JP6659143B2 - Method for producing toner particles - Google Patents

Description

  The present invention relates to a method for producing toner particles used for image formation by an electrophotographic method, an electrostatic recording method, and a toner jet recording method.

  In recent years, quality requirements for image forming apparatuses such as copiers and printers have become severe, and the performance required for toner has also become advanced. In particular, in a full-color copying machine, a full-color printer, and the like, it is required to realize high-quality printing regardless of the type of paper, and further improvements in durability and low-temperature fixability are required. The toner is also required to have better storage stability and low-temperature fixability.

  In response to the demand, there is a method of obtaining a toner having high image quality and excellent storage stability by using a polyester resin obtained by using a diol component including isosorbide and 1,3-propanediol (for example, Patent Document 1). ). However, in long-term use, there are still some issues regarding durability.

  Further, there is a method of obtaining a toner having excellent chargeability and storage stability by using a polyester resin obtained by using isosorbide and two kinds of divalent acid monomers (for example, Patent Document 2). However, in long-term use, there are still some issues regarding durability.

  In addition, by using a polar resin containing a specific catalyst and having a certain range of acid value and granulating in an aqueous medium, it has excellent low-temperature fixability, high-temperature offset resistance, transferability, and high definition and high quality. There is a method of obtaining a toner capable of stably obtaining a stable image (for example, Patent Document 3). However, there are still some problems in terms of fusing to the toner layer regulating member and the toner carrying member and storability during long-term use.

JP 2012-73304 A Japanese Patent No. 740313 JP 2005-62818A

  An object of the present invention is to provide a method for producing toner particles having excellent storage stability, durability and low-temperature fixability.

  The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, have found the following method.

That is, the present invention provides a granulation step of forming particles of a polymerizable monomer composition containing a polymerizable monomer and a polyester resin in an aqueous medium, and the particles of the polymerizable monomer composition. A polymerization step of obtaining toner particles by polymerizing the polymerizable monomer contained in, the method for producing toner particles,
Having a step of obtaining inorganic fine particles by mixing a phosphate aqueous solution and an aqueous solution of an aluminum compound,
Aqueous medium in the polymerization step, it contains the inorganic fine particles containing elemental aluminum, the proportion of aluminum element of the metal element that constitutes the inorganic fine particles is less than 5.0atm% 70.0atm% And a method for producing toner particles.

  According to the present invention, toner particles having excellent durability and storage stability even after long-term use can be obtained.

It is a figure showing an example of a transmittance curve at the time of measuring a styrene-hexane solubility index of a polyester resin of the present invention. It is a figure which shows an example of the transmittance | permeability curve of the thing by which the difference by the presence or absence of the aluminum element in an inorganic fine particle results in the interaction between the polyester resin for shells used by this invention, and the inorganic fine particle containing an aluminum element. FIG. 9 is a diagram illustrating a difference in methanol concentration when the toner wettability of the toner particles 1 and 5 to 12 is 50%. FIG. 9 is a diagram showing the results of confirming the effect of the ratio of an aluminum element in a metal element constituting inorganic fine particles when a styrene-acrylic resin 1 is used (toner particles 70) without using a polyester resin.

  Hereinafter, the present invention will be described in detail.

The present invention provides a granulating step of forming particles of a polymerizable monomer composition containing a polymerizable monomer and a polyester resin in an aqueous medium, and the particles of the polymerizable monomer composition are included in the granulation step. Polymerizing the polymerizable monomer to obtain toner particles, and a method for producing toner particles,
The aqueous medium in the polymerization step contains inorganic fine particles containing an aluminum element, and the ratio of the aluminum element in the metal element constituting the inorganic fine particles is set to 5.0 to 70.0 atm% to form a toner. The effect of the present invention can be obtained by manufacturing.

  Although the reason why the effects of the present invention are realized is not always clear, the present inventors think as follows.

  A method of forming toner particles by forming particles of the polymerizable monomer composition in an aqueous medium and polymerizing the polymerizable monomer contained in the particles, and a core-shell by using an appropriate material. A toner having a structure is obtained.

  Generally, a styrene-acryl resin, a polyester resin, a polyurethane resin, or the like is used as the shell material used at that time. Generally, in order to improve the storability of the toner, it is necessary to contain a large amount of a shell material. However, when the content of the shell material is increased, the low-temperature fixability deteriorates. This is because the material for the shell has excellent heat resistance, and at the time of fixing, acts as a factor that hinders fixing. Therefore, in order to achieve both the storage stability and the low-temperature fixability of the toner, it is necessary to contain the shell material as little as possible and then to efficiently distribute the material on the surface of the toner particles. Then, as a result of studying a method of efficiently distributing the shell material on the toner particle surface, the following was found. Specifically, a polyester resin is used as a material for the shell, and a toner particle is produced by a method in which inorganic particles containing a certain amount of an aluminum element are contained in the aqueous medium in the polymerization step for producing the toner particles. The material was efficiently distributed on the toner particle surface. As for the ratio of the aluminum element contained in the inorganic fine particles, the ratio of the aluminum element in the metal element constituting the inorganic fine particles needs to be not less than 5.0 atm% and not more than 70.0 atm%. More preferably, the ratio of the aluminum element in the metal element constituting the inorganic fine particles is at least 10.0 atm% and at most 50.0 atm%.

  This is because the affinity between the polyester resin and the inorganic fine particles containing a certain amount of the aluminum element is strong. When producing the toner particles, the inorganic fine particles in the aqueous medium adhere to the particle surface of the polymerizable monomer composition containing the polymerizable monomer and the polyester resin. In this case, the polyester resin in the particles of the polymerizable monomer composition is attracted to the inorganic fine particles when the inorganic fine particles contain the aluminum element in a specified amount. As a result, the polyester resin is unevenly distributed on the surface of the particles of the polymerizable monomer composition (because it is in contact with the aqueous medium), and the shell layer is formed efficiently. Therefore, the obtained toner particles can achieve both low-temperature fixability and storage stability. At this time, the inorganic fine particles containing an aluminum element are solid, and are not ions or the like, so that the polyester resin is attracted and adhered, and is not drawn into the inside of the particles of the polymerizable monomer composition even when adhered. , The polyester resin can be unevenly distributed on the surface of the toner particles and held.

  When the proportion of the aluminum element in the metal element constituting the inorganic fine particles is less than 5.0 atm%, the affinity between the polyester resin and the inorganic fine particles is insufficient, which is not desirable. If the proportion of the aluminum element in the metal element constituting the inorganic fine particles is more than 70.0 atm%, the affinity is too strong, and the particles of the polymerizable monomer composition aggregate during the polymerization step. As a result, the toner particles are undesirably coarsened or deformed.

  Elements such as calcium, barium, magnesium, and zinc other than aluminum can be used as metal elements constituting the inorganic fine particles containing an aluminum element used in the present invention. In particular, it is desirable to be an element of calcium, barium, and magnesium. Particularly desirable are the elements of calcium and barium. This is because the effect of the aluminum element is not hindered and the affinity with the polyester resin is excellent.

  As a method for producing the inorganic fine particles containing an aluminum element, inorganic fine particles obtained by mixing an aqueous solution of an aluminum compound such as an aluminum chloride aqueous solution with a phosphate aqueous solution, a sulfate aqueous solution, a carbonate aqueous solution or the like are preferable. Particularly preferred are inorganic fine particles obtained by mixing an aqueous solution of an aluminum compound with an aqueous solution of a phosphate. This is because the affinity with the polyester resin is particularly excellent. In addition, the distribution of the electron cloud is optimized by the interaction with the aluminum element, so that the particle size distribution of the toner is good, and the inorganic fine particles can be easily removed in the step of removing the inorganic fine particles by acid washing after the completion of the polymerization reaction. This is desirable because the chargeability of the toner is excellent.

  The zeta potential of the inorganic fine particles containing an aluminum element is desirably -10.0 mV or more and 25.0 mV or less. When the zeta potential of the inorganic fine particles is -10.0 mV or more, the affinity with the polyester resin is further increased, and when the zeta potential is 25.0 mV or less, aggregation between toner particles is suppressed, so that irregular-shaped particles are formed. Is desirable because it is suppressed.

<Measurement of zeta potential of inorganic fine particles>
The zeta potential of the inorganic fine particles having an aluminum element and the standard deviation with respect to the average value of the zeta potential were measured using Zetasizer Nano ZS (manufactured by MALVERN) and dedicated software “Dispersion Technology software 4” for analyzing measurement conditions and measurement data. .20 "(manufactured by MALVERN). The specific measuring method is as follows.

After the production of the aqueous medium containing the inorganic fine particles was completed, a part of the aqueous medium was extracted and kept at 30 ° C. Thereafter, zeta potential adjustment or pH adjustment, which roughly corresponded to the polymerization in each example, was performed. Zeta potential adjustment: Addition of aqueous solution containing charge determining ions pH adjustment: Addition of 0.1N sodium hydroxide aqueous solution

A part of the adjusted aqueous medium was withdrawn and transferred to a syringe having a volume of 10 ml. Next, the tip of the syringe was inserted into one of the sample ports of a zeta potential measurement capillary cell (DTS1060-Clear disposable zeta cell), which had been co-washed twice with ion-exchanged water, and the aqueous medium was slowly added so that air bubbles did not occur. Poured. After confirming that the liquid was injected into the capillary portion without any gap, the two sample ports were plugged. The cell was inserted into the cell holder of the measuring device, and the lid of the detection unit was closed. The measurement was performed under the following measurement conditions.
F (ka) Selection Model: Smoluchowski
Dispersant: Water
Temperature: temperature during polymerization (usually 70 ° C.)
Result Calculation: General Purpose

  After the measurement was completed, the value of “Zeta Potential” was used as the average value of the zeta potential on the displayed report screen of the measurement result.

<Quantification of aluminum element ratio in metal element of inorganic fine particles>
The measurement of the fluorescent X-ray of each element conforms to JIS K 0119-1969, and is specifically as follows.

