JP6028584B2 - Method for producing toner for developing electrostatic image - Google Patents

Description

  The present invention relates to a method for producing a toner for developing an electrostatic charge image that is suitably used for a copying machine, a printer, a fax machine, and the like, and further used for a toner jet type printer.

  In recent years, in copiers, printers, fax machines, etc., in order to further improve the quality of printed images, or to reduce the cost, size, power consumption, and resources of machines, Improved resolution and gradation of printed images by reducing particle size, thinning toner layer, reducing waste toner amount, reducing toner consumption per page, (2) by lowering fixing temperature Reduction of power consumption, (3) Simplification of machine by oilless fixing, (4) Improvement of hue, transparency and gloss in full color image, (5) Hazardous VOC (volatile organic compound) at fixing of toner Reduction is required.

  In particular, with color toners in which cyan pigments, magenta pigments, yellow pigments or other chromatic pigments or dyes are dispersed in a binder, the printed image has vivid color developability and multicolor printing was performed. It has excellent transparency in color superposition and has clear color reproducibility without color turbidity, or enables printing with resolution and gradation equivalent to offset printing. There is a need for print image characteristics.

  Against this background, toners that are excellent in resolution, gradation, and color development of printed images can be obtained, and toners (hereinafter referred to as chemical toners) based on polymerization methods and emulsion dispersion methods have been actively developed. It was. In particular, the emulsification dispersion method can easily cope with the reduction in the particle size and spheroidization of the toner, and in addition to the polymerization method, 1) the selection range of the binder resin is widened, and 2) the residual monomer is reduced. 3) It is advantageous in that the concentration of the organic pigment or the like can be arbitrarily changed from a low concentration to a high concentration, and is also advantageous in the production of a color toner.

As an example of such a production method, as a technique particularly effective for reducing the particle size and spheroidizing of a toner, for example, a binder resin is dissolved in an organic solvent, and then an aqueous medium is added and emulsified to transfer to a room temperature level. A so-called coalescence method is known in which an emulsifier and an electrolyte are added under the temperature conditions to coalesce the dispersed particles to obtain particles having a predetermined particle size, and then the organic solvent is removed and dried to produce a toner. (See Patent Document 1 below).
However, although the method described in Patent Document 1 is effective for reducing the particle size and spheroidization of the finally obtained toner particles, a large amount of emulsifier is required and sufficient charging characteristics of the toner cannot be obtained. In addition, a neutralization step is required, and when neutralizers are removed, or when a strong alkali such as caustic soda is used, a reverse neutralization step is further required and the process is complicated and inferior in productivity. The printed material was inferior in gloss and inferior in gloss.
In addition, as a technique for producing a toner having a narrow particle size distribution with easy control of the toner particle size, a polyester having a sodium sulfonate group is dispersed in water in a solvent-free state, an alkali halide is added, and the toner is aggregated by heating. A manufacturing technique is known (Patent Document 2 below).
However, according to such a technique, although toner particles having a small particle size and a small particle size distribution can be obtained, in addition to inferior electric resistance characteristics of the toner, irregularly shaped toner particles other than true spheres are easily generated, and the gloss of the printed image is also obtained. Therefore, high quality printed matter could not be obtained.

Japanese Patent No. 4247669 Japanese Patent No. 4068250

  Therefore, the problem to be solved by the present invention is that the generation of irregular shaped particles can be suppressed, and a chemical toner close to a true sphere can be produced industrially with high productivity, and the obtained toner is remarkably excellent in charging characteristics and gloss of printed matter. Another object of the present invention is to provide a novel method for producing a toner for developing an electrostatic image.

  As a result of extensive research, the present inventors have dissolved or dispersed a polyester resin having a sulfonic acid metal group in the resin structure in an organic solvent, added an aqueous medium, transferred emulsion, and united fine particles by adding an electrolyte. This makes it possible to obtain a chemical toner with a small particle size, a small particle size distribution, and close to a true sphere, and with excellent charging characteristics and quality of printed matter, but its industrial productivity. The present invention has been completed by finding that the production method is excellent.

  That is, the present invention comprises (i) a step of producing a resin solution or a resin dispersion by dissolving or dispersing a polyester resin having a sulfonic acid metal group in a resin structure in an organic solvent, and (ii) using the resin solution as an aqueous medium. A step of producing a suspension in which fine particles of the resin solution or resin dispersion are suspended in the aqueous medium by mixing, and then (iii) adding an electrolyte under a temperature condition of 30 ° C. or lower. The step of forming a unity of the fine particles, (iv) removing the unitary organic solvent, and (v) separating the unity from the aqueous medium and drying are sequentially performed. The present invention relates to a method for producing a toner for developing a charge image.

  According to the present invention, the generation of irregularly shaped particles can be suppressed, and a chemical toner close to a true sphere can be produced industrially with high productivity, and the resulting toner can be remarkably excellent in charging characteristics and gloss of printed matter. A method for producing a toner for developing an electrostatic image can be provided.

The present invention will be described in detail below. In the production method of the present invention, the following steps are essential production steps.
Resin solution adjustment step: A polyester resin contained in a resin structure having a sulfonic acid metal group is dissolved or dispersed in an organic solvent to produce a resin solution or a resin dispersion [step (i)].
Emulsification step: Next, an aqueous medium is added to the resin solution or resin dispersion to form a suspension (fine particles) of the resin solution in the aqueous medium [step (ii)].
Coalescence step: An electrolyte is sequentially added to the aqueous medium under a temperature condition of 30 ° C. or less to form a coalescence of fine particles in the suspension [step (iii)].
Separation / drying step: Thereafter, the organic solvent in the coalescence is removed [step (iv)], and then the coalescence after desolvation is separated from the aqueous medium and dried to produce a toner [step (v) ]].

  In the present invention, aggregating and integrating the fine particles of the resin solution containing the organic solvent generated in the step (ii) is referred to as “unification”, and the step (iii) is referred to as “unification step”. Say. Further, the particles formed by the step (iii) are referred to as “integrated”. Furthermore, a method for producing toner through a coalescence process is referred to as a “manufacturing method”.

  In the step (i), a resin solution containing a polyester resin and an organic solvent is prepared by charging or dissolving or dispersing the polyester resin in an organic solvent. In this case, if necessary, a wax component, a colorant, or other additives can be used together with a polyester resin or the like, but any of them needs to be finely dispersed or dissolved below the toner particle size.

  As a means for dissolving or dispersing the polyester resin and various additives such as a wax component and a colorant which are added to the organic solvent as necessary, the following method is preferably used.

  1) A mixture containing various additives such as the above polyester resin, wax component, colorant, etc. is heated above the softening point of the resin used by using a pressure kneader, a heated two-roll, two-screw extrusion kneader, etc. Heat to a temperature below the decomposition temperature and knead. Thereafter, the kneaded chips obtained are dissolved or dispersed in an organic solvent by a stirrer such as a desper or a disperser using media. Alternatively, 2) Various additives such as a polyester resin, a wax component, and a colorant are mixed with an organic solvent, and these are wet kneaded with a high-speed stirrer such as a desper or a ball mill to produce a resin solution or a resin mixture. be able to.

  Among the above 1) and 2), the production method 2) is particularly preferable because the polymer component (gel component) of the polyester resin is not cut, and particularly when produced by the method 2), the polyester resin and the organic solvent. And a wax solution in which a wax component is mixed with a polyester resin or an organic solvent in advance, while a colorant is prepared by melting and kneading a pigment and a polyester resin to adjust a colorant master chip, It is preferable to use a mixture of these in step (ii) from the point that each component becomes fine particles by emulsification.

  Examples of the organic solvent for dissolving or dispersing the polyester resin include hydrocarbons such as pentane, hexane, heptane, benzene, toluene, xylene, cyclohexane, petroleum ether; methylene chloride, chloroform, dichloroethane, dichloroethylene, trichloroethane, trichloroethylene, Halogenated hydrocarbons such as carbon tetrachloride; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate and butyl acetate are used. These solvents can be used in combination of two or more, but from the viewpoint of solvent recovery, it is preferable to use the same type of solvent alone. The organic solvent dissolves or disperses the polyester resin, preferably has a low boiling point and has a relatively low toxicity and is easy to remove the solvent in a subsequent process. As such a solvent, methyl ethyl ketone is most preferable.

  Next, in step (ii), which is an emulsification step, a suspension (fine particles) of the resin solution is added to the aqueous medium by adding the aqueous medium to the resin solution or resin dispersion obtained in step (i). Let it form. In this case, the resin solution prepared by the above method may be mixed with an aqueous medium in the presence of a basic neutralizing agent and emulsified, but in the present invention, substantially without using a neutralizing agent, The toner can be emulsified, so that the charging characteristics of the finally obtained toner can be dramatically improved. Specifically, the step (ii) is preferably a method in which an aqueous medium (water or a liquid medium containing water as a main component) is gradually added to the resin solution or resin dispersion. In that case, by gradually adding water to the organic continuous phase of the mixture, a discontinuous phase of water-in-oil is formed, and by adding additional water, oil-in-water is added. In this way, a suspension / emulsion is formed in which the mixture floats as particles (droplets) in an aqueous medium (hereinafter, this method is referred to as “phase inversion emulsification”).

  In phase inversion emulsification, water is added so that the ratio of water to the total amount of the organic solvent and added water is 30 to 80% by mass. More preferably, it is 35-70 mass%, and it is especially preferable that it is 40-70 mass%. The aqueous medium used is preferably water, more preferably deionized water.

  As described above, the polyester resin used in the present invention is a polyester resin having a sulfonic acid metal base and has self-water dispersibility. Here, the abundance of the sulfonic acid metal base is such that the strength [S / Kα] of the sulfur atom when the polyester resin is measured by fluorescent X-ray analysis is in the range of 0.030 to 0.090. It is preferable from the viewpoint that phase inversion emulsification in ii) is easy, dispersibility is good, toner particle size is reduced and sphericity is good, and printed matter having excellent gloss can be obtained. . Here, although a salt structure site such as a sulfonic acid metal base usually lowers the charging characteristics of the final toner, the present invention exhibits excellent emulsification stability while maintaining excellent emulsion stability. It should be noted that it does not have any negative effect on the charging characteristics.

