carrier is spherical, flat or irregular, and any of them can be used.
  • a method has been used in which magnetic carrier core particles are formed in advance by baking and granulating the above inorganic oxidized product, and then coating the resin.
  • the method of kneading the inorganic oxide and the resin, pulverizing and classifying to obtain a low-density dispersed carrier, and further, directly mixing the inorganic oxide and the monomer It is also possible to utilize a method of subjecting a kneaded product of the above to suspension polymerization in an aqueous medium to obtain a true spherical 'magnetic carrier.
  • a coated carrier obtained by coating the surface of the above-mentioned carrier particles with a resin is particularly preferable.
  • a method in which a resin is dissolved or suspended in a solvent and the solution or suspension is applied to and adhered to a carrier, or a method in which a resin powder and carrier particles are simply mixed and adhered can be applied. .
  • the coating material on the surface of the carrier particles varies depending on the toner material, but, for example, polytetrafluoroethylene, mono-oral trifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, and acrylic resin Resin, polyamide, polyvinyl butyral, amino acrylate resin No. These may be used alone or in combination.
  • the magnetic properties of the carrier are preferably as follows.
  • the magnetization intensity ( ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ) at 79.6 kA / m (lk Oersted) after magnetic saturation is preferably 30 to 300 emu / cm 3 .
  • To further achieve high image quality I spoon preferably has 1 0 0 to 2 5 0 emuZcm 3. When it is larger than 300 emu / cm 3, it is difficult to obtain a bulky toner image. On the other hand, when it is less than 30 emu / cm 3 , the magnetic binding force is reduced, so that the carrier is easily attached.
  • SF-1 indicating the degree of roundness is 180 or less
  • SF-2 indicating the degree of unevenness is 250 or less.
  • S F—1 S F—2 is defined by the following equation, and is measured by Luze XII I manufactured by Nireco.
  • the toner of the present invention preferably contains a wax having a needle-like or rod-like shape when observing the tomographic plane of the toner using a transmission electron microscope ( ⁇ ). Representative examples are shown in Figures 5 5, 5 ⁇ , and 5C. By having these shapes, heat in the fixing step is easily transmitted, and the low-temperature fixing performance is further improved.
  • the dispersion state may be a mononuclear or polynuclear dispersion state, but is more preferably a polynuclear state. Heat in the fixing process is easily transmitted, and the low-temperature fixing performance is further improved. Representative examples are shown in Figures 6 and 6.
  • the difference in the fine structure of the crystalline phase and the amorphous phase between the wax component used and the binder resin constituting the outer shell is used to determine the electron component of one component by the heavy metal. It is preferable to use an electronic dyeing method in which the density is increased to give a contrast between materials.
  • the toner is contained in a cold-setting epoxy resin. After one particle is sufficiently dispersed, it is cured at an ambient temperature of 40 ° C.
  • the mixing ratio is 2 to 15% by mass, preferably 4 to 13% by mass as a small toner concentration in the developer. Then usually good results are obtained.
  • Dimroth reflux condenser De an- S Tark water separator benzene 1 900 parts by a four-necked flask equipped with, myristic acid (C 14 H 28 0 2) , palmitic acid (C 16 H 32 0 2) , stearic acid (C 18 H 36 0 2) , Arakin acid (C 20 H 40 O 2) , behenic acid (C 2 .H 4 .0 2) a mixture consisting of (carboxylic acid component) 1400 parts by weight, heptyl alcohol Honoré (C 4 H 10 O), myristyl alcohol (C 14 H 30 O), palmityl alcohol (C 16 H 34 0), stearyl alcohol (C 18 H 38 0), a mixture consisting ⁇ La kill alcohol (C 20 H 42 O) (Alcohol component) 1300 parts by mass and 130 parts by mass of p-toluenesulfonic acid were added, and the mixture was subjected to dry distillation with stirring for 6 hours, and then
  • Ester waxes 2 to 4 were prepared in the same manner as in Preparation Example 1 for ester wax, except that the types and amounts of the carboxylic acid component and the alcohol component were changed. table 1
  • Esterex 1 and polymethylene wax 1 were used as a crystalline resin in combination as follows.
  • 'Wax Dispersion B consisting of 19 parts by weight of ester wax is kept at 65 ° C for 5 minutes with stirring, and 2 parts by weight of 2,2,2-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator
  • the polymerizable monomer composition to which the part was added was charged into the aqueous dispersion medium, and granulated for 15 minutes while maintaining a rotation speed of 12000 rpm. After that, the high-speed stirrer was changed to a normal propeller stirrer, the rotation speed of the stirrer was maintained at 150 rpm, polymerization was performed at an internal temperature of 70.0 ° C for 6 hours, and the temperature was raised to 80.
  • the temperature was raised to 0 ° C, and polymerization was performed for 4 hours. After completion of the polymerization, the internal temperature was cooled to 24.'0 ° C at a cooling rate of 0.40 ° CZ while maintaining the rotation. While maintaining the inner temperature at 20.0 to 25.0 ° C, dilute hydrochloric acid was added to the aqueous dispersion medium to dissolve the poorly water-soluble dispersant. Further washing and drying were performed to obtain toner particles.
  • dry silica (BET specific surface area) having a primary particle diameter of 12 nm treated with silicone oil and hexamethyldisilazane was used.
  • Toner 1 having a weight average particle size of 6.3 ⁇ .
  • This toner 1 was evaluated according to the test method described below.
  • Tables 3 to 6 show the physical properties and evaluation results of Toner 1.
  • the toner is measured by the first scan of toner 1.
  • the DSC curve obtained is shown in Fig. 2, and the DSC curve obtained by measuring the toner in the second scan is shown in Fig. 3.
  • Both low-temperature fixing performance and anti-offset performance were excellent.
  • the development stability performance the image density was high in both the initial image and the durable image, and the image was clear and high in image quality without any capri.
  • the charge amount of the toner after the endurance did not decrease compared to the initial state. Furthermore, the storage stability was excellent.
  • Toner 1 0.2 g is weighed into a pressure molding machine, and molded under a normal temperature and normal pressure environment with a load of 200 kgf for 2 minutes to produce a cylindrical sample having a diameter of about 8 mm and a height of about 2 mm. It was adjusted.
  • a flow tester manufactured by Shimadzu Corporation
  • the columnar sample was set in a device modified to a SUS-316 plate without holes instead of a die for placing the sample. After holding this at 35.0 ° C for 5 minutes, apply a load of 10 kgf to the pressurized jig, heat the columnar sample to 120.0 ° C in 1.0 ° CZ minutes, and heat the sample. The displacement of the pressing jig in contact with was measured.
  • Toner 1 and a ferrite carrier (average particle size 42 ⁇ ) surface-coated with a silicone resin were mixed so that the toner concentration became 6% by mass, to prepare a two-component developer.
  • An unfixed toner image (0.6 mg / cm 2 ) was formed on a receiving paper (80 g / m 2 ) using a commercially available full-color digital copying machine (CLC 700, manufactured by Canon Inc.).
  • a commercially available full-color digital copier (CLC 700, manufactured by Canon Inc.) was modified so that the fixing unit could be removed from the fixing unit, and used to perform a fixing test on unfixed images.
  • the process speed was set to 200 mm / s, and the toner image was fixed at each temperature while changing the set temperature from 130 ° C to 230 ° C every 5 ° C. .
  • the temperature at which the low-temperature offset is no longer observed is defined as the low-temperature starting point of the offset resistance, which is 5 times lower than the temperature at which the high-temperature offset is visually observed or the temperature at which the receiving paper wraps around the fuser.
  • the temperature lower by ° C was taken as the hot end point.
  • the fixed image obtained by the above test was rubbed with lens-cleaning paper under a load of 50 g / cm 2, density reduction rate before and after the rubbing is below 5% and comprising fixing temperature low-temperature fixability of the low-temperature side start point
  • the point at which the maximum value of Daros was reached was taken as the high-temperature end point.
  • the temperature at which the high temperature offset was visually observed or the temperature at which the receiving paper was wound around the fixing device by 5 ° C was set as the high temperature side end point.
  • the development stability performance was evaluated based on the following criteria.
  • the image density was measured using a “Macbeth reflection densitometer RD 918” (manufactured by Macbeth Co., Ltd.) to measure the relative density of the white background portion of the original with a density of 0.000 to the printout image.