  As a measuring device, a wavelength-dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical) and dedicated software "SuperQ ver.4.0F" (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data are used. ) Is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. When a light element is measured, a proportional counter (PC) is used, and when a heavy element is measured, a scintillation counter (SC) is used.

  As a measurement sample, about 4 g of inorganic fine particles were put into a dedicated aluminum ring for press and flattened, and then, using a tablet molding and compression machine “BRE-32” (manufactured by Maekawa Testing Machine Co., Ltd.), at 20 MPa, Pressurized for 60 seconds, and a pellet molded to a thickness of about 2 mm and a diameter of about 39 mm is used.

The measurement is performed under the above conditions, the element is identified based on the obtained X-ray peak position, and its concentration is calculated from the count rate (unit: cps) which is the number of X-ray photons per unit time. The calculation formula is as follows.
Aluminum element ratio [atm%] in metal element of inorganic fine particles (alias: atomic%) = (content of aluminum element in inorganic fine particles) / (content of all metal elements in inorganic fine particles) × 100

  In the fluorescent X-ray analysis method, calibration curves are respectively prepared by an X-ray fluorescence analyzer using oxide particles having a known content of a metal element such as an aluminum element, and the composite oxide particles are prepared using the calibration curves. The content of a metal element such as an aluminum element therein is determined.

The quantitative determination of a metal element such as an aluminum element by a fluorescent X-ray analyzer can be performed, for example, according to the following procedure.
(1) First, a sample for preparing a calibration curve is prepared. A pellet for measurement is prepared by adding a known amount of an oxide of each metal element such as an aluminum element to 100 parts by mass of styrene powder. Specifically, in the case of an aluminum element, a known amount of aluminum oxide is added to 100 parts by mass of styrene powder to prepare a measurement pellet for aluminum oxide.
(2) Each of the produced pellets is measured by a fluorescent X-ray analyzer, and a calibration curve is prepared from the peak intensity obtained from each sample for aluminum oxide or other metal oxide in styrene powder.
(3) Next, the inorganic fine particles containing an aluminum element used in the present invention are measured by an X-ray fluorescence spectrometer, and the obtained peak intensities are compared with a calibration curve to determine the content of a metal element such as an aluminum element. Quantify the amount.

  The polyester resin used preferably has an isosorbide unit represented by the following formula (1). This is because when the polyester resin has an isosorbide unit represented by the following formula (1), in addition to being excellent in rigidity, the polyester resin has a stronger affinity with inorganic fine particles containing a fixed amount of aluminum element. This is because the shell layer can be formed more efficiently, and the durability of the toner is excellent.

  When the toner of the present invention is manufactured in an aqueous medium, the acid value of the polyester resin is preferably from 1.0 mgKOH / g to 30.0 mgKOH / g, and more preferably from 1.0 mgKOH / g to 15.0 mgKOH / g. It is more preferable that it is the following. This is because, when the acid value of the polyester resin is 1.0 mg KOH / g or more, the polyester resin is distributed on the aqueous phase side, so that the formation of the shell layer in the toner particle production process is further reduced. Therefore, it is desirable in terms of storage stability and the like. Further, when the acid value of the polyester resin is 30.0 mgKOH / g or less, the polyester resin forming the shell layer does not become excessively hygroscopic, which is particularly desirable in terms of chargeability under a high temperature and high humidity environment. .

<Measurement of acid value of the polyester resin or styrene-acrylic resin>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992, and specifically, is measured according to the following procedure.

  Titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potentiometric titrator AT-510, manufactured by Kyoto Electronics Industry Co., Ltd.). 100 mL of 0.100 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. The 0.100 mol / L hydrochloric acid used is prepared according to JIS K 8001-1998.

The measurement conditions for measuring the acid value are shown below.
Titrator: Potentiometric titrator AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Control software for titrator: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration are as follows.
Titration parameters Titration mode: Blank titration Titration format: Total titration Maximum titer: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic control parameterer end point judgment potential: 30 dE
End point judgment potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data sampling potential: 4 mV
Data collection titer: 0.1 mL

main exam;
0.100 g of the measurement sample is precisely weighed in a 250 mL tall beaker, 150 mL of a mixed solution of toluene / ethanol (3: 1) is added, and the mixture is dissolved for 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.

Blank test;
The same titration as in the above procedure is performed except that no sample is used (that is, only a mixed solution of toluene / ethanol (3: 1) is used).

The obtained result is substituted into the following equation to calculate the acid value.
A = [(CB) × f × 5.61] / S
(Where A: acid value (mgKOH / g), B: amount of potassium hydroxide solution added in blank test (mL), C: amount of potassium hydroxide solution added in main test (mL), f: hydroxylation Potassium solution factor, S: sample (g).)

  It is desirable that the ratio of styrene contained in the polymerizable monomer be 60% by mass or more, and the styrene-hexane solubility index of the polyester resin be 15.0 or more and 27.0 or less.

  This is because if the constituents of the binder resin are mainly composed of styrene, the solubility of the polyester resin in the polymerizable monomer is considered to be 15.0 or more when the polyester resin has a styrene-hexane solubility index of 15.0 or more. Is sufficient, so that pigment dispersion and the like become good. Further, it has a sufficient affinity with the binder resin, so that a uniform shell layer is formed. Further, when the styrene-hexane solubility index of the polyester resin is 27.0 or less, phase separation from the binder resin becomes sufficient and a strong shell layer is formed, so that the fusion of the toner to the toner layer regulating member is suppressed. It is desirable in terms of durability.

  This is particularly noticeable when the polyester resin contains an isosorbide unit represented by the formula (1).

  Since the polyester resin has a strong orientation of the isosorbide unit, the polyester resin has excellent durability. However, simply using a polyester resin containing an isosorbide unit represented by the formula (1), particles of the polymerizable monomer composition are formed in an aqueous medium, and the particles of the polymerizable monomer composition are added to the particles of the polymerizable monomer composition. Even when a toner is manufactured by a method for obtaining toner particles by polymerizing the polymerizable monomer contained therein, the dispersibility of the pigment is deteriorated. This is because the orientation of the isosorbide unit is strong and the self-cohesive force of the polyester resin is strong. As a result, the distribution of the polyester resin becomes non-uniform, and in many cases, the resulting toner is inferior in durability, storage stability, and coloring power.

  On the other hand, when the ratio of styrene contained in the polymerizable monomer is set to 60% by mass or more and the styrene-hexane solubility index of the polyester resin is set to 15.0 or more and 27.0 or less, the coloring power is improved. Excellent toner can be obtained. Using the polyester resin containing the isosorbide unit represented by the formula (1), particles of the polymerizable monomer composition are formed in an aqueous medium, and the particles contained in the particles of the polymerizable monomer composition are formed. In the process of polymerizing the polymerizable monomer, the amount of the polymerizable monomer decreases as the polymerization reaction proceeds. That is, the solvent of the polyester resin decreases as the polymerization proceeds. Therefore, when the styrene-hexane solubility index of the polyester resin is 15.0 or more, the timing at which the polyester resin precipitates is appropriately late. As a result, the precipitated polyester resin does not disturb the dispersion state of the pigment, which is desirable in terms of the coloring power of the toner particles. When the styrene-hexane solubility index of the polyester resin is 27.0 or less, the phase separation of the toner particles formed from the polymerizable monomer having a styrene ratio of 60% by mass or more with the binder resin is reduced. This is sufficient and the shell layer has a sufficient thickness, which is desirable in terms of durability.

  As a method of adjusting the styrene-hexane solubility index of the polyester resin, changing the monomer composition of the polyester resin has the greatest effect. In addition, it can be slightly changed by changing the acid value or the molecular weight of the polyester resin. However, if the fluctuation is not considerably large, the influence is small as compared with the change in the monomer composition. When the styrene-hexane solubility index is adjusted by changing the monomer composition of the polyester resin, when the polyester resin has an isosorbide unit, it can be changed by the ratio of the isosorbide unit. Furthermore, by using a monomer having a low molecular weight such as ethylene glycol and adjusting the ratio thereof, the adjustment can be made by changing the ester concentration of the polyester resin.

  Further, the polyester resin contains a terephthalic acid unit, and the content of the terephthalic acid unit is preferably at least 85.00 mol%, more preferably at least 95.00 mol%, based on all dicarboxylic acid monomer units. And more preferably 100.00 mol%.

  This is because, compared to phthalic acid, isophthalic acid, and aliphatic dicarboxylic acid, by using a high ratio of terephthalic acid having high symmetry and linearity as a molecular structure, the orientation of the obtained polyester resin is increased, This is because it becomes a rigid molecule. In particular, when the content of the terephthalic acid unit is 100.00 mol% based on the total dicarboxylic acid monomer units, the composition unevenness of the polyester resin is reduced, and a strong shell can be formed. Further, when the content of the terephthalic acid unit is 100.00 mol% based on the total dicarboxylic acid monomer units, π-electron interaction derived from a benzene ring is strongly exhibited due to the high orientation of terephthalic acid. It is desirable because the molecular orientation is high and the durability is improved, and the chargeability is also excellent.

  When the polyester resin has an isosorbide unit, the content of the isosorbide unit is preferably from 0.10 mol% to 20.00 mol%, more preferably from 0.50 mol% to 10.00 mol%, based on all monomer units. The content is more preferably not more than 1.00 mol% and more preferably not more than 8.00 mol%.

  This is because the orientation between the isosorbide units is very high, and the rigidity of the obtained polyester resin is improved. If the content of the isosorbide unit contained in the polyester resin is less than 0.10 mol% based on all monomer units, the resulting polyester resin has insufficient rigidity, which is not desirable. If it exceeds 20.00 mol%, the solubility is poor, the dispersion state of the pigment is disturbed, and the coloring power is undesirably reduced.