This phase inversion emulsification can be performed by homomixer (Special Machine Industries Co., Ltd.), Thrasher (Mitsui Mining Co., Ltd.), Cavitron (Eurotech Co., Ltd.), Microfluidizer (Mizuho Industry Co., Ltd.), Menton Gorin homogenizer (Gorin Inc.) ), Nanomizer (Nanomizer Co., Ltd.), Static Mixer (Noritake Company), etc., high-share emulsifying disperser, continuous emulsifying disperser, agitator as disclosed in JP-A-9-114135, and anchor blade , Turbine mixer, fouller blade, full zone blade, max blend blade, meniscus blade and the like.
Among these, a stirring apparatus as disclosed in JP-A-9-114135, a stirring mixer having an anchor blade, a turbine blade, a fiddler blade, a full zone blade, a max blend blade, a meniscus blade, etc. From the viewpoint of uniformity, it is preferable to use a stirrer / mixer having large blades having excellent uniform mixing properties such as Max Blend blades and full zone blades.

  When using a stirring mixer having a large blade, the peripheral speed of the stirring blade in the emulsification step (phase inversion emulsification step) for forming fine particles of the mixture in the aqueous medium is in the range of 0.2 to 10 m / s. It is preferable that water is dripped while stirring at a low shear of less than 0.2 to 8 m / s. Especially preferably, it is the range of 0.2-6 m / s. When the peripheral speed of the stirring blade is faster than 10 m / s, the dispersion diameter during phase inversion emulsification tends to be large. On the other hand, if the peripheral speed is lower than 0.2 m / s, the stirring is not uniform, phase inversion is likely to be uneven, and coarse particles tend to be generated. Moreover, the temperature at the time of phase inversion emulsification is not particularly limited, but is not preferable because the higher the temperature, the more coarse particles are generated. On the other hand, when the temperature is too low, the viscosity of the mixture containing the polyester resin and the organic solvent is increased, and the generation of coarse particles is increased, which is not preferable. Therefore, the specific temperature range during phase inversion emulsification is preferably in the range of 10 to 40 ° C, particularly preferably in the range of 15 to 30 ° C.

  The peak volume particle size of the fine particles of the resin solution produced in the emulsification step is in the range of 1 μm to 5 μm, more preferably in the range of 1 μm to 3 μm, so that the particle size of the toner finally obtained can be reduced. At the same time, it is preferable from the viewpoint that the colorant in the toner and the encapsulation of the wax component with the polyester resin can be satisfactorily and a toner excellent in charging characteristics and emulsification characteristics can be obtained. The particle size distribution of the fine particles of the colored resin solution produced in the emulsification step is such that the volume particle size ratio of 10 μm or more is 1% or less, more preferably 0.5% or less, and the volume particle size ratio of 5 μm or more is It is preferably 3% or less, more preferably 1% or less.

  Next, the coalescing step is a step in which the fine particles of the resin solution obtained in the emulsification step are coalesced to generate coalesced particles and form toner particles having a desired particle diameter.

  In this coalescence step, the dispersion of fine particles obtained in the emulsification step is diluted with water to adjust the amount of solvent, and coalescence is advanced by dropping an aqueous electrolyte solution under a temperature condition of 30 ° C. or less. This is a step of obtaining an aggregate having a particle size.

  The fine particles obtained in the emulsification step, which is the previous step, are stably dispersed in the aqueous medium by the action of the electric double layer by the carboxylate. In the coalescing step, the particles are destabilized by adding an electrolyte that destroys or reduces the electric double layer to the aqueous medium in which the fine particles are dispersed.

  Examples of the electrolyte that can be used here include acidic substances such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and oxalic acid. In addition, organic and inorganic water-soluble salts such as sodium sulfate, ammonium sulfate, potassium sulfate, magnesium sulfate, sodium phosphate, sodium dihydrogen phosphate, sodium chloride, potassium chloride, ammonium chloride, calcium chloride, sodium acetate, etc. It can be used effectively as an electrolyte. These electrolytes may be used alone or in combination of two or more substances. Among them, monovalent cation sulfates such as sodium sulfate and ammonium sulfate are preferable for promoting uniform coalescence. In the production method of the present invention, the fine particles obtained in the emulsification step are swollen by a solvent, and the electric double layer of the particles is in an unstable state due to the addition of an electrolyte, so that the low shear (low shear) The coalescence easily proceeds even when the particles collide with each other by the agitation of force.

In such a coalescence process, a small amount of an inorganic dispersion stabilizer such as hydroxyapatite or an ionic or nonionic surfactant is used as a dispersion stabilizer and is added to the system in advance before adding the electrolyte. Alternatively, a dispersion stabilizer may be added into the system together with the aqueous electrolyte solution.
Examples of the dispersion stabilizer that can be used here include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester. , Polyoxyethylene sorbitan fatty acid esters and the like, or various nonionic emulsifiers such as pluronics, alkyl sulfate ester type anionic emulsifiers, and quaternary ammonium salt type cationic dispersion stabilizers. Among these, even if an anion type or nonionic type dispersion stabilizer is added in a small amount, the dispersion stability of the system is effective, which is preferable. The cloud point of the nonionic surfactant is preferably 40 ° C. or higher. The surfactants described above may be used alone or in combination of two or more.

By using the above-mentioned dispersion stabilizer, the dispersion stability of the fine particles in the system is further improved. However, if the amount used is increased, the charging characteristics of the toner are lowered and the pigment dispersibility is also lowered. It becomes. In the present invention, since the resin polyester resin itself has excellent dispersibility in the emulsification step, even when this dispersion stabilizer is used, the amount used can be kept low. Specifically, the amount of the dispersion stabilizer used is preferably in the range of 0.25% by mass or less with respect to the solid content of the fine particles, and the effect of improving the dispersion stability by using the dispersion stabilizer is recognized. In particular, the range of 0.1 to 0.25% by mass is preferable.
When using a dispersion stabilizer, as described above, it may be added to the system in advance before adding the electrolyte, or a dispersion stabilizer may be added to the system together with the electrolyte aqueous solution. From the viewpoint of easily improving the property, it is desirable to add the electrolyte in advance before adding the electrolyte, and then drop the electrolyte aqueous solution.

  The stirring conditions in the coalescence step are preferably performed under the same conditions as described above for the type of stirring blade and the stirring conditions in the emulsification step, from the point that uniform unity is obtained.

  In the case of producing a unity, it is preferable to further dilute the fine particle dispersion obtained by phase inversion emulsification in the emulsification step with water. The amount of the solvent contained in the system before adding the electrolyte is preferably in the range of 15 to 45% by mass. If the amount of the solvent is 15% by mass or more, it is possible to reduce the electrolytic mass required for coalescence, and if the amount of the solvent is 45% by mass or less, the obtained unity has good uniformity. . The amount of the solvent is more preferably in the range of 18 to 30% by mass, and particularly preferably in the range of 20 to 25% by mass from the point that such an effect becomes remarkable.

  Moreover, it is preferable that the quantity of the electrolyte to be used exists in the range of 0.5-15 mass% with respect to solid content content of microparticles | fine-particles. It is more preferably within a range of 1 to 12% by mass, and particularly preferably within a range of 1 to 10% by mass. When the amount of the electrolyte is less than 0.5% by mass, the coalescence does not proceed sufficiently, which is not preferable. On the other hand, when the amount of the electrolyte is more than 15% by mass, coalescence becomes non-uniform, and aggregates and coarse particles are likely to be generated, resulting in a decrease in yield.

  Moreover, the temperature at the time of a coalescence process is 30 degrees C or less. When the temperature is higher than 30 ° C., the coalescence speed is increased, and aggregates and coarse particles are easily generated. In addition, when the coalescence temperature is low, coalescence is difficult to proceed, and therefore, it is particularly preferably in the range of 10 ° C to 30 ° C.

  Here, in order to maintain the frictional charging performance of the toner satisfactorily, it is effective to prevent the colorant from being exposed on the surface of the toner particles, that is, to have a toner structure in which the colorant is included in the toner particles. It is. The deterioration in chargeability associated with the reduction in the particle size of the toner is caused by part of the colorant and other additives (usually wax components) contained being exposed on the toner particle surface. That is, even when the content (% by mass) of the colorant and the like is the same, the surface area of the toner particle is increased by reducing the particle size, and the ratio of the colorant and the wax component exposed on the toner particle surface is increased. As a result, the composition of the toner particle surface changes greatly, and the frictional charging performance of the toner particles changes greatly, making it difficult to obtain an appropriate chargeability.

  The toner particles produced according to the present invention are characterized in that a colorant, a wax component and the like are encapsulated in a polyester resin. Whether the colorant, the wax component or the like is not exposed on the toner particle surface can be easily determined by observing the cross section of the particle with a TEM (transmission electron microscope), for example. More specifically, the cross section of the toner particles embedded in the resin and cut with a microtome is dyed with ruthenium oxide or the like, if necessary, and is observed with a TEM. It can be confirmed that the particles are uniformly dispersed.

  The unitary shape obtained in the uniting process can be changed from an indeterminate shape to a sphere depending on the degree of uniting, but the spherical shape of the toner that can be finally simmered is highly spherical. It is preferable from the point of becoming high.

  Next, the separation / drying step removes the organic solvent in the coalescence obtained in the coalescence step [step (iv)], and then separates the coalescence after desolvation from the aqueous medium and drys it. It comprises a step of producing a toner [step (v)].

  Here, examples of the solvent removal step of step (iv) include a method of solvent removal in which the unity is performed under normal pressure or reduced pressure. In order to remove the solvent quickly under a low temperature condition, it is preferably carried out under reduced pressure.

  Next, as a step (v), the combined solvent after solvent removal is separated from the aqueous medium and dried. Separation from the aqueous medium can be performed by a known and commonly used means such as a centrifugal separator, a filter press, a belt filter or the like. The desired toner particles can then be obtained by drying the particles. Toner particles produced using an emulsifier or a dispersion stabilizer are preferably washed more thoroughly.

  As the drying method, any known and commonly used method can be employed. For example, a method in which the toner particles are dried at normal or reduced pressure at a temperature at which the toner particles are not thermally fused or agglomerated, a method of freeze-drying, and the like. It is done. Another example is a method of simultaneously separating and drying toner particles from an aqueous medium using a spray dryer or the like. In particular, a method in which powder is stirred and dried under reduced pressure while heating at a temperature at which toner particles are not thermally fused or agglomerated, or a flash jet drier that instantly dries using a heated and dried air stream (Seishin Corporation) Etc.) is efficient and preferable.

