WO2013019014A2 - Procédé de préparation de toner - Google Patents

Procédé de préparation de toner Download PDF

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Publication number
WO2013019014A2
WO2013019014A2 PCT/KR2012/005906 KR2012005906W WO2013019014A2 WO 2013019014 A2 WO2013019014 A2 WO 2013019014A2 KR 2012005906 W KR2012005906 W KR 2012005906W WO 2013019014 A2 WO2013019014 A2 WO 2013019014A2
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Prior art keywords
dispersion
toner
polyester resin
weight
particles
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English (en)
Korean (ko)
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WO2013019014A3 (fr
Inventor
김성열
김진영
김보영
김동원
박무언
김성순
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Lotte Fine Chemical Co Ltd
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Samsung Fine Chemicals Co Ltd
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Publication of WO2013019014A2 publication Critical patent/WO2013019014A2/fr
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/0802—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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08755—Polyesters

Definitions

  • the present invention relates to a manufacturing method of a toner, and more particularly, to a manufacturing method of a toner having a uniform particle size distribution and excellent fixability, transparency and gloss.
  • toner is prepared by adding a colorant, a mold release agent, or the like to a thermoplastic resin serving as a binder resin. Further, in order to impart fluidity to the toner or to improve physical properties such as charge control or cleaning property, fine inorganic metal powders such as silica and titanium oxide may be added to the toner as an external additive.
  • toner production methods there are physical methods such as grinding method and chemical methods such as suspension polymerization method and emulsion aggregation method.
  • the toner manufacturing method by emulsion coagulation of the above chemical methods involves radical polymerization
  • vinyl resin can be used as the binder resin.
  • VOC volatile organic compounds
  • a toner is prepared by mixing a styrene-acrylate monomer and a low molecular weight polyester resin together, which also causes unreacted monomer to remain in the toner and dissolve the binder resin.
  • a toner is prepared by mixing a styrene-acrylate monomer and a low molecular weight polyester resin together, which also causes unreacted monomer to remain in the toner and dissolve the binder resin.
  • the carboxyl group is present on the surface of the polyester resin, the cohesive force varies depending on the content and type of the coagulant used in the coagulation process using the coagulant, which may result in rapid growth and low growth of particles in the coagulation process and the unification process. Careful attention is required.
  • polyester resins have advantages such as improved pigment dispersibility, excellent transparency, low fixation temperature, and narrow glass transition temperature than vinyl resins such as styrene-acrylic copolymer resins, binding of toners for high-speed printers or color printers It is suitable as a resin.
  • the zeta potential value of each step can be controlled to impart dispersion stability of raw material particles, control the flocculation process and flocculation fixing process, and affect the physical properties of final toner particles. have.
  • US2010 / 0159386 shows a process control result by controlling the zeta potential of the process step.
  • the toner manufacturing method disclosed herein firstly mixes a granule mixture containing a binder resin and a colorant with an aqueous medium to form a toner material dispersion, and then physically
  • a fine pulverization process includes preparing a dispersion containing particles having a size of 500 nm and then agglomerating them. In this case, since the size of the dispersed particles is large, the attraction force due to van der waal's force is large, and according to DLVO theory, dispersion stability is maintained only when a high level of electric repulsion is present.
  • a large amount (more than 4% of solids) of surfactant must be added to maintain dispersion stability in a wide pH range.
  • the zeta potential of the dispersion is formed much lower than ⁇ 30 mV, and even after addition of the flocculant.
  • the structure of the toner particles cannot be controlled because the toner agglomerates are again agglomerated, and the agglomeration must be performed at a low pH due to the excessive use of a polyvalent coagulant. Additives should be added.
  • an object of the present invention is to provide a method for producing a toner using a polyester resin as a binder resin, to provide a method for producing a toner having a uniform particle size distribution, excellent gloss, fixability and chargeability, and excellent image quality. do.
  • the polyester resin dispersion has a zeta potential of -10 to -20mV, the average particle diameter of the resin particles in the dispersion is 100 to 300nm, 80% A manufacturing method is provided, wherein the span value (d 90 -d 10 ) / d 50 is less than 0.20.
