JP5505687B2 - Method for producing toner for developing electrostatic image, and toner - Google Patents

Description

  The present invention relates to a method for producing toner used as a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, and the like, a toner, and an electrophotographic developing apparatus using the toner. More particularly, the present invention relates to a method for producing a toner for electrophotography used in a copying machine, a laser printer, a plain paper fax machine or the like using a direct or indirect electrophotographic developing method, a toner, and an image forming method using the toner.

  In recent years, the strong demand for higher image quality from the market has spurred the development of an electrophotographic apparatus suitable for it and a toner developer used therefor. As a toner corresponding to high image quality, it is essential that the toner has a uniform particle size. When the toner particle size is uniform and the particle size distribution becomes sharp, the behavior of individual toner particles during development is aligned, and the reproducibility of minute dots is remarkably improved.

  In addition to suspension polymerization, the polymerization toner method includes emulsion polymerization method and dissolution suspension method, which are relatively easy to modify, and has a smaller particle size and sharper particle size distribution than the pulverized toner method. It is easy to obtain. An organic solvent is used to dissolve or disperse the binder resin, and oil droplets are formed in water to obtain a desired particle size. Then, the organic solvent is removed, washed, and dried to obtain a powder toner. Most of the organic solvent in the oil droplets is removed under heating and reduced pressure in the solvent removal step, and a part of the remaining organic solvent is extracted into water in the washing step and further completely removed in the drying step. However, when there is a large amount of remaining organic solvent, there is a problem that it takes time for the removal in the washing step and the drying step and the production efficiency is lowered.

  When a polar solvent is used to dissolve the binder resin, water and a part of the polar solvent are mixed, and water and the polar solvent azeotrope during the solvent removal. In order to completely remove the organic solvent, the azeotropic effect cannot be ignored, and in the vicinity of the end point of the solvent removal, the majority of the liquid that evaporates is water, and there is a problem that the energy efficiency is lowered. For efficient evaporation, it is necessary to increase the degree of vacuum or increase the heating temperature. However, when the degree of decompression is increased, it is necessary to lower the cooling temperature of the condenser. On the other hand, when the heating temperature is increased, the toner is fused and coarsened, the particle size distribution becomes broad, and the image quality is deteriorated. . In addition, accumulation of toner fusion products in the manufacturing facility may cause production trouble.

  About the dehydration method of water and organic matter using a separation membrane module, as described in Patent Document 1 (Patent No. 274336), separation is performed using a polyimide separation membrane that defines a water vapor transmission rate and an organic matter evaporation rate. There has been proposed a method for obtaining an organic vapor having a reduced water vapor content by selectively permeating water vapor from the supply side to the permeation side of the membrane and removing the water vapor from the vapor mixture. In Patent Document 2 (Japanese Patent No. 3876561), regarding the separation membrane module and the gas separation method, the flow of the carrier gas and the flow of the mixed gas are counter-current across the hollow fiber membrane of the gas separation membrane module. There has been proposed a method for efficiently performing gas separation by configuring the outer peripheral portion of the hollow fiber bundle with a film-like substance.

  Patent Document 3 (Japanese Patent No. 2454429) proposes an aromatic polyimide having a repeating unit as a material for a separation membrane used in the pervaporation separation method of an organic compound.

  A method for removing volatile organic components such as residual polymerizable monomers of a polymerized toner using a silicone hollow fiber gas separation membrane module is proposed in Patent Document 4 (Japanese Patent Laid-Open No. 2005-225698). Yes. However, there is no description of a method for removing a solvent from an emulsion obtained by dissolving or dispersing a binder resin in an organic solvent.

So far, as a method for removing the organic solvent of the polymerized toner, a method for selectively removing water from an azeotropic mixture of water and an organic solvent using a separation membrane module using an aromatic polyimide has not been proposed. However, this is a technique that cannot be applied without careful study of various conditions regarding the conditions for organic solvent removal.
Japanese Patent No. 274336 Japanese Patent No. 3877561 Japanese Patent No. 254429 JP 2005-225698 A

  The objects of the present invention are as follows: (1) providing a highly efficient toner production method by shortening the time of the organic solvent removal step; and (2) removing the organic solvent from the emulsion and simultaneously purifying the organic solvent. Thus, the heat energy for solvent removal is effectively used, and (3) the toner particle size distribution is sharpened.

The present inventors have completed the present invention to solve the above-described problems. That is, the said subject is solved by this invention containing the following means.
(1) A toner material including at least a binder resin and / or a binder resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent, and an oil phase composed of the solution or the dispersion is converted into an aqueous system. A method for producing a toner for an electrostatic charge image phenomenon, comprising emulsifying in a medium, granulating particles, and removing the solvent from the emulsion to obtain toner particles,
In the step of removing the organic solvent from the emulsion, a separation membrane module is used, and water vapor is selected from the azeotropic mixture of the organic solvent and the aqueous medium by using the differential pressure between the discharge side and the liquid introduction side of the separation membrane. A method for producing a toner for an electrostatic charge image phenomenon, wherein the organic solvent is removed from the emulsified liquid.
(2) A compound having at least an active hydrogen group, a polymer having a site capable of reacting with an active hydrogen group, a binder resin, a colorant, a release agent, and a kneaded composite of a modified layered inorganic mineral and the binder resin. The toner material is dissolved or dispersed in an organic solvent, and an oil phase composed of the solution or dispersion is dispersed and emulsified in an aqueous medium containing resin fine particles. The compound having the active hydrogen group, the active hydrogen group, A method for producing a toner comprising a step of removing the organic solvent after reacting or reacting a polymer having a reactable site,
In the step of removing the organic solvent from the emulsion, a separation membrane module is used, and water vapor is selected from the azeotropic mixture of the organic solvent and the aqueous medium by using the differential pressure between the discharge side and the liquid introduction side of the separation membrane. A method for producing a toner for an electrostatic charge image phenomenon, wherein the organic solvent is removed from the emulsified liquid.
(3) In the step of removing the organic solvent from the emulsion, the discharge side of the separation membrane module is in a reduced pressure state of 30 to 200 mmHg. Manufacturing method of toner for electrostatic charge image phenomenon.
(4) The method for producing a toner for an electrostatic charge image phenomenon according to any one of (1) to (3), wherein the separation membrane of the separation membrane module is made of aromatic polyimide. .
(5) The method for producing a toner for developing an electrostatic charge image according to any one of (1) to (4), wherein the organic solvent is ethyl acetate.
(6) The electrostatic image developing toner according to any one of (1) to (5), wherein the toner for electrostatic image phenomenon is 40 to 70 ° C. Manufacturing method.
(7) In the step of removing the organic solvent from the emulsion, the processing temperature of the emulsion and the azeotrope of the emulsion and the aqueous medium is lower than the glass transition point of the toner for electrostatic image phenomenon. The method for producing a toner for developing an electrostatic charge image according to any one of the above items (1) to (6) .