  Regarding the particle size distribution of the toner obtained by the production method of the present invention, 50% volume particle size / 50% number particle size is 1.25 or less as measured by Multisizer TAII type (aperture tube diameter: 100 μm) manufactured by Coulter. It is preferable that there is, and more preferably 1.20 or less. It is preferable that it is 1.25 or less because good images can be easily obtained. Moreover, GSD is preferably 1.30 or less, and more preferably 1.25 or less. The GSD is a value obtained from the square root of (16% volume particle size / 84% volume particle size) as measured by a multisizer TAII type manufactured by Coulter. The smaller the GSD value, the sharper the particle size distribution and the better the image.

  The toner obtained by the production method of the present invention preferably has a volume average particle size in the range of 1 to 13 μm from the viewpoint of image quality to be obtained, and about 3 to 10 μm is matched with the current machine. It is more preferable because it is easy to obtain. For a color toner, a range in which the volume average particle diameter is 3 to 8 μm is preferable. When the volume average particle size is reduced, not only the gloss of the printed material is improved, but also the effect that the thickness of the toner layer for forming the printed image is reduced and the toner consumption per page is reduced is exhibited.

  Further, the average circularity of the finally obtained toner is preferably higher. Specifically, the average circularity is 0.97 or more, particularly 0.98 or more. This is preferable from the viewpoint of improving efficiency and improving gloss of printed matter. In particular, as the particle size decreases, the difference in terms of powder flowability, transfer efficiency, and toner consumption increases between spherical and irregular shapes.

  Here, the average circularity is a value obtained by image analysis and calculation of the finally obtained toner particles using a flow type particle image analyzer “FPIP-1000” manufactured by Toa Medical Electronics Co., Ltd. Can be determined as follows.

  First, a sample is prepared by suspending toner particles in water containing a small amount of a surfactant. Next, this sample is allowed to flow down into a transparent and flat cell provided in the flow type particle image analyzer “FPIP-1000”. A light source that emits pulsed light is installed on one side of the cell, and an imaging camera is provided on the opposite side of the cell so as to face the light source. The toner particles in the sample flowing down the cell of “FPIP-1000” are captured as a still image by the camera facing the light source with the pulse light irradiated by the pulse light.

Based on the image of the toner particle thus captured, the contour of each toner particle is extracted by the image analysis device, and the projected area and peripheral length of the toner particle image (peripheral length of the toner particle projected image) are calculated. The Further, from the calculated projected area of the toner particle image, the circumference of a circle having the same area (the circumference of the circle having the same area as the toner particle projected area) is calculated.
The average circularity in the present invention is obtained by dividing the circumference of a circle having the same area as the toner particle projection area thus calculated by the circumference of the toner particle projection image.

The conditions for measurement with the above apparatus are as follows.
(1) Preparation of toner particle suspension
0.1 g of surfactant (ELCLEAR (manufactured by Chugai Photo Chemical Co., Ltd.)) is added to 20 g of water, 0.04 g of toner as a sample is further added, and the toner particles are suspended in water with an ultrasonic disperser. Make it cloudy.
(2) Measurement conditions Measurement temperature: 25 ° C
Measuring humidity: 60%
Number of measured toner particles: 5000 ± 2000

  The binder resin used in the present invention is a polyester resin having a sulfonic acid metal group in the resin structure. In the present invention, as described above, the sulfonic acid metal base has a sulfur atom strength [S / Kα] in the range of 0.030 to 0.080 when the polyester resin is measured by fluorescent X-ray analysis. It is preferable from the viewpoint of excellent emulsification stability in the emulsification step, a toner having few irregular shaped particles and high average circularity, and excellent glossiness in printed matter. Such a polyester resin is, for example, a metal sulfonate. An aromatic dicarboxylic acid having a group or a dialkyl ester thereof can be used as a raw material acid component, and a divalent aliphatic diol can be used as a raw material alcohol component. By using a divalent aliphatic diol as the raw material alcohol component, not only the average circularity of the toner is improved, but the compatibility between the polyester resin and the wax component is improved, and the offset resistance is improved. Moreover, fixing property at low temperature is improved by softening the polyester main chain.

  The aromatic dicarboxylic acid having a sulfonic acid metal group or dialkyl ester thereof which can be used as a raw material for the polyester resin is specifically 2-sulfoterephthalic acid sodium salt, 2-sulfoterephthalic acid potassium salt, 2 -Sulfoterephthalic acid lithium salt, terephthalic acid dimethyl-2-sulfonic acid sodium salt, terephthalic acid dimethyl-2-sulfonic acid potassium salt, terephthalic acid dimethyl-2-sulfonic acid lithium salt, terephthalic acid diethyl-2-sulfonic acid sodium salt , Terephthalic acid diethyl-2-sulfonic acid potassium salt, terephthalic acid diethyl-2-sulfonic acid lithium salt, terephthalic acid dibutyl-2-sulfonic acid sodium salt, terephthalic acid dibutyl-2-sulfonic acid potassium salt, terephthalic acid dibutyl-2 -Sulfo Sulfoterephthalic acid alkali metal salts such as lithium acid salts and C1-4 alkyl esters thereof; 5-sulfoisophthalic acid sodium salt, 5-sulfoisophthalic acid potassium salt, 5-sulfoisophthalic acid lithium salt, isophthalic acid dimethyl-5-sulfone Acid sodium salt, isophthalic acid dimethyl-5-sulfonic acid potassium salt, isophthalic acid dimethyl-5-sulfonic acid lithium salt, isophthalic acid diethyl-5-sulfonic acid sodium salt, isophthalic acid diethyl-5-sulfonic acid potassium salt, isophthalic acid Sulfo-5-sulfonic acid lithium salt, isophthalic acid dibutyl-5-sulfonic acid sodium salt, isophthalic acid dibutyl-5-sulfonic acid potassium salt, isophthalic acid dibutyl-5-sulfonic acid lithium salt, etc. So C1-4 alkyl ester; sulfosuccinic acid sodium salt, sulfosuccinic acid potassium salt, sulfosuccinic acid lithium salt, sulfosuccinic acid dioctyl sodium salt, sulfosuccinic acid dioctyl potassium salt, sulfosuccinic acid dioctyl lithium salt, sulfosuccinic acid diethylhexyl sodium salt, sulfosuccinic acid diethylhexyl Examples thereof include alkaline metal salts of sulfosuccinic acid such as potassium salt and diethylhexyl lithium succinate, and alkyl esters thereof.

  In the present invention, alkali sulfonates such as alkali metal sulfoterephthalate and its C1-4 alkyl ester, sulfoisophthalic acid alkali metal salt and its C1-4 alkyl ester, etc., are particularly excellent in emulsification stability in the emulsification process. An aromatic dicarboxylic acid containing a metal salt or a C1-4 alkyl ester thereof is preferable, and in particular, a sulfoisophthalic acid alkali metal salt and a C1-4 alkyl ester thereof have a sharp particle size distribution and an average circularity. This is preferable because a high toner can be obtained.

  On the other hand, the divalent aliphatic alcohol is, for example, 1,4-cyclohexanedimethanol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, Neopentyl glycol, butanediol, pentanediol, hexanediol, polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide random copolymer diol, ethylene oxide-propylene oxide block copolymer diol, ethylene oxide-tetrahydrofuran copolymer Diols such as diol and polycaprocactone diol are listed. Among these, an alkanediol having 2 to 6 carbon atoms is preferable from the viewpoint that a polyester resin finally obtained is excellent in solvent solubility and easily obtains a toner having a high average circularity, and 1,2-propane is particularly preferable. Diols are preferred from the point that the effect becomes remarkable.

  In the present invention, as a raw material component, in addition to each of these components, a polyester resin obtained by using a trifunctional or higher polyfunctional carboxylic acid, an anhydride or an ester thereof, or a trihydric or higher polyhydric alcohol in combination. This is preferable because the degree of crosslinking increases, the molecular weight increases moderately, and the hot offset is good while maintaining excellent low-temperature fixing.

  Here, the trifunctional or higher polyfunctional carboxylic acid, its anhydride, or its ester includes trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, or alkyl esterified products thereof.

  On the other hand, trihydric or higher polyhydric alcohols include sorbitol, 1,2,3,6-hexanetetraol, 1,4-sorbitan, pentaerythritol, 1,2,4-butanetriol, 1,2,5- Examples include pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trimethylolbenzene.

  Among these trivalent or higher raw material components, trimellitic anhydride is preferable in terms of particularly improving the degree of crosslinking and improving the glass transition point of the resulting resin.

  In the present invention, in addition to the above-described components as the raw acid component of the polyester resin, other polybasic acid compounds within the range not impairing the effects of the present invention, or for the purpose of adjusting to the desired sulfonic acid metal salt amount May be used. Examples of the polybasic acid compound include phthalic anhydride, terephthalic acid, orthophthalic acid, adipic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, cyclohexane. Examples thereof include dicarboxylic acids such as dicarboxylic acid, succinic acid, malonic acid, glutaric acid, azelaic acid, and sebacic acid, or derivatives or esterified products thereof.

   When manufacturing the said polyester resin, you may use a polyvalent epoxy compound together as a crosslinking agent. Examples of such polyvalent epoxy compounds include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, ethylene glycol diglycidyl ether, hydroquinone diglycidyl ether, N, N-diglycidyl aniline, glycerin tri Glycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, pentaerythritol tetraglycidyl ether, tetrakis 1,1,2,2 (p-hydroxyphenyl) ethane tetraglycidyl ether, cresol novolac type epoxy resin, phenol novolak Type epoxy resin, polymer or copolymer of an epoxy group-containing vinyl compound, epoxidized resorcinol-acetone condensate Partially epoxidized polybutadiene, polymers of vinyl compounds having an epoxy group, or a copolymer, semi-drying or drying fatty acid ester epoxy compound, and the like.

  Among the epoxy compounds used as the crosslinking agent described above, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, glycerin triglycidyl ether, trimethylolpropane Triglycidyl ether, trimethylolethane triglycidyl ether, and pentaerythritol tetraglycidyl ether are more preferably used.

  Specifically, DIC Corporation's Epicron 850, Epicron 1050, Epicron 2055, Epicron 3050, etc. are examples of bisphenol A type epoxy resins, and DIC Corporation's Epicron 830, Epicron 520 are examples of bisphenol F type epoxy resins. Etc., as examples of orthocresol novolac type epoxy resins, Epicron N-660, N-665, N-667, N-670, N-673, N-680, N-690, N-695, etc. manufactured by DIC Corporation However, examples of the phenol novolac type epoxy resin include DIC Corporation Epicron N-740, N-770, N-775, N-865, and the like. Examples of the polymer or copolymer of a vinyl compound having an epoxy group include a homopolymer of glycidyl (meth) acrylate, an acrylic copolymer, and a copolymer with styrene.

