JP2023056124A - Toner for electrostatic charge image development and method of manufacturing the same - Google Patents

Abstract

To provide toner for electrostatic charge image development that is superior in superior low-temperature fixability and fixation separability, and compatibly has excellent varnish processability, in-machine contamination prevention effect and glossiness unevenness prevention effect.SOLUTION: Provided is toner for electrostatic charge image development that includes toner base particles containing at least binding resin and a release agent, and the binding resin contains at least crystalline resin. Here, the toner for electrostatic charge image development satisfies the relation represented by expressions (1a) and (2a): 11≤W(1)p-C(1)p≤23 (1a) and 5≤Tf1/2-W(1)p≤36 (2a), where W(1)p is an endothermic peak temperature (°C) observed in a first temperature rise process of differential scan calorimetry of the toner for electrostatic charge image development, C(1)p is an endothermic peak temperature (°C) of the crystalline resin and Tf1/2 is a softening point temperature (°C) measured by a flow evaluation device.SELECTED DRAWING: None

Description

The present invention relates to a toner for electrostatic charge image development and a method for producing the same. More particularly, the present invention relates to a toner for electrostatic image development which is excellent in low-temperature fixability and fixation separability, and which achieves both good varnish processability, the effect of preventing contamination inside the machine, and the effect of preventing gloss unevenness.

2. Description of the Related Art In recent years, in electrophotographic image forming apparatuses, there has been a demand for an electrostatic charge image developing toner (hereinafter also simply referred to as “toner”) with improved low-temperature fixability.
For such a toner, it is necessary that the melting temperature and melt viscosity of the binder resin are low.
Therefore, conventionally, it has been proposed to improve the low-temperature fixability by using a toner containing a release agent with a low melting point and a crystalline resin. The difference is disappearing (for example, see Patent Document 1 and Patent Document 2).

In order to improve low-temperature fixability, it is useful to use a toner containing a low-melting release agent and a crystalline resin. Then, mixed crystals of both are formed, and there is a problem that the sharp melting property and fixing separation property of the toner are worse than expected.

In addition, when mixed crystals are formed, when varnishing is performed after forming a toner image, the varnish is less likely to permeate into the toner image, resulting in a problem of deterioration in varnishing properties.

In order to improve the low-temperature fixability, it is useful to use a toner containing a low-melting release agent that has a large difference between the softening point and the melting point of the toner. During image transport during formation, the release agent present on the surface layer of the image remains in a melted state.
When the release agent in the above state comes into contact with a member such as a conveying roller, the release agent cools and adheres to the contact portion, which causes problems such as conveyance failure and contamination inside the machine.
The above problem can be solved by using a toner containing a release agent with a high melting point that has a small difference between the softening point and the melting point of the toner. There is a problem in that it is difficult to achieve the same, and gloss unevenness occurs.

JP 2006-251564 A JP 2017-21157 A

The present invention has been made in view of the above-mentioned problems and circumstances, and the problem to be solved is to achieve both excellent low-temperature fixability and fixation separation property, good varnishing property, and effect of preventing stains inside the machine and effect of preventing gloss unevenness. An object of the present invention is to provide a toner for developing an electrostatic charge image and a method for producing the same.

In order to solve the above problems, the present inventors investigated the causes of the above problems, and found that the endothermic properties derived from the release agent observed during the first temperature rise process in the differential scanning calorimetry of the toner for electrostatic image development. The inventors have found that the above problems can be solved by controlling the peak temperature, the endothermic peak temperature of the crystalline resin, and the softening point temperature measured by the heat flow evaluation device so as to satisfy the relationship within a certain range, and have reached the present invention. rice field.
That is, the above problems related to the present invention are solved by the following means.