  When the polyester resin has an isosorbide unit, the polyester resin contains an ethylene glycol unit, and the ethylene glycol unit is preferably from 5.00 mol% to 43.00 mol%, more preferably from 15.00 mol% to 43.00 mol%, based on all alcohol monomer units. The content is desirably not more than 00 mol%.

  When the polyester resin has an isosorbide unit, the polyester resin contains an ethylene glycol unit, and when the ethylene glycol unit is at least 5.00 mol% and not more than 43.00 mol% based on all alcohol monomer units, the obtained polyester resin will have an isosorbide unit. In addition to the rigidity due to the ethylene glycol unit, the resin has flexibility due to the ethylene glycol unit. Furthermore, when the toner particles are formed in an aqueous medium due to the polarity of the isosorbide unit and the ethylene glycol unit, the polyester resin forms a shell layer so that the durability is excellent, and the polarity of the polyester resin forming the shell is moderate. Is desirable because the toner has excellent chargeability.

  Therefore, the aliphatic diol compound used for the polyester resin having an isosorbide unit includes 1,2-propanediol, 1,2-butanediol, 2,3-butanediol, and 2-methyl-1,3-propanediol. Or neopentyl glycol may be used. However, such aliphatic diol compounds having a branched structure in which an alkyl group such as a methyl group is bonded to a carbon atom to which a hydroxyl group is bonded or a carbon atom adjacent thereto are sterically hindered by the branched alkyl group. Therefore, it is desirable to use ethylene glycol as the aliphatic diol compound from the viewpoint of the flexibility of the polyester resin. Further, with a diol compound having a straight-chain structure having 3 or more carbon atoms, the flexibility of the polyester resin tends to be excessive. Therefore, when having an isosorbide unit, ethylene glycol is desirable as the aliphatic diol used for the polyester resin.

  When the sum of the isosorbide unit and the ethylene glycol unit of the polyester resin is 20.00 mol% or more and 65.00 mol% or less based on the total alcohol monomer units, the above-mentioned effect is particularly large, and even when the polyester resin is used for a long period of time, the fog and the image density are reduced. It is desirable because the decrease can be suppressed.

  This is because the isosorbide unit and the ethylene glycol unit among the constituent units of the polyester resin have particularly strong polarities and greatly affect the shell formation. The polyester resin is necessary for forming a strong shell, and has appropriate polarity to have appropriate hygroscopicity under a high-temperature and high-humidity environment. .

  Further, when the particles of the polymerizable monomer composition are formed in an aqueous medium, the molecules of the polyester resin in the polymerizable monomer composition, the strength of the orientation by the isosorbide unit and terephthalic acid unit. In addition, by giving an appropriate degree of freedom to the molecule by the ethylene glycol unit, the molecule of the polyester resin is appropriately spread in the polymerizable monomer composition, and the molecular size becomes an appropriate size. As a result, the molecular size is reduced due to too strong orientation, and the solubility of the polymerizable monomer functioning as a solvent molecule is not too low. In addition, the degree of freedom of the molecules is too high and the molecular size is too large, so that the pigment is not depleted and aggregated. Therefore, while maintaining the coloring power of the toner particles in a high state, since the molecular orientation is moderately strong, a shell layer having sufficient strength is formed, so that a toner having excellent durability and coloring power can be obtained. .

  In particular, in the polyester resin, the sum of isosorbide units and ethylene glycol units is 15.00 mol% or more and 50.00 mol% or less based on all alcohol monomer units, and the content of the terephthalic acid units is When the content is 100 mol% as a reference, the above-described effects are large, the coloring power of the toner is high, and the contamination of the developer carrying member and the toner layer regulating member with the toner is preferably suppressed.

<Structural analysis of the polyester resin and the binder resin of the toner>
The structure of the polyester resin can be determined using a nuclear magnetic resonance apparatus ( ¹ H-NMR, ¹³ C-NMR) and an FT-IR spectrum. The apparatus used below is described.

Each resin sample may be collected and collected from the toner and analyzed.
(I) ¹ H-NMR, ¹³ C-NMR
JEOL FT-NMR JNM-EX400 (used solvent deuterated chloroform)
(Ii) FT-IR spectrum Thermo Fisher Scientific Inc. AVATAR360FT-IR

<Measurement of styrene-hexane solubility index>
The styrene-hexane solubility index defined in the present invention is the amount of hexane at which the polyester resin component starts to precipitate when hexane, which is a poor solvent, is added to a solution of a polyester resin in styrene, which is a good solvent. It is specified by. In the method for producing a toner of the present invention, the ratio of styrene contained in the polymerizable monomer is 60% by mass or more, and a large amount of styrene is contained. Therefore, the polymerization reaction proceeds from a state in which the polyester resin is dissolved in the polymerizable monomer containing a large amount of styrene, and the amount of the polymerizable monomer containing styrene decreases as the polymerization reaction proceeds. By adding hexane to the styrene solution of the polyester resin, the ratio of styrene in the styrene solution of the polyester resin decreases, and the styrene-hexane solubility index corresponds to the actual change in the state of the polymerization reaction. Become. Therefore, the smaller the styrene-hexane solubility index is, the more the polyester resin is precipitated in the early stage of the polymerization reaction.

  Further, by using hexane which is a nonpolar solvent in this measurement, a polyester resin having a higher polarity is precipitated at a stage where the amount of hexane added is smaller. Therefore, the smaller the styrene-hexane solubility index is, the more the polyester resin precipitated along with the progress of the polymerization reaction on the surface of the toner on the aqueous phase side.

(Sample preparation)
A styrene solution (solution temperature: 25 ° C.) prepared by dissolving 4.0 parts by mass of a polyester resin in 100.0 parts by mass of styrene is prepared. The resin dissolved and left for 12 to 24 hours is filtered through a sample treatment filter (pore size: 0.45 μm) to filter out styrene-insoluble components, and the filtrate is used as a measurement sample.

(Measuring method)
As a measuring device, for example, a powder wettability tester WET-101P manufactured by Resca Corporation can be mentioned. As a specific measurement operation, the above-prepared measurement sample is placed in a tall beaker container, n-hexane is used as a dropping reagent, and measurement is performed using a hexane dropping transmittance curve.

  Next, while stirring the sample solution for measurement at a speed of 280 to 300 rpm, n-hexane was continuously added at a dropping speed of 0.8 ml / min, and the transmittance was measured with light having a wavelength of 780 nm. -Create a hexane drop transmittance curve. From the obtained n-hexane dropping curve, the n-hexane concentration at the time when the light transmittance is 50% is defined as the styrene-hexane solubility index of the polyester resin. FIG. 1 shows a schematic diagram of a transmittance curve of a typical example. In this measurement, a circular tall beaker having a diameter of 5 cm and a thickness of 1.75 mm made of glass was used. As a stirrer, a spindle having a length of 25 mm and a maximum diameter of 8 mm was coated with a fluororesin. A magnetic stirrer was used.

  The content of the polyester resin in the toner is preferably from 1.0% by mass to 20.0% by mass, and more preferably from 1.0% by mass to 15.0% by mass with respect to 100 parts by mass of the binder resin. The content is more preferably not more than 1.0% by mass and more preferably not less than 1.0% by mass and not more than 10.0% by mass.

  When the content of the polyester resin in the toner is 1.0% by mass or more based on 100 parts by mass of the binder resin, it is sufficient to form a shell layer on the surface of the toner. It is desirable from the viewpoint of storage properties and storage stability. Also, when the content is 20.0% by mass or less, the dispersion state of the pigment is easily maintained in the coloring power of the toner, and it is desirable from the viewpoint of fixability.

  Further, the weight average molecular weight (Mw) of the polyester resin is preferably from 5,000 to 25,000, and more preferably from 8,000 to 20,000.

  It is desirable from the viewpoint of durability that the polyester resin has a weight average molecular weight (Mw) of 5,000 or more because the polyester resin is tough as a molecule. When the weight average molecular weight (Mw) of the polyester resin is 25,000 or less, neither the solubility nor the molecular size of the polyester resin is too large, which is desirable from the viewpoint of toner coloring power.

<Molecular weight and molecular weight distribution of the polyester resin>
The molecular weight and the molecular weight distribution of the polyester resin are calculated by gel permeation chromatography (GPC) in terms of polystyrene. When measuring the molecular weight of a resin having an acid group, the column elution rate also depends on the amount of the acid group, so it is necessary to prepare a sample in which the acid group is capped in advance. For capping, methyl esterification is preferable, and a commercially available methyl esterifying agent can be used. Specifically, a method of treating with trimethylsilyldiazomethane may be mentioned.

The measurement of the molecular weight by GPC is performed as follows. First, a measurement sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Maisho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: 7 columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL

  In calculating the molecular weight of the measurement sample, a standard polystyrene resin (for example, “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-20, -10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ”, manufactured by Tosoh Corporation).

  In particular, it is desirable that the polyester resin has a weight average molecular weight (Mw) of 8000 to 20,000 and an acid value of 1.0 mgKOH / g to 15.0 mgKOH / g. This is desirable because a moderately strong polyester resin has a moderate polarity to form a strong shell, and thus has excellent storage stability and chargeability of the toner.

  Further, the glass transition temperature (Tg) of the polyester resin is desirably from 65 ° C to 85 ° C. It is preferable that the polyester resin has a glass transition temperature (Tg) of 65 ° C. or higher from the viewpoint of high heat resistance and storage stability. Further, it is desirable that the glass transition temperature (Tg) of the polyester resin is 85 ° C. or less from the viewpoint of toner fixability.

<Glass transition temperature of polyester resin>
The glass transition temperature of the toner particles of the present invention is measured using a differential scanning calorimeter (DSC measurement device).

  The differential scanning calorimeter uses a differential scanning calorimeter “Q1000” (manufactured by TA Instruments) and measures as follows according to ASTM D3418-82. The measurement sample is precisely weighed from 2 to 5 mg, preferably 3 mg. Place it in an aluminum pan and use an empty aluminum pan for control. After maintaining the equilibrium at 20 ° C. for 5 minutes, measurement is performed at a rate of temperature increase of 10 ° C./min between 20 and 180 ° C. In the present invention, the glass transition temperature can be determined by the midpoint method.