  Moreover, the said epoxy compound can also be used in combination of 2 or more types, Furthermore, you may use a monoepoxy compound together as a modifier | denaturant of resin. Examples of the monoepoxy compound include phenyl glycidyl ether, alkylphenyl glycidyl ether, alkyl glycidyl ether, alkyl glycidyl ester, glycidyl ether of alkylphenol alkylene oxide adduct, α-olefin oxide, monoepoxy fatty acid alkyl ester, and the like.

  By using these monoepoxy compounds in combination, fixability and resistance to offset at high temperatures are improved. Among these, alkyl glycidyl esters are particularly preferably used. Specific examples include neodecanoic acid glycidyl ester (Cardura E; manufactured by Shell Japan).

  The polyester resin used in the present invention can be obtained, for example, by performing a dehydration condensation reaction or a transesterification reaction in the presence of a catalyst using the above raw material components. The reaction temperature and reaction time at this time are not particularly limited, but are usually 150 to 300 ° C. and 2 to 24 hours.

  As a catalyst for performing the above reaction, for example, tetrabutyl titanate, zinc oxide, stannous oxide, dibutyltin oxide, dibutyltin dilaurate, paratoluenesulfonic acid, and the like can be used as appropriate.

  The glass transition temperature (Tg) of the polyester resin used in the present invention is preferably 50 to 85 ° C., among which the Tg of 55 to 75 ° C. is particularly preferable. When the Tg is lower than 50 ° C., a blocking phenomenon (thermal aggregation) tends to occur when the toner is stored, transported, or exposed to a high temperature inside the developing device of the machine. If it is higher than 85 ° C., the low-temperature fixability is lowered, which is not preferable.

  Moreover, as a softening point of the polyester resin used for this invention, the thing of the range of 90 degreeC or more, especially 90 degreeC-180 degreeC is preferable, More preferably, it is the range of 95 degreeC-160 degreeC. When the softening point is less than 90 ° C., the toner tends to agglomerate during storage and printing, and when it exceeds 180 ° C., the fixability often deteriorates.

  The reaction ratio of each of the above raw material components is not particularly limited, and the degree of polymerization should be adjusted so that the predetermined amount of sulfonic acid metal base is obtained, and preferably within the softening point range of 90 to 180 ° C. However, when the above-described trifunctional or higher polyfunctional carboxylic acid, its anhydride, or its ester is used, it is preferably used in a ratio of 1 to 5% by mass in the total raw material acid component. When using the polyhydric alcohol more than a valence, it is preferable to use in the ratio used as 1-5 mass% in a raw material whole alcohol component.

  Furthermore, when using the said polyvalent epoxy compound together, it is preferable to use it in the ratio which will be 0.5-2.0 mass% in all the raw material components, and also when using a monoepoxy compound together, all the raw materials are used. It is preferable to use it in the ratio which becomes 2.0-10.0 mass% in a component.

  In the present invention, the particle size and particle size distribution are substantially determined in the step (ii) and the step (iv). In the production method of the present invention, excellent emulsification stability is exhibited in step (ii), which is an emulsification step, and therefore a toner having a sharp particle size distribution can be obtained.

  The polyester resin having a sulfonic acid metal group used in the present invention in the resin structure may be used by blending a plurality of resins having different softening points. By blending a plurality of resins having different softening points, it is possible to obtain a balance between offset resistance in a wide temperature range and good low-temperature fixability as compared with a single resin. The resin having a high softening point is preferably a cross-linked polyester resin, and the softening point is preferably in the range of 150 to 230 ° C, and preferably 160 to 200 ° C. On the other hand, a linear polyester resin is preferable as the low softening point resin, and the softening point is in the range of 80 to 130 ° C, preferably 90 to 120 ° C. The use ratio (mass ratio) of the high softening point resin and the low softening point resin is in the range of 20/80 to 70/30, preferably 30/70 to 60/40.

  When blending a plurality of resins having different softening points, it is preferable to use a polyester resin crosslinked with a polyvalent epoxy compound as the high softening point resin.

The softening point of the resin in the present invention is a value defined by a T1 / 2 temperature measured using a “flow tester CFT-500” manufactured by Shimadzu Corporation, which is a constant load extrusion capillary rheometer. At this time, the measurement conditions with the “flow tester CFT-500” were as follows: piston cross-sectional area 1 cm ² , cylinder pressure 0.98 MPa, die length 1 mm, die hole diameter 1 mm, measurement start temperature 50 ° C., heating rate 6 ° C. / The conditions are min and the sample mass is 1.5 g.

  In the production method of the present invention, as described above, a wax component can be used. As this wax component, for example, a wax component selected from the group of hydrocarbon waxes such as polypropylene wax, polyethylene wax, and Fischer-Tropsch wax, and natural ester waxes such as synthetic ester wax, carnauba wax, and rice wax Is used. Of these, hydrocarbon waxes such as natural ester waxes such as carnauba wax and rice wax, synthetic ester waxes obtained from polyhydric alcohols and long-chain monocarboxylic acids, and Fischer-Tropsch waxes are preferably used. As the synthetic ester wax, for example, “WEP-5” (manufactured by NOF Corporation) is preferably used. If the content of the wax component in the toner is less than 1% by mass, the releasability tends to be insufficient, and if it exceeds 40% by mass, the wax is likely to be exposed on the toner particle surface, and the chargeability and storage stability are improved. Since it falls easily, the inside of the range of 1-40 mass% is preferable.

  Here, when the wax component is used, as described above, a method in which the wax component is mixed with an organic solvent and the polyester resin to prepare a resin solution, which is subjected to step (ii) is preferable. Specifically, the method for producing the resin solution is to prepare an emulsion by previously stirring and mixing the wax component with an aqueous medium, and then adding a polyester resin having the sulfonic acid metal group in the resin structure to the organic solvent. And adding and mixing.

  As the colorant used in the production method of the present invention, known and commonly used colorants are used. For example, black colorants that can be used in the toner of the present invention include carbon blacks such as furnace black, channel black, acetylene black, thermal black, and lamp black classified by the production method, or C.I. I. Pigment Black 11 and other iron oxide pigments, C.I. I. Pigment Black 12 and other iron-titanium complex oxide pigments and blue colorants include phthalocyanine C.I. I. Pigment Blue 1, 2, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 15, 16, 17: 1, 27, 28, 29, 56, 60, 63, and the like. The blue colorant is preferably C.I. I. Pigment Blue 15: 3, 15, 16, 60, and most preferably C.I. I. Pigment Blue 15: 3,60.

  Examples of yellow colorants include C.I. I. Pigment Yellow 1, 3, 4, 5, 6, 12, 13, 14, 15, 16, 17, 18, 24, 55, 65, 73, 74, 81, 83, 87, 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 113, 116, 117, 120, 123, 128, 129, 133, 138, 139, 147, 151, 153, 154, 155, 156, 168, 169, 170, 171, 172, 173, 180, 185 and the like. Preferably, C.I. I. Pigment Yellow 17, 74, 93, 97, 110, 155, and 180, and more preferably C.I. I. Pigment Yellow 74, 93, 97, 180, and C.I. I. Pigment Yellow 93, 97, 180 is preferable.

  Further, examples of red colorants include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 15, 17, 18, 22, 23, 31, 37, 38, 41, 42, 48: 1 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53: 1, 54, 57: 1, 58: 4, 60: 1 63: 1, 63: 2, 64: 1, 65, 66, 67, 68, 81, 83, 88, 90, 90: 1, 112, 114, 115, 122, 123, 133, 144, 146, 147, 149,150,151,166,168,170,171,172,174,175,176,177,178,179,185,187,188,189,190,193,194,202,208,209,214, 216, 220, 221, 224, 2 2,243,243: 1,245,246,247, and the like. Preferably, C.I. I. Pigment Red 48: 1, 48: 2, 48: 3, 48: 4, 53: 1, 57: 1, 122 and 209, most preferably C.I. I. Pigment Red 57: 1, 122 and 209.

  The content of the colorant is preferably 1 to 20% by mass with respect to the whole toner. Especially, it is more preferable that it is 2-18 mass%, and it is especially preferable that it is 2-15 mass%. These colorants can be used alone or in combination of two or more.

  Further, as described above, the colorant is prepared by melting and kneading each colorant and the polyester resin having the sulfonic acid metal group in the resin structure to prepare a colorant master chip. It is preferable to use for the process (ii) with the resin solution or resin dispersion of the polyester resin which has in a, and the resin solution containing a wax component.

  In the production method of the present invention, a charge control agent can be used. The positively chargeable charge control agent is not particularly limited, and known and commonly used nigrosine compounds, quaternary ammonium compounds, onium compounds, triphenylmethane compounds, and the like can be used for toner. A basic group-containing compound such as an amino group, an imino group, or an N-heterocycle, such as a tertiary amino group-containing styrene acrylic resin, can also be used in combination with the nigrosine dye as a positively chargeable charge control agent. Depending on the application, a small amount of a negative charge control agent such as an azo dye metal complex or a salicylic acid derivative metal complex salt may be used in combination. Negative charge control agents include trimethylethane dyes, metal complexes of salicylic acid, metal complexes of benzyl acid, copper phthalocyanine, perylene, quinacridone, azo pigments, metal complex azo dyes, azochrome complexes, and other heavy metal-containing acids. Examples thereof include dyes, calixarene-type phenol condensates, cyclic polysaccharides, resins containing carboxyl groups and / or sulfonyl groups, and the like.

  The content of the charge control agent is preferably 0.01 to 10% by mass. It is especially preferable that it is 0.1-6 mass%. Here, the charge control agent is mixed in the resin solution or resin dispersion during the resin solution adjustment step of the step (i) in a state of being dispersed in a solvent so as to have a particle size smaller than the toner particle size. That's fine. At this time, the dispersion diameter of the charge control agent is preferably in the range of 0.01 to 0.5 μm. In particular, the range of 0.01 to 0.2 μm is preferable because the dispersibility of the charge control agent in the finally obtained toner particles is good and easily uniform.