  As will be apparent from the following detailed description, the method for producing a toner for developing an electrostatic charge image according to the present invention can shorten the time of the organic solvent removal step, and simultaneously removes the organic solvent from the emulsion and simultaneously purifies the organic solvent. Thus, the heat energy for solvent removal can be used effectively. The toner obtained by the method for producing a toner for developing an electrostatic charge image of the present invention has a sharp particle size distribution, excellent low-temperature fixability, little residual toner in an apparatus using blade cleaning, high image quality and high This provides an extremely excellent effect of providing a resolution image.

It is the figure which showed the batch type solvent removal apparatus using the solvent removal pot with a jacket as an example of the apparatus figure of this invention. It is the figure which showed the continuous type apparatus using the mechanical stirring centrifugal thin film type | mold solvent removal apparatus as an example of the apparatus figure of this invention. It is the figure which showed the continuous type apparatus using the vertical falling liquid film type | mold solvent removal apparatus as an example of the apparatus figure of this invention. 1 is a cross-sectional configuration diagram of a main part of an example of an image forming apparatus according to the present invention.

Conventionally, at least a binder resin and / or a binder resin precursor, a colorant, and a release agent are dissolved or dispersed in an organic solvent, and an oil phase composed of the solution or the dispersion is emulsified in an aqueous medium. In the step of granulating the particles and removing the organic solvent from the emulsion, the organic solvent and water azeotrope, and thus heating is performed under reduced pressure for a long time in order to reduce the amount of residual solvent in the toner.
In the toner production method of the present invention, the organic solvent can be removed regardless of vapor-liquid equilibrium by selectively allowing water vapor to permeate from the azeotropic mixture of the organic solvent and water using the separation membrane module. Moreover, the organic solvent and water can be separated with high purity by a single solvent removal operation, and the thermal energy efficiency required for solvent removal is good.

  In the toner manufacturing method of the present invention, the permeation side (discharge side) of the separation membrane module is in a reduced pressure state of 30 to 200 mmHg, and the water vapor is selectively selected by maintaining the differential pressure from the non-permeation side (liquid introduction side). Can be transmitted. An aromatic polyimide is preferable as a separation membrane that selectively allows water vapor to pass therethrough. In the case of aromatic polyimide, when an organic solvent having a low boiling point and water are azeotroped with water, when the molar fraction of the organic solvent is minimal, that is, in the vicinity of the end point of desolvation, the evaporation temperature is similar to that of water under reduced pressure. Of about 29 ° C. at 30 mmHg and about 66 ° C. at 200 mmHg.

  In the toner production method of the present invention, it is particularly preferable to use ethyl acetate among polar solvents. When a polyester resin having excellent glossiness of a fixed image is used as a binder resin, ethyl acetate is excellent in solubility of the polyester resin and has a relatively low boiling point of about 77 ° C. at atmospheric pressure. In addition, it is an organic solvent that can be easily removed.

  The glass transition point of the toner of the present invention is preferably 40 to 70 ° C. When the glass transition point is lower than 40 ° C., the heat resistance during storage is poor, and when the glass transition point is higher than 70 ° C., the low temperature fixability is poor. . Further, when the organic solvent is removed, when the pressure is reduced to 30 to 200 mmHg, the evaporation temperature is about 30 to 65 ° C. Therefore, the glass transition point of the toner is preferably 40 to 70 ° C. It is possible to prevent production troubles due to accumulation of toner melts.

  The processing temperature of the emulsion, the emulsion after removal of the organic solvent, and the azeotrope of the emulsion and water should be lower than the glass transition point of the toner to prevent the accumulation of fused materials and toner particle coarsening. From the point of view, it is preferable.

Hereafter, the measuring method regarding the property of the toner of this invention is shown.
In the present invention, the concentration of ethyl acetate in dispersed particles in the emulsion is specifically determined by the following procedure.
[Measurement equipment conditions]
Measuring device: GC-2010 (Shimadzu gas chromatograph)
Injection volume: 2.0μL
Sample vaporization chamber injection mode: Split vaporization chamber temperature: 180 ° C
Carrier gas: He
Pressure: 40.2kPa
Total flow rate: 56.0mL / min
Column flow rate: 1.04mL / min
Linear velocity: 20.0cm / sec
Purge flow rate: 3.0mL / min
Split ratio: 50.0

[column]
Column name: ZB-50
Liquid phase film thickness 0.25μm
Length 30.0m
Inner diameter: 0.32mmID
Maximum column temperature: 340 ° C

[Column oven]
Column temperature: 60 ° C
Column oven temperature program:
60 ° C hold 6 min → Temperature rise rate 60 ° C / min → 230 ° C hold 5 min

[Detector]
Detector temperature: 250 ° C
Make-up gas: N2 / Air
Make-up flow rate: 30.0mL / min
H2 flow rate: 47.0mL / min
Air flow rate: 400mL / min

[Measuring method]
Preparation of internal standard solution: Weigh 4 g of toluene in a volumetric flask and dilute to 500 mL with DMF.
Preparation of measurement sample: After 1.5 g of the emulsion to be measured is diluted to about 50 mL with DMF, 10 mL of the internal standard solution is collected with a whole pipette and charged. After stirring the measurement sample with a stirrer at 400 rpm for 4 minutes, the sample is set on the autosampler of the measuring instrument GC and measurement is performed. After the measurement, the amount of ethyl acetate in the emulsion is calculated by the internal standard method from the ratio of toluene and ethyl acetate as the internal standard substance.