  • the weight average molecular weight of the polyester resin may be 10,000 to 50,000, the number average molecular weight is 4,000 to 10,000, PDI is 4 to 20, MP may be 5,000 to 10,000.
  • the polyester resin may have an acid value of 10 to 20 mgKOH / g.
  • the polyester resin dispersion may have a solid content of 20% by weight to 45% by weight.
  • toner particles having a uniform particle size distribution, excellent gloss, chargeability and fixability, and excellent image quality.
  • FIG. 1 is a graph showing an embodiment of a flow curve of a sample by a temperature rising method using a constant load extruded tubular rheometer.
  • Method for producing a toner comprises the steps of preparing a mixture of a polyester resin dispersion, colorant dispersion and wax dispersion;
  • the polyester resin dispersion has a zeta potential of -10 to -20mV, the average particle diameter of the resin particles in the dispersion is 100 to 300nm, 80% A manufacturing method is provided in which the span value is less than 0.20.
  • d10, d50, and d90 refer to particle size values corresponding to 10%, 50%, and 90%, respectively, for the highest value in the cumulative distribution of particles.
  • the average particle diameter of the resin particles in the dispersion is 100 to 300 nm, and has a narrow particle size with an 80% span value of less than 0.2, various valence cations are formed.
  • a toner having a narrow particle size distribution and a uniform toner can be stably produced using the flocculant included.
  • the stability of the polyester resin dispersion may be poor, and the toner may be poor, or the particle size of the dispersion may be too small to control the viscosity of the reaction solution.
  • the zeta potential value is smaller than -20 mV or the average particle diameter is larger than 300 nm, the stability of the dispersion is so high that the aggregation of the particles is difficult, and the particle size of the dispersion is too large to control the structure and shape of the toner particles.
  • the 80% span value is 0.2 or more, the distribution variation between the dispersed particles is large, so that coagulation control is difficult, and the toner particles may not be made uniform.
  • toner When toner is prepared using a polyester resin dispersion having a zeta potential, an average particle diameter, and an 80% span value within the above ranges, the structure and shape control of the toner such as the core / shell can be controlled during the coagulation / unification process. A toner excellent in amount, fluidity and fixability can be produced.
  • the zeta potential, average particle diameter, and span value of the polyester resin dispersion as described above can obtain a desired value by adjusting the surfactant, the type of dispersion stabilizer, the acid value of the resin, and the like used in preparing the dispersion.
  • the manufacturing method of the toner may further include washing and drying the united toner particles.
  • Dispersion manufacturing process can be divided into three categories. That is, polyester resin dispersion preparation, colorant dispersion preparation, and wax dispersion preparation are included.
  • the polyester resin dispersion may be prepared by stirring a mixture of a dispersion stabilizer, a surfactant, a polar solvent, and an organic solvent incompatible with the polar solvent to prepare a solvent emulsion; A polyester resin may be added to the solvent emulsion, followed by heating to remove the organic solvent.
  • the polyester resin is dispersed in a polar solvent containing a dispersion stabilizer, it is possible to produce a stable dispersion. At this time, the polyester resin terminal is ionized by the dispersion stabilizer to form a stable dispersed state.
  • the polar solvent includes water, methanol, ethanol, butanol, acetonitrile, acetone, ethyl acetate and the like, and water is most preferred.
  • the polar solvent may be used in an amount of 100 to 400 parts by weight per 100 parts by weight of the polyester resin.
  • Polyester resin used in the present invention may have a glass transition temperature of 60 °C to 70 °C.
  • the polyester resin has a weight average molecular weight of 10,000 to 50,000, a number average molecular weight of 4,000 to 10,000, PDI of 4 to 20, the peak molecular weight (Mp; Max Peak Position) measured by gel permeation chromatography is 5,000 to 10,000, constant
  • the T 1/2 value measured by the load extruded tubular rheometer may be between 100 and 160.
  • the constant-load extruded tubular rheometer is a means for easily measuring the performance of thermal properties, viscosity characteristics, and the like of a resin, and measures the viscous resistance when the melt passes through the tubule.
  • the flow tester CFT-500 by Shimadzu Seisakusho is mentioned.
  • the measurement by the temperature raising method using this apparatus is carried out by heating up at a constant rate with the passage of the test time, and continuously the process from the solid zone to the transition zone through the transition zone and the rubbery elastic zone Can be measured.
  • the shear rate and the viscosity of each temperature in the flow zone can be easily measured.