  The toner particles thus obtained can be used as a developer as they are, but external additives such as known and commonly used inorganic oxide fine particles and organic polymer fine particles are added to the toner particle surfaces as external additives for toner. Is preferred. That is, inorganic oxide fine particles such as hydrophobic silica and titanium oxide, or organic polymer fine particles are externally added to toner particles, and when used as a dry developer by electrostatic printing, physical properties such as fluidity and chargeability It has the effect of improving the physical characteristics. As the type of external additive, hydrophobic silica treated with various silicone oils is preferably used. Examples thereof include hydrophobic silica treated with dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, fluorine-modified silicone oil, and olefin-modified silicone oil. The external addition method is processed using a known and commonly used model.

  By mixing a carrier with the toner particles, an electrostatic charge image developer can be obtained. The electrostatic charge image developer comprises a toner produced by the production method of the present invention and a magnetic carrier, preferably a magnetic carrier whose surface is coated with a resin.

  Iron powder, magnetite, ferrite, etc. used in the usual two-component development system can be used as the carrier core agent (magnetic carrier) used in the electrostatic image developer, but the true specific gravity is low, the resistance is high, and the environment Ferrite or magnetite that is excellent in stability and easy to be spherical and has good fluidity is preferably used. The shape of the core agent can be used without any problem, such as a spherical shape or an indefinite shape. The average particle size is generally 10 to 200 μm, but 30 to 110 μm is preferable for printing a high resolution image.

  Examples of coating resins for coating these core agents include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether polyvinyl ketone, vinyl chloride / vinyl acetate. Copolymers, styrene / acrylic copolymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluorine resins, (meth) acrylic resins, polyesters, polyurethanes, polycarbonates, phenol resins, amino resins, melamine resins, benzoguanamine resins Urea resin, amide resin, epoxy resin and the like can be used.

  Among these, silicon resin and (meth) acrylic resin are particularly excellent in charging stability and coating strength, and can be used more suitably. Further, the charging characteristics of a developer composed of toner particles and a carrier can be adjusted by adjusting the coating amount of a coating agent such as silicon, adding a charge control agent, or adding a conductive material typified by carbon. That is, the resin-coated carrier used in the present invention is a resin-coated magnetic carrier coated with one or more resins selected from silicon resin and (meth) acrylic resin using ferrite or magnetite as a core agent. Therefore, it is preferable to adjust the charging characteristics by adding a charge control agent, carbon or the like during coating.

  Further, the toner produced by the production method of the present invention can be used in a normal non-magnetic one-component developing type printing apparatus, a two-component developing type printing apparatus, a magnetic one-component developing type printing apparatus, or the like. Further, on a flexible printed circuit board having an electrode having a function of adjusting the amount of toner passing through a powder toner that has been frictionally charged using a non-magnetic one-component developing device having a developer carrying roll and a layer regulating member. Therefore, it can be suitably used for a so-called toner jet type printer in which an image is formed by spraying directly on the paper on the back electrode through the hole. The toner produced by the production method of the present invention forms an electrostatic image on the latent image carrier, and develops the obtained electrostatic image using a developer carried on the developer carrier, Printing can be performed by an image forming method in which the toner image formed on the cargo image carrier is transferred onto a transfer material such as paper or film, and the toner image on the transfer material is thermally fixed by a heat roll.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In Examples and Comparative Examples, unless otherwise indicated, “part” means “mass part” and “water” means deionized water. A synthesis example of the binder resin used for preparing the toner first is shown below.

Synthesis Examples 1 to 3, 5, and 7 (Synthesis of polyester resin)
Polybasic acid (a1) and polyhydric alcohol (a2) shown in Tables 1 and 2 below were charged into a 5-liter four-necked flask equipped with a thermometer, stirring rod, condenser and nitrogen inlet tube at the top of the flask, As an example, tetraisopropyl titanate (TIPT) was added in an amount of 0.2% by weight based on the total monomers, and a transesterification reaction was performed at 180 ° C. for 5 hours under a normal pressure nitrogen stream. Thereafter, the remaining polybasic acids (a1) listed in Tables 1 and 2 were added, and the temperature was raised to 210 ° C. and reacted for 2 hours. Next, after the temperature was lowered to 185 ° C., a predetermined amount of TMAn described in Tables 1 and 2 was added and reacted for 2 hours, and then the temperature was raised to 205 ° C. and a reduced pressure reaction was performed at a vacuum level of 666 Pa or less. Got. Tables 1 and 2 show the composition and physical property values (characteristic values) of the synthesized polyester resin.

Synthesis Examples 4, 6, 8 (Synthesis of polyester resin)
Predetermined amounts of polybasic acid (a1) and polyhydric alcohol (a2) shown in Tables 1 and 2 below were added to a 5-liter four-necked flask equipped with a thermometer, a stirring rod, a condenser and a nitrogen inlet tube at the top of the flask. Then, 0.2 wt% of tetraisopropyl titanate (TIPT) as a catalyst was added with respect to the total amount of monomers, reacted at 245 ° C. for 4 hours under a normal pressure nitrogen stream, and then cooled to 185 ° C. ( A predetermined amount of a3) was added and reacted for 2 hours, and then the temperature was raised to 230 ° C. and a reduced pressure reaction was performed at a vacuum of 666 Pa or less to obtain a polyester resin. The reaction was traced by measuring the viscosity with a digital cone viscometer (manufactured by Toa Kogyo Co., Ltd.) “CV-1S”. When the viscosity reached a predetermined viscosity, the reaction was stopped to obtain various polyester resins. Table 2 shows the composition and physical property values (characteristic values) of the synthesized polyester resin.

Here, the property value of each polyester resin in Tables 1 and 2 is a value measured by the following method.
<Content of sodium sulfonate base in polyester resin (S / Kα strength)>
As a method for quantifying the amount of sulfonic acid group monomer in the resin, the X-ray fluorescence (EDX) apparatus (EDX-700, manufactured by Shimadzu Corporation) was used to determine the resin from the X-ray detection intensity of the characteristic X-ray energy Kα ray of S element. The amount of S element in the medium sulfonic acid group was analyzed and expressed as S / Kα intensity.

<Molecular weight>
Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Tosoh Corporation guard column HXL-H
+ Tosoh Corporation TSKgel G5000HXL
+ Tosoh Corporation TSKgel G4000HXL
+ Tosoh Corporation TSKgel G3000HXL
+ Tosoh Corporation TSKgel G2000HXL
Detector: RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate 1.0 ml / min Standard; polystyrene sample; 0.4% by weight tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

<Softening point (T1 / 2 temperature)>
It is the melting temperature (° C.) by the 1/2 method measured under the following conditions.
Measuring instrument: Shimadzu flow tester CFT-500D
Measurement conditions: temperature rising rate 6 ° C./min, nozzle 1.0 mmφ × 10 mm, load 10 kgf, sample amount 1.5 g

<Glass transition temperature>
The glass transition temperature is a value (° C.) measured under the following conditions.
Measuring device: Seiko Electronics Co., Ltd. DSC220C
Measurement conditions: 10 ° C./min, Sample: About 10 mg of sample is put in an aluminum container and the lid is closed.
Measuring method: DSC (Suggested scanning calorimetry) method

表１及び表２中の略号は以下の通りである。
ＤＭＴ：テレフタル酸ジメチル
ＴＰＡ：テレフタル酸
ＩＰＡ：イソフタル酸
ＳＩＰＭ：イソフタル酸ジメチル−５−スルホン酸ナトリウム
ＳＩＰＡ：イソフタル酸−５−スルホン酸ナトリウム
ＥＧ：エチレングリコール
ＮＰＧ：２，２−ジメチル−１，３−プロパンジオール
ＰＧ：１，２−プロパンジオール
ＴＭＡｎ：無水トリメリット酸

Abbreviations in Table 1 and Table 2 are as follows.
DMT: dimethyl terephthalate TPA: terephthalic acid IPA: isophthalic acid SIPM: sodium dimethyl-5-sulfonate isophthalate SIPA: sodium isophthalate-5-sulfonate EG: ethylene glycol NPG: 2,2-dimethyl-1,3- Propanediol PG: 1,2-propanediol TMAn: trimellitic anhydride

(Preparation example of wax master)
Carnauba wax "Carnauba Wax No. 1" (Yoko Kato imports) 30 parts by weight was heated to 120 ° C and dissolved, and then emulsifier "Neogen SC-F" (Daiichi Kogyo Seiyaku Co., Ltd.) was added to 57 parts by weight of ion-exchanged water. The carnauba wax dissolved in the emulsifier-mixed warm water heated to 90 ° C. was added in 0.11 part by weight, and emulsified with a forced emulsifier “TK Homomixer” (Primix Co., Ltd.). Thereafter, the mixture was cooled to 30 ° C. or less while stirring, and adjusted to a solid content of 35% by mass to obtain a wax emulsion.
70 parts by mass of the polyester resin R7 obtained in Synthesis Example 7 was dispersed in 85.6 parts by mass of ethyl acetate using a desper for 60 minutes at a rotational speed of 750 rpm, and then 87.9 parts by mass of the wax emulsion. The mixture was dispersed and premixed for 5 minutes at a rotation speed of 750 min ⁻¹ with a death bar, and then 90 minutes at a peripheral speed of 13.3 m / s with an Eiger motor mill (“M-1000” manufactured by Eiger, USA). The wax master (1) was prepared by dispersing.

(Preparation example of comparative wax master)
A wax master (2) was prepared in the same manner as in the above “Preparation Example of Wax Master” except that the polyester resin R8 obtained in Synthesis Example 8 was used instead of the polyester resin R7 obtained in Synthesis Example 7.

(Example of production of colorant master chip)
2000 parts by mass of cyan pigment (Cyan Pigment “Ket Blue111” CI Pigment B-15: 3 manufactured by DIC Corporation) and 2000 parts by mass of polyester resin R7 obtained in Synthesis Example 7 The mixture was charged into a 20 L Henschel mixer (Mitsui Mine) equipped with an AO stirring blade, and stirred at 698 min ⁻¹ for 2 minutes to obtain a mixture. The mixture was melt-kneaded using an open roll continuous extrusion kneader (Mitsui Mine Needex "MOS140-800") to obtain a colorant master chip (hereinafter referred to as "cyan master chip MC"). .
Also, the cyan pigment is changed to a magenta pigment (Clariant Japan's magenta pigment “Permanentorbin F6B”), yellow pigment (Clariant Japan ’s yellow pigment “Toner Yellow HG”), and black pigment (Cabot Japan ’s carbon black “ELFTEX8”). Thus, master chips (hereinafter referred to as “magenta master chip MM”, “yellow master chip YM”, and “black master chip BM”, respectively) were obtained.
Moreover, when the master chip of each color obtained was diluted with the polyester resin R12 and ethyl acetate, and the microdispersion state of the colorant and the presence or absence of coarse particles were observed with a 400-fold optical microscope, there was no coarse particles, and it was uniform. It was finely dispersed. The composition of the master chip of each colorant is cyan master chip: colorant / resin 2 = (50) / (50), magenta: colorant / resin 2 = (50) / (50), yellow: Colorant / Resin 2 = (55) / (45), Black: Colorant / Resin 2 = (40) / (60).