(Circularity and particles below 2 μm)
In the present invention, a flow type particle image analyzer (“FPIA-2100”; manufactured by Sysmex Corporation) is used to measure toner having a particle size of 2 μm or less, and analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10) is measured. ) Was used for analysis. Specifically, 0.1 to 0.5 ml of 10 wt% surfactant (alkylbenzene sulfonate Neogen SC-A; Daiichi Kogyo Seiyaku) is added to a glass 100 ml beaker, and each toner 0.1 to 0 is added. 0.5 g was added and stirred with a microspatel, and then 80 ml of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). The shape and distribution of the toner were measured using the FPIA-2100 until the density of the dispersion was 5000 to 15000 / μl. In this measurement method, it is important that the concentration of the dispersion liquid is 5000 to 15000 / μl from the viewpoint of measurement reproducibility of the average circularity. In order to obtain the dispersion concentration, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated. If the amount is too small, the toner cannot be sufficiently wetted. It becomes insufficient. Further, the toner addition amount differs from the particle size, and it is necessary to decrease the small particle size and increase the large particle size. When the toner particle size is 3 to 7 μm, the toner amount is 0.1 to 0. By adding 0.5 g, the dispersion concentration can be adjusted to 5000 to 15000 / μl.

(Toner shape)
The shape factors SF-1 and SF-2 used in the present invention were obtained by randomly sampling 300 SEM images of the toner obtained by measurement using an FE-SEM (S-4200) manufactured by Hitachi, Ltd. Were introduced into an image analysis apparatus (LuzexAP) manufactured by Nireco through an interface and analyzed, and values obtained from the following equations were defined as SF-1 and SF-2. The values of SF-1 and SF-2 are preferably values obtained by the above Luzex, but are not particularly limited to the FE-SEM device and the image analysis device as long as similar analysis results can be obtained.

  In the case of a true sphere, both SF-1 and SF-2 become 100, and the value becomes larger from 100 and becomes an indeterminate shape. In particular, SF-1 represents the shape of the whole toner (ellipse, sphere, etc.), and SF-2 is a shape factor indicating the degree of surface irregularities.

(Toner particle size)
The average particle size and the particle size distribution of the toner are determined by the car Coulter counter method. Examples of the measuring device for the particle size distribution of toner particles include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). In the present invention, measurement was performed using a Coulter Counter TA-II type connected to an interface (Nichiken Giken) that outputs number distribution and volume distribution and a PC9801 personal computer (manufactured by NEC).

The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated.
As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm. The volume-based volume average particle diameter (Dv) obtained from the volume distribution according to the present invention and the number average particle diameter (Dn) obtained from the number distribution and the ratio Dv / Dn were obtained.

  According to a further study of the present invention, a polyester resin is used as a binder resin in order to effectively exhibit low-temperature fixability while maintaining heat-resistant storage stability and to impart offset resistance after modification with a prepolymer. Preferably, the polyester resin has a THF-soluble component weight average molecular weight of 1,000 to 30,000. This is because when the amount is less than 1,000, the oligomer component increases, the heat-resistant storage stability is deteriorated, and when it exceeds 30,000, the modification with the prepolymer is insufficient due to steric hindrance and the offset resistance is deteriorated.

The molecular weight according to the present invention is measured by GPC (gel permeation chromatography) as follows. Stabilize the column in a heat chamber at 40 ° C., flow THF at a flow rate of 1 ml / min through the column at this temperature, and prepare a THF sample solution of resin prepared at a sample concentration of 0.05 to 0.6% by weight. Is measured by injecting 50 to 200 μl. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the prepared calibration curve and the count using several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Alternatively, the molecular weights of Toyo Soda Kogyo Co., Ltd. are 6 × 10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9. It is appropriate to use x10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

  In addition, by adjusting the acid value of the polyester resin to 1.0 to 50.0 (KOHmg / g), grain size control by adding a basic compound, low temperature fixability, high temperature offset resistance, heat resistant storage stability, charging stability It is possible to make the toner characteristics such as higher quality. That is, when the acid value exceeds 50.0 (KOHmg / g), the extension or crosslinking reaction of the modified polyester becomes insufficient, and the high-temperature offset resistance is affected, and when it is less than 1.0 (KOHmg / g) This is because a dispersion stabilizing effect due to the base compound during production cannot be obtained, and the elongation or cross-linking reaction of the modified polyester tends to proceed, resulting in a problem in production stability.

The method for measuring the acid value of the polyester resin of the present invention is based on a method based on JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.
The acid value is specifically determined by the following procedure.
Measuring device: potentiometric automatic titrator DL-53 Titrator
(Metler Toledo)
Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
Analysis software: LabX Light Version 1.00.000
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 23 ° C
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

(Measurement method of acid value)
Measurement is performed under the following conditions in accordance with the measurement method described in JIS K0070-1992. Sample preparation: 0.5 g of polyester (0.3 g for ethyl acetate-soluble component) is added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, and specifically, the calculation is performed as follows. Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

  In the present invention, the heat-resistant storage performance of the main component of the polyester resin after modification, that is, the binder resin depends on the glass transition point of the polyester resin before modification, so that the glass transition point of the polyester resin is 35 ° C. to 65 ° C. It is preferable to design. That is, if it is less than 35 ° C., the heat-resistant storage stability is insufficient, and if it exceeds 65 ° C., it adversely affects low-temperature fixing.