  As a method for producing a polyester resin, for example, a method utilizing a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound, or a transesterification reaction is employed. As the catalyst, general acidic or alkaline catalysts used for the esterification reaction, such as zinc acetate and titanium compounds, may be used. Thereafter, high purity may be obtained by a recrystallization method, a distillation method, or the like.

  A particularly preferred production method is a dehydration condensation reaction between a carboxylic acid compound and an alcohol compound because of the variety of raw materials and the ease of reaction.

  The composition of the polyester when the polyester is used as the condensation resin will be described below.

  It is preferable that 43 to 57 mol% of all components of the polyester is an alcohol component, and 57 to 43 mol% is an acid component.

  In producing the polyester resin used in the present invention, a known alcohol component can be used other than the isosorbide or the isosorbide derivative represented by the formula (1) as long as the effects of the present invention are not impaired. Examples of the alcohol component include ethylene glycol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and the following formula (I)

（式中、Ｒはエチレン又はプロピレン基を示し、ｘ，ｙはそれぞれ１以上の整数を示し、かつｘ＋ｙの平均値は２〜１０を示す。）で示されるビスフェノー誘導体、又は下記式（ＩＩ）

(Wherein, R represents an ethylene or propylene group, x and y each represent an integer of 1 or more, and the average value of x + y represents 2 to 10), or the following formula (II)

で示されるジオールの如きジオール類が挙げられる。

And diols such as diols represented by

  Examples of the divalent carboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, diphenyl-PP'-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, and diphenylmethane- Benzenedicarboxylic acids or their anhydrides such as PP'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, and 1,2-diphenoxyethane-PP'-dicarboxylic acid; succinic acid, adipic acid, sebacine Acid, azelaic acid, glutaric acid, cyclohexanedicarboxylic acid, triethylenedicarboxylic acid, alkyldicarboxylic acids such as malonic acid or anhydrides thereof, or succinic acid or a succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms Anhydrides such as fumaric acid, maleic acid, citraconic acid, itaconic acid Saturated dicarboxylic acid or an anhydride thereof.

  Particularly preferred alcohol components are bisphenol derivatives represented by the above formula (I) and ethylene glycol, and acidic components include terephthalic acid or anhydride thereof, succinic acid, n-dodecenylsuccinic acid or anhydride thereof, and fumaric acid. And dicarboxylic acids such as maleic acid and maleic anhydride. Particularly, terephthalic acid is preferred.

  The polyester unit can be obtained by synthesizing from a divalent dicarboxylic acid and a divalent diol, but in some cases, a polycarboxylic acid or polyol having a valence of 3 or more may be used within a range that does not adversely affect the present invention. You may use a small amount.

  Examples of the trivalent or higher polycarboxylic acid include trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acids, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and 1,2,4-butanetricarboxylic acid. Acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxylpropane, 1,3-dicarboxyl-2-methyl-methylenecarboxylpropane, tetra (methylenecarboxyl) methane, 1,2 , 7,8-octanetetracarboxylic acid and their anhydrides.

  Examples of the trivalent or higher polyol include sulbitol, 1,2,3,6-hexanetetol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2,4-methanetriol Glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

  From the viewpoint of efficiently exhibiting the effects of the polyester resin of the present invention, the tricarboxylic acid or higher polycarboxylic acid is 10.00. mol% or less is desirable. Similarly, the polyol having a valency of 3 or more has a total of 10.00. mol% or less is desirable.

  This means that the tricarboxylic acid or higher polycarboxylic acid is 10.00. When the content is at most mol%, the insoluble content due to crosslinking is small, which is desirable from the viewpoint of pigment dispersibility. Even when the production method is devised so as not to generate insoluble components, the proportion of the branched polyester resin is small and the strength is excellent, which is desirable from the viewpoint of durability.

<Confirmation of Influence of Inorganic Fine Particles on Amount of Polyester Resin on Toner Particle Surface>
Since the hydrophobicity of the toner particle surface decreases as the ratio of the polyester resin present on the toner particle surface increases, the hydrophobicity was measured in a methanol wettability test. Methanol wettability of the toner particles was measured to determine the degree of hydrophobicity. The smaller the degree of hydrophobicity, the more the polyester resin as the polar resin is distributed on the surface of the toner particles.

  In the present invention, the degree of hydrophobicity of the toner particles is determined from a methanol drop transmittance curve obtained as described below.

  First, 70 ml of ion-exchanged water is placed in a cylindrical glass container having a diameter of 5 cm and a thickness of 1.75 mm, and dispersed with an ultrasonic disperser for 5 minutes to remove bubbles and the like in the measurement sample.

  Next, the toner particles are shaken with a mesh having a mesh size of 500 μm, 0.1 g of the toner particles passing through the mesh are precisely weighed, and added to the container containing the ion-exchanged water to prepare a sample liquid for measurement. .

Then, the sample liquid for measurement is set in a powder wettability tester “WET-101P” (manufactured by Resca Corporation). This measurement sample liquid is stirred at a speed of 6.7 s ^-1 (400 rpm) using a magnetic stirrer. As the rotor of the magnetic stirrer, a spindle type rotor coated with a fluororesin and having a length of 25 mm and a maximum body diameter of 8 mm is used.

  Next, the transmittance was measured with light having a wavelength of 780 nm while continuously adding methanol at a dropping rate of 0.8 ml / min to the sample liquid for measurement through the above-described apparatus, as shown in FIG. A methanol drop transmittance curve is created.

  From the obtained methanol dropping curve, the difference between the presence and absence of the aluminum element in the inorganic fine particles with respect to the methanol concentration at the time when the light transmittance is 50% is determined by the shell polyester resin used in the present invention and the inorganic element containing the aluminum element. FIG. 2 shows a schematic diagram of a transmittance curve of a representative example of the result of the interaction with the fine particles.

(wax)
The toner of the present invention may contain a wax. In this case, at least one of the waxes preferably has a melting point (the temperature corresponding to the maximum endothermic peak of the DSC endothermic curve in the temperature range of 20 to 200 ° C.) of 30 ° C. or more and 120 ° C. or less, and 50 ° C. or more and 100 ° C. or less. It is more preferred that: Further, it is preferably a wax which is solid at room temperature, and in particular, a solid wax having a melting point of 50 ° C. or more and 100 ° C. or less is preferred from the viewpoints of blocking resistance, durability of a large number of sheets, low-temperature fixability and offset resistance.

  Examples of the wax include paraffin wax, polyolefin wax, polymethylene wax such as microcrystalline wax and Fischer-Tropsch wax, petroleum wax such as amide wax and petrolatum and derivatives thereof, montan wax and derivatives thereof, carnauba wax and candelilla wax and the like. Use of known waxes such as natural waxes and their derivatives, hydrogenated castor oil and its derivatives, vegetable waxes, animal waxes, higher fatty acids, long-chain alcohols, ester waxes, ketone waxes and their derivatives such as graft compounds and block compounds Is possible. These can be used alone or in combination.

  The content of the wax in the toner of the present invention is preferably 3 parts by mass to 30 parts by mass, more preferably 3 parts by mass to 20 parts by mass, and more preferably 4 parts by mass to 15 parts by mass with respect to 100 parts by mass of the binder resin. It is more preferably at most part by mass. When the amount of the wax added is equal to or more than the lower limit, the offset prevention effect does not decrease, and when the amount is less than the upper limit, the anti-blocking effect does not decrease, and the anti-offset effect is hardly adversely affected. Fusing of the developing sleeve hardly occurs.

  When a hydrocarbon wax is used in the present invention, the anti-blocking effect and the anti-offset effect are more excellent, and the toner is less likely to be fused to the toner layer regulating member or the toner carrier. This indicates that the poor solvent used for the measurement of the styrene-hexane solubility index of the polyester resin used in the present invention is n-hexane, which is a hydrocarbon. This is because When the styrene-hexane solubility index of the polyester resin is 15.0 or more and 27.0 or less, the polyester resin has a phase separation property that can prevent the hydrocarbon wax from being exposed from the toner surface, and exudes wax at the time of fixing. This is because the polyester resin has an affinity with the hydrocarbon wax to such an extent as not to hinder the reaction.

  In the case where it is necessary to extract the wax from the toner in obtaining the above physical properties, the extraction method is not particularly limited, and any method can be used. For example, a predetermined amount of toner is subjected to Soxhlet extraction with toluene, the solvent is removed from the obtained toluene-soluble component, and then a chloroform-insoluble component is obtained. Thereafter, identification analysis is performed by an IR method or the like.

  In addition, quantitative analysis is performed by DSC or the like. In the present invention, the measurement is performed using DSC-2920 manufactured by TA Instruments Japan.

  The intersection between the line at the midpoint of the baseline before and after the specific heat change during the measurement and the differential heat curve is defined as the glass transition point. Further, the maximum endothermic peak temperature of the wax component is obtained from the obtained DSC curve at the time of temperature rise.

(Charge control agent)
In the toner of the present invention, a known charge control agent can be used. The content of the charge control agent is preferably 0.01 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin in the toner. Is more preferred.

(Pigment)
The toner of the present invention contains a pigment as a colorant. As the pigment used for the cyan colorant, a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound can be used. Specifically, the following are mentioned. C. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3 and C.I. I. Pigment Blue 15: 4.

  Examples of the pigment used for the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, the following are mentioned. C. I. Pigment Violet 19, C.I. I. Pigment Red 31, C.I. I. Pigment Red 32, C.I. I. Pigment Red 122, C.I. I. Pigment Red 150, C.I. I. Pigment Red 254, C.I. I. Pigment Red 264 and C.I. I. Pigment Red 269.