  • the AB region (softening curve) represents the stage in which the sample is deformed under compression weighting and the internal void gradually decreases.
  • Point B is a temperature at which the internal void disappears and becomes a single transparent body or phase with a uniform appearance with a nonuniform stress distribution, and represents an inflection point from the solid region to the transition region. This temperature is defined as the softening temperature (Ts).
  • the BC region shows no apparent change in the position of the piston within a finite time, and also represents the region until the sample starts to flow out from the die and includes the rubbery elastic region of the sample. In the case of crystalline polymers, this region is short, and the softening temperature shows a value close to the outflow start temperature described later.
  • the point C represents the temperature at which the sample begins to flow out of the die of the flow meter due to the decrease in viscosity, and this temperature is defined as the outflow start temperature Tfb.
  • the CDE region (outflow curve) represents the region in which the sample flows out of the die and is mainly composed of irreversible viscous flow.
  • the melting temperature (T 1/2 ) by the 1/2 method represents the temperature at the half point of the piston stroke of the flow meter between the outflow start temperature (Tfb) and the outflow end temperature (Tend) of the outflow curve.
  • the peak molecular weight (Mp) in a gel permeation chromatography (GPC) is molecular weight calculated
  • the measurement conditions of GPC measurement are as follows.
  • the calibration curve was created using standard polystyrene, and the peak molecular weight (Mp) was calculated
  • Examples of standard polystyrene samples for preparing calibration curves include TSK standard, A-500 (molecular weight 5.0 ⁇ 10 2 ), A-2500 (molecular weight 2.74 ⁇ 10 3 ), F-2 (molecular weight 1.96 ⁇ 10 4) ), F-20 (molecular weight 1.9 ⁇ 10 5 ), F-40 (molecular weight 3.55 ⁇ 10 5 ), F-80 (molecular weight 7.06 ⁇ 10 5 ), F-128 (molecular weight 1.09 ⁇ 10 6 ), F-288 ( Molecular weight 2.89 ⁇ 10 6 ), F-700 (molecular weight 6.77 ⁇ 10 6 ), and F-2000 (molecular weight 2.0 ⁇ 10 7 ) were used.
  • the peak value of the dissolution curve is a point at which the dissolution curve indicates the maximum, and when the maximum value is two or more points, the dissolution curve gives the maximum value.
  • the eluent is not particularly limited, and in addition to THF, it is also possible to use a solvent in which the polyester resin is dissolved, for example, chloroform.
  • the PDI value of the polyester resin is not particularly limited, but the fixability of the toner obtained can be improved by being in the above range.
  • the acid value of the polyester resin is not particularly limited, but may be preferably 10 to 20mgKOH / g.
  • an inorganic base of a monovalent metal may be used, and examples thereof include NaOH, LiOH, KOH, and the like.
  • the polyester resin may be prepared by polycondensing an acid component and an alcohol component, and a polyester resin is prepared using polyhydric carboxylic acid mainly for an acid component and polyhydric alcohols mainly for an alcohol component.
  • polyhydric alcohol component examples include polyoxyethylene- (2,0) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene- (2,0) -2,2-bis (4 -Hydroxyphenyl) propane, polyoxypropylene- (2,2) -polyoxyethylene- (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2,3) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2,3) -2,2 -Bis (4-hydroxyphenyl) propane, polyoxypropylene- (2,4) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (3,3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1, 4-but
  • the polyhydric carboxylic acid component specifically includes aromatic polyhydric acids and / or alkyl esters thereof conventionally used for producing polyester resins.
  • aromatic polyacids include terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4 Naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2,7,8-octanetetracarboxylic acid and the like and / or alkyl esters of these carboxylic acids.
  • Methyl, ethyl, propyl, butyl group, etc. are mentioned.
  • the aromatic polyacids and / or alkyl esters thereof may be used alone or in combination of two or more thereof.
  • organic solvent used in the polyester resin dispersion one or more selected from the group consisting of dimethyl ether, diethyl ether, 1,1-dichloroethane, 1,2-dichloroethane, dichloromethane, and chloroform may be used. It is not necessarily limited to these.
  • the surfactant used for the said polyester resin dispersion liquid in the quantity of 0.4-3.0 weight part and an organic solvent 15-200 weight part with respect to 100 weight part of polyester resins.
  • the dispersion stabilizer is preferably used in an amount of 0.4 to 1.0 parts by weight per 100 parts by weight of the polyester resin.
  • the polyester resin dispersion may have a solid content of 23% by weight to 45% by weight.
  • the zeta potential of the polyester resin dispersion is not particularly limited in the measurement method.
  • ZEECOM manufactured by Microtech Nition Co., Ltd.