In the present invention, the glass transition point is measured with a Rigaku THRMOFLEX TG8110 manufactured by Rigaku Corporation under a temperature increase rate of 10 ° C./min.
A method for measuring Tg will be outlined. As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used.
First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 min, the sample was cooled to room temperature and left for 10 min, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement was performed by heating at min. Tg was calculated from the tangent of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

  According to a further study of the present invention, a polymer having a site capable of reacting with an active hydrogen group is an important binder resin component for realizing low-temperature fixability and high-temperature offset resistance, and its weight average molecular weight is 3 , 50,000 to 50,000 are preferred. That is, when the weight average molecular weight is less than 3,000, it becomes difficult to control the reaction rate, and problems in production stability begin to occur. On the other hand, when the weight average molecular weight exceeds 50,000, sufficient modified polyester cannot be obtained and the offset resistance starts to be affected.

Further examination of the present invention revealed that the toner acid value is a more important index than the binder resin acid value for low-temperature fixability and high-temperature offset resistance. The toner acid value of the present invention is derived from the terminal carboxyl group of the unmodified polyester. This unmodified polyester preferably has an acid value of 0.5 to 40.0 (KOHmg / g) in order to control low-temperature fixability (fixing lower limit temperature, hot offset occurrence temperature, etc.) as a toner. In other words, when the toner acid value exceeds 40.0 (KOHmg / g), the modified polyester is insufficiently stretched or cross-linked, affecting high-temperature offset resistance, and less than 0.5 (KOHmg / g). In this case, the dispersion stabilizing effect due to the base compound at the time of production cannot be obtained, and the extension or crosslinking reaction of the modified polyester tends to proceed, resulting in a problem in production stability.
According to a method based on JIS K0070. However, when the sample does not dissolve, a solvent such as dioxane or THF is used as the solvent.
The acid value is specifically determined by the following procedure.
Measuring device: potentiometric automatic titrator DL-53 Titrator
(Metler Toledo)
Electrode used: DG113-SC (Metler Toledo)
Analysis software: LabX Light Version 1.00.000
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 23 ° C
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

(Measurement method of acid value)
Measurement is performed under the following conditions in accordance with the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate soluble component) is added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation is performed as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

The glass transition point of the toner of the present invention is preferably 40 to 70 ° C. in order to obtain low temperature fixability, heat resistant storage stability and high durability. That is, when the glass transition point is less than 40 ° C., blocking in the developing machine and filming to the photoreceptor are liable to occur, and when it exceeds 70 ° C., the low-temperature fixability tends to deteriorate. The toner of the present invention is obtained by dispersing and granulating an oil phase containing at least a toner composition and / or a toner composition precursor in an aqueous medium, or at least in a compound having an active hydrogen group in an organic solvent. A kneaded composite of a binder resin with a layered inorganic mineral in which at least a part of the ions of a polymer having a reactive site, a binder resin, a colorant, a release agent, and a layered inorganic mineral is modified with an organic ion. Dissolve or disperse, disperse the solution or dispersion in an aqueous medium containing resin fine particles, and react the polymer having a site capable of reacting with the compound having an active hydrogen group, or while reacting, the organic It was obtained by removing the solvent, washing and drying.

Examples of the polymer having a site capable of reacting with an active hydrogen group used in the present invention include a reactive modified polyester resin (RMPE) capable of reacting with active hydrogen. For example, a polyester prepolymer (A) having an isocyanate group Etc. Examples of the prepolymer (A) include a polycondensate of a polyol (PO) and a polycarboxylic acid (PC) and a polyester having active hydrogen further reacted with a polyisocyanate (PIC). Examples of the group containing active hydrogen in the polyester include a hydroxyl group (alcoholic hydrogen group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable. An amine is used as a crosslinking agent for the reactive modified polyester resin, and a diisocyanate compound (diphenylmethane diisocyanate or the like) is used as an extender. The amines described in detail later act as a crosslinking agent and an extender for the modified polyester capable of reacting with active hydrogen.
Modified polyester such as urea-modified polyester obtained by reacting the polyester prepolymer (A) having an isocyanate group with an amine (B) can easily adjust the molecular weight of the polymer component, and is a dry toner, particularly oilless low-temperature fixing. It is convenient to ensure the characteristics (wide releasability and fixability without a release oil application mechanism to the fixing heating medium). Particularly, a polyester prepolymer whose end is modified with urea can suppress adhesion to a heating medium for fixing while maintaining high fluidity and transparency in the fixing temperature range of the unmodified polyester resin itself.

  A preferred polyester prepolymer used in the present invention is a polyester having an active hydrogen group such as an acid group or a hydroxyl group at the terminal, and a functional group such as an isocyanate group that reacts with the active hydrogen. A modified polyester (MPE) such as urea-modified polyester can be derived from this prepolymer, but in the case of the present invention, a preferred modified polyester used as a toner binder is a polyester prepolymer (A) having an isocyanate group. It is a urea-modified polyester obtained by reacting amines (B) as a crosslinking agent and / or an extender. The polyester prepolymer (A) having an isocyanate group is obtained by further reacting a polyester having an active hydrogen group, which is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), with a polyisocyanate (PIC). Can do. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

  Examples of the polyol (PO) include a diol (DIO) and a trivalent or higher polyol (TO), and (DIO) alone or a mixture of (DIO) and a small amount of (TO) is preferable. Diol (DIO) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, Bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. Examples of the trivalent or higher polyol (TO) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trivalent or higher phenols (Tris) Phenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or more polyphenols.