1. An electrostatic charge image developing toner containing toner base particles containing at least a binder resin and a release agent, wherein the binder resin contains at least a crystalline resin, Let W ₍₁₎ p (°C) be the endothermic peak temperature derived from the releasing agent observed in the first temperature rising process in scanning calorimetry, and C ₍₁₎ p (°C) be the endothermic peak temperature of the crystalline resin. ), and the softening point temperature measured by the thermal fluid evaluation device is Tf _1/2 (° C.), an electrostatic charge image characterized by satisfying the relationships represented by the following formulas (1a) and (2a): developer toner.
11≦W ₍₁₎ p−C ₍₁₎ p≦23 (1a)
5≦Tf _1/2 −W ₍₁₎ p≦36 (2a)

2. The softening point temperature Tf _1/2 (° C.) measured by the heat flow evaluation device and the endothermic peak temperature C ₍₁₎ p( °C) satisfies the relationship represented by the following formula (3).
Tf _1/2 −C ₍₁₎ p≦48 (3)

3. The endothermic peak temperature W ₍₁₎ p (°C) derived from the release agent observed in the first temperature rising process in the differential scanning calorimetry and the endothermic peak temperature C ₁ p (°C) of the crystalline resin are 3. The toner for electrostatic image development according to item 1 or 2, wherein the toner satisfies the relationship represented by the following formula (1b).
14≦W ₍₁₎ p−C ₍₁₎ p≦17 (1b)

4. The softening point temperature Tf _1/2 (°C) measured by the thermal flow evaluation device and the endothermic peak temperature W ₍₁₎ p derived from the release agent observed in the first temperature rising process in the differential scanning calorimetry. (° C.) satisfies the relationship represented by the following formula (2b).
11≦Tf _1/2 −W ₍₁₎ p≦30 (2b)

5. 5. The endothermic peak temperature W ₍₁₎ p (° C.) derived from the release agent is in the range of 64 to 100 (° C.). toner for developing electrostatic charge images.

6. Any one of items 1 to 5, wherein the softening point temperature Tf _1/2 (°C) measured by the thermal fluid evaluation device is in the range of 90 to 115 (°C). 3. The toner for electrostatic charge image development described in .

7. 7. The electrostatic image developing toner according to any one of items 1 to 6, wherein the crystalline resin contains a crystalline polyester.

8. 8. The crystalline resin according to any one of items 1 to 7, wherein the crystalline resin is a hybrid crystalline polyester resin in which a crystalline polyester polymer segment and a vinyl resin polymer segment are combined. A toner for developing an electrostatic charge image as described above.

9. 9. The electrostatic image developing toner according to any one of items 1 to 8, wherein the binder resin contains at least styrene-acrylic resin.

10. 10. A method for producing the toner for developing an electrostatic charge image according to any one of items 1 to 9, wherein in the step of producing toner particles, amorphous resin fine particles What is claimed is: 1. A method for producing a toner for electrostatic charge image development, comprising a step of adding a crystalline resin fine particle dispersion to a dispersion and allowing toner particles to grow at a temperature equal to or higher than the melting point of the crystalline resin.

By the means of the present invention, it is possible to provide a toner for electrostatic image development which is excellent in low-temperature fixability and fixation separability, and which satisfies both good varnish processability, an effect of preventing in-machine contamination, and an effect of preventing gloss unevenness.
Although the expression mechanism or action mechanism of the effects of the present invention has not been clarified, it is speculated as follows.

According to the present invention, the endothermic peak temperature derived from the release agent and the endothermic peak temperature of the crystalline resin observed in the first temperature rising process in the differential scanning calorimetry of the toner for electrostatic charge image development, and the heat flow evaluation device By controlling the softening point temperature to be measured so as to satisfy the relationship within a certain range, excellent low-temperature fixability and fixation separability, good varnish workability, effect of preventing in-machine contamination and effect of preventing gloss unevenness are obtained. can be compatible.

If the temperature obtained by subtracting the endothermic peak temperature of the crystalline resin from the endothermic peak temperature of the release agent observed in the first temperature rising process in the differential scanning calorimetry of the toner for developing an electrostatic charge image is lower than 11°C, the separation occurs. The stencil agent and the crystalline resin become mixed crystals during toner production, and the low-temperature fixability of the toner deteriorates due to the compatibility of the crystalline resin with the binder resin. Inferior in fixation separability.
Also, when each component contained in the toner is crystallized on the image, the release agent and the crystalline resin form mixed crystals, which hinder the permeation of the varnish, thereby deteriorating the workability of the varnish.
Therefore, the temperature obtained by subtracting the endothermic peak temperature of the crystalline resin from the endothermic peak temperature derived from the release agent observed in the first temperature rising process in differential scanning calorimetry of the toner for electrostatic image development is set to 11° C. or higher. As a result, good low-temperature fixability and fixability, and good varnish workability are realized.