  • ZEECOM can be used to determine the zeta potential of the average value by randomly measuring 200 particles by setting the cell position to 15 mm and the voltage to 70 V.
  • the particle size distribution is narrowed by adjusting the magnitude of the zeta potential value of the reaction liquid in the flocculation step, the freezing, and the unification step of the toner manufacturing process or by changing the sign of the zeta potential value.
  • Toner particles were prepared, in which case it is impossible to ensure quality through the structure control of the particles.
  • the zeta potential, the average particle diameter, and the 80% span value of the polyester resin dispersion corresponding to 90% of the raw material are controlled to improve the stability of the resin dispersion, and as a result, the physical properties of the toner particles can be improved.
  • the structure control of the toner particles having a core / shell structure is facilitated.
  • the colorant dispersion may be dispersed in water using a dispersant such as a surfactant, or may be dispersed using an organic solvent.
  • a dispersant such as a surfactant
  • anionic surfactants and nonionic surfactants are preferable, and anionic surfactants are more preferable.
  • a dispersion is prepared using a master batch in which a pigment and a polyester resin are kneaded. Specifically, after the master batch and the organic solvent are put into a ball mill and milled for about 24 hours, the mixed solution is added to water containing a surfactant and a dispersion stabilizer to obtain a master batch pigment dispersion. Moreover, you may disperse
  • the dispersion stabilizer used may be a dispersion stabilizer such as NaOH used in preparing a polyester resin dispersion.
  • the colorant may be appropriately selected from black pigments, cyan pigments, magenta pigments, yellow pigments, and mixtures thereof, which are commonly used pigments.
  • the content of the colorant may be sufficient to color the toner to form a visible image by development, for example, 3 to 15 parts by weight based on 100 parts by weight of the polyester resin. If the content is less than 3 parts by weight, the coloring effect may be insufficient. If the content is more than 15 parts by weight, the electric resistance of the toner is lowered, so that sufficient triboelectric charge may not be obtained, resulting in contamination.
  • Wax dispersions can be prepared by dispersing natural or synthetic waxes in water or in organic solvents.
  • wax a known wax can be used.
  • natural waxes such as carnauba wax and rice wax
  • synthetic waxes such as polypropylene wax and polyethylene wax
  • petroleum wax such as montan wax, alcohol wax, and ester wax etc.
  • Wax may be used individually by 1 type, and may use 2 or more types together.
  • a dispersion is obtained by using a surfactant or a dispersion stabilizer and dispersing using a disperser such as a high pressure or high speed homogenizer.
  • a disperser such as a high pressure or high speed homogenizer.
  • the wax can be dispersed in the same manner as in the case of producing a polyester resin dispersion. That is, a solvent emulsion is prepared by adding an organic solvent to water containing a surfactant and a dispersion stabilizer, and a wax is added to a solid state to prepare a dispersion.
  • 0.5-20 weight part is preferable with respect to 100 weight part of polyester resin, and, as for wax content, 1-10 weight part is more preferable.
  • the toner particles are agglomerated by adding the flocculant and the acid while stirring the respective dispersions prepared in the above dispersion preparation step.
  • the coagulation process is preferably performed at room temperature, it may be heated up to the glass transition temperature (Tg) of the polyester resin, and the particle diameter and shape are uniform by stirring the mixed liquid of each dispersion liquid by using a stirrer and mechanical shear force. Agglomerates can be formed in one particle state.
  • the inorganic salt of the monovalent metal used as the flocculant may be NaCl or KCl.
  • the amount of the flocculant used is 0.3 to 5% by weight, preferably 0.5 to 3% by weight, based on the total solids content of the flocculation step reaction solution. If the amount of the flocculant is less than 0.3% by weight, aggregation may not occur, and when the amount of the flocculant is greater than 5% by weight, the aggregated particles may be too large.
  • the pH may be adjusted by addition of acid in the flocculation process, and the preferred pH may be 4.5 to 6.5.
  • the coagulation step may be performed by stirring the reaction solution at 1.0 to 7.0 m / sec at a temperature of 40 to 60 °C.
  • a monovalent metal ion derived from an inorganic base of a monovalent metal used as a dispersion stabilizer in preparing a polyester resin dispersion may serve as a coagulant, and thus a small amount of coagulant. Also excellent coagulation effect can be obtained by using.
  • the temperature of the reaction solution is maintained and the pH is raised to 10.
  • an inorganic base such as NaOH, KOH or LiOH is added.