  As the pigment used for the yellow colorant, a condensed azo compound, an isoindolinone compound, an anthraquinone compound, an azo metal complex, a methine compound, and an allylamide compound can be used. Specifically, the following are mentioned. C. I. Pigment yellow 74, C.I. I. Pigment Yellow 93, C.I. I. Pigment yellow 120, C.I. I. Pigment Yellow 139, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 155, C.I. I. Pigment Yellow 180 and C.I. I. Pigment Yellow 185.

  As the black colorant, carbon black, a magnetic material, and a black color tone using the above-mentioned yellow, magenta and cyan colorants can be used.

  Pigment is carbon black, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Red 122, C.I. I. Pigment Red 150, C.I. I. Pigment Red 32, C.I. I. Pigment Red 269, C.I. I. Pigment yellow 155, C.I. I. Pigment Yellow 93, C.I. I. Pigment yellow 74, C.I. I. Pigment Yellow 180 and C.I. I. Pigment Yellow 185 is desirable because the effect of the present invention is high. Although the reason is not clear, it seems to be due to high affinity with the isosorbide unit. In particular, in the case of carbon black, the pH is preferably 6 or more and the oil absorption (DBP) is preferably 30 (cc / 100 g) or more and 120 (cc / 100 g) or less.

  The addition amount of these pigments is preferably 1 part by mass or more and 20 parts by mass or less based on 100 parts by mass of the binder resin.

(Other additives)
In the toner of the present invention, various known inorganic and organic additives can be used for the purpose of imparting various properties as long as the effects of the present invention are not impaired. The additive used preferably has a particle size of 3/10 or less of the weight average particle size of the toner particles from the viewpoint of durability when added to the toner. The particle size of the additive means the average particle size of the toner particles obtained by observing the surface of the toner particles with a scanning electron microscope.

  The content of these additives is preferably 0.01 to 5 parts by mass, more preferably 0.02 to 3 parts by mass, based on 100 parts by mass of the toner.

  These additives may be used alone or in combination of two or more.

  Further, these additives may be subjected to a hydrophobic treatment. As a method of the hydrophobic treatment, various coupling agents such as a silane coupling agent or a titanium coupling agent can be used, but it is preferable to increase the degree of hydrophobicity by using silicone oil. This is because moisture adsorption of the inorganic fine powder under high humidity can be suppressed, and furthermore, contamination of the regulating member and the charging member can be suppressed, so that a high-quality image can be obtained.

  The weight average particle size (D4) of the toner is preferably from 4.0 μm to 12.0 μm, and more preferably from 4.0 μm to 9.0 μm. This is because if the weight average particle diameter is less than 4.0 μm, the specific surface area of the toner is large, so that problems tend to occur in long-term use such as durability and heat resistance. It is not desirable because it is inferior in coloring power and image resolution.

<Weight average particle diameter (D4), number average particle diameter (D1) of toner particles>
The weight average particle diameter (D4) and the number average particle diameter (D1) of the toner particles are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube by a pore electric resistance method is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter) is used. The measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, one prepared by dissolving a special grade sodium chloride in ion-exchanged water so as to have a concentration of 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter) can be used.

  Before performing the measurement and analysis, the dedicated software is set as follows. On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count number in the control mode to 50,000 particles, set the number of measurements to 1, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained by using the following method. By pressing the “threshold / noise level measurement button”, the threshold and the noise level are automatically set. Also, the current is set to 1600 μA, the gain is set to 2, and the electrolytic solution is set to ISOTON II, and a check is made in “Flush aperture tube after measurement”. In the “pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to a logarithmic particle size, the particle size bin is set to a 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measuring method is as follows.
(1) 200 mL of the electrolytic aqueous solution is placed in a glass 250 mL round bottom beaker for Multisizer 3 and set on a sample stand, and the stirrer rod is agitated counterclockwise at 24 revolutions / second. Then, the dirt and air bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) 30 mL of the electrolytic aqueous solution is put into a glass 100 mL flat bottom beaker. A 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument having a pH of 7 comprising a nonionic surfactant, an anionic surfactant, and an organic builder as a dispersant is used as a dispersant therein, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted by 3 times with ion-exchanged water, and 0.3 mL of a diluent is added.
(3) An ultrasonic disperser “Ultrasonic Dispersion System Tetra 150” (manufactured by Nikkaki Bios) having an electrical output of 120 W, in which two oscillators having an oscillation frequency of 50 kHz are shifted in phase by 180 degrees, is prepared. 3.3 L of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and 2 mL of contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the aqueous electrolytic solution in the beaker becomes maximum.
(5) 10 mg of toner is added little by little to the electrolytic aqueous solution in the beaker of (4) in a state where the electrolytic aqueous solution is irradiated with ultrasonic waves, and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. The ultrasonic dispersion is appropriately adjusted so that the water temperature of the water tank is 10 ° C. or more and 40 ° C. or less.
(6) The aqueous electrolyte solution of (5) in which the toner is dispersed is dropped into the round bottom beaker of (1) installed in the sample stand using a pipette so that the measured concentration becomes 5%. Then, measurement is performed until the number of particles to be measured reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the apparatus, and the weight average particle diameter (D4), number average particle diameter (D1), volume-based median diameter, and number-based median diameter are calculated. When the graph / volume% is set with the dedicated software, the “average diameter” on the “analysis / volume statistics (arithmetic average)” screen is the weight average particle diameter (D4), and the “medium diameter” is It is a volume-based median diameter (Dv50). When the graph / number% is set in the dedicated software, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1), and the “medium diameter” is It is a number-based median diameter (Dn50).

  The glass transition temperature of the toner particles is preferably from 53 ° C. to 75 ° C. When the glass transition temperature of the toner particles is 53 ° C. or more and 75 ° C. or less, it is desirable because both storage stability and fixability are achieved.

<Glass transition temperature of toner particles>
The glass transition temperature of the toner particles of the present invention is measured using a differential scanning calorimeter (DSC measurement device).

  The differential scanning calorimeter uses a differential scanning calorimeter “Q1000” (manufactured by TA Instruments) and measures as follows according to ASTM D3418-82. The measurement sample is precisely weighed from 2 to 5 mg, preferably 3 mg. Place it in an aluminum pan and use an empty aluminum pan for control. After maintaining the equilibrium at 20 ° C. for 5 minutes, the measurement is performed at a rate of 1 ° C./min with a modulation rate of 1.0 ° C./min over a measurement range of 20 to 140 ° C. In the present invention, the glass transition temperature can be determined by the midpoint method.

  The average circularity of the toner particles is preferably 0.975 or more. This is because the toner particles are likely to be frictionally charged uniformly between the toner particles, the toner carrier, and the toner layer regulating member, and the stress applied to the toner particles is also made uniform. Therefore, it is desirable in terms of chargeability and fusion to the toner layer regulating member.

<Method of measuring average circularity of toner particles>
The average circularity of the toner particles was measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration work.

  The specific measuring method is as follows. First, about 20 ml of ion-exchanged water from which impurity solids and the like have been removed in advance is placed in a glass container. A 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument having a pH of 7 comprising a nonionic surfactant, an anionic surfactant, and an organic builder as a dispersant is used as a dispersant therein, manufactured by Wako Pure Chemical Industries, Ltd. ) Was diluted about 3 times by mass with ion-exchanged water, and about 0.2 ml of a diluent was added. Further, about 0.02 g of a measurement sample is added, and a dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. At that time, the dispersion is appropriately cooled so that the temperature of the dispersion is 10 ° C. or more and 40 ° C. or less. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser having an oscillation frequency of 50 kHz and an electric output of 150 W (for example, “VS-150” (manufactured by Vervocreer)) is used. Pour ion-exchanged water and add about 2 ml of the contaminone N into the water tank.

  For the measurement, the flow type particle image analyzer equipped with "LUCPFLN" (magnification: 20 times, numerical aperture: 0.40) as an objective lens was used, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as a sheath liquid. It was used. The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, and 2,000 toner particles are measured in a total count mode in an HPF measurement mode. Then, the binarization threshold at the time of particle analysis was set to 85%, the analysis particle diameter was limited to a circle equivalent diameter of 1.977 μm or more and less than 39.54 μm, and the average circularity of the toner particles was obtained.

  In the measurement, automatic focus adjustment is performed using standard latex particles (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5100A” manufactured by Duke Scientific) with ion-exchanged water before the start of the measurement. Thereafter, it is preferable to perform the focus adjustment every two hours from the start of the measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been calibrated by Sysmex Corporation and has been issued a calibration certificate issued by Sysmex Corporation was used. The measurement was performed under the measurement and analysis conditions when the calibration certificate was obtained, except that the analysis particle size was limited to a circle equivalent diameter of 1.977 μm or more and less than 39.54 μm.

(Polymerizable monomer)
As the polymerizable monomer used in the present invention, besides styrene, a vinyl polymerizable monomer capable of radical polymerization may be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. As the monofunctional polymerizable monomer, styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p Styrene derivatives such as -phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, -Ethylhexyl acrylate Acrylic polymerizable monomers such as n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate , N-nonyl methacrylate, diethyl phosphate ethyl methacrylate Methacrylic polymerizable monomers such as phosphate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylates; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinyl methyl ether And vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; and vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  Examples of polyfunctional polymerizable monomers include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tripropylene glycol. Diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxy diethoxy) phenyl) propane, 2,2′-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethanetetramethacrylate, divinylbenzene, divinylnaphthalene, divinylether, and the like.

  In the present invention, the above-mentioned monofunctional polymerizable monomers are used alone or in combination of two or more, or the above-mentioned monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. I do.

  Examples of the polymerizable monomer other than styrene include styrene derivatives, acrylate-based polymerizable monomers such as n-butyl acrylate and 2-ethylhexyl acrylate, and methacrylate-based monomers such as n-butyl methacrylate and 2-ethylhexyl methacrylate. Polymerizable monomers are preferred. This is because the binder resin obtained by polymerizing the polymerizable monomer is excellent in strength and flexibility.

