JP6711043B2 - Method for producing resin particle dispersion and method for producing electrostatic image developing toner - Google Patents

Description

The present invention relates to a method for producing a resin particle dispersion and a method for producing an electrostatic charge image developing toner.

A method of visualizing image information through an electrostatic charge image such as an electrophotographic method is currently used in various fields. In the electrophotographic method, an electrostatic charge image is formed on a photoconductor by a charging and exposing process, and the electrostatic charge image is developed with a developer containing an electrostatic charge image developing toner (hereinafter sometimes simply referred to as “toner”). Then, the electrostatic charge image is visualized through the transfer and fixing steps.
As a method for producing the above-mentioned toner, there is, for example, an emulsion polymerization aggregation method, and toner particles are produced from a dispersion of resin particles, a dispersion of a release agent, etc. through an aggregation step and the like. At this time, a method of phase inversion emulsification of an organic solvent solution of the resin is used as a method of making the resin into particles.
On the other hand, as a method for forming resin particles in the absence of an organic solvent, a method is known in which the resin is melted at high temperature and dispersed as particles in water. For example, in Patent Document 1, melt-mixing a resin in the absence of an organic solvent, adding a surfactant to the resin as necessary, and adding a basic agent and water to the resin Forming an emulsion of resin particles.

JP, 2009-191271, A

The problem to be solved by the present invention is to provide a method for producing a resin particle dispersion liquid, in which a resin particle dispersion liquid in which a decrease in the molecular weight of the resin in the resin particles is suppressed can be obtained.
Another object of the present invention is to provide a method for producing an electrostatic charge image developing toner which can obtain an electrostatic charge image developing toner excellent in color developability.

The above-mentioned problems of the present invention have been solved by the means described in <1> or <4> below. It will be described below together with <2> to <3> which are preferable embodiments.
<1> A dispersion step of mixing a raw material containing at least a resin, a base, a surfactant, and water to obtain an aqueous dispersion of resin particles, wherein the dispersion step includes a screw shaft inside and a raw material supply barrel. Is carried out by a kneader having a means having heating and cooling means, the screw rotation speed (rpm) of the kneader is n, and the barrel inner diameter (m) of the kneader is D, the supply amount (kg/h) of the raw material, F, the raw material measured by a flow tester at a set temperature of the barrel for adding the first resin dispersion composition counted from the raw material supply barrel of the kneader +10° C. When the viscosity (Pa·s) of is represented by μ, the following formula (1) is satisfied, the method for producing a resin particle dispersion,
300≦(μ×n ² ×d ³ )/F≦8,000 (1)
<2> The method for producing a resin particle dispersion liquid according to <1>, wherein the raw material contains two or more resins,
<3> The method for producing a resin particle dispersion liquid according to <1> or <2>, wherein the raw material contains a colorant and/or a release agent.
<4> A step of aggregating resin particles in a dispersion liquid containing a resin particle dispersion liquid obtained by the method for producing a resin particle dispersion liquid according to any one of <1> to <3> to obtain agglomerated particles And a step of heating and aggregating the agglomerated particles to produce an electrostatic charge image developing toner.

According to the invention described in the above <1>, there is provided a method for producing a resin particle dispersion liquid, in which a resin particle dispersion liquid in which a decrease in the molecular weight of the resin in the resin particles is suppressed is obtained, as compared with the case where the present structure is not provided. Provided.
According to the invention described in the above <2>, resin particles capable of obtaining a resin particle dispersion liquid in which a decrease in the molecular weight of the resin in the resin particles is suppressed as compared with the case where the raw material does not contain two or more resins. A method of making a dispersion is provided.
According to the invention described in the above <3>, a resin particle dispersion liquid in which a decrease in the molecular weight of the resin in the resin particles is suppressed as compared with the case where the raw material does not include a colorant and/or a release agent. A method for producing the resulting resin particle dispersion is provided.
According to the invention described in the above item <4>, an electrostatic image developing toner having excellent color developability can be easily produced, as compared with the case where the present configuration is not provided.

It is a schematic block diagram which shows an example of the manufacturing apparatus used suitably for this embodiment. FIG. 1 is a schematic configuration diagram showing an example of an image forming apparatus preferably used in this embodiment. It is a schematic structure figure showing an example of a process cartridge used suitably for this embodiment.

The present embodiment will be described below.
In addition, in this embodiment, description with "AB" represents not only the range between A and B but the range which includes A and B which are the both ends. For example, if "A to B" is in the numerical range, it represents "A or more and B or less" or "B or more and A or less".
In the present embodiment, a combination of preferable modes is a more preferable mode.

(Method for producing resin particle dispersion)
The method for producing a resin particle dispersion of the present embodiment includes a dispersion step of obtaining an aqueous dispersion of resin particles by mixing a raw material containing at least a resin, a base, a surfactant, and water, and the dispersion step, It has a plurality of barrels equipped with a screw shaft and a raw material supply barrel, and the plurality of barrels are made by a kneader having heating and cooling means, and the screw rotation number (rpm) of the kneader is n The inner diameter (m) of the barrel of the machine is d, the feed rate (kg/h) of the raw material is F, and the first temperature of the barrel for adding the first resin dispersion composition counting from the raw material feed barrel of the kneader is +10°C. When the viscosity (Pa·s) of the raw material measured by a flow tester is μ, the following formula (1) is satisfied.
300≦(μ×n ² ×d ³ )/F≦8,000 (1)

The resin particle dispersion liquid of the present embodiment is a resin particle dispersion liquid obtained by the method for producing a resin particle dispersion liquid of the present embodiment.
Further, the resin particle dispersion obtained by the method for producing a resin particle dispersion of the present embodiment is suitably used as a resin particle dispersion for producing an electrostatic charge image developing toner.

According to the method described in Patent Document 1, the present inventors reduce the resin viscosity by applying heat of Tg or more of the resin, and increase the market share by using secondary materials (surfactant or base) and water in the resin. It has been found that the resin tends to be decomposed at the time of emulsification and the molecular weight of the resin is lowered because it is necessary to mix
Further, the present inventors have found that in the toner using the resin fine particle dispersion liquid in which the molecular weight is reduced as described above, deterioration of toner quality such as decrease of transfer efficiency and low temperature fixability is caused. .
As a result of intensive studies by the present inventors, it was found that the method for producing a resin particle dispersion liquid of the present embodiment can provide a resin particle dispersion liquid in which a decrease in the molecular weight of resin particles is suppressed.
Further, by using the resin particle dispersion obtained by the method for producing a resin particle dispersion of the present embodiment as a raw material of an electrostatic charge image developing toner, it is possible to obtain an electrostatic charge image developing toner excellent in color developability. The inventors have found out.

<Dispersion process>
The dispersion step is a step of producing an aqueous dispersion of resin particles, and is carried out without using an organic solvent. The resin particles are preferably polyester resin particles containing a polyester resin. The resin contained in the resin particles, such as a polyester resin, serves as a binder for the toner particles. The polyester resin is roughly classified into a crystalline polyester resin and an amorphous polyester resin (also referred to as “amorphous polyester resin”), but in the present embodiment, it is preferable that at least the amorphous polyester resin is contained. The resin, base, and surfactant will be described in detail later.

No organic solvent is used in the dispersion step in the present embodiment. Conventional methods such as suspension polymerization, dissolution suspension, and emulsion coagulation coalescence may use an organic solvent, but the method for producing a resin particle dispersion of the present embodiment uses an organic solvent. By mixing without doing so, it is not necessary to remove the organic solvent, and there is no odor due to the residual organic solvent, which is advantageous economically and environmentally.

The dispersion step has a plurality of barrels including a screw shaft inside and a raw material supply barrel, and the plurality of barrels are performed by a kneader having heating and cooling means, and preferably include some sub-steps. .. The sub-steps include a raw material supply section for supplying a kneader with a raw material containing a resin, preferably a polyester resin, more preferably a polyester resin having an acid group, a base supply section, and a surfactant supply section as a dispersion aid. Including a mixing step of mixing the resin, the base and the surfactant in the kneader, a water supplying step of supplying water to the kneader, the molten resin, the base and the surfactant. An example is a combination with a granulation step of kneading the agent with the water in the kneader to obtain an aqueous dispersion of resin particles. It is preferable to carry out each of the above-mentioned mixing step, water supply step and granulation step in one kneader. In the kneading machine, the resin, the base, the surfactant and the water are supplied under shearing force while kneading, and the resin is granulated while mixing these components to obtain resin particles. Is. That is, the resin supply step, the water supply step, the mixing step, and the granulation step are preferably integrated sub-steps.

By the dispersion step including these sub-steps, an aqueous dispersion of resin particles can be produced more stably without using an organic solvent.
Here, the organic solvent means a solvent containing a carbon atom for dissolving a binder resin such as a resin, and can be exemplified by ethyl acetate or the like used in the conventional phase inversion emulsification method of a resin solution.
In the method of manufacturing the electrostatic image developing toner according to the present exemplary embodiment, an aqueous dispersion of resin particles is manufactured without using any organic solvent that dissolves the resin. Further, using this aqueous dispersion, toner particles (toner mother particles) are manufactured by the aggregation and coalescence method.
Below, each of the sub-steps preferably exemplified above will be explained in order.

[Mixing process]
The mixing step is one of the sub-steps of the dispersion step, and is a mixing step of supplying the raw material containing the resin, the base, and the surfactant, and mixing under heating, and melting the resin. Then, the step of mixing the molten raw material containing the resin, the base, and the surfactant is preferable.
The supply of the raw material containing the resin to the kneading machine is not particularly limited, but preferably, the raw material containing the resin having an acid group is supplied to the kneading machine together with a dispersing aid, such as a base and a surfactant. It is preferable.
The raw material containing the resin, the base, and the surfactant may be supplied to the kneader at the same time or sequentially. The resin-containing raw material, the base, and the surfactant may be independently supplied, or the mixture of the resin-containing raw material and the base and the surfactant may be separately supplied. Above all, it is preferable to first mix the resin-containing raw material and the base and then supply the surfactant.

In the mixing step, preferably, the resin is melted or softened under heating, and the melted resin is mixed with the base and the surfactant. The mixing step is preferably a step of kneading in a kneader while applying a shearing force. The mixing step may be a continuous type or a batch type. The temperature in the barrel of the kneader is not particularly limited as long as it is equal to or higher than the softening temperature or melting temperature of the resin, but from the viewpoint of dispersibility, it is preferably 70°C to 100°C, and 80°C to 99°C. It is more preferable that the temperature is 85°C to 99°C.
The kneader adjusts the barrel set temperature (barrel temperature) so that the resin is heated to the above temperature range.

[Water supply process]
The water supply step is one of the sub-steps of the dispersion step, and is performed subsequent to the above mixing step. That is, it is a step of supplying water, which is a dispersion medium, to the mixture of the molten resin, the base and the surfactant. However, the base or surfactant may be supplied as an aqueous solution. The water supply step is a step of supplying only water.
In the water supplying step, water is supplied to the mixture of the molten resin, the base and the surfactant, preferably while applying a shearing force.
As water, well water, tap water, ion-exchanged water and distilled water are used, and ion-exchanged water is preferably used. The water may contain a water-miscible aqueous solvent, but preferably does not contain it.
In the water supply step, it is preferable that the water is heated to a temperature sufficient to maintain the molten state of the resin. Specifically, the barrel temperature of the kneader to which the water supply port is connected is preferably 70° C. to 99° C., and preheated water is preferably supplied. It should be noted that water may be heated to a temperature of 100° C. or higher as long as the kneading machine can apply pressure to prevent boiling of water.
As a method of adding water in the water supplying step, the water may be added in a divided manner or may be added in a single time, but it is preferable to add the water in two or more times, and the water is added in three or more times. Is more preferable. According to the above aspect, even if the amounts of the base and the surfactant used are small, an aqueous dispersion of resin particles having excellent granulation properties and a narrower particle size distribution can be obtained.
The total amount of water used is not particularly limited, but the solid content concentration of the aqueous dispersion of the obtained resin particles is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, It is particularly preferably from 10 to 50% by mass.

[Granulation process]
The granulation step is a step of kneading the molten resin in the water in the presence of the base and the surfactant to form resin particles. In the granulation step, the melted resin is kneaded together with the base and the surfactant in a kneading machine, and is made into resin particles by shearing force to be an aqueous dispersion. The granulation step is a step in which a single kind or a mixture of resins is melted or softened under heating to become resin particles having a gradually smaller average particle diameter by a shearing force, and starts from the above mixing step, After the water supply step, a final dispersion of resin particles having an average particle diameter in water is formed and discharged from the kneader.
The average particle size (volume average particle size) of the resin particles in the finally obtained dispersion liquid of resin particles is preferably in the range of 60 nm to 300 nm, and more preferably in the range of 80 nm to 250 nm. Within the above range, the cohesiveness of the resin particles is sufficient, and the particle size distribution of the toner can be narrowed.
The volume average particle diameter of the particles in the obtained dispersion liquid of the resin particles is, for example, Microtrac (manufactured by Nikkiso Co., Ltd., Microtrac UPA9340), laser diffraction particle size distribution analyzer (manufactured by Horiba, Ltd., LA-700), and more preferably Microtrac (manufactured by Nikkiso Co., Ltd., Microtrac UPA9340). Specific examples of the measuring method include the following methods. The sample in the state of dispersion is adjusted to have a solid content of about 2 g, and ion-exchanged water is added to this to make about 40 ml. This is put into a cell until it reaches an appropriate concentration, and after waiting for about 2 minutes, the measurement is performed when the concentration in the cell becomes almost stable. The volume average particle diameters of the obtained channels are accumulated from the smaller volume average particle diameter, and the point at which the cumulative 50% is reached is defined as the volume average particle diameter (D ₅₀ ).

[Kneading machine]
In the dispersion step in the present embodiment, the dispersion step is performed by a kneader having a screw shaft inside and a plurality of barrels including a raw material supply barrel, the plurality of barrels having heating and cooling means.
The plurality of barrels may have a means for adding a resin dispersion composition containing a surfactant and/or water or the like, if necessary.
The mixing step following the resin etc. supplying step and the granulation step of the resin particles may be carried out by using one apparatus which is common, or each step may be carried out by another apparatus. Further, a plurality of different devices may be used for each process. The whole process may be batch type, batch continuous type, or continuous type. Agitating tank may be used for resins with low melt viscosity, but batch type mixing such as pressure kneader, Banbury mixer, Labo Plastomill, etc. is also possible in order to support higher viscosity resins. The apparatus is preferable, and in the case of a continuous type, an extruder, particularly a twin-screw extruder or a multi-screw extruder having good mixing properties is preferable. Also, these devices may be used in combination. The twin-screw kneading extruder is commercially available, and the SS series manufactured by Toshiba Machine Co., Ltd. can be exemplified.