  • the mixed liquid containing the toner particles is heated to uniform the particle size and shape of the aggregated toner particles. It is preferable to adjust to a particle diameter of 1 to 20 ⁇ m by heating to a temperature higher than or equal to the glass transition temperature (Tg) of the polyester resin, whereby toner particles having almost uniform particle sizes and shapes can be obtained.
  • Tg glass transition temperature
  • the surface properties of the particles can be improved by heating to a temperature above the glass transition temperature (Tg) of the polyester resin, and the polyester resin dispersion or polystyrene butylacryl before heating to a temperature above the glass transition temperature (Tg) of the polyester resin.
  • the latex is added to cover the toner particles generated in the flocculation process once, thereby preventing the pigment or wax contained therein from coming out and making the toner firm.
  • the polyester resin dispersion or polystyrene butyl acrylate latex added may use a resin dispersion having the same physical properties (Tg, molecular weight) as the polyester resin dispersion used in the previous step. You may use it.
  • Tg When using Tg and a higher molecular weight, Tg is 60-85 degreeC, and it is preferable that molecular weight is 10,000-300,000.
  • This additionally added resin dispersion may increase the particle size while wrapping the toner particles produced in the flocculation step. To prevent this, a surfactant is added or the pH is adjusted, and the temperature is raised above the glass transition temperature of the polyester resin. The coalescing process can proceed.
  • the toner particles obtained in the coalescence process are washed with water and dried.
  • the mixed liquid containing toner is cooled to room temperature, the mixed liquid is filtered, the filtrate is removed, and the toner is washed with water.
  • the washing of the toner using pure water may be performed batchwise or continuously.
  • the cleaning of the toner using pure water is performed to remove unnecessary components other than toner components such as impurities that may affect the chargeability of the toner and unnecessary coagulants that do not participate in aggregation.
  • the toner obtained after the washing step is dried using a fluidized bed dryer, a flash jet dryer, or the like.
  • a desired external additive may be added to the toner obtained by drying.
  • a 3L reactor equipped with a stirrer, a nitrogen gas inlet, a thermometer, and a cooler was installed in the oil chain oil tank.
  • 45 g of terephthalic acid, 39 g of isophthalic acid, 75 g of 1,2-propylene glycol, and 3 g of trimellitic acid were added to the reactor thus installed, and 500 ppm of dibutyltin oxide was added to the total weight of the monomer as a catalyst.
  • the temperature was raised to 150 ° C. while the reactor was stirred at 150 rpm.
  • the reaction was carried out for 6 hours, the temperature was raised to 220 ° C., the reactor was depressurized to 0.1torr to remove the side reactants, and the reaction was performed for 15 hours under the same pressure condition to obtain a polyester resin.
  • the acid value of the obtained polyester resin was 13 mgKOH / g, the weight average molecular weight was 28,000, the number average molecular weight was 6,000, the Mp value was 7,000, the PDI was 8.0, the glass transition temperature was 65 ° C., and the T1 / 2 value was 125 ° C. It became.
  • the sample was heated to 20 ° C. to 200 ° C. at a heating rate of 10 ° C./min, quenched to 10 ° C. at a cooling rate of 20 ° C./min, and then again to 10 ° C. It measured by heating up at the heating rate of / min.
  • the acid value (mgKOH / g) was measured by dissolving the resin in dichloromethane, cooling it, and titrating with 0.1 N KOH methyl alcohol solution.
  • the weight average molecular weight, number average molecular weight, Mp and PDI values of the binder resin were measured by gel permeation chromatography (GPC) using a calibration curve using a polystyrene standard sample.
  • Peak molecular weight (Mp) was calculated
  • the peak value of an elution curve is a point where an elution curve shows a maximum value, and when a maximum value is two or more points, it is a point which gives the maximum value of an elution curve.
  • signal intensity I (Mp) of the GPC curve in the position of a peak molecular weight, and signal intensity I (M100000) of the GPC curve in the position of molecular weight 100,000 are respectively signal intensity and a base in the position of a peak molecular weight. It is the difference of the signal intensity of a line, the difference of the signal intensity in the position of molecular weight 100,000, and the signal intensity of a baseline, and is shown by electric potential.
  • Filtration conditions filter the sample solution with 0.45 ⁇ m Teflon® membrane filter
  • Standard polystyrene sample for calibration curve preparation TSK standard, A-500 (molecular weight 5.0 ⁇ 10 2 ), A-2500 (molecular weight 2.74 ⁇ 10 3 ), F-2 (molecular weight 1.96 ⁇ 10 4 ) F-20 (molecular weight 1.9 ⁇ 10 5 ), F-40 (molecular weight 3.55 ⁇ 10 5 ), F-80 (molecular weight 7.06 ⁇ 10 5 ), F-128 (molecular weight 1.09 ⁇ 10 6 ), F-288 (molecular weight 2.89 ⁇ 10 6 ), F-700 (molecular weight 6.77 ⁇ 10 6 ), F-2000 (molecular weight 2.0 ⁇ 10 7 ).