If the temperature obtained by subtracting the endothermic peak temperature of the crystalline resin from the endothermic peak temperature of the release agent observed in the first temperature rising process in the differential scanning calorimetry of the toner for electrostatic charge image development is higher than 23° C., the toner Crystal growth of each component contained in the toner crystallized earlier at the time of production advances excessively, causing bleeding out from the toner, resulting in production defects.
Therefore, the temperature obtained by subtracting the endothermic peak temperature of the crystalline resin from the endothermic peak temperature derived from the release agent observed in the first temperature rising process in differential scanning calorimetry of the toner for electrostatic image development is set to 23° C. or less. As a result, good toner manufacturability was ensured.

The temperature obtained by subtracting the endothermic peak temperature derived from the release agent observed in the first temperature rising process in the differential scanning calorimetry from the softening point temperature measured by the thermal fluidity evaluation apparatus for the toner for electrostatic image development is 5°C. If it is too low, the balance between the wetting and spreading of the resin and the melting balance of the release agent is deteriorated, making it difficult to obtain smooth images and causing uneven glossiness.
Therefore, the temperature obtained by subtracting the endothermic peak temperature derived from the release agent observed in the first temperature rising process in the differential scanning calorimetry from the softening point temperature measured by the heat flow evaluation device for the toner for electrostatic image development is 5. °C or higher, the effect of preventing uneven gloss was realized.

The temperature obtained by subtracting the endothermic peak temperature derived from the release agent observed in the first temperature rising process in the differential scanning calorimetry from the softening point temperature measured by the thermal fluidity evaluation apparatus for the toner for electrostatic image development is above 36°C. If it is too high, the low-temperature fixability can be ensured, but the melting point of the release agent is too low, and the inside of the machine is contaminated by the release agent.
Therefore, the temperature obtained by subtracting the endothermic peak temperature derived from the release agent observed in the process of the first temperature rise in the differential scanning calorimetry from the softening point temperature measured by the thermal flow evaluation apparatus for the toner for electrostatic image development was 36. By keeping the temperature below ℃, we have achieved the effect of preventing in-flight pollution.

The electrostatic image developing toner of the present invention is an electrostatic image developing toner containing toner base particles containing at least a binder resin and a release agent, wherein the binder resin contains at least a crystalline resin. Let W ₍₁₎ p (° C.) be the endothermic peak temperature derived from the release agent observed in the first temperature rise process in the differential scanning calorimetry of the toner for developing an electrostatic charge image, and the temperature of the crystalline resin Assuming that the endothermic peak temperature is C ₍₁₎ p (°C) and the softening point temperature measured by the heat flow evaluation device is Tf _1/2 (°C), the following formulas (1a) and (2a) are obtained. It is characterized by satisfying relationships.
This feature is a technical feature common to or corresponding to each of the following embodiments (aspects).

As an embodiment of the present invention, the softening point temperature Tf _1/2 (° C.) measured by the heat flow evaluation device and the endothermic endotherm of the crystalline resin observed in the first temperature rising process in the differential scanning calorimetry It is preferable that the peak temperature C ₍₁₎ p (° C.) satisfies the relationship represented by the formula (3) from the viewpoint of the melting balance between the electrostatic image developing toner and the crystalline resin.

The endothermic peak temperature W ₍₁₎ p (°C) derived from the releasing agent and the endothermic peak temperature C ₍₁₎ p (°C) of the crystalline resin observed in the first heating process in the differential scanning calorimetry. However, it is preferable to satisfy the relationship represented by the above formula (1b) from the viewpoint of improving the melting balance without forming mixed crystals of the release agent and the crystalline resin.

The softening point temperature Tf _1/2 (°C) measured by the thermal flow evaluation device and the endothermic peak temperature W ₍₁₎ p derived from the release agent observed in the first temperature rising process in the differential scanning calorimetry. (° C.) preferably satisfies the relationship represented by the formula (2b) from the viewpoint of the melting balance between the electrostatic image developing toner and the release agent.