(Polymerization initiator)
Examples of the polymerization initiator used when producing the present invention by a suspension polymerization method include the following. 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4- Peroxide polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide; These polymerization initiators are preferably added in an amount of 0.5 to 20% by mass based on the polymerizable monomer, and may be used alone or in combination.

(Production method)
Although the suspension polymerization is used as the method for producing the toner of the present invention, the toner can be directly produced by the following production method. A polyester resin, a release agent, a colorant, a cross-linking agent, and other additives are added to the polymerizable monomer, and the polymerizable monomer composition uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser, or the like. Is dispersed in an aqueous medium having a dispersion stabilizer using a conventional stirrer, a homomixer, a homogenizer, or the like. At this time, the stirring speed and time are adjusted so that the droplets of the polymerizable monomer composition have a desired toner size, and the particles are granulated to form particles of the polymerizable monomer composition. Thereafter, stirring may be performed to such an extent that the state of the particles is maintained and sedimentation of the particles is prevented by the action of the dispersion stabilizer. The polymerization reaction is allowed to proceed by adding a polymerization initiator. The polymerization is carried out at a polymerization temperature of 40 ° C. or higher, usually 50 to 95 ° C. (preferably 55 to 85 ° C.). The temperature may be raised in the latter half of the polymerization reaction, and the pH may be changed if necessary. Further, in order to remove unreacted polymerizable monomers and by-products which cause odor at the time of fixing, the aqueous medium may be partially distilled off in the latter half of the reaction or after completion of the reaction. After the reaction, the generated toner particles are collected by washing and filtration, and dried.

  The pH in the aqueous medium during granulation is not particularly limited, but the pH is preferably 3.0 or more and 13.0 or less, more preferably 3.0 or more and 7.0 or less, and particularly preferably 3.0 or more and 6 or less. 0.0 or less. If the pH is less than 3.0, dissolution may occur in a part of the dispersion stabilizer, making it difficult to stabilize the dispersion and making granulation impossible. When the pH exceeds 13.0, components added to the toner may be decomposed, and sufficient charging ability may not be exhibited. When the granulation is performed in the acidic region, the content of the metal derived from the dispersion stabilizer in the toner can be suppressed from being excessive, and a toner satisfying the requirements of the present invention can be easily obtained. Become.

  When the inorganic fine particles containing an aluminum element are added from the granulation step, the pH in the aqueous medium is particularly preferably 3.0 or more and 6.0 or less. This is because, when the pH is 3.0 or more, the inorganic fine particles containing the aluminum element dissolve only a small amount in the aqueous medium, and exist as a solid, so that the boundary between the polymerizable monomer composition and the aqueous medium is reduced. This is because the polyester resin is likely to be unevenly distributed on the surface of the toner because the polyester resin is continuously present on the surface. When the pH is 6.0 or less, the formation of inorganic fine particles of aluminum hydroxide alone can be suppressed, the affinity with the polyester resin is excellent, and the toner particles are coarsened or deformed due to aggregation of the toner particles. This is desirable from the viewpoint of chargeability because it is possible to suppress the occurrence of charge.

  Further, it is preferable to wash the toner particles with an acid having a pH of 2.5 or less, more preferably 1.5 or less. By performing the washing of the toner particles with an acid, the amount of the dispersion stabilizer present on the surface of the toner particles can be reduced. The acid used for washing is not particularly limited, and inorganic acids such as hydrochloric acid and sulfuric acid can be used. Thereby, the chargeability of the toner particles can be adjusted to a desired range.

  As the inorganic fine particles as the dispersion stabilizer used in the present invention, other than the inorganic fine particles containing an aluminum element, other inorganic fine particles may be used. Other inorganic fine particles that may be used include, for example, magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, and metasilicate. Examples include inorganic fine particles such as calcium, calcium sulfate, barium sulfate, and hydroxyapatide. In particular, hydroxyapatite is desirable because toner particles having a sharp particle size distribution can be obtained without disturbing the interaction between the inorganic fine particles containing an aluminum element and the polyester resin forming the shell by being distributed on the surface of the toner.

  Furthermore, as these inorganic fine particles, commercially available inorganic fine particles may be used as they are, but in consideration of controlling the particle size of the inorganic fine particles, it is preferable to generate the inorganic fine particles in an aqueous medium. For example, in the case of hydroxyapatite, it may be obtained by mixing an aqueous sodium phosphate solution and a calcium chloride solution under high stirring.

  Organic compounds such as polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, and starch may be used in combination with the dispersion stabilizer.

  It is preferable to use 0.01 to 2.0 parts by mass of these dispersion stabilizers with respect to 100 parts by mass of the polymerizable monomer.

  Further, a surfactant of 0.001 to 0.1 part by mass may be used in combination with 100 parts by mass of the polymerizable monomer to make the dispersion stabilizer finer. Specifically, commercially available nonionic, anionic and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate are preferably used.

  The inorganic fine particles containing an aluminum element essential for the present invention may be added at any time during the polymerization step or during the granulation step, since they are effective. However, the presence of the inorganic fine particles containing an aluminum element from the time of the granulation step is desirable because uneven distribution of the polyester resin to the surface of the toner particles is efficiently performed. When the inorganic fine particles containing an aluminum element are added during the polymerization step, the conversion of the polymerizable monomer is desirably 60% or less. This is because if the conversion is 60% or less, the polymerizable monomer remains sufficiently, so that the polyester resin can move in the polymerizable monomer composition and is easily localized on the toner particle surface. That's why.

  In particular, it is desirable to have a step of obtaining the inorganic fine particles by mixing a phosphate aqueous solution and an aluminum compound aqueous solution. This is because the composition of the inorganic fine particles is made uniform by mixing the aqueous solutions of the homogeneous system to generate the inorganic fine particles, and the effect of the present invention is enhanced, and the inorganic fine particles become a compound with phosphate. This is because the affinity with the polyester resin is improved.

  Further, in the polymerization step, the pH of the aqueous medium is desirably 3.0 or more and 6.0 or less. This is because, when the pH is 3.0 or more, the inorganic fine particles containing the aluminum element dissolve only a small amount in the aqueous medium, and exist as a solid, so that the boundary between the polymerizable monomer composition and the aqueous medium is reduced. This is because the polyester resin is likely to be unevenly distributed on the surface of the toner because the polyester resin is continuously present on the surface. When the pH is 6.0 or less, the formation of inorganic fine particles of aluminum hydroxide alone can be suppressed, the affinity with the polyester resin is excellent, and the toner particles are coarsened or deformed due to aggregation of the toner particles. This is desirable from the viewpoint of chargeability because it is possible to suppress the occurrence of charge.

<Method of measuring polymerization conversion of toner particles>
The polymerization conversion of the toner particles is measured using gas chromatography (GC) as follows.

About 500 mg of the toner particle dispersion is precisely weighed and placed in a sample bottle. About 10 g of acetone weighed precisely was added thereto, and the lid was closed. After mixing well, the mixture was thoroughly mixed, and put into a desktop ultrasonic cleaner (trade name "B2510J-MTH", manufactured by Branson) having an oscillation frequency of 42 kHz and an electric output of 125 W. To irradiate ultrasonic waves for 30 minutes. Thereafter, the solution is filtered using a solvent-resistant membrane filter “Maisho Disc” (manufactured by Tosoh Corporation) having a pore size of 0.2 μm, and 2 μL of the filtrate is analyzed by gas chromatography. Then, the “residual amount” of the remaining polymerizable monomer is calculated from a calibration curve prepared using the polymerizable monomer used in advance. Then, the polymerization conversion (mass%) of the toner particles is defined according to the following formula.
(Formula) 100 × (1− (remaining amount of polymerizable monomer) / (total amount of used polymerizable monomer))

(manufacturing device)
In the present invention, known means can be used. Examples of the stirring means in the granulation step include paddle blades, inclined paddle blades, three retreating blades, anchor blades, full zones (manufactured by Shinko Pantech Co., Ltd.), and Max Blend ( Sumitomo Heavy Industries, Ltd.), Supermix (manufactured by Satake Chemical Machinery Co., Ltd.), Hi-F mixer (manufactured by Soken Chemical Co., Ltd.) or the like having a stirring blade can be used. Further, a production method capable of imparting high shearing force and achieving uniform circulation is more preferable. As the high-shear stirrer, one having a stirring chamber formed by a stirring rotor rotating at high speed and a screen provided so as to surround the stirring rotor is preferably used. Specifically, Ultra Turrax (manufactured by IKA), Polytron (manufactured by Kinematica), T.V. K. Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), CLEARMIX (manufactured by M Technique Co., Ltd.) and the like are used.

<PH measurement of aqueous medium>
One minute before charging the toner composition into the aqueous medium, 1.0 liter of the aqueous medium is collected, and the pH meter is immersed in the aqueous medium within 30 seconds. Then, the value 60 seconds after the pH meter is immersed in the aqueous medium is recorded. It is also confirmed that the temperature at the time of measurement is not lower than the temperature of the aqueous medium at the time of sampling by 2 ° C. or more. The pH meter used was HA406 manufactured by Yokogawa Electric Corporation. In addition, the pH meter performs temperature and pH value calibration in advance according to a manual.

  Hereinafter, the present invention will be described in more detail with reference to specific production methods, examples, and comparative examples, but this does not limit the present invention in any way.

[Production of polyester resin 1]
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device,
Terephthalate 29.9 parts by mass Bisphenol A-propylene oxide 2 mol adduct 48.5 parts by mass Isosorbide 1.2 parts by mass Ethylene glycol 4.5 parts by mass Tetrabutoxy titanate 0.125 parts by mass The above polyester monomer was charged and placed under a nitrogen atmosphere. The reaction was carried out at 200 ° C. under normal pressure for 5 hours, and thereafter, 2.1 parts by mass of trimellitic acid and 0.120 parts by mass of tetrabutoxytitanate were added, and the mixture was reacted at 220 ° C. for 3 hours, and further reduced under reduced pressure of 10 to 20 mmHg. The polyester resin 1 was obtained by reacting under the following conditions for 2 hours. Table 2 shows the physical properties of the obtained polyester resin 1.