  • toner particles were obtained in the same manner as in Example 1 except that ester wax 2 was used instead of beauty / rewax 1 and polymethylene wax 2 was used instead of polymethylene wax 1. Weight average particles in the same manner as in Example 1. Toner 2 having a diameter of 6.5 ⁇ was prepared and evaluated. Tables 3 to 6 show the physical properties and evaluation results of Toner 2. Compared with Example 1, the anti-offset performance and the low-temperature fixing performance were slightly reduced, but other than that, there was no problem at all and good.
  • Example 2 After completion of the polymerization, the internal temperature was cooled to 24.0 ° C at a cooling rate of 0.40 ° C / min while maintaining the rotation. While maintaining the internal temperature at 20.0 to 25.0 ° C, dilute hydrochloric acid was added to the aqueous dispersion medium to dissolve the poorly water-soluble dispersant. After further washing and drying, toner particles were obtained.
  • Toner 3 having a weight average particle diameter of 6.4 ⁇ was prepared and evaluated. Tables 3 to 6 show the physical properties and evaluation results of Toner 3. Compared with Example 1, the low-temperature fixing performance was slightly lowered, but other than that, there was no problem at all and good. .
  • Toner particles were obtained in the same manner as in Example 3, except that polymethylene wax 3 was not used and the amount of ester wax 3 was changed to 18 parts by mass.
  • Example 2 In the same manner as in Example 1, a toner 4 having a weight average particle diameter of 6.3 ⁇ was prepared and evaluated. Tables 3 to 6 show the physical properties and evaluation results of Toner 4. Compared with Example 1, the anti-offset performance and the low-temperature fixing performance were slightly lowered, but other than that, there was no problem at all, and it was good.
  • Toner particles were obtained in the same manner as in Example 1 except that Esterex 4 was used instead of Esterex 1 and the amount of the polymerization initiator was changed to 7 parts by mass.
  • Toner 5 having a weight average particle diameter of 5.9 ⁇ was prepared and evaluated.
  • Tables 3 to 6 show the physical properties and evaluation results of Toner 5.
  • the low-temperature fixing performance was good, the maximum gloss value was reached at 195 ° C.
  • the toner was soaked into the paper and the image quality deteriorated.
  • images with 5,000 sheets A decrease in the image density was observed, and the charge amount of the toner was lower than the initial value.
  • the storage stability performance was poor.
  • Toner particles were obtained in the same manner as in Example 4, except that Esterex 5 was used instead of Esterex 3 and the amount of the polymerization initiator was changed to 7 parts by mass.
  • Example 2 In the same manner as in Example 1, a toner 6 having a weight average particle size of 6.8 zm was prepared and evaluated. Tables 3 to 6 show the physical properties and evaluation results of Toner 6. The storage stability performance was almost good, but the low-temperature fixing performance was poor. In addition, the end point of the fixing performance on the high temperature side decreased. Further, a decrease in image density was observed in the image after 500 sheets of durability, and the toner charge amount was also lower than the initial value.
  • Toner particles were obtained in the same manner as in Example 4, except that Esterex 4 was used instead of Esterex 3, and the amount of the polymerization initiator was changed to 0.8 parts by mass.
  • a toner 7 having a weight average particle diameter of 6.5 ⁇ m was prepared and evaluated.
  • Tables 3 to 6 show the physical properties and evaluation results of Toner 7. Although the storage stability performance and the low-temperature fixing performance were good, winding of the receiving paper occurred at '185 ° C. Further, in the image after 50,000 sheets of durability, the image density was reduced, and the toner charge amount was lower than the initial value.
  • Example 2 Same as Example 1 except that ester wax 4 was used instead of ester wax 1, the amount of the polymerization initiator added was 7 parts by mass, and the cooling rate after the completion of the polymerization was 10.0 ° C.Z. Thus, toner particles were obtained.
  • Example 2 In the same manner as in Example 1, a toner 8 having a weight average particle diameter of 6.0 m was prepared and evaluated. Tables 3 to 6 show the physical properties and evaluation results of Toner 8. Although the low-temperature fixing performance was good, the maximum gloss value was reached at 195 ° C, and at temperatures higher than that, toner was soaked into the paper and the image quality was degraded. In the initial image density, the density is slightly Although the degree was low, a clear decrease in image density was observed in the image after 50,000 sheets of durability, and the charge amount of the toner was significantly lower than the initial level. Furthermore, the storage stability performance was poor.