The endothermic peak temperature W ₍₁₎ p (° C.) derived from the release agent is preferably in the range of 64 to 100 (° C.) from the viewpoint of the productivity of the toner for electrostatic image development.

From the viewpoint of the meltability of the electrostatic image developing toner, the softening point temperature Tf _1/2 (° C.) measured by the thermal flow evaluation apparatus is preferably in the range of 90 to 115 (° C.).

It is preferable that the crystalline resin contains a crystalline polyester from the viewpoint of promoting the crystallization of the release agent in the toner for electrostatic charge image development.

The crystalline resin is a hybrid crystalline polyester resin in which a crystalline polyester polymerized segment and a vinyl resin polymerized segment are combined to suppress bleeding out of the crystalline polyester in the toner for electrostatic image development. It is preferable from the viewpoint of

It is preferable that the binder resin contains at least a styrene-acrylic resin from the viewpoint of suppressing excessive exudation of the release agent.

The method for producing a toner for developing an electrostatic charge image of the present invention is a method for producing the toner for developing an electrostatic charge image of the present invention, wherein in the step of producing toner particles, amorphous The method is characterized by including a step of adding a crystalline resin fine particle dispersion into a resin fine particle dispersion and growing toner particles at a temperature equal to or higher than the melting point of the crystalline resin.
As a result, a toner having the desired thermophysical properties described above can be obtained.

DETAILED DESCRIPTION OF THE INVENTION The present invention, its constituent elements, and embodiments and modes for carrying out the present invention will be described in detail below. In the present application, "-" is used to mean that the numerical values before and after it are included as the lower limit and the upper limit.

[Summary of electrostatic charge image developing toner of the present invention]
The electrostatic image developing toner of the present invention is an electrostatic image developing toner containing toner base particles containing at least a binder resin and a release agent, wherein the binder resin contains at least a crystalline resin. Let W ₍₁₎ p (° C.) be the endothermic peak temperature derived from the release agent observed in the first temperature rise process in the differential scanning calorimetry of the toner for developing an electrostatic charge image, and the temperature of the crystalline resin Assuming that the endothermic peak temperature is C ₍₁₎ p (°C) and the softening point temperature measured by the heat flow evaluation device is Tf _1/2 (°C), the following formulas (1a) and (2a) are obtained. It is characterized by satisfying relationships.
11≦W ₍₁₎ p−C ₍₁₎ p≦23 (1a)
5≦Tf _1/2 −W ₍₁₎ p≦36 (2a)

1. Characteristics of Thermophysical Properties of Toner for Developing Electrostatic Charge Images The properties of the toner according to the present invention (hereinafter also simply referred to as "toner") are measured by differential scanning calorimetry as thermophysical properties when heat is applied. The endothermic temperature and the softening point temperature measured by the heat flow evaluation device satisfy the relationships represented by the above formulas (1a) and (2a).
The method and conditions for measuring thermophysical properties of the toner of the present invention are described below.

(1.1) Measuring Method by Differential Scanning Calorimetry In the present invention, the thermophysical properties of the toner are measured by differential scanning calorimetry (hereinafter also referred to as “DSC”) as follows.
In the present invention, "heat flux DSC", that is, a measurement method in which the temperature difference between a sample and a reference substance is detected while changing the temperature according to a controlled program and converted into a heat flow is used. Specifically, the procedure is as follows.

A measurement sample is placed in a measurement container called a pan and measured.
A pan containing a sample to be measured is placed on the sample sensor, and an empty pan is placed on the reference substance (reference) sensor for measurement.

Specifically, 5 mg of the sample to be measured (each release agent and crystalline resin) was placed in an aluminum pan KITNO. B0143013, set in the sample holder of the thermal analysis device "Diamond DSC (manufactured by PerkinElmer)", heating (first temperature rising process), cooling, heating (second temperature rising process) in order of temperature to fluctuate.