  The composition of the obtained polyester resin 1 was the same as the charged amount shown in Table 1. The isosorbide in the table is a compound having a structure represented by the following formula (2).

[Production of polyester resins 2-33]
The same operations as in the case of the polyester resin 1 were carried out under the raw material monomer charge amounts and the temperature conditions for the polycondensation reaction shown in Table 1 to produce polyester resins 2-33. Table 2 shows the physical properties of the obtained resin. Regarding the adjustment of the molecular weight and the acid value of each polyester resin, the reaction time was appropriately adjusted so that the physical properties of the polyester resin were achieved.

[Production of styrene-acrylic resin 1]
100 parts by mass of propylene glycol monomethyl ether was heated while being replaced with nitrogen, and refluxed at a liquid temperature of 120 ° C. or higher, and a mixture of the following materials was added dropwise thereto over 3 hours.
Styrene 91.7 parts by mass Methyl methacrylate 2.50 parts by mass Methacrylic acid 3.30 parts by mass 2-hydroxyethyl acrylate 2.50 parts by mass ditert-butyl peroxide (trade name “Perbutyl D” manufactured by NOF Corporation) )
1.25 parts by mass After the completion of the dropwise addition, the solution was stirred for 3 hours, and then distilled under normal pressure while raising the liquid temperature to 170 ° C. After the liquid temperature reached 170 ° C, the solvent was distilled off under reduced pressure at 1 hPa for 1 hour. Thus, a resin solid was obtained. The solid was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was separated by filtration to obtain a polymer component (A-1). The composition and physical properties of the obtained polymer component (A-1) were as follows.
Mw = 15000, acid value = 20 mgKOH / g, hydroxyl value = 10 mgKOH / g, Tg (midpoint method) = 90 ° C.

[Production of Resin 1 Having Sulfonic Acid, Sulfonate Group, and Sulfonate Ester]
100 parts by mass of toluene, 350 parts by mass of methanol, 470 parts by mass of styrene, 40 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid, 40 parts by mass of acrylic acid in a 2 L flask equipped with a stirrer, a condenser, a thermometer and a nitrogen inlet tube. -Ethylhexyl (70 parts by mass), benzyl methacrylate (20 parts by mass), and lauryl peroxide (10 parts by mass) were charged, and solution polymerization was carried out at 65 ° C for 10 hours with stirring and nitrogen introduction. Next, the content was taken out of the flask, washed with isopropyl alcohol, dried under reduced pressure at 40 ° C. for 96 hours, crushed with a hammer mill, and further dried under reduced pressure at 40 ° C. for 48 hours. Resin 1 having a sulfonic acid, a sulfonic acid group, and a sulfonic acid ester was produced. Physical properties of the obtained resin were Mw = 24000, Tg = 67 ° C., and residual monomer = 350 ppm.

  In addition, the acid value of the obtained resin 1 having a sulfonic acid, a sulfonic acid group and a sulfonic acid ester was 20 mgKOH / g.

[Production of hydrophobic silica 1]
100 parts by mass of silica (AEROSIL 200CF, manufactured by Nippon Aerosil Co., Ltd.) was treated with 10 parts by mass of hexamethyldisilazane, and further treated with 20 parts by mass of dimethyl silicone oil to obtain hydrophobic silica 1. The primary particle diameter of the hydrophobic silica 1 was 12 nm, and the degree of hydrophobicity was 97.

[Production of hydrophobic titanium oxide 1]
100 parts by mass of titanium oxide (P25, manufactured by Nippon Aerosil) were treated with 20 parts by mass of γ-mercaptopropyltrimethoxysilane in toluene, filtered and dried to obtain hydrophobic titanium oxide 1. The primary particle diameter of the hydrophobic titanium oxide 1 was 25 nm, and the degree of hydrophobicity was 60.

(Production of inorganic fine particles 4 and aqueous medium 4)
In tank A, 24.26 parts by mass of aluminum chloride hexahydrate and 33.63 parts by mass of calcium chloride dihydrate were added to 100 parts by mass of water, and aluminum chloride and chloride were added. An aqueous solution of calcium was prepared. On the other hand, in a granulation tank, a liquid obtained by adding 25.0 parts by mass of sodium phosphate to 6.66 parts by mass of 10% hydrochloric acid to 1000 parts by mass of water was used as a stirrer, CLEARMIX (M Technic Co., Ltd.). Was heated to 60 ° C. while stirring at a peripheral speed of 33 m / s. Next, the inside of the granulation tank was replaced with nitrogen, and the aqueous solutions of aluminum chloride and calcium chloride adjusted in tank B were added. Thereafter, stirring was continued for 30 minutes to obtain an aqueous medium 4 containing the inorganic fine particles 4.

  When the zeta potential of the obtained aqueous medium 4 at 70 ° C. (polymerization reaction temperature) was measured, Δt (zeta potential) = + 9.10 mV. The pH of the aqueous medium 4 was 5.2. Table 2 shows the physical properties of the obtained inorganic fine particles 4 and the pH of the aqueous medium 4.

(Production Examples 1 to 3 and 5 to 20 of inorganic fine particles and aqueous medium)
Except having changed the kind and content of each raw material as described in Tables 3 and 4, inorganic fine particles and aqueous media 1-3, 5-20 were produced in the same manner as the inorganic fine particles 4 and the aqueous medium 4. . Tables 3 and 4 show physical properties and the like of the obtained inorganic fine particles and aqueous media 1 to 3 and 5 to 20.

(Toner Production Example 1)
55 parts by mass of styrene Carbon black (trade name "Printex35" manufactured by Orion Engineered Carbons)
7 parts by mass, 0.25 parts by mass of charge control agent (manufactured by Orient: Bontron E-89)

The above material was charged into an attritor dispersing machine (Mitsui Miike Kakoki Co., Ltd.), and further dispersed using zirconia particles having a diameter of 1.7 mm at 220 rpm for 5 hours to obtain a colorant dispersion.

In the colorant dispersion,
20 parts by weight of styrene 25 parts by weight of n-butyl acrylate 5 parts by weight of polyester resin 1 Resin 1 having a sulfonic acid or a sulfonic acid salt group or a sulfonic acid ester
0.3 parts by mass. 9 parts by mass of Fischer-Tropsch wax (manufactured by Schumann Sazole, trade name “C80”: melting point: 83.0 ° C.) were added.

  The above material was kept at 65 ° C. in a separate container. K. Using a homomixer (manufactured by Tokushu Kika Kogyo), the mixture was uniformly dissolved and dispersed at 500 rpm. 2.5 parts by mass of a polymerization initiator t-hexyl peroxypivalate (trade name “Perhexyl PV”, manufactured by NOF Corporation, molecular weight: 202, 10-hour half-life temperature: 53.2 ° C.) was dissolved therein, A polymerizable monomer composition was prepared.

The polymerizable monomer composition was charged into the aqueous medium 4 in the granulation tank, 70 ° C., under N ₂ purge, T. K. The mixture was stirred with a homomixer at 10,000 rpm for 5 minutes and granulated at pH 5.2. Thereafter, the mixture was transferred to a polymerization tank, and the mixture was stirred at 30 times / minute with a paddle stirring blade at 70 ° C. for 6 hours (conversion rate was 95%), further heated to 90 ° C., and reacted for 2 hours.

  After the completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved with stirring at a pH of 2 by adding 10% hydrochloric acid for 2 hours. The emulsion is filtered under pressure and washed with 2,000 parts by mass or more of ion-exchanged water. The obtained cake is again returned to 1000 parts by mass of ion-exchanged water, and washed again while adding 2% hydrochloric acid to adjust the pH to 1 or less while stirring for 2 hours. In the same manner as described above, the emulsion was filtered under pressure, washed with 2,000 parts by mass or more of ion-exchanged water, sufficiently ventilated, dried and classified by wind to obtain black colored particles (toner particles 1).

  100 parts by mass of the obtained black colored particles, 1.5 parts by mass of hydrophobic silica 1 and 0.3 parts by mass of hydrophobic titanium oxide 1 were added, and the mixture was added using a Mitsui Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.). After mixing, a toner 1 having an external additive was obtained. Table 6 shows the physical properties and the like of Toner 1 thus obtained.

(Toner Production Examples 2 to 19, 22 to 69, 71 to 73)
Toners 2 to 19, 22 to 69, and 71 to 73 having external additives were produced in the same manner as in Toner Production Example 1 except that the types and contents of the respective raw materials were changed as described in Table 5. . Table 6 shows the physical properties and the like of the obtained toners 2 to 19, 22 to 69, and 71 to 73.

  At this time, the toner Nos. In which the styrene ratio in the polymerizable monomer shown in Table 5 was changed. With respect to 2 to 4, n-butyl acrylate was increased or decreased in accordance with the increase or decrease in styrene, so that the total of styrene and n-butyl acrylate was the same.

(Toner Production Example 20)
・ Styrene 60 parts by mass ・ Carbon black (trade name “Printex35” manufactured by Orion Engineered Carbons)
7 parts by mass, a charge control agent (manufactured by Orient: Bontron E-89) 0.25 parts by mass The above materials were charged into an attritor dispersing machine (Mitsui Miike Kakoki Co., Ltd.), and zirconia particles having a diameter of 1.7 mm were further used. The mixture was dispersed at 220 rpm for 5 hours to obtain a colorant dispersion.

In the colorant dispersion,
20 parts by mass of styrene 20 parts by mass of n-butyl acrylate 5 parts by mass of polyester resin 1 Resin 1 having a sulfonic acid or a sulfonic acid base and a sulfonic acid ester
0.3 parts by mass. 9 parts by mass of Fischer-Tropsch wax (manufactured by Schumann Sazole, trade name “C80”: melting point: 83.0 ° C.) were added.