  • Example 4 Same as Example 4 except that Ester Pex 4 was used instead of Ester I. Tas 3, the amount of the polymerization initiator added was 7 parts by mass, and the cooling rate after the completion of the heavy duty was 10.0 ° C CZ minutes. Thus, toner particles were obtained.
  • Example 2 In the same manner as in Example 1, a toner 9 having a weight average particle diameter of 6.4 ⁇ was prepared and evaluated. Tables 3 to 6 show the physical properties and evaluation results of Toner 9. Although the low-temperature fixing performance was good, the image receiving paper was wrapped at 185 ° C. In addition, although the initial image density was slightly lower, the image density after the endurance of 500 sheets clearly decreased, and the toner charge amount was significantly lower than the initial level. Furthermore, the storage stability performance was poor. .
  • Esterox 5 was used in place of Esterox 3, the amount of the polymerization initiator was 0.8 parts by mass, and the cooling rate after the completion of the polymerization was 10.0 ° CZ. Thus, toner particles were obtained.
  • Example 2 In the same manner as in Example 1, a toner 10 having a weight average particle diameter of 6.6 ⁇ was prepared and evaluated. Tables 3 to 6 show the physical properties and evaluation results of Toner 10. The storage stability performance was almost good, but the low-temperature fixing performance was clearly inferior. Also, the end point of the fixing performance on the high temperature side decreased. Further, a decrease in image density was observed in the image after 50,000 sheets of durability, and the toner charge amount was also lower than the initial value.
  • Toner particles were obtained in the same manner as in Example 1 except that the cooling rate after the completion of the polymerization was 0.10 ° C./min. ''
  • Example 2 In the same manner as in Example 1, a toner 11 having a weight average particle diameter of 6.3 m was prepared. Evaluation was performed. Tables 3 to 6 show the physical properties and evaluation results of Toner 11.
  • Toner particles were obtained in the same manner as in Example 3, except that the addition amount of the polymerization initiator was changed to 3.5 parts by mass.
  • Toner particles were obtained in the same manner as in Example 3, except that the addition amount of the polymerization initiator was 4.5 parts by mass.
  • Example 3 In the same manner as in Example 3, a toner 13 having a weight average particle diameter of 6.4 ⁇ was prepared and evaluated. Tables 3 to 6 show the physical properties and evaluation results of Toner 13.
  • Wax wax wax shape
  • Example 1 1 1 1 0.40 6.3 5.2 0.15 0.978 21800 198000 23200 8.5 27.8 (C) Needle-like (b) Polynuclear Example 2 2 2 2 0.40 6.5 5.4 0.16 0.977 21500 197000 22900 8.6 27.9) Needle-like (b) Polynuclear Example 3 3 3 3 0.40 6.4 5.3 0.19 0.975 21700 204000 23100 8.8 27.6 (b) Rod (a) mononuclear Example 4 4 3-0.40 6.3 5.3 0.18 0.971 21200 201000 22800 8.8 26.9 (a) Spherical (b) polynuclear Comparative Example 1 5 4 1 0.40 5.9 4.5 0.22 0.970 12800 169000 15300 1 1.0 27.7 (C) Acicular (b) Polynuclear Comparative Example 2 6 5 One 0.40 6.8 4.9 0.23 0.971 13500 72000 15600 UO 28.1 (a) Spherical (a) Mononuclear Comparative Example 3 7
  • Example 1 56.7 46.1 10.6 3.2 59.6 / 87.3 87.4 10.7 1.3 8.23 6.8 6.6 1.03
  • Example 2 59.2 49.7 9.5 3.2 68.8 / 93.5 68.9 / 98.4 9.3 3.2 2.91 F.3 6.8 1.07
  • Example 3 58.3 50.2 8.1 3.1 63.8 / 73.9 63.9 / 73.6 16.3 6.2 2.63 5.6 5.2 1.08
  • Example 4 56.8 50.4 6.4 3.3 63.6 63.3 18.2 8.9 2.04----Comparative example 1 52.1 49.4 2.7 42.8 54.2 / 88.1 54.5 / 88.3 3.8 2.1 1.81 6.9 6.6 1.05
  • Comparative example 2 65.8 65.1 0.7 41.9.
  • Example 1 50.2 61.1 54.6 0.06 59.4 2.00 0.40
  • Example 2 52.6 63.2 56.3 0.06 61.3 2.01 0.39
  • Example 3 51.7 63.4 56.1 0.05 61.4 1.99 0.37
  • Example 4 48.8 61.3 54.0 0.07 59.5 2.01 0.35
  • Comparative 3 49.0 68.8 55.4 0.05 67.1 1.99 0.17
  • Comparative example 5 43.5 51.7 48.8 0.06 51.2 2,00 0.81 Comparative example 6 55.4 65.9 62.4 0.06 65.1 2.01 0.72
  • Example 5 51.3 61.0 55.4 0.05 59.4
  • Example 4 135 230 135 220 A 1.54 32.8 1.46 31.9 Compare Example 1 130 220 135 195 C 1.49 34.8 1.37 29.2 Comparative Example 2 150 230 150 210 B 1.48 33.6 1.38 29.1 Comparative Example 3 130 185 135 185 A 1.47 31.7 1.28 22.3 Comparative Example 4 130 220 135 195 D, 1.41 29.3 1.19 19.3 Comparative Example 5 130 185 135 185 D 1.38 28.6 1.14 18.8 Comparative Example 6 155 230 160 220 A 1,51 33.1 1.39 28.7