(Manufacture of comparative colorant master chip)
Instead of the polyester resin R7 obtained in Synthesis Example 7, the colorant master chip of each color was obtained in the same manner as in the above “Production Example of Colorant Master Chip” except that the polyester resin R8 obtained in Synthesis Example 8 was used. Got. Here, "Cyan Master Chip MC2" using cyan pigment, "Magenta Master Chip MM2" using magenta pigment, "Yellow Master Chip YM2" using yellow pigment, and black pigment were used. This is referred to as “black master chip BM2”.

Example 1
(Resin solution preparation process)
42 parts by weight of black master chip BM, 158.0 parts by weight of polyester resin R1 obtained in Synthesis Example 1 above, and 159.9 parts by weight of ethyl acetate in the range of 40 to 45 ° C. with a blade diameter of 230 mm (ASADA Iron Works) Using a high-speed stirrer manufactured by Tokoro Co., Ltd. for 1 hour at 777 min ⁻¹ for dissolution / dispersion. Then, 241.6 parts by mass of the wax master (1) is added and dispersed for 30 minutes with a desper. A colorant-containing resin solution was prepared (Step 1).

(Emulsification process)
After charging 601.5 parts by mass of the colorant-containing resin solution obtained in Step 1 (solid content: 300.1 parts by mass) into a cylindrical container having a desper with a blade diameter of 230 mm as a stirring blade and stirring at 777 min ⁻¹ The temperature was adjusted to 35 ° C. Next, the stirring speed was changed to 1100 min-1, and 310 parts by mass of deionized water was added dropwise at 20 parts by mass / min to prepare a suspension. The peripheral speed of the stirring blade at this time was 13.2 m / s. As deionized water was added, the viscosity of the system increased, but water was taken into the system at the same time as the dropwise addition, and stirring and mixing were uniform. After adding 200 parts by weight of deionized water, a sharp drop in viscosity was observed (phase inversion emulsification). Furthermore, after adding a predetermined amount of the remaining deionized water, when the slurry is observed with an optical microscope, it is observed that the fine particles of the resin, the pigment and the wax are stably dispersed, and no unemulsified material is observed. It was. Furthermore, the rotation speed was reduced to 777 min ⁻¹ , and an aqueous solution prepared by dissolving 1.1 parts by mass of an anionic emulsifier “Neogen SC-F (Daiichi Kogyo Seiyaku Co., Ltd.) in 184.7 parts by mass of deionized water in advance. Was added (step 2).

(Joint process)
Next, after the suspension obtained in the emulsification step was transferred to a cylindrical container attached to “Max Blend Wing” (registered trademark, manufactured by Sumitomo Heavy Industries, Ltd.) having a blade diameter of 340 mm, the stirring speed was maintained at 85 min ⁻¹ . The temperature was adjusted to 26 ° C. Thereafter, the number of revolutions was adjusted to 120 min ⁻¹ , 120 parts by mass of a 3.5 mass% sodium sulfate aqueous solution was added dropwise at 10 parts by mass / min. Stirring was continued for 20 minutes at 47 min−1. The peripheral speed of the stirring blade at this time was 0.47 m / s. Subsequently, the rotational speed was adjusted to 120 min ⁻¹ , 20 mass parts of a sodium sulfate aqueous solution having a concentration of 5.0 mass% was dropped at 10 mass parts / min, and 5 minutes after the completion of the dropping, the rotational speed was adjusted to 85 rpm in the same manner as described above. The stirring speed was further lowered stepwise for 5 minutes, and the stirring was continued at 47 min-1 for 20 minutes. Thereafter, the operation of dropping and stirring a sodium sulfate aqueous solution having a concentration of 5.0% by mass was repeated three times, and diluting water was added when the particle diameter grew to 6.5 μm, and the coalescence operation was completed.

(Separation and drying process)
After adding 0.0068 parts by mass of antifoaming agent “BY22-517” (manufactured by Toray Dow Corning Silicone Co., Ltd.), ethyl acetate and water were distilled off under reduced pressure until the degree of vacuum was 4 kPa. The slurry after the solvent removal was repeatedly washed by solid-liquid separation and redispersion, and then a utcake of colorant resin particles was obtained by a basket type centrifuge. Thereafter, the mixture was dried with a powder mixer (“Nautamixer” manufactured by Hosokawa Micron Corporation) to obtain toner mother particles. The toner base particles had a volume average particle size (d50) of 5.7 μm, a volume average particle size / number average particle size = 1.08, and an average circularity of 0.985.
(External addition process)
One part of hydrophobic silica (“Silica H13TM” manufactured by Clariant Japan Co., Ltd.) is added to 100 parts of the toner base particles, and the toner base particles are treated with a Henschel mixer for 5 minutes at 35 m / sec. A toner for developing a charge image was produced.
Example 2
Toner base particles were obtained in the same manner as in Example 1 except that the resin R2 was used instead of the resin R1 in Table 1 of Example 1. The toner base particles had a volume average particle size (d50) of 5.8 μm, a volume average particle size / number average particle size = 1.08, and an average circularity of 0.986.
(External addition process)
One part of hydrophobic silica (“Silica H13TM” manufactured by Clariant Japan Co., Ltd.) is added to 100 parts of the toner base particles, and the toner base particles are treated with a Henschel mixer for 5 minutes at 35 m / sec. An electrostatic charge image toner was manufactured from a charge image developing toner.

Example 3
Toner mother particles were obtained in the same manner as in Example 1 except that the resin R3 was used instead of the resin R1 in Table 1 of Example 1. The toner base particles had a volume average particle size (d50) of 5.8 μm, a volume average particle size / number average particle size = 1.07, and an average circularity of 0.985.
(External addition process)
One part of hydrophobic silica (“Silica H13TM” manufactured by Clariant Japan Co., Ltd.) is added to 100 parts of the toner base particles, and the toner base particles are treated with a Henschel mixer for 5 minutes at 35 m / sec. An electrostatic charge image toner was manufactured from a charge image developing toner.

Example 4
Toner base particles were obtained in the same manner as in Example 1 except that the resin R4 was used instead of the resin R1 in Table 1 of Example 1. The toner base particles had a volume average particle size (d50) of 5.9 μm, a volume average particle size / number average particle size = 1.08, and an average circularity of 0.985.
(External addition process)
One part of hydrophobic silica (“Silica H13TM” manufactured by Clariant Japan Co., Ltd.) is added to 100 parts of the toner base particles, and the toner base particles are treated with a Henschel mixer for 5 minutes at 35 m / sec. An electrostatic charge image toner was manufactured from a charge image developing toner.

Example 5
Toner mother particles were obtained in the same manner as in Example 1, except that the resin R5 was used instead of the resin R1 in Table 1 of Example 1. The toner base particles had a volume average particle size (d50) of 5.7 μm, a volume average particle size / number average particle size = 1.08, and an average circularity of 0.985.
(External addition process)
One part of hydrophobic silica (“Silica H13TM” manufactured by Clariant Japan Co., Ltd.) is added to 100 parts of the toner base particles, and the toner base particles are treated with a Henschel mixer for 5 minutes at 35 m / sec. An electrostatic charge image toner was manufactured from a charge image developing toner.

Comparative Example 1 [Example of solvent removal treatment after emulsification step and before coalescence step]
(Resin solution preparation process)
As a colorant master chip, 42 parts by mass of black master chip BM, 158.0 parts by mass of polyester resin R3 obtained in Synthesis Example 3 above, and 159.9 parts by mass of ethyl acetate in the range of 40 to 45 ° C. Using a 230 mm Desper (Asada Iron Works Co., Ltd. high-speed stirrer), the mixture was mixed at 777 min ⁻¹ for 1 hour to dissolve and disperse, and then 241.6 parts by mass of the wax master (1) was added. For 30 minutes to prepare a colorant-containing resin solution.
(Emulsification process)
A cylindrical container having a disper with a blade diameter of 230 mm as a stirring blade was charged with 601.5 parts by mass of the colorant-containing resin composition (solid content 300.1 parts by mass) obtained in the “resin solution preparation step”, and 777 min ^−. After stirring at ¹ , the temperature was adjusted to 35 ° C. Next, the stirring speed was changed to 1100 min ⁻¹ and 310 parts by mass of deionized water was added dropwise at 20 parts by mass / min to prepare a suspension. The peripheral speed of the stirring blade at this time was 13.2 m / s. As deionized water was added, the viscosity of the system increased, but water was taken into the system at the same time as the dropwise addition, and stirring and mixing were uniform. After adding 200 parts by weight of deionized water, a sharp drop in viscosity was observed (phase inversion emulsification). Further, when a predetermined amount of the remaining deionized water was added and the slurry was observed with an optical microscope, it was observed that the resin, the pigment and the wax fine particles were dispersed. No unemulsified material was observed. Since the fine particles are stably dispersed in the aqueous medium, it is considered that the resin is adsorbed on the surface of the fine particles. Furthermore, the rotation speed was reduced to 777 min ⁻¹ , and an aqueous solution in which 1.1 parts by mass of an anionic emulsifier Neogen SC-F (Daiichi Kogyo Seiyaku Co., Ltd.) was dissolved in 184.7 parts by mass of deionized water in advance. Added (step 2).
(Desolvation process)
After adding 0.0068 parts by mass of antifoaming agent “BY22-517” (manufactured by Toray Dow Corning Silicone Co., Ltd.), ethyl acetate and water were distilled off under reduced pressure until the degree of vacuum was 4 kPa.