  Examples of the polycarboxylic acid (PC) include dicarboxylic acid (DIC) and trivalent or higher polycarboxylic acid (TC), and DIC alone or a mixture of DIC and a small amount of (TC) is preferable. Dicarboxylic acids (DIC) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalene) Dicarboxylic acid and the like). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (TC) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (PC), you may make it react with a polyol (PO) using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.). The ratio of the polyol (PO) and the polycarboxylic acid (PC) is usually 2/1 to 1/1, preferably 1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

As polyisocyanate (PIC), aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanate (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactams, etc. And a combination of two or more of these.
The ratio of the polyisocyanate (PIC) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, when a modified polyester is used, the urea content in the ester becomes low and the hot offset resistance deteriorates. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1 to B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. As (B6) which blocked the amino group of (B1) to (B5), ketimine compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of (B1) to (B5), And oxazolidine compounds. Among these amines (B), preferred are (B1) and a mixture of (B1) and a small amount of (B2).

  Furthermore, if necessary, the molecular weight of the polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the polyester is lowered and the hot offset resistance is deteriorated.
In the present invention, the polyester resin (polyester) preferably used as the binder resin is a urea-modified polyester (UMPE), but this polyester may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.
Modified polyester such as urea-modified polyester (UMPE) is produced by a one-shot method or the like. The weight average molecular weight of the modified polyester such as urea-modified polyester (UMPE) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of a modified polyester such as a urea-modified polyester is not particularly limited when a non-modified polyester (PE) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. In the case of a modified polyester such as UMPE alone, the number average molecular weight is usually 2000-15000, preferably 2000-10000, and more preferably 2000-8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color device are deteriorated.

  In the present invention, the above modified polyester such as polyester modified with urea bond (UMPE) is not only used alone, but can also contain unmodified polyester (PE) as a binder resin component. . By using PE together, the low-temperature fixability and the gloss when used in a full-color apparatus are improved, which is preferable to single use. Examples of PE include polycondensates of polyol PO and polycarboxylic acid PC similar to the polyester component of UMPE, and preferred ones are also the same as in UMPE. The weight average molecular weight (Mw) of PE is 10,000 to 300,000, preferably 14,000 to 200,000. Its Mn (number average molecular weight) is 1000 to 10000, preferably 1500 to 6000. For UMPE, not only unmodified polyesters but also those modified with chemical bonds other than urea bonds, such as those modified with urethane bonds, can be used in combination. UMPE and PE are preferably at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component of UMPE and PE preferably have similar compositions. The weight ratio of UMPE to PE when PE is contained is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, particularly preferably 7/93. ~ 20/80. When the weight ratio of UMPE is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The hydroxyl value (mgKOH / g) of PE is preferably 5 or more, and the acid value (mgKOH / g) of PE is usually 1 to 30, preferably 5 to 20. By giving an acid value, it tends to be negatively charged, and further, the affinity between the paper and the toner is good when fixing to paper, and the low-temperature fixability is improved. However, when the acid value exceeds 30, there is a tendency to deteriorate with respect to the stability of charging, particularly the environmental fluctuation. In the polymerization reaction, if the acid value is touched, it will cause blurring in the granulation process, making it difficult to control the emulsification.

Specifically, the hydroxyl value and acid value of PE are determined by the following procedure.
Measuring device: potentiometric automatic titrator DL-53 Titrator
(Metler Toledo)
Electrode used: DG113-SC (Metler Toledo)
Analysis software: LabX Light Version 1.00.000
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 23 ° C
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
at maximum volume [mL] 10.0
at potential No
at slope No
after number EQPs Yes
n = 1
comb. termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No

(Measurement method of acid value)
Measurement is performed under the following conditions in accordance with the measurement method described in JIS K0070-1992. Sample preparation: 0.5 g of polyester (0.3 g for ethyl acetate-soluble component) is added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation is performed as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

(Measurement method of hydroxyl value)
Weigh accurately 0.5 g of sample into a 100 ml volumetric flask and add 5 ml of acetylating reagent correctly. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1-2 hours, the flask is removed from the bath, allowed to cool, water is added and shaken to decompose acetic anhydride. Furthermore, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the OH value (according to JISK0070-1966).

  In the present invention, the glass transition point (Tg) of the binder resin is usually 40 to 70 ° C, preferably 40 to 60 ° C. If it is less than 40 ° C., the heat resistance of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of a modified polyester such as a urea-modified polyester resin, the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with a known polyester-based toner.

(Modified layered inorganic mineral)
The modified layered inorganic mineral layer used in the toner of the present invention is preferably a layer having a smectite basic crystal structure modified with an organic cation. Examples of the layered inorganic mineral modified with an organic cation include montmorillonite or bentonite, beidellite, nontronite, saponite, hectorite and the like.
Examples of the organic cation modifier for the modified layered inorganic mineral include quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts, and the like, and quaternary alkyl ammonium salts are desirable. Examples of the quaternary alkyl ammonium include trimethyl stearyl ammonium, dimethyl stearyl benzyl ammonium, dimethyl octadecyl ammonium, oleyl bis (2-hydroxyethyl) methyl ammonium, and the like.

  Examples of the modified layered inorganic mineral include BENTONE 34, BENTONE 52, BENTONE 38, BENTONE 27, BENTONE 57, BENTONE SD, BENTONE CRYTONE 34, CENTONE 34, CENTONE 34, CENTONE 34 , CRAYTONE HY, etc., made by HOJUN, such as Esben, Esben E, Esben C, Esben NZ, Esben NZ70, Esven W, Esben N400, Esven NX, Esven NX80, Esven NO12S, Esven NEZ, Esven NO12, Esben WX, Esben NE, etc. Kunibis 110 manufactured by Kunimine Industry Co., Ltd. Kunibisu 120, Kunibisu 127, and the like.