Landscapes

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

Abstract

Toner qui excelle dans sa capacité de fixation et ses propriétés d'anti-maculage, ainsi que dans son aptitude au stockage dans un processeur de développement. Dans une courbe d'analyse calorimétrique différentielle (ACD) obtenue en mesurant le toner au moyen d'un calorimètre à balayage différentiel, le toner présente une température de transition vitreuse (Tg1) déterminée par le premier balayage de 50,0 à 70,0°C and présente une différence de température (Tg1-Tg2) entre la température de transition vitreuse (Tg1) déterminée par le premier balayage et la température de transition vitreuse (Tg2) déterminée par le deuxième balayage de 3,0 à 20,0°C.
PCT/JP2004/018438 2003-12-05 2004-12-03 Toner et procede de fabrication de toner WO2005071493A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP20040801658 EP1693711B1 (fr) 2003-12-05 2004-12-03 Toner et procede de fabrication de toner
JP2005517200A JP4721429B2 (ja) 2003-12-05 2004-12-03 トナー及びトナーの製造方法
US11/122,031 US7250241B2 (en) 2003-12-05 2005-05-05 Toner and process for producing toner
US11/688,704 US7300737B2 (en) 2003-12-05 2007-03-20 Process for producing toner

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003406968 2003-12-05
JP2003-406968 2003-12-05

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/122,031 Continuation US7250241B2 (en) 2003-12-05 2005-05-05 Toner and process for producing toner

Publications (1)

Publication Number Publication Date
WO2005071493A1 true WO2005071493A1 (fr) 2005-08-04

Family

ID=34805267

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/018438 WO2005071493A1 (fr) 2003-12-05 2004-12-03 Toner et procede de fabrication de toner

Country Status (4)