Hereinafter, as an example of a continuous type, a case where a twin-screw kneading extruder is used as a kneading machine suitably used in the present embodiment will be described with reference to FIG.
The twin-screw kneading extruder 10 has a barrel 12 having a twin-screw screw inside for kneading and granulating. The barrel 12 has a raw material charging port 14 containing a resin and an alkali metal hydroxide (aqueous solution) charging. It has a port 16, a surfactant charging port 18, water charging ports 20, 21, 22 and a discharge port 24. A supply line 26 for supplying a raw material is connected to each of the inlets, and each supply line 26 is provided with a pump 28 capable of adjusting the supply amount as needed. A resin feeder 30 is connected to the raw material inlet 14 by a supply line. An alkali metal hydroxide (aqueous solution) charging port 16 is provided on the side wall of the raw material charging port 14 so as to project. The alkali metal hydroxide (aqueous solution) charging port 16 is connected to the alkali metal hydroxide aqueous solution tank 32 by a supply line. Are connected. A surfactant aqueous solution tank 34 is connected to the surfactant input port 18 by a supply line, and the surfactant aqueous solution tank 34 is provided with a temperature control device 36 such as a constant temperature bath. A pure water tank 38 is connected to the water inlets 20, 21, and 22 by a supply line, and a heater 40 is provided in the pure water tank 38.
The barrel 12 in the twin-screw kneading extruder 10 is divided into about 10 sections, and for example, the structure of the twin-screw screw can be changed or the set temperature can be adjusted for each barrel. The twin-screw kneading extruder 10 is equipped with a temperature adjusting device for each barrel. The resin, the alkali metal hydroxide aqueous solution, the surfactant, and the water sequentially charged into the barrel are mixed and kneaded, and finally discharged from the discharge port 24 as an aqueous dispersion of the resin particles. As a preferred mode of this embodiment, first, a resin and an alkali metal hydroxide aqueous solution are supplied to the twin-screw kneading extruder 10, and discharged from a resin supply barrel 42 to which a raw material supply port of the twin-screw kneading extruder 10 is connected. Out of about 10 barrels up to the outlet 24, the surfactant inlet 18 is connected to the barrel in the first half, and the water inlets 20, 21, 22 are connected to the three barrels in the latter half from the center. ing. When the twin-screw kneading extruder is used in the present embodiment, after the resin and the alkali metal hydroxide aqueous solution are supplied to the first barrel 1, the barrel 12 is kept in the constant temperature region 44 from the second barrel to the 10th barrel. It is preferable to adjust the heating temperature of each barrel so that the internal temperature of the barrel is maintained in the temperature range of 85°C to 99°C.

In the present embodiment, the screw rotational speed (rpm) of the kneader is n, the barrel inner diameter (m) of the kneader is d, the supply amount (kg/h) of the raw material is F, and the raw material supply barrel of the kneader is counted. When the viscosity (Pa·s) of the raw material measured with a flow tester at the set temperature of the barrel to which the first resin dispersion composition is added +10° C. is μ, the following formula (1) is satisfied.
300≦(μ×n ² ×d ³ )/F≦8,000 (1)

The rotation speed n is preferably 1,500 rpm or less, and more preferably 240-1,500 rpm.
The raw material supply amount F varies depending on the kneader size, and is preferably barrel inner diameter d ³ (m)/raw material supply amount (kg/h) F=2.2×10 ^{−5 to} 1.8×10 ⁻⁷ .
For example, when the barrel inner diameter is 0.026 m, it is preferably 0.8 kg/h to 95 kg/h.
The viscosity μ of the raw material measured by a flow tester at the kneading machine set temperature +10° C. is preferably 20,000 Pa·s or less, and more preferably 500 to 15,000 Pa·s.
The viscosity μ can be measured by crushing the raw material for 30 seconds with a sample mill and then leaving it for 24 hours at room temperature of 10° C./humidity of 15% to measure the viscosity with a flow tester. A flow tester with a die diameter of φ0.5 mm was used, and the measurement conditions were an initial hold time of 300 seconds and a heating rate of 1° C./min. ..

Hereinafter, the resin-containing raw material, the base, and the surfactant used in the present embodiment will be described in order.

[Raw material containing resin]
-Amorphous polyester resin-
In the present embodiment, it is preferable that the resin in the resin-containing raw material contains an amorphous polyester resin.
Hereinafter, the polycarboxylic acid and the polyol used for the synthesis of the amorphous polyester resin will be described. As the raw material monomer for the amorphous polyester resin, a dihydric or higher valent secondary alcohol and/or a divalent or higher valent aromatic carboxylic acid compound is preferable. Examples of the dihydric or higher secondary alcohol include a propylene oxide adduct of bisphenol A, an ethylene oxide adduct of bisphenol A, propylene glycol, 1,3-butanediol, and glycerol. Among these, a propylene oxide adduct of bisphenol A and/or an ethylene oxide adduct of bisphenol A is preferable.
As the divalent or higher aromatic carboxylic acid compound, terephthalic acid, isophthalic acid, phthalic acid, dodecenylsuccinic acid and trimellitic acid are preferable, and terephthalic acid and trimellitic acid are more preferable.

Further, hydroxycarboxylic acid can also be used as a raw material for producing an amorphous polyester resin. Specific examples of the hydroxycarboxylic acid include hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, malic acid, tartaric acid, mucus acid and citric acid.

When the non-crystalline polyester resin is used, the glass transition temperature Tg of the non-crystalline polyester resin is preferably 50°C to 80°C, more preferably 50°C to 65°C. When the Tg is 50° C. or higher, the cohesive force of the binder resin itself in the high temperature range is good, and therefore the hot offset property at the time of fixing is excellent. Further, when Tg is 80° C. or lower, sufficient melting is obtained, and the minimum fixing temperature does not easily rise. The glass transition temperature of the binder resin refers to the value measured by the method (DSC method) specified in ASTM D3418-82.

The weight average molecular weight of the amorphous polyester resin is preferably 5,000 to 100,000, more preferably 10,000 to 90,000, and further preferably 20,000 to 80,000. preferable.
When the weight average molecular weight of the non-crystalline polyester resin is within the range of the above numerical values, image strength and fixability are compatible with each other, which is preferable. The above weight average molecular weight can be obtained by measuring the molecular weight of a soluble component of tetrahydrofuran (THF) by gel permeation chromatography (GPC) method. The molecular weight of the resin is calculated by measuring the THF-soluble material with TSK-GEL (GMH (manufactured by Tosoh Corporation)) and the like in a THF solvent and using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample. To be done.

The melt viscosity at 105° C. (105° C. melt viscosity) of the amorphous polyester resin used in this embodiment is preferably 20,000 Pa·s or less at a shear rate of 2.6 s ⁻¹ , and 2,000 to More preferably, it is 20,000 Pa·s. The melt viscosity at 105° C. can be measured by a shear test using a flow tester CFT-500F type (manufactured by Shimadzu Corporation) at a shear rate (strain rate) of 2.6 s ⁻¹ .

The method for producing the amorphous polyester resin is not particularly limited, and can be produced by a general polyester polymerization method in which a polyol component and a polycarboxylic acid component are reacted, for example, direct polycondensation, transesterification, etc. , Which is used properly according to the kind of the monomer. Further, it is preferable to use a polycondensation catalyst such as a metal catalyst or a Bronsted acid catalyst.
In the case of directly polycondensing the above-mentioned polyol and polycarboxylic acid, the non-crystalline polyester resin is provided with, for example, the above-mentioned polyol and polycarboxylic acid, and if necessary, a catalyst, a thermometer, a stirrer, and a downflow condenser. Blended in a reaction vessel and heated at 150° C. to 250° C. in the presence of an inert gas (such as nitrogen gas) to continuously remove low molecular weight compounds such as by-produced water out of the reaction system to obtain a predetermined acid. It is produced by stopping the reaction when the value is reached, cooling, and obtaining the desired reaction product.

Further, the resin-containing raw material used in this embodiment preferably contains two or more resins, and more preferably contains two or more polyester resins.
When the resin-containing raw material contains two or more polyester resins, it is preferable to contain at least one type of non-crystalline polyester resin, and it is preferable to use two types of non-crystalline polyester resins in combination or to use non-crystalline polyester resin. , And is preferably used in combination with a crystalline polyester resin.

The raw material containing the resin used in this embodiment preferably contains a colorant and/or a release agent.
Hereinafter, the crystalline polyester resin, the colorant, and the release agent will be described.

-Crystalline polyester resin-
The crystalline polyester resin used in the present embodiment is preferably composed of an aliphatic dicarboxylic acid and an aliphatic diol, and a straight chain type dicarboxylic acid having a main chain having 4 to 20 carbon atoms, a straight chain type aliphatic Diols are more preferred. When it is a straight chain type, the polyester resin has excellent crystallinity and an appropriate crystal melting point, so that it is excellent in toner blocking resistance, image storability, and low temperature fixability. When the carbon number is 4 or more, the ester bond concentration is low, the electric resistance is appropriate, and the toner charging property is excellent. Further, if it is 20 or less, it is easy to obtain a practical material. The carbon number is more preferably 14 or less.

Examples of the aliphatic dicarboxylic acid preferably used for synthesizing the crystalline polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelic acid, sebacic acid, and 1,9-nonane. Dicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid Examples thereof include, but are not limited to, acids, 1,18-octadecanedicarboxylic acid and the like, or lower alkyl esters and acid anhydrides thereof. Of these, sebacic acid and 1,10-decanedicarboxylic acid are preferable in consideration of availability.
Specific examples of the aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. 1,1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol , 1,18-octadecanediol, 1,14-eicosanedecanediol, and the like, but are not limited thereto. Of these, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in consideration of availability.
Examples of trihydric or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. These may be used alone or in combination of two or more.

The content of the aliphatic dicarboxylic acid in the polycarboxylic acid component is preferably 80 mol% or more, more preferably 90 mol% or more. When the content of the aliphatic dicarboxylic acid is 80 mol% or more, the crystallinity of the polyester resin is excellent and the melting point is appropriate, so that the toner blocking resistance, the image storability and the low temperature fixing property are excellent.
The content of the aliphatic diol component in the polyhydric alcohol component is preferably 80 mol% or more, more preferably 90 mol% or more. When the content of the aliphatic diol component is 80 mol% or more, the crystallinity of the polyester resin is excellent and the melting point is appropriate, so that the toner blocking resistance, the image storability and the low temperature fixing property are excellent.

In the present embodiment, the melting temperature Tm of the crystalline polyester resin is preferably 50 to 100°C, more preferably 50 to 90°C, and further preferably 50 to 80°C. Within the above range, the releasability and the low temperature fixability are excellent, and the offset is further reduced, which is preferable.
Here, for the measurement of the melting temperature of the crystalline polyester resin, a differential scanning calorimeter is used, and JIS K-7121 is used when the temperature is measured from room temperature (20° C.) to 180° C. at a temperature rising rate of 10° C./min. : 87 can be obtained as the melting peak temperature of the input compensation differential scanning calorimetry. The crystalline polyester resin may show a plurality of melting peaks, but in this embodiment, the maximum peak is the melting temperature.

The weight average molecular weight of the crystalline polyester resin is preferably 10,000 to 60,000, more preferably 15,000 to 45,000, and further preferably 20,000 to 30,000. ..
When the weight average molecular weight of the crystalline polyester resin is within the range of the above numerical values, image strength and fixability are compatible with each other, which is preferable. The above weight average molecular weight can be measured by the same method as the weight average molecular weight of the non-crystalline polyester resin.

The method for producing the crystalline polyester resin is not particularly limited, and the crystalline polyester resin can be produced by the same method as the above-mentioned method for producing the amorphous polyester resin.

-Colorant-
As the colorant used in the present embodiment, a colorant known in the field of toner can be used, and it is arbitrarily selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. Just select it.
Specifically, various pigments such as Watch Young Red, Permanent Red, Bryrianka Mine 3B, Bryrianka Mine 6B, Dayon Oil Red, Pyrazolone Red, Resor Red, Rhodamine B Lake, Lake Red C Rose Bengal, and acridine-based pigments. , Xanthene, azo, benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane Examples thereof include various colorants such as system, thiazine, thiazole, and xanthene.
Further, as the colorant, specifically, for example, carbon black, nigrosine dye (CINo.50415B), aniline blue (CINo.50405), calco oil blue (CINo.azoic Blue3), chrome yellow (CINo.14090) , Ultramarine Blue (CINo.77103), DuPont Oil Red (CINo.26105), Quinoline Yellow (CINo.47005), Methylene Blue Chloride (CINo.52015), Phthalocyanine Blue (CINo.74160), Malachite Green Oxalate (CINo. 42000), lamp black (CI No. 77266), rose bengal (CI No. 45435), and mixtures thereof can be preferably used.
The colorant may be a surface-treated colorant, if necessary, or may be used in combination with a dispersant. Further, a plurality of kinds of colorants may be used in combination.
The amount of the colorant used is preferably 0.1 to 40 parts by mass and more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the raw material containing the resin. As the colorant, these pigments, dyes and the like can be used alone or in combination of two or more.

-Release agent-
Specific examples of the release agent include, for example, ester wax, polyethylene, polypropylene or a copolymer of polyethylene and polypropylene, polyglycerin wax, microcrystalline wax, paraffin wax, carnauba wax, sazol wax, montanic acid ester wax, and deoxidizing agent. Acid carnauba wax, palmitic acid, stearic acid, montanic acid, brassic acid, eleostearic acid, unsaturated fatty acids such as valinaric acid, stearyl alcohol, aralkyl alcohol, bephenyl alcohol, carnaubayl alcohol, ceryl alcohol, melicyl Saturated alcohols such as alcohols or long-chain alkyl alcohols having a longer-chain alkyl group; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylenebisstearin Saturated fatty acid bisamides such as acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide, ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N,N′-dioleyl adipic acid Unsaturated fatty acid amides such as amides, N,N′-dioleyl sebacic acid amides; aromatic bisamides such as m-xylene bisstearic acid amides, N,N′-distearylisophthalic acid amides; calcium stearate, Fatty acid metal salts such as calcium laurate, zinc stearate and magnesium stearate (generally referred to as metallic soap); waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid. And the like; partial esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like. Of these, waxes are preferable.
The release agents may be used alone or in combination of two or more.
The content of the release agent is preferably 1 to 40 parts by mass, more preferably 3 to 30 parts by mass, with respect to 100 parts by mass of the raw material containing the resin. Within the above range, both good fixing and good image quality can be achieved.

〔base〕
In the dispersion process of this embodiment, a base (basic compound) is used to dissociate the acid groups of the resin. Examples of the base include alkali metal hydroxide (alkali metal hydroxide), alkaline earth hydroxide (alkaline earth metal hydroxide), alkali carbonate (alkali metal carbonate), and organic amine. Specifically, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide are preferable. Examples of the base that can be used in combination with the alkali metal hydroxide include oxides or hydroxides of alkaline earth metals such as magnesium hydroxide and calcium hydroxide. Alkaline earth metal hydroxides can be used in combination, but alkali metal hydroxides are preferably used alone, potassium hydroxide or sodium hydroxide is more preferable, and sodium hydroxide is particularly preferable. The base used in the present embodiment may be used alone or in combination of two or more. The amount of alkali metal hydroxide used may be sufficient to dissociate the acid groups of the resin, and may be used in a small excess.
The amount of the base used depends on the content of the acid group of the resin used, but it is preferably sufficient to neutralize the acid group. It is preferably 0.001 to 10 parts by mass, more preferably 0.005 to 5 parts by mass, still more preferably 0.01 to 2 parts by mass, and 0.1 to 100 parts by mass of the resin. It is particularly preferable that the amount is 01 to 1 part by mass. Within the above range, the granulation property and the dispersion stability are excellent, and the transferability of the toner is excellent.
The base is preferably supplied to the kneader as an aqueous solution of the base, more preferably as a highly concentrated aqueous solution of the base. The concentration of the high-concentration base in the aqueous solution is preferably 4-70% by mass, more preferably 10-65% by mass, depending on the solubility of the base, the liquid temperature, the supersaturated state, and the like. More preferably, it is from 60 to 60% by mass. In the above aspect, although the mechanism is unknown, a resin particle dispersion liquid having a better dispersibility and a narrower particle size distribution can be obtained.