(Joint process)
Next, after the suspension was transferred to a cylindrical container attached to a Max Blend blade (registered trademark, manufactured by Sumitomo Heavy Industries, Ltd.) having a blade diameter of 340 mm, the temperature was maintained at 26 ° C. while maintaining the stirring speed at 85 min ^−1. It was adjusted. Thereafter, the number of revolutions was adjusted to 120 min ⁻¹ , 120 parts by mass of a 3.5% by mass aqueous sodium sulfate solution was added dropwise at 10 parts by mass / min. Stirring was continued for 20 minutes at a typical rotational speed of 47 min ⁻¹ . The peripheral speed of the stirring blade at this time was 0.47 m / s. Subsequently, the rotational speed was adjusted to 120 min ⁻¹ , and 20 parts by mass of a sodium sulfate aqueous solution having a concentration of 5.0% by mass was added dropwise at 10 parts by mass / min. The stirring speed was further lowered stepwise for 5 minutes, and the stirring was continued for 20 minutes at 47 min ⁻¹ . Thereafter, the operation of dropping and stirring the sodium sulfate aqueous solution having a concentration of 5.0% by mass was repeated three times, and the particle growth stopped when the particle diameter was 2.3 μm. Therefore, the diluting water was added to complete the coalescence operation. .

(Separation and drying process)
The combined slurry was repeatedly washed by solid-liquid separation and redispersion, and then a utcake of colorant resin particles was obtained by a basket type centrifuge. Thereafter, toner mother particles were obtained by drying with a Nauta mixer (manufactured by Hosokawa Micron Corporation). The toner mother particles had a volume average particle size (d50) of 2.0 μm, a volume average particle size / number average particle size = 1.08, and an average circularity of 0.957.
(External addition process)
To the toner base particles, 1 part of silica H13TM (manufactured by Clariant Japan Co.) is added to 100 parts of the toner base particles, and these are processed with a Henschel mixer at 35 m / sec for 5 minutes to develop an electrostatic charge image developing toner. Manufactured.

Comparative Example 2 [Example of solvent removal treatment after the emulsification step and before the coalescence step, followed by heat fusion]
(Emulsification process)
601.5 parts by mass (solid content 300.1 parts by mass) of the colorant-containing resin composition obtained in the “resin solution preparation step” of Comparative Example 1 was added to a cylindrical container having a desper with a blade diameter of 230 mm as a stirring blade. After charging and stirring at 777 min ⁻¹ , the temperature was adjusted to 35 ° C. Next, the stirring speed was changed to 1100 min ⁻¹ and 310 parts by mass of deionized water was added dropwise at 20 parts by mass / min to prepare a suspension. The peripheral speed of the stirring blade at this time was 13.2 m / s. As deionized water was added, the viscosity of the system increased, but water was taken into the system at the same time as the dropwise addition, and stirring and mixing were uniform. After adding 200 parts by weight of deionized water, a sharp drop in viscosity was observed (phase inversion emulsification). Further, when a predetermined amount of the remaining deionized water was added and the slurry was observed with an optical microscope, it was observed that the resin, the pigment and the wax fine particles were dispersed. No unemulsified material was observed. Since the fine particles are stably dispersed in the aqueous medium, it is considered that the resin is adsorbed on the surface of the fine particles. Furthermore, the rotation speed was reduced to 777 min ⁻¹ , and an aqueous solution in which 1.1 parts by mass of an anionic emulsifier Neogen SC-F (Daiichi Kogyo Seiyaku Co., Ltd.) was dissolved in 184.7 parts by mass of deionized water in advance. Added.
(Desolvation process)
After adding 0.0068 parts by mass of antifoaming agent “BY22-517” (manufactured by Toray Dow Corning Silicone Co., Ltd.), ethyl acetate and water were distilled off under reduced pressure until the degree of vacuum was 4 kPa.

(Joint process)
Next, after the suspension was transferred to a cylindrical vessel attached to a Max Blend blade (registered trademark, manufactured by Sumitomo Heavy Industries) with a blade diameter of 340 mm, the temperature was maintained at 70 ° C. while maintaining the stirring speed at 85 min ^−1. It was adjusted. Thereafter, the number of revolutions was adjusted to 120 min ⁻¹ , 120 parts by mass of a 3.5% by mass aqueous sodium sulfate solution was added dropwise at 10 parts by mass / min. Stirring was continued for 20 minutes at a typical rotational speed of 47 min ⁻¹ . The peripheral speed of the stirring blade at this time was 0.47 m / s. Subsequently, the rotational speed was adjusted to 120 min ⁻¹ , and 20 parts by mass of a sodium sulfate aqueous solution having a concentration of 5.0% by mass was added dropwise at 10 parts by mass / min. The stirring speed was further lowered stepwise for 5 minutes, and the stirring was continued for 20 minutes at 47 min ⁻¹ . Thereafter, the operation of dropping and stirring the sodium sulfate aqueous solution having a concentration of 5.0% by mass was repeated three times, and the particle growth stopped when the particle size was 6.4 μm. .

(Separation and drying process)
The combined slurry was repeatedly washed by solid-liquid separation and redispersion, and then a utcake of colorant resin particles was obtained by a basket type centrifuge. Thereafter, toner mother particles were obtained by drying with a Nauta mixer (manufactured by Hosokawa Micron Corporation). The toner mother particles had a volume average particle size (d50) of 5.7 μm, a volume average particle size / number average particle size = 1.15, and an average circularity of 0.968.
(External addition process)
To the toner base particles, 1 part of silica H13TM (manufactured by Clariant Japan Co.) is added to 100 parts of the toner base particles, and these are processed with a Henschel mixer at 35 m / sec for 5 minutes to develop an electrostatic charge image developing toner. Manufactured.

Comparative Example 3 (Example using polyester resin without sodium sulfonate)
(Resin solution preparation process)
42 parts by weight of black master chip BM2, 158.0 parts by weight of polyester resin R6 obtained in Synthesis Example 3 above, and 159.9 parts by weight of ethyl acetate in a range of 40 to 45 ° C. with a blade diameter of 230 mm (ASADA Iron Works) Using a high-speed stirrer manufactured by Tokoro Co., Ltd. at 777 min ⁻¹ for 1 hour to dissolve and disperse. Then, 241.6 parts by mass of the wax master (2) is added and dispersed with a desper for 30 minutes. And a colorant-containing resin solution was prepared.
(Emulsification process)
In a cylindrical container having a blade with a blade diameter of 230 mm as a stirring blade, 601.5 parts by mass of the colorant-containing resin composition obtained in the resin solution preparation step (solid content 300.1 parts by mass) was charged, and then 1N After adding 40 parts by mass of aqueous ammonia and stirring at 777 min ⁻¹ , the temperature was adjusted to 35 ° C. Next, the stirring speed was changed to 1100 min ⁻¹ and 350 parts by mass of deionized water was added dropwise at 20 parts by mass / min to prepare a suspension. The peripheral speed of the stirring blade at this time was 13.2 m / s. As deionized water was added, the viscosity of the system increased, but water was taken into the system at the same time as the dropwise addition, and stirring and mixing were uniform. After adding 200 parts by weight of deionized water, a sharp drop in viscosity was observed (phase inversion emulsification). Further, when a predetermined amount of the remaining deionized water was added and the slurry was observed with an optical microscope, it was observed that the resin, the pigment and the wax fine particles were dispersed. No unemulsified material was observed. Since the pigment and wax fine particles are stably dispersed in the aqueous medium, it is considered that the resin is adsorbed on the surfaces of the fine particles. Further, the rotational speed was reduced to 777 min ⁻¹ , and the remaining 10 parts of 1N ammonia water and 1.1 parts by mass of “Neogen SC-F” (Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic emulsifier were added to deionized water. An aqueous solution previously dissolved in 184.7 parts by mass was added.

(Joint process)
Next, after the suspension was transferred to a cylindrical container attached to a Max Blend blade (registered trademark, manufactured by Sumitomo Heavy Industries, Ltd.) having a blade diameter of 340 mm, the temperature was maintained at 26 ° C. while maintaining the stirring speed at 85 min ^−1. It was adjusted. Thereafter, the rotational speed was adjusted to 120 min ⁻¹ , 120 parts by mass of a 3.5 mass% sodium sulfate aqueous solution was added dropwise at 10 parts by mass / min, and 5 minutes after the completion of dropping, the rotational speed was 85 min ⁻¹ for 5 minutes and 65 min. ^The mixture was stirred for 5 minutes at ^-1 and continued for 20 minutes at 47 min- ¹ . The peripheral speed of the stirring blade at this time was 0.47 m / s. Subsequently, the rotational speed was adjusted to 120 min ⁻¹ , 20 parts by mass of a sodium sulfate aqueous solution having a concentration of 5.0% by mass was dropped at 10 parts by mass / min, and 5 minutes after the completion of the dropping, the rotational speed was 85 min ⁻¹ for 5 minutes. Stirring was performed at 65 min ⁻¹ for 5 minutes, and stirring was continued at 47 min ⁻¹ for 20 minutes. Thereafter, the operation of dropping and stirring a sodium sulfate aqueous solution having a concentration of 5.0% by mass was repeated three times, and diluting water was added when the particle diameter grew to 6.5 μm, and the coalescence operation was completed.
(Separation and drying process)
The combined slurry was repeatedly washed by solid-liquid separation and redispersion, and then a utcake of colorant resin particles was obtained by a basket type centrifuge. Thereafter, toner mother particles were obtained by drying with a Nauta mixer (manufactured by Hosokawa Micron Corporation). The toner base particles had a volume average particle size (d50) of 5.8 μm, a volume average particle size / number average particle size = 1.08, and an average circularity of 0.984.
(External addition process)
To the toner base particles, 1 part of silica H13TM (manufactured by Clariant Japan Co.) is added to 100 parts of the toner base particles, and these are processed with a Henschel mixer at 35 m / sec for 5 minutes to develop an electrostatic charge image developing toner. Manufactured.