Country Link
EP (1) EP1693711B1 (fr)
JP (1) JP4721429B2 (fr)
CN (1) CN1886700A (fr)
WO (1) WO2005071493A1 (fr)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007047522A (ja) * 2005-08-11 2007-02-22 Canon Inc フルカラー一成分現像用トナーおよび一成分現像方法
JP2007058138A (ja) * 2005-08-26 2007-03-08 Fuji Xerox Co Ltd 静電荷像現像用トナー及びその製造方法、静電潜像現像剤、画像形成方法
JP2007072333A (ja) * 2005-09-09 2007-03-22 Ricoh Co Ltd 画像形成用トナー及びその製造方法と現像剤並びにこれを用いた画像形成方法と画像形成装置
JP2007193253A (ja) * 2006-01-23 2007-08-02 Canon Inc 乳化凝集法トナー
JP2011028162A (ja) * 2009-07-29 2011-02-10 Canon Inc トナー
JP2011133753A (ja) * 2009-12-25 2011-07-07 Kyocera Mita Corp トナー用ワックス、電子写真用トナー、及び現像剤
JP2011144358A (ja) * 2009-12-17 2011-07-28 Sanyo Chem Ind Ltd 樹脂粒子
JP2011197659A (ja) * 2010-02-26 2011-10-06 Konica Minolta Business Technologies Inc 静電潜像現像用トナーおよびその製造方法
JP2012008528A (ja) * 2010-05-26 2012-01-12 Ricoh Co Ltd トナー
JP2012022331A (ja) * 2011-09-13 2012-02-02 Ricoh Co Ltd トナー、及びそれを用いた画像形成方法
JP2012063559A (ja) * 2010-09-15 2012-03-29 Ricoh Co Ltd トナー及びその製造方法
JP2014112205A (ja) * 2012-10-29 2014-06-19 Mitsubishi Chemicals Corp 静電荷像現像用トナー
JP2015028616A (ja) * 2013-06-27 2015-02-12 キヤノン株式会社 トナーおよびトナーの製造方法
CN105182706A (zh) * 2014-06-19 2015-12-23 柯尼卡美能达株式会社 静电荷图像显影用调色剂
JP2017142404A (ja) * 2016-02-10 2017-08-17 日油株式会社 トナー用ワックス組成物
JP2017156472A (ja) * 2016-02-29 2017-09-07 キヤノン株式会社 トナーの製造方法
JP2018005257A (ja) * 2017-10-13 2018-01-11 三洋化成工業株式会社 トナーの製造方法
JP2019139218A (ja) * 2018-02-08 2019-08-22 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ 機械超微粒子（ｕｆｐ）の排出の削減を示すトナーおよび関連する方法
JP2022000675A (ja) * 2020-06-19 2022-01-04 東芝テック株式会社 トナー、トナーカートリッジ、画像形成装置
JP2022029612A (ja) * 2020-08-05 2022-02-18 東芝テック株式会社 トナー、トナーカートリッジ、画像形成装置
JP7490450B2 (ja) 2020-05-18 2024-05-27 キヤノン株式会社 トナー

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101261106B1 (ko) * 2008-02-25 2013-05-06 캐논 가부시끼가이샤 토너
CN102047186B (zh) * 2008-05-28 2013-07-31 佳能株式会社 调色剂
JP4565054B2 (ja) * 2009-02-27 2010-10-20 キヤノン株式会社 黒トナー
JP2012008530A (ja) * 2010-05-28 2012-01-12 Ricoh Co Ltd トナー及びその製造方法
JP5956124B2 (ja) * 2010-08-31 2016-07-27 株式会社リコー トナー、トナーの製造方法、及び画像形成方法
JP2013148862A (ja) 2011-12-20 2013-08-01 Ricoh Co Ltd トナー、現像剤、及び画像形成装置
WO2014103961A1 (fr) * 2012-12-28 2014-07-03 キヤノン株式会社 Toner
JP5751266B2 (ja) * 2013-02-08 2015-07-22 コニカミノルタ株式会社 静電荷像現像用トナー
WO2014179777A1 (fr) * 2013-05-03 2014-11-06 Virdia, Inc. Procédé de préparation de fractions de lignine stable de façon thermique
JP6666936B2 (ja) * 2017-03-10 2020-03-18 三洋化成工業株式会社 トナーバインダー及びトナー