  The kneaded composite of the modified layered inorganic mineral and the binder resin, that is, the masterbatch can be obtained by mixing and kneading the binder resin and the layered inorganic mineral modified with an organic cation with high shear force to obtain a masterbatch. . At this time, an organic solvent can be used to enhance the interaction between the modified layered inorganic mineral and the binder resin. Also, a so-called flushing method is a method in which an aqueous paste containing the modified layered inorganic mineral and water is mixed and kneaded together with a resin and an organic solvent, and the modified layered inorganic mineral is transferred to the resin side to remove moisture and organic solvent components. Also, since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

In the kneaded composite of the modified layered inorganic mineral and the binder resin, ie, the master batch, the volume average particle diameter Dv of the modified layered inorganic mineral is 0.1 μm to 0.55 μm, and the volume average particle diameter is 1 μm or more. The frequency of the modified layered inorganic mineral needs to satisfy 15% or less. When the volume average particle diameter Dv exceeds 0.55 μm, or the frequency of the particle diameter of 1 μm or more exceeds 15%, the effect on the toner shape and toner charging performance decreases.
The modified layered inorganic mineral is preferably contained in the toner in an amount of 0.1 to 5%. If it is less than 0.1%, the effect on the toner shape and the toner charging performance is lowered, and if it exceeds 5%, the fixing performance is deteriorated.

(Release agent)
As the wax used in the toner of the present invention, a low melting point wax having a melting point of 50 to 120 ° C. works more effectively as a release agent in the dispersion with the binder resin between the fixing roller and the toner interface, This shows an effect against high temperature offset resistance without applying a release agent such as oil to the fixing roller.
The melting point of the wax in the present invention was the maximum endothermic peak measured by a differential scanning calorimeter (DSC). The following materials can be used as the wax component that functions as a release agent that can be used in the present invention. That is, as specific examples, waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax and rice wax, animal waxes such as beeswax and lanolin, mineral waxes such as ozokerite and cercin, And petroleum waxes such as paraffin, microcrystalline, and petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax, and synthetic waxes such as esters, ketones and ethers can be used. Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon, and poly n-stearyl methacrylate, poly n-lauryl methacrylate, which are low molecular weight crystalline polymer resins A crystalline polymer having a long alkyl group in the side chain, such as a polyacrylate homopolymer or copolymer (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.) can also be used.

(Coloring agent)
As the colorant used in the present invention, known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow oxidation Iron, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faisa Red, Parachlor Rutonitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazo Red, polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green , Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

  The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the modified and unmodified polyester resins mentioned above, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substituted products thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α- Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. The

Furthermore, in order to reduce the viscosity of the dispersion medium containing the toner composition, a solvent in which a polyester such as urea-modified polyester or prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp.
The solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred. The usage-amount of the solvent with respect to 100 parts of prepolymers (A) is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts. When a solvent is used, the solvent (solvent) is removed from the obtained reaction product under normal pressure or reduced pressure after the extension and / or crosslinking reaction of the modified polyester (prepolymer) with an amine.

  The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

  A method for producing an electrophotographic toner in which particles comprising a colorant and a resin and particles comprising at least charge control agent particles are mixed together in a container using a rotating body in order to adhere and immobilize the charge control agent on the toner particle surface. However, in this method, the object of the present invention is to include a step of mixing at a peripheral speed of the rotating body of 40 to 150 m / sec in a container without a fixing member protruding from the inner wall of the container. Toner particles are obtained. Next, the used toner will be described.

  The toner of the present invention may contain a charge control agent as necessary. Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified 4 Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinaclide And azo pigments, and other high molecular compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents and mold release agents can be melt-kneaded together with the masterbatch and resin, and of course, they may be added when dissolved and dispersed in an organic solvent.

An external additive is used to assist the fluidity, developability, and chargeability of the colored particles obtained in the present invention. As this external additive, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, as the fluidity imparting agent, it is preferable to use hydrophobic silica fine particles and hydrophobic titanium oxide fine particles in combination. In particular, when stirring and mixing is performed using an average particle size of both fine particles of 50 mμ or less, the electrostatic force and van der Waals force with the toner are remarkably improved, so that a desired charge level is obtained. It is clear that even with stirring and mixing inside the developing machine, a fluidity-imparting agent is not detached from the toner, a good image quality that does not generate fireflies and the like can be obtained, and the residual toner can be further reduced. became.

  Titanium oxide fine particles are excellent in environmental stability and image density stability, but have a tendency to deteriorate the charge rise characteristics. Therefore, if the amount of titanium oxide fine particles added is larger than the amount of silica fine particles added, the effect of side effects is large. It is possible to become. However, when the addition amount of the hydrophobic silica fine particles and the hydrophobic titanium oxide fine particles is in the range of 0.3 to 1.5 wt%, the charge rising characteristics are not greatly impaired, and the desired charge rising characteristics can be obtained, that is, repeated copying. It has been found that stable image quality can be obtained and toner blowing can be suppressed even if the process is performed.

  The resin for toner binder can be produced by the following method. Polyol (PO) and polycarboxylic acid (PC) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc., and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (PIC) at 40 to 140 ° C. to obtain a polyester prepolymer (A) having an isocyanate group. Further, this A is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester (UMPE) modified with a urea bond. The number average molecular weight of this modified polyester is 1000 to 10000, preferably 1500 to 6000. When reacting PIC and when A and B are reacted, a solvent may be used as necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to isocyanates (PIC), such as tetrahydrofuran (such as tetrahydrofuran). When polyester (PE) that is not modified with a urea bond is used in combination, PE is produced in the same manner as the polyester having a hydroxyl group, and this is dissolved in the solution after completion of the UMPE reaction and mixed.