[Surfactant]
Examples of the surfactant used in this embodiment include various surfactants such as anionic surfactants, amphoteric surfactants, cationic surfactants, and nonionic surfactants. Among them, anionic surfactants are preferable, sulfuric acid ester type or sulfonic acid type anionic surfactants are more preferable, sulfonic acid type anionic surfactants are further preferable, and disulfonic acid type anionic surfactants are Particularly preferred.

As the anionic surfactant, any of carboxylic acid type, sulfuric acid ester type, sulfonic acid type, and phosphoric acid ester type can be used. For example, fatty acid salt, rosinate, naphthenate, ether carboxylate, alkenyl succinate, primary alkyl sulfate, secondary alkyl sulfate, alkyl polyoxyethylene sulfate, alkylphenyl polyoxyethylene sulfate, Sulfate monoacylglycerin salt, acylamino sulfate ester salt, sulfated oil, sulfated fatty acid alkyl ester, α-olefin sulfonate, secondary alkane sulfonate, α-sulfo fatty acid salt, acyl isethionate, dialkyl sulfosuccinate, Alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl diphenyl ether disulfonate, petroleum sulfonate, lignin sulfonate, alkyl phosphate, alkyl polyoxyethylene phosphate, alkylphenyl polyoxyethylene phosphate, perfluoro Examples thereof include alkylcarboxylic acid salts, perfluoroalkylsulfonic acid salts, and perfluoroalkylphosphoric acid esters. Among these, alkyl diphenyl ether disulfonate is preferable, and sodium dodecyl diphenyl ether disulfonate is more preferable.

An amphoteric surfactant is a surfactant that has both a cation group and an anion group in its molecular structure, and has charge separation within the molecular structure, but no charge as a whole molecule. Means As the zwitterionic surfactant, for example, N-alkyl nitrilotriacetic acid, N-alkyl dimethyl betaine, N-alkyloxymethyl-N,N-diethyl betaine, N-alkyl sulfobetaine, N-alkyl hydroxy sulfobetaine, lecithin, Perfluoroalkylsulfonamidoalkyl betaines may be mentioned.

Examples of the cationic surfactant include N-acylamine salt, quaternary ammonium salt, and imidazolium salt, and specific examples thereof include fatty acid polyethylene polyamide, alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, and alkyl. Dimethylbenzylammonium salt, alkylpyridinium salt, acylaminoethylmethyldiethylammonium salt, acylaminopropyldimethylbenzylammonium salt, acylaminopropyldimethylhydroxyethylammonium salt, acylaminoethylpyridinium salt, diacylaminoethylammonium salt, diacyloxyethylmethyl Examples thereof include hydroxyethylammonium salt, alkyloxymethylpyridinium salt, and 1-acylaminoethyl-2-alkylimidazolium salt.

Examples of nonionic surfactants include esters of polyhydric alcohols and fatty acids, ethers such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene glycol, fatty acids to which ethylene oxide is added, Examples thereof include a polyhydric alcohol fatty acid ester to which ethylene oxide is added, a fatty acid alkanolamide in which a hydrophobic group and a hydrophilic group are bonded by an amide bond, and an alkyl polyglycoside.
The anionic surfactant, amphoteric surfactant, cationic surfactant, and nonionic surfactant are not limited to those exemplified above, and in addition to the above, known anionic surfactants. You may use surfactant, amphoteric surfactant, cationic surfactant, and nonionic surfactant. The surfactants used in this embodiment may be used alone or in combination of two or more.

The amount of the surfactant used in the dispersion step is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin. More preferably, it is a part. Within the above range, the granulation property and the dispersion stability are excellent, and the transferability of the toner is excellent.

The surfactant is preferably supplied to the kneader as an aqueous solution of the surfactant, more preferably as a high-concentration aqueous solution of the surfactant. The surfactant concentration of the aqueous surfactant solution depends on the solubility of the surfactant, the liquid temperature, the supersaturated state, etc., but is preferably 5 to 60% by mass, more preferably 10 to 55% by mass. It is preferably 20 to 50% by mass, and further preferably. Although the mechanism is unclear in the above aspect, a resin particle dispersion liquid having a better granulation property and dispersion stability and a narrower particle size distribution can be obtained.

(Method for manufacturing electrostatic image developing toner)
The electrostatic image developing toner of the present embodiment (hereinafter, also simply referred to as “toner”) binds the resin particles dispersed in the resin particle dispersion obtained by the method for producing the resin particle dispersion of the present embodiment. It is a toner used at least as a resin.
The method for producing an electrostatic image developing toner according to the present exemplary embodiment includes a step of aggregating resin particles in a dispersion liquid containing a resin particle dispersion obtained by the method for producing a resin particle dispersion according to the present embodiment to obtain aggregated particles. And a step of heating and aggregating the agglomerated particles.

<Coagulation process>
The method for producing a toner according to this exemplary embodiment is a step of aggregating resin particles in a dispersion liquid containing the resin particle dispersion obtained by the method for producing a resin particle dispersion to obtain aggregated particles (also referred to as “aggregation step”). ) Is preferably included.
In the aggregating step, the resin particle dispersion produced by the method for producing a resin particle dispersion of the present embodiment, and, if necessary, a colorant dispersion, each particle in the release agent dispersion is an aqueous medium. Aggregate in to form agglomerated particles of the desired volume average particle size. The aggregated particles are formed by heteroaggregation or the like, and a surfactant or an aggregating agent may be added for the purpose of stabilizing the aggregated particles and controlling the particle size/particle size distribution. Further, it is preferable to form the agglomerated particles by adding the aggregating agent while stirring with a rotary shearing homogenizer. The temperature in the aggregating step is not particularly limited as long as the aggregation proceeds, but is preferably 10°C to 55°C.

In the present embodiment, depending on the purpose, at least one of the resin particle dispersion, the colorant dispersion and the release agent dispersion, an internal additive, a charge control agent, an inorganic particle, an organic particle Other components such as a lubricant, an abrasive and the like may coexist. Further, for example, other components may be allowed to coexist in at least one of the resin particle dispersion liquid, the colorant dispersion liquid, and the release agent dispersion liquid, or the resin particle dispersion liquid, the colorant dispersion liquid, and the release agent. You may mix the dispersion liquid which adds another component in the mixed liquid which mixes a mold agent dispersion liquid.

[Colorant dispersion]
In the method of manufacturing an electrostatic image developing toner according to the present exemplary embodiment, the colorant dispersion liquid may be used in combination with the resin particle dispersion liquid in the aggregation step, if necessary.
As the colorant, those known in the field of toner can be used, and may be arbitrarily selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner.
Specific examples thereof include the same colorants as those exemplified in the raw material containing the above resin.
The colorant may be a surface-treated colorant, if necessary, or may be used in combination with a dispersant. Further, a plurality of kinds of colorants may be used in combination.
The amount of the colorant used is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the electrostatic image developing toner. As the colorant, these pigments, dyes and the like can be used alone or in combination of two or more.
As a method for dispersing the colorant, an arbitrary method, for example, a general shearing method such as a rotary shearing homogenizer, a ball mill having a medium, a sand mill, a dyno mill, or the like can be used without any limitation. Further, these colorant particles may be added together with other particle components in the mixed solvent at once, or may be divided and added in multiple stages.
Water can be exemplified as the dispersion medium in the colorant dispersion liquid and the dispersion liquid such as the release agent dispersion liquid, and is preferably used.
As the water used in this embodiment, deionized water or ion-exchanged water is preferably used.
Further, water may be mixed with a water-miscible organic solvent to form an aqueous medium. Examples of the water-miscible organic solvent include ethyl alcohol, acetone, acetic acid and the like.

-Method for producing colorant dispersion-
The colorant dispersion liquid is a dispersion liquid in which a colorant is dispersed in water in the form of particles.
The colorant is dispersed by a known method, but for example, a media type disperser such as a rotary shearing homogenizer, a ball mill, a sand mill, an attritor, or a high pressure opposed collision type disperser is preferably used. Further, as the colorant, a polar ionic surfactant may be used, and the colorant particle dispersion liquid may be prepared by dispersing in a water-based solvent using the homogenizer as described above. The colorants may be used alone or in combination of two or more. The volume average particle diameter of the colorant (hereinafter, sometimes simply referred to as average particle diameter) is preferably 1 μm or less, more preferably 0.5 μm or less, and 0.01 to 0.5 μm. Is particularly preferable.
Further, as a dispersant added to further stabilize the dispersion stability of the colorant in the aqueous medium and reduce the energy of the colorant in the toner, rosin, a rosin derivative, a coupling agent, a polymer dispersion Agents and the like.

[Release agent dispersion]
In the aggregation step in the method for producing a toner according to the exemplary embodiment, a release agent dispersion liquid may be used in combination, and a release agent dispersion liquid is preferably used in combination, if necessary.
Specific examples of the release agent include the same release agents as the release agent exemplified in the raw material containing the above resin.
The release agents may be used alone or in combination of two or more.
The content of the release agent is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass, based on 100 parts by mass of the binder resin. Within the above range, both good fixing and good image quality can be achieved.

[Surfactant]
In the toner manufacturing method of the present embodiment, a surfactant can be used for the purpose of stabilizing the dispersion of the colorant dispersion liquid and the release agent dispersion liquid in the aggregation step.
Examples of the surfactant include anionic surfactants such as sulfate ester-based, sulfonate-based, phosphate ester-based, and soap-based; cationic surfactants such as amine salt-type and quaternary ammonium salt-type; polyethylene. Examples thereof include nonionic surfactants such as glycol-based, alkylphenol ethylene oxide adduct-based, polyhydric alcohol-based and the like. Among these, ionic surfactants are preferable, and anionic surfactants and cationic surfactants are more preferable.

In the method for producing a toner, an anionic surfactant is generally used because it has a strong dispersive power and is excellent in dispersing the resin particles and the colorant. Further, it is advantageous to use an anionic surfactant as the surfactant for dispersing the release agent.
The nonionic surfactant is preferably used in combination with the anionic surfactant or the cationic surfactant. The surfactants may be used alone or in combination of two or more.

The content of the surfactant in the colorant dispersion and the release agent dispersion may be such that it does not hinder the present embodiment, and is generally a small amount, specifically 0.01 mass. % Or more and 3 mass% or less, preferably 0.05 mass% or more and 2 mass% or less, and more preferably 0.1 mass% or more and 1 mass% or less. preferable. Within the above range, each dispersion liquid such as the colorant dispersion liquid and the release agent dispersion liquid is stable, neither aggregation nor release of specific particles occurs, and the effects of the present embodiment are sufficiently obtained.

[Flocculant]
In the aggregating step, particles having a toner particle diameter containing a binder resin and a colorant can be prepared by causing aggregation due to a pH change or the like. At the same time, an aggregating agent may be added for stable and rapid agglomeration of particles or for obtaining agglomerated particles having a narrower particle size distribution.
As the aggregating agent, a compound having a charge of monovalent or higher is preferable, and specific examples of the compound include the aforementioned ionic surfactants, water-soluble surfactants such as nonionic surfactants, hydrochloric acid, and sulfuric acid. Acids such as nitric acid, acetic acid, oxalic acid, (poly)aluminum chloride, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, aluminum nitrate, silver nitrate, copper sulfate, inorganic acid metal salts such as sodium carbonate, sodium acetate, formic acid Examples thereof include metal salts of aliphatic acids such as potassium, sodium oxalate, sodium phthalate, and potassium salicylate, aromatic acids, metal salts of phenols such as sodium phenolate, and the like.

Considering the stability of the agglomerated particles, the stability of the aggregating agent against heat and aging, and the removal during washing, a metal salt of an inorganic acid is preferable as the aggregating agent in terms of performance and use. Specific examples include metal salts of inorganic acids such as (poly)aluminum chloride, magnesium chloride, sodium chloride, aluminum sulfate, calcium sulfate, aluminum nitrate, silver nitrate, copper sulfate and sodium carbonate.
The addition amount of these aggregating agents varies depending on the valence number of the charge, but it is preferable that the addition amount is small in each case. Is preferably 0.5% by mass or less. Since it is preferable that the amount of the aggregating agent is small, it is preferable to use a compound having a high valence.

<Shell attachment process>
The toner manufacturing method of the present embodiment is a step of adding resin particles to the dispersion liquid containing the aggregated particles after the aggregation step of forming aggregated particles in order to obtain toner mother particles having a so-called core-shell structure. And a shell adhering step of adhering the resin particles to the surface of the agglomerated particles to coat the agglomerated particles. As the resin particles, it is preferable to use the resin particle dispersion liquid produced by the method for producing a resin particle dispersion liquid of the present embodiment. That is, it is preferable that the addition step is a step of further adding the resin particle dispersion liquid used in the aggregation step to the dispersion liquid containing the aggregated particles.

The addition amount of the resin particles in the adding step is not particularly limited, but is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the total mass of the agglomerated particles obtained in the aggregating step, and 0. The amount is more preferably 5 to 8 parts by mass, further preferably 1 to 5 parts by mass.
As the aggregating agent used in the shell attaching step, the aggregating agent added in the aggregating step may be used as it is or may be newly added.
The temperature of the dispersion liquid in the shell attaching step is not particularly limited as long as it is a temperature at which the resin particles can be attached to the surface of the agglomerate, but the preferred temperature is the same as the temperature of the dispersion liquid in the aggregating step. ..
Further, in the aggregating step and the shell attaching step, the shell attaching step may be performed while the resin particle adding step is performed, or the shell attaching step may be performed after the adding step. It is good, however, in the addition step subsequent to the shell attaching step, it is preferable to take an interval in the shell attaching step in consideration of the time when the resin particles added in the aggregating step adhere to the surface of the agglomerated particles.
In the adding step and/or the shell attaching step, a surfactant may be added or pH may be adjusted for the purpose of stabilizing the aggregate and controlling the particle size/particle size distribution.

<Fusion process>
The method for producing the electrostatic image developing toner according to the exemplary embodiment preferably includes a step of heating and aggregating the agglomerated particles (also referred to as a “fusing step”).
In the fusing step, toner particles are formed by fusing the aggregated particles.
In the fusing step, the binder resin in the agglomerated particles is melted under a temperature condition equal to or higher than its melting point or glass transition temperature, and the agglomerated particles change from an amorphous shape to a more spherical shape.
The heating temperature in the fusion step is preferably in the range of (melting temperature of used crystalline resin +0 to 50)°C or (glass transition temperature of used amorphous resin particles +0 to 50°C), The melting temperature of the crystalline resin used +0 to 40°C) or (glass transition temperature of non-crystalline polyester resin +10 to 40°C) is more preferable.
The heating time may be such that the resin particles in the agglomerated particles are fused together, and is preferably 0.5 to 10 hours.
After coalescing the agglomerated particles, cooling is performed to obtain fused particles. In the cooling process, recrystallization of the release agent or the binder resin is performed by increasing the cooling rate near the melting temperature of the release agent or the binder resin (melting temperature ±10°C range), so-called rapid cooling. You may suppress and surface exposure may be suppressed.