  The above material was kept at 65 ° C. in a separate container. K. Using a homomixer (manufactured by Tokushu Kika Kogyo), the mixture was uniformly dissolved and dispersed at 500 rpm. 2.5 parts by mass of a polymerization initiator t-hexyl peroxypivalate (trade name “Perhexyl PV”, manufactured by NOF Corporation, molecular weight: 202, 10-hour half-life temperature: 53.2 ° C.) was dissolved therein, A polymerizable monomer composition was prepared.

The polymerizable monomer composition was charged into the aqueous medium 20 in the granulation tank, 70 ° C., under N ₂ purge, T. K. The mixture was stirred at 10,000 rpm for 5 minutes with a homomixer, and granulated at pH 5.3. Then, the mixture was transferred to a polymerization tank and stirred at 30 ° C./minute with a paddle stirring blade at 70 ° C. for 1.5 hours (conversion rate was 45%). The reaction was continued for an additional 4.5 hours. Thereafter, the temperature was further raised to 90 ° C., and the reaction was performed for 2 hours.

  After the completion of the polymerization reaction, the reaction vessel is cooled, and the dispersion stabilizer is dissolved with stirring at a pH of 2 by adding 10% hydrochloric acid for 2 hours. The emulsion is filtered under pressure and washed with 2,000 parts by mass or more of ion-exchanged water. The obtained cake is again returned to 1000 parts by mass of ion-exchanged water, and washed again while adding 2% hydrochloric acid to adjust the pH to 1 or less while stirring for 2 hours. In the same manner as described above, the emulsion was filtered under pressure, washed with 2,000 parts by mass or more of ion-exchanged water, sufficiently ventilated, dried, and air-classified to obtain black colored particles (toner particles 20).

  100 parts by mass of the obtained black colored particles, 1.5 parts by mass of hydrophobic silica 1 and 0.3 parts by mass of hydrophobic titanium oxide 1 were added, and mixed with a Mitsui Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.). Thus, a toner 20 having an external additive was obtained. Table 6 shows the physical properties and the like of the obtained toner 20.

(Toner Production Example 21)
As shown in Table 5, a toner 21 having an external additive was produced in the same manner as in Toner Production Example 20, except that the addition time of the aqueous medium 4 was changed at a conversion rate of 70%. Table 6 shows the physical properties and the like of the obtained toner 21.

(Toner Production Example 70)
A toner 70 having an external additive was produced in the same manner as in Toner Production Example 1 except that the styrene-acryl resin 1 was used instead of the polyester resin. Table 6 shows the physical properties and the like of the obtained toner 70.

<Confirmation of Influence of Inorganic Fine Particles on Amount of Polyester Resin on Toner Particle Surface>
In order to confirm the effect of the aluminum element ratio in the metal element constituting the inorganic fine particles, the methanol concentration and the aqueous medium 1 at a methanol wettability of 50% when toner particles were prepared using only the aqueous medium 20 were prepared. FIG. 3 is a graph showing the difference in methanol concentration between the toner particles 1 and 5 to 12 prepared from the toner particles No. 9 to No. 9 and the methanol wettability at a transmittance of 50%.

  The results in FIG. 3 suggest that the surface of the toner particles becomes more hydrophilic, that is, the polyester resin is distributed more on the surface of the toner particles as the ratio of the aluminum element in the metal element constituting the inorganic fine particles increases.

  FIG. 4 shows the result of confirming the effect of the ratio of the aluminum element in the metal element constituting the inorganic fine particles when the styrene-acryl resin 1 was used without using the polyester resin. It was suggested that even if the aluminum element was included in the metal element constituting the inorganic fine particles, there was no change and there was no effect.

[Examples 1 to 69]
Each of the toners 1 to 69 was evaluated for various images using an evaluator. Table 13 shows the evaluation results.

[Comparative Examples 1-4]
Each of the toners 70 to 73 was evaluated for various images using an evaluator. Table 13 shows the evaluation results.

  Various image evaluations were performed as follows.

<Fog>
For the measurement of fog, an endurance test was performed by using an evaluator described below as an image forming apparatus, and a durability test was performed in a system in which the printing was performed for 1 minute at a printing rate of 1% and the printing was stopped for 1 minute each time. After that, it was left in each environment for 6 days.

The fog amount of the first image sample was measured using REFECT METER MODEL TC-6DS manufactured by Tokyo Denshoku Co., Ltd., and calculated by the following equation. A4 size plain paper (GF-C081A4, manufactured by Canon Marketing Japan Inc.) was used as a recording material used in the durability test.
Fog amount (%) = (whiteness of recording material before printout) − (whiteness of non-image forming portion (white background) of recording material after printing)

<Image density>
The initial image density was measured under a normal temperature and normal humidity environment (N / N: temperature: 23.5 ° C., humidity: 60% RH), and the amount of toner applied on the paper was 0.38 (mg / cm ² ) using an evaluator described later. ) Was printed on one sheet, and the image density of each image was measured. The density of the image sample was measured using REFLECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. A4 size plain paper (GF-C081A4, manufactured by Canon Marketing Japan Inc.) was used as the recording material.

<Fusing or fixing toner to toner carrier and toner layer regulating member>
The fusion and fixation of the toner to the toner carrier and the toner layer regulating member are performed in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), and in a high temperature and high humidity environment (H / H: temperature). (32.5 ° C., humidity 80% RH) using a below-described evaluator. A durability test was carried out in a system in which printing was paused for 1 minute each time two sheets were printed at a printing rate of 1%, and the 8000th sheet of the image sample from the beginning was visually evaluated. A4 size plain paper (GF-C081A4, manufactured by Canon Marketing Japan) was used as a recording material. The evaluation criteria are shown below.

<Filming to latent image carrier>
Filming on the latent image carrier is performed in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), and in a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH). The durability test was performed by continuous printing at a printing rate of 1% using an evaluator described later. From the initial stage, the 2000th image sample of durability was visually evaluated. A4 size plain paper (GF-C081A4, manufactured by Canon Marketing Japan) was used as a recording material. The evaluation criteria are shown below.

<Evaluation of storage stability of toner>
To evaluate the storage stability of the toner, 10 g of the toner was weighed into a 100 ml polycup, left in a constant temperature layer at 50 ° C. and 55 ° C. for 3 days, and then evaluated by a 200-mesh (mesh opening) sieve. As a measuring device, a powder tester (manufactured by Hosokawa Micron Corporation) having a digital vibrometer (manufactured by DEGIVAL VIBRATIONMETERMODEL 1332 SHOWA SOKKI CORPORATION) was used.

  As a measuring method, a toner for evaluation was put on a 200-mesh sieve (opening: 75 μm), and the displacement value of the digital vibrometer was adjusted to 0.50 mm (peak-to-peak) for 30 seconds. Vibration was applied. Thereafter, the storage stability was evaluated from the state of the aggregate of the toner remaining on each sieve. The evaluation criteria are shown below.

<Fixing property>
Under a low-temperature and low-humidity environment (L / L: temperature 10 ° C., humidity 10% RH), using an evaluator described later, a state in which the machine and the cartridge filled with the toner are adapted to the environment (after being left in the environment for 24 hours). Turned on. Immediately after the weight-up, a horizontal line pattern having a width of 200 μm (width 200 μm, interval 200 μm) was printed out, and the 50th printed image was used for evaluation of fixability. The fixing property was evaluated by rubbing the image with a 100-g load in 5 reciprocations on a silk-bon paper, and evaluating the peeling of the image by the average of the reflection density reduction rate (%).

  Bond paper having a surface smoothness of 10 [sec] or less was used for the evaluation. The evaluation criteria are shown below.

<Decrease in image density>
Under normal temperature and normal humidity environment (N / N: temperature 25 ° C., humidity 60% RH) and high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 85% RH), the cartridge filled with the toner is loaded. After standing for 2 weeks, an endurance test was carried out using an evaluator to be described later, in which the printing was stopped for 1 minute every time two sheets were printed at a printing rate of 2%. From the initial stage, the 10,000th image sample of durability was visually evaluated. A4 size plain paper (GF-C081A4, manufactured by Canon Marketing Japan) was used as a recording material. The evaluation criteria are shown below.

(Evaluation machine)
The process speed of a commercially available LBP-2710 (manufactured by Canon Inc.) was modified to 220 mm / s, the toner was extracted from a commercially available magenta cartridge, and the inside was cleaned with an air blow. Thereafter, 260 g of the toner of the present invention was filled, and the other cyan, yellow and black cartridges were used after removing the toner and inserting the cartridges into the respective stations.

Claims (5)

A granulating step of forming particles of a polymerizable monomer composition containing a polymerizable monomer and a polyester resin in an aqueous medium, and the polymerizable monomer contained in the particles of the polymerizable monomer composition; A polymerization step of obtaining the toner particles by polymerizing the monomer, and
Having a step of obtaining inorganic fine particles by mixing a phosphate aqueous solution and an aqueous solution of an aluminum compound,
Aqueous medium in the polymerization step, it contains the inorganic fine particles containing elemental aluminum, the proportion of aluminum element of the metal element that constitutes the inorganic fine particles is less than 5.0atm% 70.0atm% A method for producing toner particles. The method for producing toner particles according to claim 1, wherein the polyester resin has an isosorbide unit represented by the following formula (1).

  3. The method for producing toner particles according to claim 1, wherein the polyester resin has an acid value of 1.0 mgKOH / g or more and 30.0 mgKOH / g or less.   The method for producing toner particles according to any one of claims 1 to 3, wherein in the polymerization step, the pH of the aqueous medium is adjusted to 3.0 or more and 6.0 or less. The method for producing toner particles according to any one of claims 1 to 4 , wherein the inorganic fine particles are contained in the aqueous medium in the granulating step.

Images