The toner of the present invention can be produced by the following method, but is not limited thereto.
(Toner production method in aqueous medium)
As the aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.
In the present invention, a urea-modified polyester (UMPE) or the like can be obtained by reacting a reactive modified polyester such as a polyester prepolymer (A) having an isocyanate group with an amine (B) in an aqueous medium. As a method for stably forming a dispersion comprising a modified polyester such as urea-modified polyester or a reactive modified polyester such as prepolymer (A) in an aqueous medium, a modified polyester such as urea-modified polyester or a pre-polymer can be used in an aqueous medium. Examples thereof include a method in which a composition of a toner raw material composed of reactive modified polyester such as polymer (A) is added and dispersed by shearing force. Reactive modified polyester such as prepolymer (A) and other toner composition (hereinafter referred to as toner raw material), colorant, colorant masterbatch, release agent, charge control agent, unmodified polyester resin, etc. Although mixing may be performed when forming the dispersion in the medium, it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion of the urea-modified polyester or prepolymer (A) has a low viscosity and is easy to disperse.

  The amount of the aqueous medium used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts of the toner composition containing a polyester such as urea-modified polyester and prepolymer (A). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

Various dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed are used in the liquid containing water. Such a dispersant includes a surfactant, an inorganic fine particle dispersant, a polymer fine particle dispersant and the like.
As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. It is.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be increased in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11 ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carvone Acids and metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- ( 2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.

Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos). In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C 6 -C 10) sulfonamidopropyltrimethylammonium salt which right the fluoroalkyl group, Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (manufactured by Asahi Glass), Florard FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries, Ltd.) ), Megafuck F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos).
Moreover, tricalcium phosphate, calcium carbonate, acid value titanium, colloidal silica, hydroxyapatite, etc. can be used as an inorganic compound dispersant which is hardly soluble in water.

Further, the same effect as that of the inorganic dispersant was confirmed for the resin fine particles. For example, MMA polymer fine particles 1 μm and 3 μm, styrene fine particles 0.5 μm and 2 μm, styrene-acrylonitrile fine particle polymer 1 μm, (PB-200H (Kao) SGP (Soken), Technopolymer SB (Sekisui Plastics), SGP-3G (Soken) Micropearl (Sekisui Fine Chemical)).
In addition, as a dispersant that can be used in combination with the above inorganic dispersant and resin fine particles, the dispersed droplets may be stabilized by a polymeric protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, pinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethylene imine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester Polyoxyethylenes such as, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

  The elongation and / or crosslinking reaction time is selected, for example, depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24. It's time. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

In addition, as an extender and / or a crosslinking agent, the above-described amines (B) are used.
The toner of the present invention can be used as a two-component developer. In this case, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier to the toner in the developer is preferably 1 to 10 parts by weight of the toner relative to 100 parts by weight of the carrier. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride and non- Monomers including a fluoro terpolymers such, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.
The image forming method of the present invention is a method of using the toner of the present invention as the toner in a conventional image forming method using toner.
The image forming apparatus of the present invention is an apparatus using the toner of the present invention as the toner in a conventional image forming apparatus using toner.

  Hereinafter, a detailed description of FIGS. 1, 2, 3, and 4 of the present invention will be described.

  FIG. 1 shows a batch type solvent removal apparatus using a jacketed solvent removal tank as an example of the apparatus diagram of the present invention. After feeding the emulsion to the emulsion tank (11), the emulsion tank is sealed, and the vacuum pump (33) is operated to reduce the pressure. Warm water or reduced-pressure steam is supplied to the jacket (12) to heat the emulsion tank (11). An azeotropic vapor mixture of solvent and water is generated from the emulsion and sent to the separation membrane module (21). By making the permeation side (discharge side) of the separation membrane module into a reduced pressure state and maintaining the differential pressure from the non-permeation side (liquid introduction side) by the pressure regulating valve (43), water vapor can be selectively permeated. Then, it is cooled by the condenser (32), and water is collected in the water tank (31). On the other hand, the solvent is cooled by the condenser (42) and recovered by the organic solvent tank (41).

  FIG. 2 shows a continuous apparatus using a mechanical stirring centrifugal thin film type solvent removal apparatus as an example of the apparatus diagram of the present invention. The vacuum pump (33) is operated, and the desolventizer (13) is depressurized. The emulsion is sent to the desolventizer (13), the rotor blades are rotated at high speed, a thin film is formed on the inner cylinder wall surface of the desolventizer (13), and then collected in the emulsion tank (11). When hot water or reduced-pressure steam is supplied to the jacket (12) under reduced pressure and the desolventizer (13) is heated, an azeotropic mixture of solvent and water is generated from the emulsified liquid and is supplied to the separation membrane module (21). Sent. By making the permeation side (discharge side) of the separation membrane module into a reduced pressure state and maintaining the differential pressure from the non-permeation side (liquid introduction side) by the pressure regulating valve (43), water vapor can be selectively permeated. Then, it is cooled by the condenser (32), and water is collected in the water tank (31). On the other hand, the solvent is cooled by the condenser (42) and recovered by the organic solvent tank (41). The solvent-removed slurry recovered in the emulsion liquid tank (11) is discharged by the pump (14). The water collected in the water tank (31) is discharged by the pump (34). The solvent recovered in the organic solvent tank (41) is discharged by the pump (44). Controlling the feeding speed of the emulsion to the solvent removal apparatus (13) and the discharge speed of each processing liquid collected in the emulsion tank (11), water tank (31), and organic solvent tank (41). The solvent can be removed continuously.