<Additional optional process>
The method of manufacturing the electrostatic image developing toner according to the exemplary embodiment includes, after the fusing step, either a washing step of washing the toner particles or a drying step of drying the washed toner particles after solid-liquid separation. However, it is preferable that both are included.
That is, after the completion of the fusing step, it is preferable to produce a desired toner through an arbitrary washing step, solid-liquid separation step, drying step, external addition step and the like.
In the washing step, it is preferable to sufficiently perform displacement washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration and the like are preferably used from the viewpoint of productivity. Further, the drying step is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration type fluidized drying and the like are preferably used from the viewpoint of productivity. The toner of the present embodiment preferably has a moisture content after drying adjusted to 1.0% by mass or less, more preferably 0.5% by mass or less.

(Electrostatic charge image developing toner)
The toner according to the exemplary embodiment is configured to include toner mother particles and, if necessary, an external additive.
Further, the electrostatic image developing toner is preferably a toner in which an external additive is externally added to toner mother particles containing a colorant (hereinafter, also referred to as colored particles).

<Toner mother particles>
The toner mother particles preferably include a binder resin and a colorant, and more preferably include a binder resin, a colorant, and a release agent.
A polyester resin is preferably used as the binder resin. The polyester resin is as described above.
Further, the colorant and the release agent are as described above.

[Other additives]
Examples of other additives include known additives such as magnetic materials, charge control agents, and inorganic powders. These additives are included in the toner mother particles as internal additives.

[Characteristics of toner mother particles]
The toner mother particles may be toner mother particles having a single layer structure, or a so-called core-shell structure toner mother composed of a core portion (core particles) and a coating layer (shell layer) covering the core portion. It may be a particle.
Here, the toner mother particles having a core/shell structure include, for example, a core portion including a binder resin and, if necessary, other additives such as a colorant and a release agent, and a binder resin. And a coating layer composed of.

The volume average particle diameter (D _50v ) of the toner mother particles is preferably 2 μm or more and 10 μm or less, more preferably 4 μm or more and 8 μm or less.
In addition, various average particle diameters and various particle size distribution indexes of the toner mother particles are measured using Coulter Multisizer II (manufactured by Beckman-Coulter) and an electrolyte is measured using ISOTON-II (manufactured by Beckman-Coulter). To be done.
At the time of measurement, 0.5 mg or more and 50 mg or less of the measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant (sodium alkylbenzenesulfonate is preferable) as a dispersant. This is added to 100 ml or more and 150 ml or less of the electrolytic solution.
The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for 1 minute with an ultrasonic disperser, and a Coulter Multisizer II is used to obtain a particle size distribution of particles in a range of 2 μm or more and 60 μm or less using an aperture of 100 μm as an aperture diameter. taking measurement. The number of particles sampled is 50,000.
The cumulative distribution of the volume and number is drawn from the small diameter side with respect to the particle size range (channel) divided based on the measured particle size distribution, and the cumulative particle size is 16% as the volume particle size D _16v and several particles. The diameter D _16p and the cumulative particle diameter of 50% are _defined as a volume average particle diameter D _50v , the cumulative number average particle diameter D _50p and the cumulative particle diameter of 84% are defined as a volume particle diameter D _84v and a number particle diameter D _84p .
Using these, the volume average particle size distribution index (GSDv) is ^{_{(D 84v / D 16v) 1/2}} , the number average particle size distribution index (GSDp) is calculated as ^{_{1/2 (D 84p / D 16p)}} .

The shape factor SF1 of the toner base particles is preferably 110 or more and 150 or less, and more preferably 120 or more and 140 or less.

The shape factor SF1 is calculated by the following equation.
Formula: SF1=(ML2/A)×(π/4)×100
In the above formula, ML represents the absolute maximum length of the toner, and A represents the projected area of the toner.
Specifically, the shape factor SF1 is quantified mainly by analyzing a microscope image or a scanning electron microscope (SEM) image with an image analyzer, and is calculated as follows. That is, the optical microscope image of the particles scattered on the surface of the glass slide is captured by a video camera in a Luzex image analyzer, the maximum length and projected area of 100 particles are calculated, and the average value is calculated by the above formula. can get.

<External additive>
An external additive may be externally added to the surface of the toner, if necessary. Examples of the external additive externally added to the surface include inorganic particles and organic particles.
As the inorganic particles, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, cerium chloride, Examples thereof include red iron oxide, chromium oxide, cerium oxide, antimony trioxide, magnesium oxide, zirconium oxide, silicon carbide and silicon nitride.
Inorganic particles are generally used for the purpose of improving fluidity. The volume average primary particle diameter of the inorganic particles is preferably in the range of 1 to 200 nm. The addition amount of the inorganic particles is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the toner.
The surface of the inorganic particles is preferably subjected to a hydrophobic treatment in advance. This hydrophobizing treatment is more effective not only for improving the powder fluidity of the toner, but also for the environmental dependence of charging and carrier contamination resistance.
The hydrophobic treatment may be performed by immersing the inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include a silane coupling agent, silicone oil, a titanate coupling agent, and an aluminum coupling agent. These may be used alone or in combination of two or more. Among these, a silane coupling agent is preferable.
Organic particles are generally used for the purpose of improving cleaning properties and transfer properties, and specifically, for example, fluorine-based resin powders such as polyvinylidene fluoride and polytetrafluoroethylene, and fatty acid metal salts such as zinc stearate and calcium stearate. , Polystyrene, polymethylmethacrylate, and the like.
Among these, it is preferable to use an inorganic oxide such as titania or silica from the viewpoint of improving fluidity and charging characteristics.
The external additives may be used alone or in combination of two or more. The ratio of the external additive externally added to the toner mother particles before external addition is preferably 0.01 to 5 parts by mass, and 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the toner mother particles. Is more preferable.
The method of externally adding the inorganic particles such as silica and titania to the surface of the toner mother particles in the external addition step is not particularly limited, and a known method is used, for example, a mechanical method or a chemical method. There is a method of making it. Further, if necessary, coarse particles of toner may be removed using a vibration sieving machine, a wind sieving machine or the like.

(Electrostatic charge image developer)
The electrostatic image developer of the present embodiment (hereinafter, also referred to as “developer”) is not particularly limited as long as it contains the electrostatic image developing toner of the present embodiment, and the toner is used alone. It may be a one-component developer or a two-component developer containing a toner and a carrier. In the case of a one-component developer, it may be a toner containing magnetic metal particles or a non-magnetic one-component toner containing no magnetic metal particles.
The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is preferably toner:carrier=1:100 to 30:100, more preferably 3:100 to 20:100.
The carrier is not particularly limited as long as it is a known carrier, and iron powder-based carriers, ferrite-based carriers, surface-coated ferrite carriers and the like are used. Further, each surface-added powder may be subjected to a desired surface treatment before use.
Specific examples of carriers include the following resin-coated carriers. Examples of the carrier core particles include ordinary iron powder, ferrite, and magnetite-molded products, and the volume average particle diameter thereof is preferably 30 to 200 μm.

Examples of the coating resin for the resin-coated carrier include styrenes such as styrene, parachlorostyrene, α-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, lauryl acrylate, acrylic acid 2 -Unsaturated aliphatic monocarboxylic acid esters such as ethylhexyl, methyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; nitrogen-containing (meth)acrylic acid esters such as dimethylaminoethyl methacrylate; Vinyl nitriles such as acrylonitrile and methacrylonitrile; Vinyl pyridines such as 2-vinyl pyridine and 4-vinyl pyridine; Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone Such as vinyl ketones; olefins such as ethylene and propylene; vinyl-based fluorine-containing monomers such as vinylidene fluoride, tetrafluoroethylene, and hexafluoroethylene; and homopolymers thereof, or copolymers of two or more kinds of monomers, and the like. , Silicone resins containing methyl silicone, methylphenyl silicone, etc., polyesters containing bisphenol, glycol, etc., epoxy resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, polycarbonate resins and the like. These resins may be used alone or in combination of two or more. The coating amount of the coating resin is preferably in the range of about 0.1 to 10 parts by mass, more preferably in the range of 0.5 to 3.0 parts by mass with respect to 100 parts by mass of the core particles.

A heating type kneader, a heating type Henschel mixer, a UM mixer or the like is used for manufacturing the carrier, and a heating type fluidized rolling bed, a heating type kiln or the like is used depending on the amount of the coating resin.
As the carrier, when a carrier coated with a resin in which ferrite particles are used as a nucleus and methyl acrylate or ethyl acrylate, styrene, or the like is dispersed with carbon black or the like as a conductive agent and/or melamine beads or the like as a charge control agent is used, a coat layer is formed. Since the resistance controllability is excellent even when the film is thickened, the image quality and the image quality maintenance are excellent, which is more preferable.
The mixing ratio of the toner and the carrier in the developer is not particularly limited and is selected according to the purpose.

(Image forming method)
An image forming method using the toner of this embodiment will be described. The toner of this embodiment is used in an image forming method using a known electrophotographic method. Specifically, it is used in an image forming method having the following steps.
That is, a preferable image forming method includes a charging step of uniformly charging the surface of the electrostatic charge image carrier, a latent image forming step of forming a latent image on the surface of the charged electrostatic charge image carrier, and the electrostatic charge image. A developing step of developing a latent image formed on the surface of the holding body with a developer containing at least a toner to form a toner image, and transferring the toner image formed on the surface of the electrostatic image holding body to a transfer target. And a fixing step of fixing the toner image transferred to the transfer-receiving member, and a cleaning step of removing residual toner on the surface of the electrostatic image holding member after transfer, if necessary. Then, as the toner, the toner of the present exemplary embodiment described above is used. Further, the transfer step may use an intermediate transfer member that mediates the transfer of the toner image from the electrostatic latent image holding member to the transfer target member.

The above-mentioned steps are general steps per se, and are described in, for example, JP-A-56-40868 and JP-A-49-91231. The image forming method of this embodiment can be carried out by using an image forming apparatus such as a copier or a facsimile machine known per se.
The electrostatic latent image forming step is a step of forming an electrostatic latent image on an image carrier (photoconductor).
The developing step is a step of developing the electrostatic latent image with a developer layer on a developer holder to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic charge image developing toner of the exemplary embodiment.
The transfer step is a step of transferring the toner image onto a transfer target. Further, examples of the transferred material in the transfer process include an intermediate transfer material and a recording medium such as paper.
In the fixing step, for example, a method of fixing a toner image transferred onto a transfer paper to form a copy image by a heating roller fixing device in which the temperature of the heating roller is set to a constant temperature can be mentioned. The cleaning step is a step of removing the electrostatic image developer remaining on the image carrier.
A recording medium such as an intermediate transfer body or paper can be used as the transfer body. Examples of the recording medium include paper used in electrophotographic copying machines and printers, OHP sheets, and the like. For example, coated paper in which the surface of plain paper is coated with resin or the like, art paper for printing, etc. Etc. can be used suitably.

The image forming method according to the present exemplary embodiment may further include a recycling step. The recycling step is a step of transferring the electrostatic image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling step is carried out using an image forming apparatus such as a toner recycling system type copying machine or a facsimile machine. Further, it may be applied to a recycling system in which the cleaning step is omitted and the toner is collected at the same time as the development.

(Image forming device)
The image forming apparatus of this embodiment is an image forming apparatus using the electrostatic charge image developing toner or the electrostatic charge image developer of this embodiment.
The image forming apparatus according to the present exemplary embodiment includes an image carrier, a charging unit that charges the image carrier, and an exposing unit that exposes the charged image carrier to form an electrostatic latent image on the surface of the image carrier. Developing means for developing the electrostatic latent image with toner to form a toner image, transfer means for transferring the toner image from the image carrier to the surface of the transfer target, and transfer means for transferring the toner image to the surface of the transfer target. And a fixing unit for fixing the toner image, wherein the toner is the electrostatic image developing toner according to the exemplary embodiment.
The image forming apparatus of the present exemplary embodiment is not particularly limited as long as it includes at least the above-described image carrier, charging unit, exposure unit, developing unit, transfer unit, and fixing unit. However, it may further include a cleaning unit, a charge eliminating unit, and the like, if necessary. The transfer means may perform transfer twice or more using an intermediate transfer member. Examples of the transferred material in the transfer means include an intermediate transfer material and a recording medium such as paper.

For the image carrier and each of the above means, the configurations described in each step of the above image forming method can be preferably used. As each of the above-mentioned means, any known means in an image forming apparatus can be used. Further, the image forming apparatus of the present embodiment may include means and devices other than the above-mentioned configuration. Further, the image forming apparatus of this embodiment may simultaneously perform a plurality of the above-mentioned means.
Further, it is preferable that the image forming apparatus according to the present exemplary embodiment includes a cleaning unit that removes the electrostatic image developer remaining on the image carrier. Examples of the cleaning means include a cleaning blade and a cleaning brush, and the cleaning blade is preferable.

In this image forming apparatus, for example, a portion including the developing unit may have a cartridge structure (process cartridge) that is attached to and detached from the main body of the image forming apparatus. As the process cartridge, a developer holder is used. The process cartridge of the present embodiment, which includes at least the electrostatic charge image developer of the present embodiment, is preferably used.

FIG. 2 is a schematic configuration diagram showing a four-tandem tandem full-color image forming apparatus. The image forming apparatus shown in FIG. 2 is a first electrophotographic system that outputs an image of each color of yellow (Y), magenta (M), cyan (C), and black (K) based on color-separated image data. The fourth image forming unit 110Y, 110M, 110C, 110K (image forming means) is provided. These image forming units (hereinafter, simply referred to as “units”) 110Y, 110M, 110C, and 110K are arranged side by side in the horizontal direction so as to be separated from each other. The units 110Y, 110M, 110C and 110K may be process cartridges that are attached to and detached from the image forming apparatus main body.

Above each unit 110Y, 110M, 110C, 110K in the drawing, an intermediate transfer belt 120 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 120 is provided by being wound around a driving roller 122 and a support roller 124 that are in contact with the inner surface of the intermediate transfer belt 120 and are spaced apart from each other in the left-to-right direction in the drawing. It is designed to run in the direction of 110K. The support roller 124 is urged in a direction away from the drive roller 122 by a spring (not shown) or the like, and tension is applied to the intermediate transfer belt 120 wound around both. An intermediate transfer member cleaning device 130 is provided on the side of the image carrier of the intermediate transfer belt 120 so as to face the drive roller 122.
Further, in each of the developing devices (developing means) 4Y, 4M, 4C, 4K of the units 110Y, 110M, 110C, 110K, yellow, magenta, cyan, black stored in the toner cartridges 8Y, 8M, 8C, 8K are stored. The four color toners are supplied.

Since the first to fourth units 110Y, 110M, 110C, 110K described above have the same configuration, the first unit for forming a yellow image, which is arranged on the upstream side in the traveling direction of the intermediate transfer belt, is used here. The 110Y will be described as a representative. It should be noted that the same units as the first unit 110Y are denoted by reference numerals with magenta (M), cyan (C), and black (K) instead of yellow (Y), so that the second to fourth units are attached. The description of 110M, 110C and 110K is omitted.