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08227171A (ja) * 1994-12-05 1996-09-03 Canon Inc 静電荷像現像用トナー
JPH0943896A (ja) * 1995-05-19 1997-02-14 Canon Inc 静電荷像現像用トナー及びその製造方法
US5863697A (en) 1995-05-19 1999-01-26 Canon Kabushiki Kaisha Toner for developing electrostatic image and process for production thereof
EP1096324A1 (fr) 1999-10-26 2001-05-02 Canon Kabushiki Kaisha Révélateur sec, procédé pour sa fabrication, procédé de production d' images
JP2002108019A (ja) * 2000-07-28 2002-04-10 Canon Inc トナー、トナーの製造方法及び画像形成方法
JP2003140379A (ja) * 2001-10-31 2003-05-14 Konica Corp 静電潜像現像用トナーとその製造方法、現像剤、画像形成方法及び画像形成装置
US20030104296A1 (en) 2001-12-04 2003-06-05 Fuji Xerox Co., Ltd. Electrophotographic toner, manufacture of the same, electrostatic latent image developer, and image forming method
JP2003215842A (ja) * 2002-01-18 2003-07-30 Fuji Xerox Co Ltd 画像形成方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6475685B2 (en) * 2000-02-28 2002-11-05 Konica Corporation Electrostatically charged image developing toner, production method of the same, and an image forming method

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08227171A (ja) * 1994-12-05 1996-09-03 Canon Inc 静電荷像現像用トナー
JPH0943896A (ja) * 1995-05-19 1997-02-14 Canon Inc 静電荷像現像用トナー及びその製造方法
US5863697A (en) 1995-05-19 1999-01-26 Canon Kabushiki Kaisha Toner for developing electrostatic image and process for production thereof
EP1096324A1 (fr) 1999-10-26 2001-05-02 Canon Kabushiki Kaisha Révélateur sec, procédé pour sa fabrication, procédé de production d' images
JP2002108019A (ja) * 2000-07-28 2002-04-10 Canon Inc トナー、トナーの製造方法及び画像形成方法
JP2003140379A (ja) * 2001-10-31 2003-05-14 Konica Corp 静電潜像現像用トナーとその製造方法、現像剤、画像形成方法及び画像形成装置
US20030104296A1 (en) 2001-12-04 2003-06-05 Fuji Xerox Co., Ltd. Electrophotographic toner, manufacture of the same, electrostatic latent image developer, and image forming method
JP2003215842A (ja) * 2002-01-18 2003-07-30 Fuji Xerox Co Ltd 画像形成方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP1693711A4 *