  • T1 / 2 by a constant load extruded tubular rheometer is a value obtained by measuring under the following conditions:
  • polyester resin dispersions (2) to (9) were prepared in the same manner as in Preparation Example 2, except that NaOH loading and surfactant loading were changed when the polyester resin dispersion was prepared as shown in Table 1 below.
  • Coulter Multisizer Multisizer 3 Coulter Counter
  • an aperture was 100 ⁇ m, and an appropriate amount of a surfactant was added to 50-100 ml of ISOTON-II (Beckman Coulter Co., Ltd.), an electrolyte, and 10-15 mg of the measurement sample was added thereto.
  • ISOTON-II Beckman Coulter Co., Ltd.
  • the zeta potential measuring device was measured using a ZEECOM instrument.
  • the sample was diluted with ion-exchanged water so that the solid content concentration of the sample was 5 ppm, the cell position was set to 15 mm and the voltage was set to 70 V, and the zeta potential of 200 particles was measured at random and the average value was obtained.
  • the reactor contents were then subjected to main dispersion using a Ultimizer system (Amstec Ltd., Model HJP25030) at a pressure of 1,500 bar.
  • cyan pigment particles dispersed at a nano size having a volume average particle diameter (D50 (v)) of 150 nm were obtained.
  • the temperature of the reactor was lowered to room temperature, the toner was separated using a filtration device (device name: filter press), and the separated toner was washed with 1N aqueous nitric acid solution and washed again with distilled water to remove all surfactants and the like. Thereafter, the washed toner particles were dried using an air flow dryer. At this time, the outlet temperature of the airflow dryer was 60 ° C., and the feed rate of the raw materials was 9 kg / hr.
  • a filtration device device name: filter press
  • an external step was performed.
  • the external process was carried out using a powder mixer (2L, manufactured by Daehwa Tech).
  • the external condition was maintained for 10 seconds after 2 minutes at 8000 rpm, and then proceeded again for 2 minutes at 8000 rpm to complete the external attachment.
  • the toner was sorted out using a sieve having an eye size of 150 ⁇ ⁇ after external attachment.
  • Toner was prepared in the same manner as in Example 1, except that the polyester resin dispersion (2) obtained in Preparation Example 3 was used instead of the polyester resin dispersion (1), and 2.0 wt% of PAC was used as the flocculant. .
  • Toner was prepared in the same manner as in Example 1, except that the polyester resin dispersions (3) to (5) prepared in Preparation Examples 4 to 6 were used instead of the polyester resin dispersion (1).
  • Toner was prepared in the same manner as in Example 1, except that the polyester resin dispersions 6 to 8 prepared in Preparation Examples 7 to 10 were used instead of the polyester resin dispersion (1), respectively. .
  • the toner particles prepared in Examples 1 to 5 and Comparative Examples 1 to 4 were subjected to the following evaluation of average particle diameter, GSDp, fine fraction, image evaluation and fixability, and the results are shown in Table 2. Indicated.
  • the average particle diameter of the toner particles was measured using Coulter Multisizer III (Beckman coulter, USA), the number of particles measured was 50000 counts and the aperture used was 100 ⁇ m.
  • GSDp and GSDv are obtained by the following formulas (1) and (2).
  • the fine amount of toner particles means the ratio of the number of particles smaller than 3 ⁇ m divided by the total number of particles among the total particles measured by Coulter Multisizer III.
  • Core / shell structure control evaluations are made using Transmission electron microscopy (TEM) analysis images.
  • TEM Transmission electron microscopy
  • a toner with good core / shell structure control shows a shape in which the toner's pigments and waxes are not exposed to the surface, while a toner with poor structure control shows a shape where the pigments and waxes are exposed to the surface of the toner.
  • Image evaluation was performed by developing with a CP 2025 (HP) retrofit device which is a digital full color printer.
  • Image density (OD) was measured using spectroeye (GretagMacbeth) which is a spectrophotometer.
  • Fixability (%) [(OD after tape removal) / (OD before tape removal)] * 100
  • the fixing temperature area of 90% or more of fixability was regarded as the fixing area of the toner.
  • MFT Minimum Fusing Temperature
  • Hot Offset Temperature The lowest temperature at which hot-offset occurs
  • the chargeability of the toner was measured using a q / m meter (Epping, Germany). First, in order to pretreat the measurement sample, the carrier: toner ratio was measured at 97%: 3%, mixed in a 10 ml container, and then mixed for 90 minutes using a tumbler mixer (WAB, Switzerland). At this time, the speed of the tumbler mixer was maintained at 96 rpm.
  • the toner particles produced by the manufacturing method of the present invention have a narrow particle size distribution, excellent fixability and charging property, and excellent image quality.