The first unit 110Y has a photoconductor 1Y that functions as an image carrier. Around the photoconductor 1Y, a charging roller 2Y that charges the surface of the photoconductor 1Y, and an exposure device 3 that forms an electrostatic latent image by exposing the charged surface with a laser beam 3Y based on a color-separated image signal. A developing device (developing means) 4Y for supplying electrostatically charged toner to the electrostatic latent image to develop the electrostatic latent image; a primary transfer roller 5Y (primary transfer) for transferring the developed toner image onto the intermediate transfer belt 120. Device) and a photoconductor cleaning device (cleaning device) 6Y for removing the toner remaining on the surface of the photoconductor 1Y after the primary transfer.

The primary transfer roller 5Y is disposed inside the intermediate transfer belt 120 and is provided at a position facing the photoconductor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rollers 5Y, 5M, 5C and 5K. Each bias power source changes the transfer bias applied to each primary transfer roller under the control of a controller (not shown).

The operation of forming a yellow image in the first unit 110Y will be described below. First, prior to the operation, the surface of the photoconductor 1Y is charged to a potential of about -600V to -800V by the charging roller 2Y.

The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive (volume resistivity at 20° C.: 1×10 ⁻⁶ Ωcm or less) substrate. This photosensitive layer usually has a high resistance (a resistance of a general resin), but when irradiated with the laser beam 3Y, the specific resistance of the portion irradiated with the laser beam changes. Therefore, the laser beam 3Y is output to the surface of the charged photoconductor 1Y through the exposure device 3 according to the yellow image data sent from the control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoconductor 1Y, whereby an electrostatic latent image of a yellow print pattern is formed on the surface of the photoconductor 1Y.

The electrostatic latent image is an image formed on the surface of the photoconductor 1Y by charging, and the laser beam 3Y reduces the specific resistance of the irradiated portion of the photoconductive layer, and the charged electric charge on the surface of the photoconductor 1Y is reduced. On the other hand, it is a so-called negative latent image formed by remaining electric charges in a portion which has not been irradiated with the laser beam 3Y.
The electrostatic latent image thus formed on the photoconductor 1Y is rotated to the developing position as the photoconductor 1Y travels. Then, at this developing position, the electrostatic latent image on the photoconductor 1Y is made into a visible image (developed image) by the developing device 4Y.

In the developing device 4Y, for example, a yellow toner having a volume average particle diameter of 7 μm and containing at least a yellow colorant, a crystalline resin and an amorphous resin is stored. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, has a charge of the same polarity (negative polarity) as the electrostatic charge charged on the photoconductor 1Y, and has a developer roll (developer holder). Is held on. Then, as the surface of the photoconductor 1Y passes through the developing device 4Y, the yellow toner electrostatically adheres to the neutralized latent image portion on the surface of the photoconductor 1Y, and the latent image is developed by the yellow toner. .. The photoconductor 1Y on which the yellow toner image is formed continues to run, and the toner image developed on the photoconductor 1Y is conveyed to the primary transfer position.

When the yellow toner image on the photoconductor 1Y is conveyed to the primary transfer, the primary transfer bias is applied to the primary transfer roller 5Y, and the electrostatic force from the photoconductor 1Y to the primary transfer roller 5Y acts on the toner image. Then, the toner image on the photoconductor 1Y is transferred onto the intermediate transfer belt 120. The transfer bias applied at this time has a polarity (+) opposite to the polarity (−) of the toner, and is controlled to about +10 μA by a control unit (not shown) in the first unit 110Y, for example.
On the other hand, the toner remaining on the photoconductor 1Y is removed and collected by the photoconductor cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rollers 5M, 5C, and 5K after the second unit 110M is also controlled according to the first unit.
In this way, the intermediate transfer belt 120 to which the yellow toner image is transferred by the first unit 110Y is sequentially conveyed through the second to fourth units 110M, 110C, 110K, and the toner images of the respective colors are superposed and transferred in multiple layers.

The intermediate transfer belt 120 to which the toner images of four colors are transferred in multiples through the first to fourth units is disposed on the image transfer surface side of the intermediate transfer belt 120 and the support roller 124 that contacts the inner surface of the intermediate transfer belt 20. The secondary transfer roller (secondary transfer means) 126 thus formed reaches the secondary transfer portion. On the other hand, the recording paper (transfer target) P is fed through the supply mechanism into the gap where the secondary transfer roller 126 and the intermediate transfer belt 120 are in pressure contact with each other, and the secondary transfer bias is applied to the support roller 124. .. The transfer bias applied at this time has the same polarity (-) as the polarity (-) of the toner, and the electrostatic force from the intermediate transfer belt 120 toward the recording paper P acts on the toner image to cause the toner image on the intermediate transfer belt 120. Toner image is transferred onto the recording paper P. The secondary transfer bias at this time is determined according to the resistance detected by the resistance detecting means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

After that, the recording paper P is sent to a fixing device (fixing means) 128, the toner image is heated, and the toner images in which the colors are overlapped are melted and fixed on the recording paper P. The recording paper P on which the fixing of the color image has been completed is carried out toward the discharge section, and the series of color image forming operations is completed.
The image forming apparatus illustrated above is configured to transfer the toner image to the recording paper P via the intermediate transfer belt 120, but the invention is not limited to this configuration, and the toner image is directly transferred from the photoconductor. The structure may be such that it is transferred to a recording sheet.

(Toner cartridge, developer cartridge, process cartridge)
Each of the cartridges of the present embodiment is a cartridge that contains at least the one-component or two-component developer of the present embodiment. Further, it is preferable that the cartridge according to the present exemplary embodiment is detachable from the image forming apparatus.
When used in a developing device, an image forming method, or an image forming device, it may be a one-component toner cartridge that stores toner alone or a developer cartridge that stores two-component developer.
The process cartridge of this embodiment may be any process cartridge containing the electrostatic charge image developing toner of this embodiment or the electrostatic charge image developer of this embodiment, and is formed on the surface of the image carrier. Developing means for developing an electrostatic latent image with an electrostatic charge image developing toner or an electrostatic charge image developer to form a toner image, an image carrier, a charging means for charging the surface of the image carrier, and an image carrier. And at least one member selected from the group consisting of cleaning means for removing the toner remaining on the surface, and the electrostatic charge image developing toner according to the present embodiment as the electrostatic charge image developing toner or the electrostatic charge image developer. Alternatively, the process cartridge containing the electrostatic charge image developer of the exemplary embodiment is preferable.

FIG. 3 is a schematic configuration diagram showing a preferred example of the process cartridge containing the electrostatic image developer of the present embodiment. The process cartridge 200 includes a photosensitive member 107, a charging roller 108, a developing device 111 having a developer holding member, a photosensitive member cleaning device (cleaning means) 113, an opening portion 118 for exposure, and a charge eliminating exposure portion. The openings 117 are combined and integrated using the mounting rails 116.
The process cartridge 200 is detachable from the image forming apparatus main body including the transfer device 112, the fixing device 115, and other components (not shown). The image forming apparatus forms an image on the recording paper 300.

The process cartridge shown in FIG. 3 includes a charging roller 108, a developing device 111, a cleaning device (cleaning means) 113, an opening 118 for exposure, and an opening 117 for static elimination exposure. Are selectively combined. The process cartridge according to the present embodiment includes at least a developing device 111 having a developer holder, and includes a photoconductor 107, a charging device 108, a cleaning device (cleaning means) 113, an opening portion 118 for exposure, and static elimination exposure. May be provided with at least one selected from the group consisting of openings 117 for.

Next, the toner cartridge of this embodiment will be described.
The toner cartridge according to the present embodiment is detachably attached to the image forming apparatus, and at least in the toner cartridge that stores the toner to be supplied to the developing unit provided in the image forming apparatus, 3 is an electrostatic charge image developing toner of the embodiment. It should be noted that the toner cartridge of this exemplary embodiment may contain at least the electrostatic charge image developing toner of this exemplary embodiment. Depending on the mechanism of the image forming apparatus, for example, the electrostatic charge image developer of this exemplary embodiment may be stored. Good.

Therefore, in the image forming apparatus having a configuration in which the toner cartridge is detachable, the toner of the present embodiment is easily supplied to the developing device by using the toner cartridge containing the toner of the present embodiment.

The image forming apparatus shown in FIG. 3 is an image forming apparatus having a configuration in which the toner cartridges 8Y, 8M, 8C, and 8K are attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are the respective developing devices (colors). ) And a toner cartridge corresponding to () are connected by a toner supply pipe (not shown). Further, when the toner stored in the toner cartridge becomes low, the toner cartridge may be replaced.

The present embodiment will be described in more detail below with reference to examples and comparative examples, but the present embodiment is not limited to these examples.
In the following examples, "parts" means "parts by mass" and "%" means "% by mass" unless otherwise specified.

<Measurement method>
Regarding the molecular weight of the resin (weight average molecular weight (Mw), number average molecular weight (Mn)), tetrahydrofuran (THF)-soluble matter was obtained by GPC/HLC-8120 manufactured by Tosoh Corporation, column/TSKgel SuperHM- manufactured by Tosoh Corporation. M (15 cm) was used for measurement with a THF solvent, and the molecular weight was calculated using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.
A Microtrac (Microtrac UPA9340, manufactured by Nikkiso Co., Ltd.) was used for measuring the particle diameter of the resin particles in the resin particle dispersion liquid.
The solid content concentration was determined using a moisture content meter MA35 (manufactured by Sartorius Mechatronics Japan Co., Ltd.).

The volume average particle diameter of the toner was measured using a Coulter Multisizer II (manufactured by Beckman-Coulter). As the electrolytic solution, ISOTON-II (manufactured by Beckman-Coulter) was used.
As the measuring method, first, 0.5 mg or more and 50 mg or less of a measurement sample is added to 2 ml of a 5% aqueous solution of a surfactant, preferably sodium alkylbenzene sulfonate as a dispersant, and this is added to 100 ml or more and 150 ml or less of the electrolytic solution. Was added. An electrolytic solution in which this measurement sample is suspended is subjected to a dispersion treatment for about 1 minute by an ultrasonic disperser, and a particle size of 2.0 μm or more and 60 μm or less is used by the Coulter Multisizer II using an aperture having an aperture diameter of 100 μm. The particle size distribution of particles in the range was measured. The number of particles to be measured was 50,000.
For the divided particle size range (channel), the measured particle size distribution is drawn as a cumulative distribution from the smaller diameter side in terms of weight or volume, and the particle size at which cumulative 50% is defined as the weight average particle size or volume average particle size, respectively. To do.

The viscosity μ of the raw material was measured by crushing the raw material with a sample mill for 30 seconds and then leaving it for 24 hours at room temperature of 10° C./humidity of 15% for 24 hours. A die having a diameter of 0.5 mm was used, and the measurement conditions were an initial hold time of 300 s and a heating rate of 1° C./min. The flow tester viscosity value at the set temperature +10° C. of the barrel for adding the first resin dispersion composition counted from the raw material supply barrel of the kneader was taken as the representative viscosity.

(Raw material preparation)
<Synthesis of crystalline polyester resin A>
・1,10-Decanedicarboxylic acid (dodecanedioic acid): 241 parts ・1,9-Nonanediol: 174 parts The above monomer components were placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas introduction tube. After replacing the inside of the reaction vessel with dry nitrogen gas, 0.25 parts by mass of titanium tetrabutoxide was added to 100 parts by mass of the monomer component, and the mixture was stirred and reacted at 170° C. for 3 hours in a nitrogen gas stream. Further, the temperature was raised to 210° C., the pressure in the reaction vessel was reduced to 3 kPa, and the mixture was stirred and reacted under reduced pressure for 13 hours to obtain a crystalline polyester resin A. The weight average molecular weight (Mw) of the obtained crystalline resin A was 17,200. The acid value of the crystalline resin A was 11.4 mgKOH/g. The melting temperature of the crystalline polyester resin A was 75°C.

<Synthesis of Amorphous Polyester Resin B>
・Bisphenol A propylene oxide adduct: 469 parts ・Bisphenol A ethylene oxide adduct: 137 parts ・Terephthalic acid: 152 parts ・Fumaric acid: 75 parts ・Dodecenyl succinic acid: 114 parts And a reaction vessel equipped with a nitrogen gas introducing pipe, 4 parts of dibutyltin oxide was introduced as a catalyst, and nitrogen gas was introduced into the vessel to keep the temperature in an inert atmosphere and raise the temperature. The polycondensation reaction was carried out for 12 hours, and then the pressure was gradually reduced at 210° C. or higher and 250° C. or lower to synthesize an amorphous polyester resin B. The weight average molecular weight (Mw) of the obtained amorphous polyester resin B was 10,500. The acid value of the amorphous polyester resin B was 12.4 mgKOH/g. The glass transition temperature (Tg) of the amorphous polyester resin B was 60°C.

<Synthesis of Amorphous Polyester Resin C>
-Bisphenol A propylene oxide adduct: 454 parts-Bisphenol A ethylene oxide adduct: 151 parts-Terephthalic acid: 152 parts-Fumaric acid: 75 parts-Dodecenylsuccinic acid: 114 parts The above-mentioned monomer components are stirred, thermometer, condenser And a reaction vessel equipped with a nitrogen gas introduction tube, 4 parts of dibutyltin oxide was introduced as a catalyst, and nitrogen gas was introduced into the vessel to maintain an inert atmosphere and raise the temperature, and then at 150°C or higher and 230°C or lower. After the polycondensation reaction for 12 hours, the pressure is gradually reduced at 210° C. or higher and 250° C. or lower, and when the molecular weight reaches about 30,000, 20 parts of trimellitic anhydride is added and the mixture is stirred for another 2 hours and then the amorphous polyester is added. Resin C was synthesized. The weight average molecular weight (Mw) of the obtained amorphous polyester resin C was 45,900. The acid value of the amorphous polyester resin C was 131.6 mgKOH/g. The glass transition temperature (Tg) of the amorphous polyester resin C was 65°C.

(Example 1)
<Production of Resin Particle Dispersion B1 (Amorphous Polyester Resin B) in the Absence of Organic Solvent>
200 parts by mass of the amorphous polyester resin B and 0.2 parts by mass of a 50% by mass aqueous solution of sodium hydroxide are charged into a raw material charging port of a twin-screw extruder (TEM-26SS, manufactured by Toshiba Machine Co., Ltd.), and From the fourth barrel of the twin-screw extruder, 4.1 parts by mass of a 48.5% by mass aqueous solution of sodium dodecyldiphenyletherdisulfonate (Eleminol MON-7 manufactured by Sanyo Kasei Co., Ltd.) as a surfactant was charged, Each barrel was set at 95° C. and kneaded at a screw rotation speed of 240 rpm to mix the amorphous polyester resin, sodium hydroxide and a surfactant.

150 parts by mass of ion-exchanged water (ion-exchanged water 1) adjusted to 95°C from the 5th barrel of the twin-screw extruder and 150 parts by mass of ion-exchanged water (ion-exchanged water 2) adjusted to 90°C from the 7th barrel. Then, 150 parts by mass of ion-exchanged water (ion-exchanged water 3) adjusted to 90° C. from the 9th barrel was added and kneaded to obtain a resin particle dispersion B1.
The viscosity of the amorphous polyester resin measured by a flow tester at 105° C. was 3,600 Pa·s, and the average supply amount F of the raw material was 10 kg/h, which was (μ×n ² ×d ³ )/F=364.