  FIG. 3 shows a continuous apparatus using a vertical falling film type solvent removal apparatus as an example of the apparatus diagram of the present invention. The vacuum pump (33) is operated, and the desolventizer (13) is depressurized. The emulsion is sent to the desolventizer (13), and the emulsion is allowed to flow down to the inner cylinder wall surface of the desolventizer (13) to form a thin film, which is then collected in the emulsion tank (11). When hot water or reduced-pressure steam is supplied to the jacket (12) under reduced pressure and the desolventizer (13) is heated, an azeotropic mixture of solvent and water is generated from the emulsified liquid and is supplied to the separation membrane module (21). Sent. By making the permeation side (discharge side) of the separation membrane module into a reduced pressure state and maintaining the differential pressure from the non-permeation side (liquid introduction side) by the pressure regulating valve (43), water vapor can be selectively permeated. Then, it is cooled by the condenser (32), and water is collected in the water tank (31). On the other hand, the solvent is cooled by the condenser (42) and recovered by the organic solvent tank (41). The solvent-removed slurry recovered in the emulsion liquid tank (11) is discharged by the pump (14). The water collected in the water tank (31) is discharged by the pump (34). The solvent recovered in the organic solvent tank (41) is discharged by the pump (44). Controlling the feeding speed of the emulsion to the solvent removal apparatus (13) and the discharge speed of each processing liquid collected in the emulsion tank (11), water tank (31), and organic solvent tank (41). The solvent can be removed continuously.

  FIG. 4 is a cross-sectional configuration diagram of a main part of an example of the image forming apparatus. In this example, an electrophotographic copying machine is illustrated as an image forming apparatus. In FIG. 3, reference numeral (1) denotes a photosensitive drum as a latent image carrier, which rotates in the direction of the arrow in the drawing, and a charger (2) is disposed around it, corresponding to an image read from a document. The irradiated laser beam (3) is irradiated as exposure means. Further, a developing device (4), a paper feeding means (7), a transfer device (5), a cleaning device (6), and a charge eliminating lamp (9) are arranged around the photoreceptor (1). The developing device (4) further includes developing rollers (41) and (42), a paddle-shaped stirring member (43), a stirring member (44), a doctor (45), and a toner replenishing section (46). And a replenishment roller (47). The cleaning means (6) includes a cleaning brush (62) and a cleaning blade (61). Members (81) and (82) arranged above and below the developing device (4) are guide rails for attaching / detaching or supporting the developing device. The life of the cleaning blade (61) of the cleaning device can also be detected. The cleaning blade (61) always abuts on the photoconductor during image formation and wears as the photoconductor rotates. When the cleaning blade is worn, the function of removing the residual toner on the surface of the photoreceptor is lowered, and the copy image quality is deteriorated. Even if the toner is not worn, the transferability is improved when the toner is close to a true sphere and the fluidity is improved as compared with the pulverized toner. However, in cleaning, it is easy to cause defective cleaning through the installed blade. Is done. By using the toner of the present invention with respect to this problem, it can be satisfactorily cleaned.

  In other words, (1) a highly efficient toner production method is provided by shortening the time of the organic solvent removal step, and (2) the heat energy of solvent removal is obtained by removing the organic solvent from the emulsion and simultaneously purifying the organic solvent. Effectively used, (3) it is possible to sharpen the toner particle size distribution.

(FIGS. 1 to 3)
11 Emulsified liquid tank 12 Jacket 13 Solvent removal device 14 Pump 21 Separation membrane module 31 Water tank 32 Condenser 33 Vacuum pump 34 Pump 41 Organic solvent tank 42 Pressure adjustment valve 43 Pump 44 Organic solvent outlet (FIG. 4)
DESCRIPTION OF SYMBOLS 1 Photosensitive drum 2 Charger 3 Laser beam 4 Developing device 5 Transfer device 6 Cleaning device 7 Feeding means 9 Static elimination lamp 41 Developing device 42 Developing roller 43 Paddle-shaped stirring member 44 Stirring member 45 Doctor 46 Toner replenishing part 47 Replenishment Roller 61 Cleaning blade 62 Cleaning brush 81 Guide rail 82 Guide rail A Rotation direction

Claims (7)

A toner material containing at least a binder resin and / or a binder resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent, and an oil phase composed of the solution or the dispersion is dispersed in an aqueous medium. A method for producing a toner for an electrostatic charge image phenomenon, wherein the toner particles are obtained by emulsifying and granulating the particles and removing the solvent from the emulsion.
In the step of removing the organic solvent from the emulsion, a separation membrane module is used, and water vapor is selected from the azeotropic mixture of the organic solvent and the aqueous medium by using the differential pressure between the discharge side and the liquid introduction side of the separation membrane. A method for producing a toner for an electrostatic charge image phenomenon, wherein the organic solvent is removed from the emulsified liquid. For toners comprising a compound having at least an active hydrogen group, a polymer having a site capable of reacting with the active hydrogen group, a binder resin, a colorant, a release agent, and a kneaded composite of a modified layered inorganic mineral and the binder resin A material is dissolved or dispersed in an organic solvent, and an oil phase composed of the solution or dispersion is dispersed and emulsified in an aqueous medium containing resin fine particles so that the compound having active hydrogen groups can react with the active hydrogen groups. A method for producing a toner comprising a step of removing the organic solvent after reacting a polymer having a site or while reacting the polymer,
In the step of removing the organic solvent from the emulsion, a separation membrane module is used, and water vapor is selected from the azeotropic mixture of the organic solvent and the aqueous medium by using the differential pressure between the discharge side and the liquid introduction side of the separation membrane. A method for producing a toner for an electrostatic charge image phenomenon, wherein the organic solvent is removed from the emulsified liquid.   3. The method for producing a toner for an electrostatic charge image phenomenon according to claim 1, wherein in the step of removing the organic solvent from the emulsion, the discharge side of the separation membrane module is in a reduced pressure state of 30 to 200 mmHg. . 4. The method for producing a toner for an electrostatic charge image phenomenon according to claim 1, wherein the separation membrane of the separation membrane module is made of an aromatic polyimide.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the organic solvent is ethyl acetate.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 5, wherein the toner for electrostatic charge image phenomenon has a glass transition point of 40 to 70 ° C.   The processing temperature of the emulsion and the azeotropic mixture of the emulsion and an aqueous medium in the step of removing the organic solvent from the emulsion is a temperature lower than the glass transition point of the electrostatic charge image phenomenon toner. A method for producing a toner for developing an electrostatic charge image according to any one of claims 1 to 6.

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