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4546354B2 (ja) * 2005-08-11 2010-09-15 キヤノン株式会社 フルカラー一成分現像用トナーおよび一成分現像方法
JP2007047522A (ja) * 2005-08-11 2007-02-22 Canon Inc フルカラー一成分現像用トナーおよび一成分現像方法
JP2007058138A (ja) * 2005-08-26 2007-03-08 Fuji Xerox Co Ltd 静電荷像現像用トナー及びその製造方法、静電潜像現像剤、画像形成方法
JP4517982B2 (ja) * 2005-08-26 2010-08-04 富士ゼロックス株式会社 静電荷像現像用トナー、静電潜像現像剤、画像形成方法
JP4708129B2 (ja) * 2005-09-09 2011-06-22 株式会社リコー 画像形成用トナー及びその製造方法と現像剤並びにこれを用いた画像形成方法と画像形成装置
JP2007072333A (ja) * 2005-09-09 2007-03-22 Ricoh Co Ltd 画像形成用トナー及びその製造方法と現像剤並びにこれを用いた画像形成方法と画像形成装置
JP2007193253A (ja) * 2006-01-23 2007-08-02 Canon Inc 乳化凝集法トナー
JP2011028162A (ja) * 2009-07-29 2011-02-10 Canon Inc トナー
JP2011144358A (ja) * 2009-12-17 2011-07-28 Sanyo Chem Ind Ltd 樹脂粒子
JP2011133753A (ja) * 2009-12-25 2011-07-07 Kyocera Mita Corp トナー用ワックス、電子写真用トナー、及び現像剤
JP2011197659A (ja) * 2010-02-26 2011-10-06 Konica Minolta Business Technologies Inc 静電潜像現像用トナーおよびその製造方法
JP2012008528A (ja) * 2010-05-26 2012-01-12 Ricoh Co Ltd トナー
JP2012063559A (ja) * 2010-09-15 2012-03-29 Ricoh Co Ltd トナー及びその製造方法
JP2012022331A (ja) * 2011-09-13 2012-02-02 Ricoh Co Ltd トナー、及びそれを用いた画像形成方法
JP2014112205A (ja) * 2012-10-29 2014-06-19 Mitsubishi Chemicals Corp 静電荷像現像用トナー
JP2018088001A (ja) * 2013-06-27 2018-06-07 キヤノン株式会社 トナーおよびトナーの製造方法
JP2015028616A (ja) * 2013-06-27 2015-02-12 キヤノン株式会社 トナーおよびトナーの製造方法
CN105182706A (zh) * 2014-06-19 2015-12-23 柯尼卡美能达株式会社 静电荷图像显影用调色剂
JP2016004228A (ja) * 2014-06-19 2016-01-12 コニカミノルタ株式会社 静電荷像現像用トナー
JP2017142404A (ja) * 2016-02-10 2017-08-17 日油株式会社 トナー用ワックス組成物
JP2017156472A (ja) * 2016-02-29 2017-09-07 キヤノン株式会社 トナーの製造方法
JP2018005257A (ja) * 2017-10-13 2018-01-11 三洋化成工業株式会社 トナーの製造方法
JP2019139218A (ja) * 2018-02-08 2019-08-22 ゼロックス コーポレイションＸｅｒｏｘ Ｃｏｒｐｏｒａｔｉｏｎ 機械超微粒子（ｕｆｐ）の排出の削減を示すトナーおよび関連する方法
JP7490450B2 (ja) 2020-05-18 2024-05-27 キヤノン株式会社 トナー
JP2022000675A (ja) * 2020-06-19 2022-01-04 東芝テック株式会社 トナー、トナーカートリッジ、画像形成装置
JP7495827B2 (ja) 2020-06-19 2024-06-05 東芝テック株式会社 トナー、トナーカートリッジ、画像形成装置
JP2022029612A (ja) * 2020-08-05 2022-02-18 東芝テック株式会社 トナー、トナーカートリッジ、画像形成装置
JP7423470B2 (ja) 2020-08-05 2024-01-29 東芝テック株式会社 トナー、トナーカートリッジ、画像形成装置

Also Published As

Publication number Publication date
EP1693711B1 (fr) 2015-05-13
JPWO2005071493A1 (ja) 2007-07-26
JP4721429B2 (ja) 2011-07-13
EP1693711A1 (fr) 2006-08-23
EP1693711A4 (fr) 2011-03-09
CN1886700A (zh) 2006-12-27

Similar Documents

Publication Publication Date Title
WO2005071493A1 (fr) Toner et procede de fabrication de toner
US10216108B2 (en) Toner production method and polymer
US7300737B2 (en) Process for producing toner
JP5617446B2 (ja) 電子写真用トナー及び画像形成装置
JP2016218441A (ja) トナーおよびトナーの製造方法
JP3893258B2 (ja) トナー、トナーの製造方法及び画像形成方法
JP2016224420A (ja) トナー
JP2007279666A (ja) トナー及びトナーの製造方法
US20200103776A1 (en) Magnetic toner
JP2008015230A (ja) トナー
JP2019020690A (ja) トナー
JP6424981B2 (ja) 静電潜像現像用トナー
JP6497485B2 (ja) 静電潜像現像用トナー
JP4498078B2 (ja) カラートナー、及び、該カラートナーを用いたフルカラー画像形成方法
JP6775999B2 (ja) トナー
JP4564892B2 (ja) カラートナー
JP6398882B2 (ja) 静電潜像現像用トナー及びその製造方法
JP4739029B2 (ja) トナー及びトナーの製造方法
JP6011354B2 (ja) トナーセット、現像剤及び画像形成装置
JP4250515B2 (ja) 非磁性一成分トナー
JP6439708B2 (ja) 磁性トナー
JP2018197811A (ja) 静電潜像現像用トナー
JPH10133411A (ja) 静電荷像現像用トナー
JP7471842B2 (ja) トナー
JP3581496B2 (ja) 静電荷像現像用トナー

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200480035126.7

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 11122031

Country of ref document: US

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2005517200

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2004801658

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2004801658

Country of ref document: EP