The volume average particle size distribution of the particles in the obtained resin particle dispersion liquid B1 was measured by a laser diffraction particle size distribution measuring device (LA-700, manufactured by Horiba Ltd.), and as a result, a 180 nm resin particle dispersion liquid was obtained. It was

<Evaluation of reduction rate of molecular weight>
The molecular weight distribution of the resin particles in the obtained resin particle dispersion is calculated by GPC (gel permeation chromatography) using a calibration curve prepared from monodisperse standard polystyrene. The resin particle dispersion having a solid content of about 10 g was stored in a vacuum dryer at 30° C. for 24 hours to obtain a dry resin. As the sample solution, a THF sample solution in which the resin particles were dissolved in THF (tetrahydrofuran) at a sample concentration of 0.055 to 0.5 mass% was used. Based on the molecular weight measured by this method, the reduction rate of the molecular weight of the dry resin was calculated.
Ratio of decrease in molecular weight [%]=100−(molecular weight of dry resin [g/mol]/molecular weight of resin before emulsification [g/mol]×100)
Further, the rate of decrease in molecular weight was evaluated according to the following criteria. The following evaluation is preferably 1.
1: Reduction rate of molecular weight is less than 10% 2: Reduction rate of molecular weight is 10 or more and less than 20% 3: Reduction rate of molecular weight is 20% or more

<Manufacturing of developer>
[Preparation of Aqueous Dispersion A2 of Crystalline Polyester Resin Particles in the Presence of Organic Solvent]
-Crystalline polyester resin A: 100 parts-Ethyl acetate: 70 parts-Isopropyl alcohol: 15 parts The above ethyl acetate and isopropyl alcohol were charged into a 5 L separable flask, and the above resin was gradually charged into this mixed medium, The oil phase was obtained by completely stirring and stirring with a three-one motor. A 10 mass% aqueous ammonia solution was gradually added to this oil phase with a dropper so that the total amount was 3 mass parts, and further 230 mass parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml/min to carry out phase inversion emulsification, Further, the solvent was removed under reduced pressure with an evaporator to obtain an aqueous dispersion (A0) of crystalline polyester resin particles.
The volume average particle diameter D _50v of the resin particles was 165 nm. The solid content concentration was adjusted to 25.0% by mass by adjusting with ion-exchanged water.

[Preparation of Aqueous Dispersion C2 of Amorphous Polyester Resin Particles in the Presence of Organic Solvent]
Aqueous dispersion C2 of amorphous polyester resin particles in the presence of an organic solvent in exactly the same manner as in the production method of the above aqueous dispersion A2 except that the amorphous polyester resin C was used instead of the crystalline polyester resin A. Got

[Preparation of release agent dispersion]
-Release agent (manufactured by Nippon Seiro Co., Ltd., trade name: FNP0090, melting point Tw 89.7°C): 270 parts by mass-Anionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Neogen RK, amount of active ingredient) : 60% by mass): 13.5 parts by mass (3.0% by mass with respect to the release agent as an active ingredient)
-Ion-exchanged water: 721.6 parts by mass The above components are mixed, and the releasing agent is dissolved with a pressure discharge type homogenizer (Gorin homogenizer manufactured by Gorin Co., Ltd.) at an internal liquid temperature of 120°C, and then the dispersion pressure is 5 MPa. For 120 minutes, followed by dispersion treatment at 40 MPa for 360 minutes and cooling to obtain a release agent dispersion. The volume average particle diameter D _50v of the particles in this dispersion was 230 nm. Then, ion-exchanged water was added to adjust the solid content concentration to 20.0 mass% to obtain a release agent dispersion liquid.

[Preparation of colorant dispersion]
Carbon black (Cabot Co., Legal 330): 50 parts by mass Anionic surfactant (Nurex R, manufactured by NOF CORPORATION): 2 parts by mass Deionized water: 198 parts by mass The above components are mixed. , 10 minutes preliminarily dispersed with a homogenizer (IKA Ultra Turrax), and then subjected to a dispersion treatment for 15 minutes at a pressure of 245 Mpa using an ultimizer (counter-collision type wet pulverizer: manufactured by Sugino Machine Co., Ltd.) to obtain the center of the colorant particles. A colorant particle dispersion liquid 1 having a particle size of 280 nm and a solid content of 20.0% was obtained.

[Preparation of aluminum sulfate aqueous solution]
-Aluminum sulfate powder (manufactured by Asada Chemical Industry Co., Ltd.: 17 mass% aluminum sulfate): 35 parts-Ion-exchanged water: 1,965 parts The above powder and ion-exchanged water were put into a container and precipitated at 30°C. The mixture was stirred and mixed until the substance disappeared to prepare an aluminum sulfate aqueous solution as a coagulant.

[Production of toner]
The following components were placed in a stirring tank equipped with a thermometer, a pH meter, a stirrer, and a jacket and stirred for 10 minutes.
-Aqueous dispersion A2 of crystalline polyester resin particles prepared in the presence of an organic solvent A2: 57 parts by mass- Resin particle dispersion B1: 314 parts by mass prepared in the absence of an organic solvent-Prepared in the presence of an organic solvent Aqueous dispersion of amorphous polyester resin particles C2: 314 parts by mass-Colorant dispersion: 100 parts-Release agent dispersion: 115 parts-Ion-exchanged water: 200 parts-Anionic surfactant (Daiichi Kogyo) Pharmaceutical Co., Ltd., Neogen RK: 7.0 parts

While gradually adding 125 parts by mass of an aqueous solution of aluminum sulfate to the above dispersion liquid mixture placed in the stirring tank, the mixture liquid was introduced into Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) from the bottom valve of the stirring tank and dispersed for 10 minutes. did. After the addition was completed, the temperature of the jacket was started to be raised at 50° C., and after 120 minutes, the particle size was measured with a Multisizer II (aperture diameter: 50 μm, manufactured by Beckman-Coulter). It was 5.0 μm. Then, 312 parts by mass of the aqueous dispersion liquid (B1) of the additional amorphous polyester resin particles was added and held for 30 minutes. Then, a 4 mass% sodium hydroxide aqueous solution was added to the stirring tank to adjust the pH to 9.0, and then the temperature of the jacket was increased to 90° C. and maintained. When the shape and surface property of the agglomerated particles were observed with an optical microscope and a scanning electron microscope (FE SEM) every 30 minutes, coalescence of the particles was confirmed at the 4th hour, so the obtained slurry was heated to 40°C. Cooled. The cooled slurry was subjected to a sieving treatment with a vibrating sieve having openings of 15 μm (KGC800: manufactured by Kowa Industry Co., Ltd.) and then filtered with a filter press (produced by Tokyo Engineering Co., Ltd.). After that, 10 times the amount of the ion-exchanged water was passed through the toner in the filter press to wash the toner. The washed toner was dried by cyclone collection using a loop type airflow dryer (flash jet dryer FJD-2 manufactured by Seishin Enterprise Co., Ltd.) to obtain toner particles. 1.0 part by weight of hydrophobic silica (manufactured by Nippon Aerosil Co., Ltd., RY50) and 0.8 part by mass of hydrophobic titanium oxide (manufactured by Nippon Aerosil Co., Ltd., T805) per 100 parts by mass of the obtained toner particles. Were added and mixed and blended for 30 seconds at 13,000 rpm using a sample mill. After that, the toner was obtained by sieving with a vibrating sieve having openings of 45 μm.

[Production of carrier]
-Mn-Mg-Sr ferrite particles (average particle size 40 m): 100 parts
-Toluene: 14 parts-Cyclohexyl methacrylate/dimethylaminoethyl methacrylate copolymer (copolymerization mass ratio 99:1, weight average molecular weight (Mw): 80,000): 2.0 parts-Carbon black (VXC72: manufactured by Cabot Corporation) ): 0.12 part The above components excluding ferrite particles and glass beads (φ1 mm, the same amount as toluene) were stirred at 1,200 ppm for 30 minutes using a sand mill manufactured by Kansai Paint Co., Ltd. to form a resin coating layer forming solution. And Further, this resin coating layer forming solution and ferrite particles were put into a vacuum degassing type kneader to reduce the pressure, and toluene was distilled off/dried to form a resin coated carrier.

[Preparation of developer]
40 parts by mass of the toner was added to 500 parts by mass of the carrier, blended for 20 minutes with a V-type blender, and the aggregate was removed by a vibrating screen having a mesh opening of 212 μm to obtain a developer.

<Evaluation of color developability (image density)>
The color development of the obtained toner was evaluated by the image density. A Docu Center Color 400 remodeling machine manufactured by Fuji Xerox Co., Ltd. was used to perform an image output test of about 20,000 sheets under an environment of 20° C. and a relative humidity of 50 RH%. The image density after 20,000 sheets were printed was evaluated. The image density of the solid portion of the obtained image was measured using an X-rite 404 densitometer. The following evaluations were made according to the minimum optical density during the measurement of 100 sheets.
1: 1.20 or more 2: 0.80 or more and less than 1.20 3: less than 0.80

(Example 2)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion B2 (Amorphous Polyester Resin B) in the Absence of Organic Solvent>
200 parts by mass of the amorphous polyester resin B and 0.2 parts by mass of a 50% by mass aqueous solution of sodium hydroxide are charged into a raw material charging port of a twin-screw extruder (TEM-6SS, manufactured by Toshiba Machine Co., Ltd.), and From the fourth barrel of the twin-screw extruder, 4.1 parts by mass of a solution containing 48.5% by mass of sodium dodecyldiphenyl ether sulfonate as a surfactant (Eleminol MON-7, manufactured by Mitsui Chemicals, Inc.) was charged. Kneading was performed at each barrel setting temperature of 95° C. and a screw rotation speed of 900 rpm.
150 parts by mass of ion-exchanged water adjusted to 95°C from the 5th barrel of the twin-screw extruder (ion-exchanged water 1) and 150 parts by mass of ion-exchanged water adjusted to 95°C from the 7th barrel (ion-exchanged water 2) Then, 150 parts by mass of ion-exchanged water (ion-exchanged water 3) adjusted to 95° C. from the 9th barrel was added and kneaded to obtain a resin particle dispersion B2.
The viscosity of the raw material B measured by a flow tester at 105° C. was 3,600 Pa·s, and the average supply amount F of the raw material was 30 kg/h. At this time, (μ×n ² ×d ³ )/F =1,708.
The volume average particle diameter of the obtained resin particle dispersion B2 was 189 nm as a result of measurement with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.).

<Manufacture of toner>
A toner was manufactured in the same manner as in Example 1 except that the resin particle dispersion liquid B1 produced in the absence of an organic solvent was changed to the resin particle dispersion liquid B2.

(Example 3)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BC1 (Amorphous Polyester Resin B and Amorphous Polyester Resin C) in the Absence of Organic Solvent>
150 parts by mass of the amorphous polyester resin B and 150 parts by mass of the amorphous polyester resin C were put into a Henschel mixer (75 L) and mixed for 120 seconds at a screw rotation speed of 600 rpm to adjust the raw material BC.
200 parts by mass of the raw material BC and 0.2 parts by mass of a 50% by weight aqueous solution of sodium hydroxide are charged into the raw material charging port of the twin-screw extruder (TEM-26SS, manufactured by Toshiba Machine Co., Ltd.), and the twin-screw extrusion is performed. From the 4th barrel of the machine, 4.1 parts by mass of a 48.5% by mass solution of sodium dodecyldiphenyl ether sulfonate (Eleminol MON-7, manufactured by Mitsui Kasei Co., Ltd.) as a surfactant was charged, and each barrel was set. Kneading was performed at a temperature of 98° C. and a screw rotation speed of 360 rpm.
150 parts by mass of ion-exchanged water adjusted to 95°C from the 5th barrel of the twin-screw extruder (ion-exchanged water 1) and 150 parts by mass of ion-exchanged water adjusted to 95°C from the 7th barrel (ion-exchanged water 2) Then, 150 parts by mass of ion-exchanged water (ion-exchanged water 3) adjusted to 95°C from the 9th barrel was added and kneaded to obtain a resin particle dispersion liquid BC1.
The viscosity of the raw material BC at 108° C. measured by a flow tester was 7,800 Pa·s, and the average supply amount F of the raw material was 30 kg/h, which was (μ×n ² ×d ³ )/F. =592.
The obtained resin particle dispersion liquid BC1 was measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.), and as a result, the volume average particle diameter was 185 nm.

<Manufacture of toner>
The following components were placed in a stirring tank equipped with a thermometer, a pH meter, a stirrer, and a jacket and stirred for 10 minutes.
-Aqueous dispersion A2 of crystalline polyester resin particles produced in the presence of an organic solvent: 57 parts by mass-Resin particle dispersion BC1:635 parts by mass produced in the absence of an organic solvent-Colorant dispersion: 100 parts by mass Parts-Release agent dispersion: 150 parts-Ion-exchanged water: 200 parts-Anionic surfactant (Neogen RK manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): 7.0 parts

While gradually adding 125 parts by mass of an aqueous solution of aluminum sulfate to the above-mentioned dispersion mixture put in a stirrer, the mixture solution was introduced into Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) through a bottom valve of a stirring tank and dispersed for 10 minutes. did. After the addition was completed, the temperature of the jacket was started to be raised at 50° C., and after 120 minutes, the particle size was measured with Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter, Inc.). It was 5.0 μm. Then, 312 parts by mass of the resin particle dispersion liquid BC1 prepared in the absence of an organic solvent was added, and the mixture was held for 30 minutes.
A toner was prepared in the same manner as in Example 1 except for the above.

(Example 4)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion Liquid BC2 (Amorphous Polyester Resin B and Amorphous Polyester Resin C) in the Absence of Organic Solvent>
200 parts by mass of the raw material BC and 0.2 parts by mass of a 50% by mass aqueous solution of sodium hydroxide are charged into the raw material charging port of the twin-screw extruder (TEM-26SS, manufactured by Toshiba Machine Co., Ltd.), and also the twin-screw extrusion From the 4th barrel of the machine, 4.1 parts by mass of a 48.5% by mass solution of sodium dodecyldiphenyl ether sulfonate (Eleminol MON-7, manufactured by Mitsui Kasei Co., Ltd.) as a surfactant was charged, and each barrel was set. Kneading was performed at a temperature of 98° C. and a screw rotation speed of 720 rpm.
150 parts by mass of ion-exchanged water adjusted to 95°C from the 5th barrel of the twin-screw extruder (ion-exchanged water 1) and 150 parts by mass of ion-exchanged water adjusted to 95°C from the 7th barrel (ion-exchanged water 2) Then, 150 parts by mass of ion-exchanged water (ion-exchanged water 3) adjusted to 95° C. from the 9th barrel was added and kneaded to obtain a resin particle dispersion liquid BC2.
The viscosity of the raw material BC at 108° C. measured by a flow tester was 7,800 Pa·s, and the average supply amount F of the raw material was 11 kg/h, which was (μ×n ² ×d ³ )/F. = 6,461.
The volume average particle diameter of the obtained resin particle dispersion BC2 was 189 nm as a result of measurement with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

<Manufacture of toner>
A toner was manufactured in the same manner as in Example 3 except that the resin particle dispersion liquid BC1 prepared in the absence of the organic solvent was changed to the resin particle dispersion liquid BC2.