Comparative Example 4 (Example using polyester resin not having sodium sulfonate)
(Emulsification process)
A cylindrical container having a blade with a blade diameter of 230 mm as a stirring blade was charged with 601.5 parts by mass (300.1 parts by mass of the solid content) of the colorant-containing resin composition produced in Comparative Example 3, and then 1N aqueous ammonia 40 After adding part by mass and stirring at 777 min ⁻¹ , the temperature was adjusted to 35 ° C. Next, the stirring speed was changed to 1100 min ⁻¹ and 350 parts by mass of deionized water was added dropwise at 20 parts by mass / min to prepare a suspension. The peripheral speed of the stirring blade at this time was 13.2 m / s. As deionized water was added, the viscosity of the system increased, but water was taken into the system at the same time as the dropwise addition, and stirring and mixing were uniform. After adding 200 parts by weight of deionized water, a sharp drop in viscosity was observed (phase inversion emulsification). Further, when a predetermined amount of the remaining deionized water was added and the slurry was observed with an optical microscope, it was observed that the resin, the pigment and the wax fine particles were dispersed. No unemulsified material was observed. Since the pigment and wax fine particles are stably dispersed in the aqueous medium, it is considered that the resin is adsorbed on the surfaces of the fine particles. Further, the rotational speed was reduced to 777 min ⁻¹ , and the remaining 10 parts of 1N ammonia water and 1.1 parts by mass of “Neogen SC-F” (Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic emulsifier were added to deionized water. An aqueous solution previously dissolved in 184.7 parts by mass was added.
(Desolvation process)
After adding 0.0068 parts by mass of antifoaming agent “BY22-517” (manufactured by Toray Dow Corning Silicone Co., Ltd.), ethyl acetate and water were distilled off under reduced pressure until the degree of vacuum was 4 kPa.
(Joint process)
Next, after the suspension was transferred to a cylindrical container attached to a Max Blend blade (registered trademark, manufactured by Sumitomo Heavy Industries, Ltd.) having a blade diameter of 340 mm, the temperature was maintained at 26 ° C. while maintaining the stirring speed at 85 min ^−1. It was adjusted. Thereafter, the number of revolutions was adjusted to 120 min ⁻¹ , 120 parts by mass of a 3.5% by mass aqueous sodium sulfate solution was added dropwise at 10 parts by mass / min. Stirring was continued for 20 minutes at a typical rotational speed of 47 min ⁻¹ . The peripheral speed of the stirring blade at this time was 0.47 m / s. Subsequently, the rotational speed was adjusted to 120 min ⁻¹ , and 20 parts by mass of a sodium sulfate aqueous solution having a concentration of 5.0% by mass was added dropwise at 10 parts by mass / min. The stirring speed was further lowered stepwise for 5 minutes, and the stirring was continued for 20 minutes at 47 min ⁻¹ . Thereafter, the operation of dropping and stirring the sodium sulfate aqueous solution having a concentration of 5.0% by mass was repeated three times, and the particle growth stopped when the particle size was 6.4 μm. .

(Separation and drying process)
The combined slurry was repeatedly washed by solid-liquid separation and redispersion, and then a utcake of colorant resin particles was obtained by a basket type centrifuge. Thereafter, toner mother particles were obtained by drying with a Nauta mixer (manufactured by Hosokawa Micron Corporation). The volume average particle size (d50) of the toner base particles was 1.9 μm, the volume average particle size / number average particle size = 1.08, and the average circularity was 0.960.
(External addition process)
To the toner base particles, 1 part of silica H13TM (manufactured by Clariant Japan Co.) is added to 100 parts of the toner base particles, and these are processed with a Henschel mixer at 35 m / sec for 5 minutes to develop an electrostatic charge image developing toner. Manufactured.

Comparative Example 5 (Example using polyester resin without sodium sulfonate)
Toner base particles were obtained in the same manner as in Comparative Example 4 except that the temperature condition in the coalescence process was changed from 26 ° C. to 70 ° C. The toner base particles had a volume average particle size (d50) of 5.8 μm, volume average particle size / number average particle size = 1.17, and average circularity of 0.965.
(External addition process)
To the toner base particles, 1 part of silica “H13TM” (manufactured by Clariant Japan) is added to 100 parts of the toner base particles, and these are processed with a Henschel mixer at 35 m / sec for 5 minutes to develop an electrostatic image. Toner was produced.

  Table 3 content of sodium sulfonate base in the polyester resin obtained in each of the above synthesis examples, evaluation of the emulsified state after the emulsification step of Examples 1 to 5 and Comparative Examples 1 to 5, and finally obtained The evaluation results of each toner are shown. The methods for evaluating and measuring physical properties shown in Table 3 are as follows.

<Emulsification state evaluation>
The dispersed state of the fine particles after phase inversion emulsification was confirmed with an optical microscope. The magnification at the time of observation was confirmed with two visual fields of 300 times and 600 times, and the presence or absence of an emulsion or non-emulsified material of 6 μm or more was visually confirmed in the visual field.

(Evaluation criteria for emulsified state)
A: Number of emulsions of 6 μm or more or non-emulsified in a 300 × field of view: 0
○: Number of emulsions of 6 μm or more or non-emulsified in a 300 × field of view: 0 to 10
Δ: Number of emulsions not smaller than 6 μm or non-emulsified in a 300 × field of view: 10 to 20
×: Number of emulsions of 6 μm or more or non-emulsified in a 300 × field of view: 20 or more

<Evaluation method of toner properties>
(Particle size distribution)
Using a 100 micron aperture tube of Coulter Multisizer II (manufactured by Coulter Beckman), the 50% volume average diameter was taken as the average particle diameter. The particle size distribution was determined from 50% volume average diameter / 50% number average diameter.

(Average circularity)
The flow type particle image analyzer “FPIP-1000” manufactured by Toa Medical Electronics Co., Ltd. was used.
Here, the flow type particle image analyzer “FPIP-1000” is an apparatus for imaging the size and shape of fine particles such as toner particles, and the circularity is a value calculated by the following method.

  First, a sample is prepared by suspending toner particles in water containing a small amount of a surfactant. Next, this sample is allowed to flow down into a transparent and flat cell provided in the flow type particle image analyzer “FPIP-1000”. A light source that emits pulsed light is installed on one side of the cell, and an imaging camera is provided on the opposite side of the cell so as to face the light source. The toner particles in the sample flowing down the cell of “FPIP-1000” are captured as a still image by the camera facing the light source with the pulse light irradiated by the pulse light.

Based on the image of the toner particle thus captured, the contour of each toner particle is extracted by the image analysis device, and the projected area and peripheral length of the toner particle image (peripheral length of the toner particle projected image) are calculated. The Further, from the calculated projected area of the toner particle image, the circumference of a circle having the same area (the circumference of the circle having the same area as the toner particle projected area) is calculated.
The average circularity is obtained by dividing the circumference of a circle having the same area as the toner particle projection area thus calculated by the circumference of the toner particle projection image.

The conditions when measuring with the above apparatus are as follows.
(1) Preparation of toner particle suspension
0.1 g of surfactant (ELCLEAR (manufactured by Chugai Photo Chemical Co., Ltd.)) is added to 20 g of water, 0.04 g of toner as a sample is further added, and the toner particles are suspended in water with an ultrasonic disperser. Make it cloudy.
(2) Measurement conditions Measurement temperature: 25 ° C
Measuring humidity: 60%
Number of measured toner particles: 5000 ± 2000

(Particle shape)
The particles after coalescence were confirmed from the toner surface state and the state of the coalescence interface with an optical microscope (600 times) and an electron microscope (SEM) (500 times and 1000 times) and evaluated from the circularity of the toner.
Evaluation standard of particle shape A: The toner surface is smooth, the shape is spherical, and the average circularity is 0.980 or more.
○: The toner surface is smooth, the shape is substantially spherical, and the average circularity is 0.975 or more and less than 0.980.
Δ: The toner surface is smooth, but there is a coalesced interface, and the average circularity is 0.964 or more and less than 0.975.
X: The toner surface is rough, there is a particle coalescence interface, and the average circularity is less than 0.964.

(Evaluation of charge amount and charge stability)
Prepare a developer with a ratio of toner and silicon-coated ferrite carrier (Powder Tech Co., Ltd.) of 97/3, and mix in a 100 ml plastic container for 1 min, 10 min, 30 min, 60 min with a tumbler shaker mixer The charge amount was measured using a “210HS-2A” blow-off charge amount measuring device manufactured by Trek Japan. The average of these values was taken as the charge amount. In addition, the difference between the maximum charge amount and the minimum charge amount is obtained for the charge amount measured by a charge amount measuring device after mixing for 10 minutes, 30 minutes and 60 minutes with a tumbler shaker mixer, and this value is evaluated for charge stability. It was. It represents that it is excellent in charging stability, so that this value is small.

(Evaluation criteria for charge amount)
A: −45 μC / g or more ○: −40 μC / g or more, less than −45 μC / g Δ: −35 μC / g or more, less than −40 μC / g ×: less than −30 μC / g

(Heat resistant storage stability test)
3 g of the toner obtained in Examples and Comparative Examples was placed in a glass 30 cc bottle and stored at a temperature of 55 ° C./humidity of 30% for 12 hours, and toner aggregation was observed. The case where the toner was not aggregated is indicated by ◯, the case where the toner was partially aggregated is indicated by Δ, and the case where the toner was aggregated is indicated by ×.

(Glossiness evaluation)
An unfixed solid image was formed on the paper with toner, and the unfixed solid image was fixed by a separately prepared fixing tester. Fixing was performed through a heat roll (oilless type) of Ricoh Imagio DA-250 at a heat roll temperature of 160 ° C. and a speed of 90 mm / sec. The gloss on solid image printed paper after fixing was measured at a light projection / reception angle of 60 ° using a gloss meter manufactured by Nippon Denshoku Industries Co., Ltd. and evaluated according to the following criteria.
◎: Numerical value is 9 or more ○: Numerical value is 7 or more and less than 9 △: Numerical value is 5 or more and less than 7 ×: Numerical value is 3 or more and less than 5

Claims (5)

(I) a step of producing a soluble or dispersed was a resin solution or resin dispersion polyester resin in an organic solvent having a sulfonic acid metal base in a resin structure, are mixed with (ii) the resin solution or resin dispersion aqueous medium A step of producing a suspension in which fine particles of the resin solution or resin dispersion are suspended in the aqueous medium, and then (iii) adding the electrolyte under a temperature condition of 30 ° C. or less (Iv) removing the combined organic solvent, (v) separating the combined solid from the aqueous medium, and drying the electrostatic image. A method for producing a developing toner. The polyester resin is produced by using a dicarboxylic acid having a sulfonic acid metal group or a dialkyl ester thereof as a raw acid component and a linear alkylene diol having 2 to 6 carbon atoms as a raw alcohol component. Item 2. The production method according to Item 1. The polyester resin has a sulfonic acid metal base, and the strength [S / Kα] of a sulfur atom when the polyester resin is measured by fluorescent X-ray analysis is in the range of 0.030 to 0.090. Item 3. The production method according to Item 2. The production method according to claim 3, wherein the coalescence of the step ( iii ) is performed under a temperature condition of 10 to 30 ° C. The manufacturing method according to claim 4, wherein the step (i) is a method in which a colorant component and a wax component are used in combination with the polyester resin and dissolved or dispersed in an organic solvent to produce a resin solution or a resin dispersion.