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

Abstract

La présente invention concerne un procédé de préparation de toner. Le procédé de l'invention permet de préparer des particules de toner présentant d'excellentes caractéristiques en termes de capacité de fixation, de brillant et de capacité de chargement et formant des images de qualité supérieure, grâce à la régulation du potentiel zêta et de la granulométrie d'une dispersion de résine de polyester.
PCT/KR2012/005906 2011-08-04 2012-07-25 Procédé de préparation de toner Ceased WO2013019014A2 (fr)

Applications Claiming Priority (2)

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KR1020110077844A KR101825917B1 (ko) 2011-08-04 2011-08-04 토너의 제조방법
KR10-2011-0077844 2011-08-04

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WO2013019014A2 true WO2013019014A2 (fr) 2013-02-07
WO2013019014A3 WO2013019014A3 (fr) 2013-03-28

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US9964880B1 (en) * 2017-03-22 2018-05-08 Xerox Corporation Phase inversion emulsification process for controlling latex particle size

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JP2005140987A (ja) 2003-11-06 2005-06-02 Fuji Xerox Co Ltd 電子写真用トナーの製造方法、分散液、電子写真用トナー、および画像形成方法
JP4753807B2 (ja) * 2006-03-14 2011-08-24 株式会社リコー 静電荷像現像用トナーおよび該静電荷像現像用トナーを用いた画像形成装置
JP4981434B2 (ja) 2006-12-19 2012-07-18 キヤノン株式会社 トナー
KR100833920B1 (ko) 2007-02-23 2008-05-30 삼성정밀화학 주식회사 코어-쉘 구조를 갖는 토너의 제조방법 및 그 방법에 의해제조된 토너
JP5409167B2 (ja) * 2009-07-29 2014-02-05 キヤノン株式会社 トナー
JP5371608B2 (ja) 2009-07-29 2013-12-18 キヤノン株式会社 トナー
KR20110068636A (ko) * 2009-12-16 2011-06-22 삼성정밀화학 주식회사 토너의 제조방법

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KR20130015702A (ko) 2013-02-14
WO2013019014A3 (fr) 2013-03-28

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