(Example 5)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BA1 (Amorphous Polyester Resin B and Crystalline Polyester Resin A) in the Absence of Organic Solvent>
314 parts by mass of the amorphous polyester resin B and 57 parts by mass of the crystalline polyester resin A were put into a Henschel mixer (75 L) and mixed for 120 seconds at a screw rotation speed of 600 rpm to adjust the raw material BA.
200 parts by mass of the raw material BA and 0.2 parts by mass of a 50% by mass aqueous solution of sodium hydroxide are charged into the raw material charging port of the twin-screw extruder (TEM-48SS, manufactured by Toshiba Machine Co., Ltd.), and the twin-screw extrusion is performed. From the 4th barrel of the machine, 4.1 parts by mass of a 48.5 mass% solution of sodium dodecyldiphenyl ether sulfonate (Eleminol MON-7 manufactured by Mitsui Kasei Co., Ltd.) as a surfactant was charged, and each barrel was set. Kneading was performed at a temperature of 95° C. and a screw rotation speed of 360 rpm.
150 parts by mass of ion-exchanged water adjusted to 95°C from the 5th barrel of the twin-screw extruder (ion-exchanged water 1) and 150 parts by mass of ion-exchanged water adjusted to 95°C from the 7th barrel (ion-exchanged water 2) Then, 150 parts by mass of ion-exchanged water (ion-exchanged water 3) adjusted to 95° C. from the 9th barrel was added and kneaded to obtain a resin particle dispersion liquid BA1.
The viscosity of the raw material BA at 105° C. measured by a flow tester was 1,200 Pa·s, and the average supply amount F of the raw material was 35 kg/h, which was (μ×n ² ×d ³ )/F. =491.
The obtained resin particle dispersion BA1 was measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.), and as a result, the volume average particle diameter was 181 nm.

<Manufacture of toner>
The following components were placed in a stirring tank equipped with a thermometer, a pH meter, a stirrer, and a jacket and stirred for 10 minutes.
-Resin particle dispersion liquid BA1:371 parts by mass produced in the absence of organic solvent-Aqueous dispersion of amorphous polyester resin particles prepared in the presence of organic solvent C2:314 parts by mass-Colorant dispersion liquid: 100 Mass part-Release agent dispersion liquid: 150 mass parts-Ion-exchanged water: 200 mass parts-Anionic surfactant (Neogen RK manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): 7.0 mass parts

While gradually adding 125 parts by mass of an aqueous solution of aluminum sulfate to the above-mentioned dispersion mixture put in a stirrer, the mixture solution was introduced into Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) through a bottom valve of a stirring tank and dispersed for 10 minutes. did. After the addition was completed, the temperature of the jacket was started to be raised at 50° C., and after 120 minutes, the particle size was measured with Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter, Inc.). It was 5.0 μm. Thereafter, 156 parts by mass of an aqueous dispersion B2 of amorphous polyester resin particles prepared in the presence of an organic solvent, and 156 parts by mass of an aqueous dispersion C2 of amorphous polyester resin particles prepared in the presence of an organic solvent. And added for 30 minutes.
A toner was prepared in the same manner as in Example 1 except for the above.

(Example 6)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BA2 (Amorphous Polyester Resin B and Crystalline Polyester Resin A) in the Absence of Organic Solvent>
200 parts by mass of the raw material BA and 0.2 parts by mass of a 50% by mass aqueous solution of sodium hydroxide are charged into the raw material charging port of the twin-screw extruder (TEM-48SS, manufactured by Toshiba Machine Co., Ltd.), and the twin-screw extrusion is performed. From the 4th barrel of the machine, 4.1 parts by mass of a 48.5 mass% solution of sodium dodecyldiphenyl ether sulfonate (Eleminol MON-7 manufactured by Mitsui Kasei Co., Ltd.) as a surfactant was charged, and each barrel was set. Kneading was performed at a temperature of 95° C. and a screw rotation speed of 720 rpm.
150 parts by mass of ion-exchanged water adjusted to 95°C from the 5th barrel of the twin-screw extruder (ion-exchanged water 1) and 150 parts by mass of ion-exchanged water adjusted to 95°C from the 7th barrel (ion-exchanged water 2) Then, 150 parts by mass of ion-exchanged water (ion-exchanged water 3) adjusted to 95° C. from the 9th barrel was added and kneaded to obtain a resin particle dispersion liquid BA2.
The viscosity of the raw material BA at 105° C. measured by a flow tester was 1,200 Pa·s, and the average supply amount F of the raw material was 40 kg/h, which was (μ×n ² ×d ³ )/F. = 1,720.
The obtained resin particle dispersion BA2 was measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.), and as a result, the volume average particle diameter was 186 nm.

<Manufacture of toner>
A toner was prepared in the same manner as in Example 5, except that the resin particle dispersion liquid BA1 prepared in the absence of an organic solvent was changed to the resin particle dispersion liquid BA2.

(Example 7)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion AC1 (Crystalline Polyester Resin A and Amorphous Polyester Resin C) in the Absence of Organic Solvent>
200 parts by mass of the raw material AC and 0.2 parts by mass of a 50% by mass aqueous solution of sodium hydroxide were charged into the raw material charging port of the twin-screw extruder (TEM-48SS, manufactured by Toshiba Machine Co., Ltd.), and the twin-screw extrusion was performed. From the 4th barrel of the machine, 4.1 parts by mass of a solution containing 48.5% by mass of sodium dodecyldiphenyl ether sulfonate as a surfactant (Eleminol MON-7, manufactured by Mitsui Kasei Co., Ltd.) was charged to set each barrel. Kneading was performed at a temperature of 95° C. and a screw rotation speed of 360 rpm.
150 parts by mass of ion-exchanged water adjusted to 95°C from the 5th barrel of the twin-screw extruder (ion-exchanged water 1) and 150 parts by mass of ion-exchanged water adjusted to 95°C from the 7th barrel (ion-exchanged water 2) Then, 150 parts by mass of ion-exchanged water (ion-exchanged water 3) adjusted to 95° C. from the 9th barrel was added and kneaded to obtain a resin particle dispersion AC1.
The viscosity of the raw material BA at 105° C. measured by a flow tester was 2,000 Pa·s, and the average supply amount F of the raw material was 75 kg/h, where (μ×n ² ×d ³ )/F =382.
The volume average particle diameter of the obtained resin particle dispersion AC1 was 182 nm as a result of measurement with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.).

<Manufacture of toner>
The following components were placed in a stirring tank equipped with a thermometer, a pH meter, a stirrer, and a jacket and stirred for 10 minutes.
-Resin particle dispersion AC1:371 parts by mass produced in the absence of organic solvent-Aqueous dispersion of amorphous polyester resin particles B2:314 parts by mass prepared in the presence of organic solvent-Colorant dispersion:100 Mass part-Release agent dispersion liquid: 150 mass parts-Ion-exchanged water: 200 mass parts-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 7.0 mass parts

While gradually adding 125 parts by mass of an aqueous solution of aluminum sulfate to the above-mentioned dispersion mixture put in a stirrer, the mixture solution was introduced into Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) through a bottom valve of a stirring tank and dispersed for 10 minutes. did. After the addition was completed, the temperature of the jacket was started to be raised at 50° C., and after 120 minutes, the particle size was measured with Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter, Inc.). It was 5.0 μm. Thereafter, 156 parts by mass of an aqueous dispersion B2 of amorphous polyester resin particles prepared in the presence of an organic solvent, and 156 parts by mass of an aqueous dispersion C2 of amorphous polyester resin particles prepared in the presence of an organic solvent. And added for 30 minutes.
A toner was prepared in the same manner as in Example 1 except for the above.

(Example 8)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion AC2 (Crystalline Polyester Resin A and Amorphous Polyester Resin C) in the Absence of Organic Solvent>
200 parts by mass of the raw material AC and 0.2 parts by mass of a 50% by mass aqueous solution of sodium hydroxide were charged into the raw material charging port of the twin-screw extruder (TEM-48SS, manufactured by Toshiba Machine Co., Ltd.), and the twin-screw extrusion was performed. From the 4th barrel of the machine, 4.1 parts by mass of a 48.5 mass% solution of sodium dodecyldiphenyl ether sulfonate (Eleminol MON-7 manufactured by Mitsui Kasei Co., Ltd.) as a surfactant was charged, and each barrel was set. Kneading was performed at a temperature of 95° C. and a screw rotation speed of 720 rpm.
150 parts by mass of ion-exchanged water adjusted to 95°C from the 5th barrel of the twin-screw extruder (ion-exchanged water 1) and 150 parts by mass of ion-exchanged water adjusted to 95°C from the 7th barrel (ion-exchanged water 2) Then, 150 parts by mass of ion-exchanged water (ion-exchanged water 3) adjusted to 95° C. from the 9th barrel was added and kneaded to obtain a resin particle dispersion AC2.
The viscosity of the raw material AC at 105° C. measured by a flow tester was 2,000 Pa·s, and the average supply amount F of the raw material was 50 kg/h, at which time (μ×n ² ×d ³ )/F =2,293.
The obtained resin particle dispersion BA2 was measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.), and as a result, the volume average particle diameter was 175 nm.

<Manufacture of toner>
A toner was prepared in the same manner as in Example 7 except that the resin particle dispersion liquid AC1 prepared in the absence of the organic solvent was changed to the resin particle dispersion liquid AC2.

(Example 9)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BD1 (Amorphous Polyester Resin B and Colorant) in the Absence of Organic Solvent>
254 parts by mass of the amorphous polyester resin B and 57 parts by mass of carbon black (Regal 330 manufactured by Cabot Co., Ltd.) as a colorant are charged into a Henschel mixer (75 L) and mixed for 120 seconds at a screw rotation speed of 600 rpm to adjust the raw material BD. did.
200 parts by mass of the raw material BD and 0.2 parts by mass of an aqueous solution of 50% by mass of sodium hydroxide are charged into the raw material charging port of the twin-screw extruder (TEM-58SS, manufactured by Toshiba Machine Co., Ltd.), and the twin-screw extrusion is performed. From the 4th barrel of the machine, 4.1 parts by mass of a 48.5 mass% solution of sodium dodecyldiphenyl ether sulfonate (Eleminol MON-7 manufactured by Mitsui Kasei Co., Ltd.) as a surfactant was charged, and each barrel was set. Kneading was performed at a temperature of 95° C. and a screw rotation speed of 240 rpm.
150 parts by mass of ion-exchanged water adjusted to 95°C from the 5th barrel of the twin-screw extruder (ion-exchanged water 1) and 150 parts by mass of ion-exchanged water adjusted to 95°C from the 7th barrel (ion-exchanged water 2) Then, 150 parts by mass of ion-exchanged water (ion-exchanged water 3) adjusted to 95° C. from the 9th barrel was added and kneaded to obtain a resin particle dispersion liquid BD1.
The viscosity of the raw material BD measured by a flow tester at 105° C. was 10,000 Pa·s, and the average supply amount F of the raw material was 200 kg/h, where (μ×n ² ×d ³ )/F =562.
The obtained resin particle dispersion liquid BD1 was measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.), and as a result, the volume average particle diameter was 191 nm.

<Manufacture of toner>
The following components were placed in a stirring tank equipped with a thermometer, a pH meter, a stirrer, and a jacket and stirred for 10 minutes.
Resin particle dispersion liquid BD1:440 parts by mass produced in the absence of an organic solvent Aqueous dispersion A2 of crystalline polyester resin particles A2:57 parts by mass produced in the presence of an organic solvent Manufactured in the presence of an organic solvent Aqueous dispersion of amorphous polyester resin particles C2: 314 parts by mass Release agent dispersion: 150 parts by mass Ion-exchanged water: 200 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK): 7.0 parts by mass

While gradually adding 125 parts by mass of an aqueous solution of aluminum sulfate to the above-mentioned dispersion mixture put in a stirrer, the mixture solution was introduced into Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) through a bottom valve of a stirring tank and dispersed for 10 minutes. did. After the addition was completed, the temperature of the jacket was started to be raised at 50° C., and after 120 minutes, the particle size was measured with Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter, Inc.). It was 5.0 μm. Thereafter, 156 parts by mass of an aqueous dispersion B2 of amorphous polyester resin particles prepared in the presence of an organic solvent, and 156 parts by mass of an aqueous dispersion C2 of amorphous polyester resin particles prepared in the presence of an organic solvent. And added for 30 minutes.
A toner was prepared in the same manner as in Example 1 except for the above.

(Example 10)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BD2 (Amorphous Polyester Resin B and Colorant) in the Absence of Organic Solvent>
200 parts by mass of the raw material BD and 0.2 parts by mass of an aqueous solution of 50% by mass of sodium hydroxide are charged into the raw material charging port of the twin-screw extruder (TEM-58SS, manufactured by Toshiba Machine Co., Ltd.), and the twin-screw extrusion is performed. From the 4th barrel of the machine, 4.1 parts by mass of a 48.5% by mass solution of sodium dodecyldiphenyl ether sulfonate (Eleminol MON-7, manufactured by Mitsui Kasei Co., Ltd.) as a surfactant was charged, and each barrel was set. Kneading was performed at a temperature of 95° C. and a screw rotation speed of 600 rpm.
150 parts by mass of ion-exchanged water adjusted to 95°C from the 5th barrel of the twin-screw extruder (ion-exchanged water 1) and 150 parts by mass of ion-exchanged water adjusted to 95°C from the 7th barrel (ion-exchanged water 2) Then, 150 parts by mass of ion-exchanged water (ion-exchanged water 3) adjusted to 95° C. from the 9th barrel was added and kneaded to obtain a resin particle dispersion liquid BD2.
The viscosity of the raw material BD measured by a flow tester at 105° C. was 10,000 Pa·s, and the average supply amount F of the raw material was 300 kg/h, where (μ×n ² ×d ³ )/F =2,341.
The obtained resin particle dispersion liquid BD2 was measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.), and as a result, the volume average particle diameter was 190 nm.

<Manufacture of toner>
A toner was prepared in the same manner as in Example 7, except that the resin particle dispersion liquid BD1 prepared in the absence of an organic solvent was changed to the resin particle dispersion liquid BD2.

(Example 11)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BF1 (Amorphous Polyester Resin B, Colorant and Release Agent) in the Absence of Organic Solvent>
254 parts by mass of amorphous polyester resin B, 57 parts by mass of carbon black as a coloring agent (manufactured by Cabot: Regal 330), 70 parts by mass of a releasing agent (manufactured by Nippon Seiro Co., Ltd., trade name: FNP0090) are used in a Henschel mixer. (75 L), and the mixture was mixed at a screw rotation speed of 600 rpm for 120 seconds to adjust the raw material BF.
200 parts by mass of the raw material BF and 0.2 parts by mass of a 50% by mass aqueous solution of sodium hydroxide are charged into the raw material charging port of the twin-screw extruder (TEM-75SS, manufactured by Toshiba Machine Co., Ltd.), and the twin-screw extrusion is performed. From the 4th barrel of the machine, 4.1 parts by mass of a 48.5% by mass solution of sodium dodecyldiphenyl ether sulfonate (Eleminol MON-7, manufactured by Mitsui Kasei Co., Ltd.) as a surfactant was charged, and each barrel was set. Kneading was performed at a temperature of 95° C. and a screw rotation speed of 240 rpm.
150 parts by mass of ion-exchanged water adjusted to 95°C from the 5th barrel of the twin-screw extruder (ion-exchanged water 1) and 150 parts by mass of ion-exchanged water adjusted to 95°C from the 7th barrel (ion-exchanged water 2) Then, 150 parts by mass of ion-exchanged water (ion-exchanged water 3) adjusted to 95° C. from the 9th barrel was added and kneaded to obtain a resin particle dispersion liquid BF1.
The viscosity at 105 ° C. of raw BF measured by a flow tester is 7,000Pa · s, the average supply amount F of the raw material is 300kg / h, (μ × n 2 × d 3) of the time / F =567.
The obtained resin particle dispersion liquid BF1 was measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.), and as a result, the volume average particle diameter was 189 nm.

<Manufacture of toner>
The following components were placed in a stirring tank equipped with a thermometer, a pH meter, a stirrer, and a jacket and stirred for 10 minutes.
-Resin particle dispersion liquid BF1: 529 parts by mass produced in the absence of organic solvent-Aqueous dispersion A2 of crystalline polyester resin particles prepared in the presence of organic solvent A2: 57 parts by mass-Prepared in the presence of organic solvent Aqueous dispersion of amorphous polyester resin particles C2: 314 parts by mass Ion-exchanged water: 200 parts by mass Anionic surfactant (Neogen RK manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): 7.0 parts by mass

While gradually adding 125 parts by mass of an aqueous solution of aluminum sulfate to the above-mentioned dispersion mixture put in a stirrer, the mixture solution was introduced into Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) through a bottom valve of a stirring tank and dispersed for 10 minutes. did. After the addition was completed, the temperature of the jacket was started to be raised at 50° C., and after 120 minutes, the particle size was measured with Multisizer II (aperture diameter: 50 μm, manufactured by Beckman Coulter, Inc.). It was 5.0 μm. Thereafter, 156 parts by mass of an aqueous dispersion B2 of amorphous polyester resin particles prepared in the presence of an organic solvent, and 156 parts by mass of an aqueous dispersion C2 of amorphous polyester resin particles prepared in the presence of an organic solvent. And added for 30 minutes.
A toner was prepared in the same manner as in Example 1 except for the above.

(Example 12)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BF2 (Amorphous Polyester Resin B, Colorant and Release Agent) in the Absence of Organic Solvent>
200 parts by mass of the raw material BF and 0.2 parts by mass of a 50% by weight aqueous solution of sodium hydroxide are charged into the raw material charging port of the twin-screw extruder (TEM-75SS, manufactured by Toshiba Machine Co., Ltd.), and the twin-screw extrusion is also performed. From the 4th barrel of the machine, 4.1 parts by mass of a 48.5% by mass solution of sodium dodecyldiphenyl ether sulfonate (Eleminol MON-7, manufactured by Mitsui Kasei Co., Ltd.) as a surfactant was charged, and each barrel was set. Kneading was performed at a temperature of 95° C. and a screw rotation speed of 520 rpm.
150 parts by mass of ion-exchanged water adjusted to 95°C from the 5th barrel of the twin-screw extruder (ion-exchanged water 1) and 150 parts by mass of ion-exchanged water adjusted to 95°C from the 7th barrel (ion-exchanged water 2) Then, 150 parts by mass of ion-exchanged water (ion-exchanged water 3) adjusted to 95° C. from the 9th barrel was added and kneaded to obtain a resin particle dispersion liquid BF2.
The viscosity of the raw material BF at 105° C. measured by a flow tester was 7,000 Pa·s, and the average supply amount F of the raw material was 700 kg/h, where (μ×n ² ×d ³ )/F = 1,141.
The volume average particle diameter of the obtained resin particle dispersion liquid BF2 was 190 nm as a result of measurement with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

<Manufacture of toner>
A toner was prepared in the same manner as in Example 9 except that the resin particle dispersion liquid BF1 prepared in the absence of an organic solvent was changed to the resin particle dispersion liquid BF2.

(Comparative Example 1)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Production of Resin Particle Dispersion B3 (Amorphous Polyester Resin B) in the Absence of Organic Solvent>
A resin particle dispersion B3 was prepared in the same manner as in Example 1 except that the screw rotation speed was 120 rpm and the average supply amount F of the raw material was 3.3 kg/h. At this time, (μ×n ² ×d ³ )/F=276.
The obtained resin particle dispersion B3 was measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.), and as a result, the volume average particle diameter was 182 nm.

<Manufacture of toner>
A toner was manufactured in the same manner as in Example 1 except that the resin particle dispersion liquid B1 prepared in the absence of an organic solvent was changed to the resin particle dispersion liquid B3.

(Comparative example 2)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion B4 (Amorphous Polyester Resin B) in the Absence of Organic Solvent>
A resin particle dispersion B4 was prepared in the same manner as in Example 1 except that the screw rotation speed was 1,200 rpm and the average supply amount F of the raw material was 10 kg/h. At this time, (μ×n ² ×d ³ )/F=9,111.
The obtained resin particle dispersion B4 was measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.), and as a result, the volume average particle diameter was 176 nm.

<Manufacture of toner>
A toner was manufactured in the same manner as in Example 1 except that the resin particle dispersion liquid B1 prepared in the absence of an organic solvent was changed to the resin particle dispersion liquid B4.

(Comparative example 3)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BC3 (Amorphous Polyester Resin B and Amorphous Polyester Resin C) in the Absence of Organic Solvent>
A resin particle dispersion liquid BC3 was prepared in the same manner as in Example 3 except that the screw rotation speed was 120 rpm and the average supply amount F of the raw material was 8 kg/h. At this time, (μ×n ² ×d ³ )/F=247.
The volume average particle diameter of the obtained resin particle dispersion liquid BC3 was 181 nm as a result of measurement with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.).

<Manufacture of toner>
A toner was manufactured in the same manner as in Example 3 except that the resin particle dispersion liquid BC1 prepared in the absence of an organic solvent was changed to the resin particle dispersion liquid BC3.

(Comparative example 4)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BC4 (Amorphous Polyester Resin B and Amorphous Polyester Resin C) in the Absence of Organic Solvent>
A resin particle dispersion liquid BC4 was prepared in the same manner as in Example 3 except that the screw rotation speed was 720 rpm and the average supply amount F of the raw material was 8.5 kg/h. At this time, (μ×n ² ×d ³ )/F=8,361.
The obtained resin particle dispersion liquid BC4 was measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.), and as a result, the volume average particle diameter was 179 nm.

<Manufacture of toner>
A toner was prepared in the same manner as in Example 3 except that the resin particle dispersion liquid BC1 prepared in the absence of an organic solvent was changed to the resin particle dispersion liquid BC4.

(Comparative example 5)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BA3 (Amorphous Polyester Resin B and Crystalline Polyester Resin A) in the Absence of Organic Solvent>
A resin particle dispersion liquid BA3 was prepared in the same manner as in Example 5 except that the screw rotation speed was 120 rpm and the average supply amount F of the raw material was 10 kg/h. At this time, (μ×n ² ×d ³ )/F=191.
The obtained resin particle dispersion BA3 was measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba, Ltd.), and as a result, the volume average particle diameter was 184 nm.

<Manufacture of toner>
A toner was prepared in the same manner as in Example 5, except that the resin particle dispersion liquid BA1 prepared in the absence of the organic solvent was changed to the resin particle dispersion liquid BA3.

(Comparative example 6)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BA4 (Amorphous Polyester Resin B and Crystalline Polyester Resin A) in the Absence of Organic Solvent>
A resin particle dispersion liquid BA4 was prepared in the same manner as in Example 5 except that the screw rotation speed was 720 rpm and the average supply amount F of the raw material was 7 kg/h. At this time, (μ×n ² ×d ³ )/F=9,828.
The obtained resin particle dispersion liquid BA4 was measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.), and as a result, the volume average particle diameter was 175 nm.

<Manufacture of toner>
A toner was prepared in the same manner as in Example 5, except that the resin particle dispersion liquid BA1 prepared in the absence of the organic solvent was changed to the resin particle dispersion liquid BA4.

(Comparative Example 7)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion AC3 (Crystalline Polyester Resin A and Amorphous Polyester Resin C) in the Absence of Organic Solvent>
A resin particle dispersion liquid AC3 was prepared in the same manner as in Example 5 except that the screw rotation speed was 120 rpm and the average supply amount F of the raw material was 15 kg/h. At this time, (μ×n ² ×d ³ )/F=212.
The obtained resin particle dispersion AC3 was measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.), and as a result, the volume average particle diameter was 183 nm.

<Manufacture of toner>
A toner was prepared in the same manner as in Example 7, except that the resin particle dispersion liquid AC1 prepared in the absence of the organic solvent was changed to the resin particle dispersion liquid AC3.

(Comparative Example 8)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion AC4 (Crystalline Polyester Resin A and Amorphous Polyester Resin C) in the Absence of Organic Solvent>
A resin particle dispersion liquid AC4 was prepared in the same manner as in Example 5 except that the screw rotation speed was 720 rpm and the average supply amount F of the raw material was 12 kg/h. At this time, (μ×n ² ×d ³ )/F=9,555.
The obtained resin particle dispersion AC4 was measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.), and as a result, the volume average particle diameter was 176 nm.

<Manufacture of toner>
A toner was prepared in the same manner as in Example 8 except that the resin particle dispersion liquid AC1 prepared in the absence of the organic solvent was changed to the resin particle dispersion liquid AC4.

(Comparative Example 9)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Production of Resin Particle Dispersion BD3 (Amorphous Polyester Resin B and Colorant) in the Absence of Organic Solvent>
A resin particle dispersion liquid BD3 was prepared in the same manner as in Example 7 except that the screw rotation speed was 120 rpm and the average supply amount F of the raw material was 95 kg/h. At this time, (μ×n ² ×d ³ )/F=296.
The resin particle dispersion liquid BD3 obtained (LA-700, (LA-700, ( As a result of measurement by Horiba Ltd., the volume average particle size was 187 nm.
<Manufacture of toner>
A toner was prepared in the same manner as in Example 7, except that the resin particle dispersion liquid BD1 prepared in the absence of the organic solvent was changed to the resin particle dispersion liquid BD3.

(Comparative Example 10)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion Liquid BD4 (Amorphous Polyester Resin B and Colorant) in the Absence of Organic Solvent>
A resin particle dispersion liquid BD4 was prepared in the same manner as in Example 7 except that the screw rotation speed was 600 rpm and the average supply amount F of the raw material was 80 kg/h. At this time, (μ×n ² ×d ³ )/F=8,780.
The obtained resin particle dispersion liquid BD4 was measured by a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.), and as a result, the volume average particle diameter was 176 nm.

<Manufacture of toner>
A toner was prepared in the same manner as in Example 7, except that the resin particle dispersion liquid BD1 prepared in the absence of the organic solvent was changed to the resin particle dispersion liquid BD4.

(Comparative Example 11)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BF3 (Amorphous Polyester Resin B, Colorant and Release Agent) in the Absence of Organic Solvent>
A resin particle dispersion liquid BF3 was prepared in the same manner as in Example 9 except that the screw rotation speed was 120 rpm and the average supply amount F of the raw material was 150 kg/h. At this time, (μ×n ² ×d ³ )/F=284.
The obtained resin particle dispersion liquid BF3 was measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.), and as a result, the volume average particle diameter was 189 nm.

<Manufacture of toner>
A toner was prepared in the same manner as in Example 9 except that the resin particle dispersion liquid BF1 prepared in the absence of an organic solvent was changed to the resin particle dispersion liquid BF3.

(Comparative Example 12)
A developer was produced in the same manner as in Example 1 except that the method for producing a resin particle dispersion in the absence of an organic solvent and the method for producing a toner were changed as follows.
Using the obtained resin particle dispersion and developer, evaluation of the molecular weight reduction ratio and evaluation of image density were carried out in the same manner as in Example 1.

<Preparation of Resin Particle Dispersion BF4 (Amorphous Polyester Resin B, Colorant and Release Agent) in the Absence of Organic Solvent>
A resin particle dispersion liquid BF4 was prepared in the same manner as in Example 9 except that the screw rotation speed was 520 rpm and the average supply amount F of the raw material was 95 kg/h. At this time, (μ×n ² ×d ³ )/F=8,406.
The obtained resin particle dispersion liquid BF4 was measured with a laser diffraction particle size distribution analyzer (LA-700, manufactured by Horiba Ltd.), and as a result, the volume average particle diameter was 171 nm.

<Manufacture of toner>
A toner was prepared in the same manner as in Example 9 except that the resin particle dispersion liquid BF1 prepared in the absence of an organic solvent was changed to the resin particle dispersion liquid BF4.

In Table 1 below, the evaluation results of the reduction ratio of the molecular weight and the evaluation results of the image density in each Example and Comparative Example are described.

1Y, 1M, 1C, 1K: photoconductor, 2Y, 2M, 2C, 2K: charging roller, 3Y, 3M, 3C, 3K: laser beam, 3: exposure device, 4Y, 4M, 4C, 4K: developing device, 5Y , 5M, 5C, 5K: primary transfer roller, 6Y, 6M, 6C, 6K: photoconductor cleaning device (cleaning means), 8Y, 8M, 8C, 8K: toner cartridge, 10: biaxial kneading extruder, 12: Barrel, 14: Raw material charging port, 16: Alkali metal hydroxide aqueous solution charging port, 18: Surfactant charging port, 20, 21, 22: Water charging port, 24: Discharge port, 26: Supply line, 28: Pump, 30: Resin feeder, 32: Alkali metal hydroxide aqueous solution tank, 34: Surfactant aqueous solution tank, 36: Temperature control device, 38: Pure water tank, 40: Heater, 42: Resin supply barrel, 44: Constant temperature region, 107: photoconductor, 108: charging roller, 110Y, 110M, 110C, 110K: image forming unit, 111: developing device, 112: transfer device, 113: photoconductor cleaning device (cleaning means), 115: fixing device, 116: Mounting rails 117, 118: openings, 120: intermediate transfer belt, 122: drive roller, 124: support roller, 126: secondary transfer roller (secondary transfer means), 128: fixing device (fixing means), 130: Intermediate transfer member cleaning device, 132: transfer roller, 200: process cartridge, 300, P: recording paper

Claims (4)

A raw material containing at least a resin, a base, a surfactant, and a dispersion step of mixing water to obtain an aqueous dispersion of resin particles,
The dispersing step has a plurality of barrels including a screw shaft inside and a raw material supply barrel, and the plurality of barrels is performed by a kneader having heating and cooling means,
Position screw rotation speed of the kneading machine (rpm) n, a barrel inner diameter (m) of said kneader d, supply amount of the raw material (kg / h) F, downstream from the raw material feed barrel of the kneader And the viscosity (Pa·s) of the raw material measured by a flow tester at the set temperature of the barrel in which at least one of the base, the surfactant, and the water is first charged +10° C. is defined as μ. At this time, the following method (1) is satisfied: A method for producing a resin particle dispersion.
300≦(μ×n ² ×d ³ )/F≦8,000 (1) The method for producing a resin particle dispersion according to claim 1, wherein the raw material contains two or more resins. The method for producing a resin particle dispersion according to claim 1, wherein the raw material contains a colorant and/or a release agent. A resin particle dispersion is produced by the method for producing a resin particle dispersion according to any one of claims 1 to 3, and the resin particles are aggregated by aggregating the resin particles in a dispersion containing the obtained resin particle dispersion. To obtain, and
A method for producing an electrostatic charge image developing toner, comprising the step of heating the aggregated particles to fuse them.

Images