During the first and second heating (heating process), the temperature was raised from 0 ° C. to 100 ° C. at a heating rate of 10 ° C./min and held at 100 ° C. for 1 minute. The temperature is lowered from 100° C. to 0° C. at a rate and maintained at 0° C. for 1 minute.
The endothermic peak temperature derived from the release agent in the endothermic curve obtained during the first heating (temperature rising process) is W ₍₁₎ p (°C), and the endothermic peak temperature of the crystalline resin is C ₍₁₎ p (°C). ).
An empty aluminum pan was used as a reference.

In the present invention, the term "endothermic peak temperature" in differential scanning calorimetry refers to the temperature corresponding to the peak in the endothermic curve obtained in the first or second heating process.
As used herein, "peak" refers to a prominent top (extremum) portion that exhibits an endothermic phenomenon with respect to the baseline.

(1.2) Thermophysical Properties Observed in the Process of First _Temperature Raise ₎ is p (° C.), the endothermic peak temperature of the crystalline resin is C ₍₁₎ p (° C.), and the softening point temperature measured by a heat flow evaluation device is Tf _1/2 (° C.). It is characterized by being adjusted so that the relationships represented by the formulas (1a) and (2a) are established, and the reason for this will be described in detail.
11≦W ₍₁₎ p−C ₍₁₎ p≦23 (1a)
5≦Tf _1/2 −W ₍₁₎ p≦36 (2a)

(a) The endothermic peak temperature W _{(1) derived from the release agent observed in the first temperature rising process in differential scanning calorimetry of the toner (1)} From p (° C.) to the endothermic peak temperature C ₍₁₎ of the crystalline resin If the temperature difference obtained by subtracting p (° C.) is lower than 11 (° C.), the release agent and the crystalline resin form mixed crystals during toner production, and the crystalline resin becomes compatible with the binder resin, resulting in a low temperature. Fixability deteriorates, and the amount of the release agent oozing onto the image surface decreases, thereby deteriorating fixing separability.
(b) In addition, when the toner is crystallized on the image during image formation using toner, a mixed crystal of the release agent and the crystalline resin is formed, which becomes a factor that hinders the permeation of the varnish during varnishing. , the varnish workability deteriorates.

(c) Endothermic peak temperature W _{(1) derived from the release agent observed in the first temperature rising process in differential scanning calorimetry of the toner (1)} From p (° C.) to endothermic peak temperature C ₍₁₎ of the crystalline resin If the temperature difference obtained by subtracting p (° C.) is higher than 23 (° C.), crystal growth of the previously crystallized material proceeds too much during toner production, causing the crystallized material to bleed out from the toner. As a result, it becomes a factor that causes manufacturing defects of toner.

(d) An endothermic peak derived from the releasing agent observed during the first temperature rising process in the differential scanning calorimetry measurement of the toner from the softening point temperature Tf _1/2 (°C) measured by the thermal flow evaluation device. When the temperature difference obtained by subtracting the temperature W ₍₁₎ p (°C) is lower than 5 (°C), the image becomes smooth due to deterioration in the balance between the wetting and spreading of the resin on the image and the melting balance of the release agent. It becomes difficult and gloss unevenness occurs.

(e) The endothermic peak temperature W derived from the release agent observed in the first temperature rising process in the differential scanning calorimetry measurement of the toner from the softening point temperature Tf _1/2 (° C.) measured by the thermal flow evaluation device ₍₁₎ If the temperature difference obtained by subtracting p (°C) is higher than 35 (°C), low-temperature fixability can be ensured, but the melting point of the release agent is too low, and the inside of the machine is contaminated by the release agent. .

Therefore, the endothermic peak temperature derived from the release agent observed in the first temperature rising process in the differential scanning calorimetry of the toner for electrostatic image development is W ₍₁₎ p (° C.), and the temperature of the crystalline resin is Assuming that the endothermic peak temperature is C ₍₁₎ p (°C) and the softening point temperature measured by the heat flow evaluation device is Tf _1/2 (°C), the above formulas (1a) and (2a) are obtained. By satisfying the relationship, the above problems (a) to (e) can be solved.

(1.2.1) Endothermic peak temperature derived from the release agent The “endothermic peak temperature derived from the release agent” according to the present invention refers to the first or second heating (temperature rising process) in the differential scanning calorimetry described above. W ₍₁₎ p (°C).
In the "endothermic peak temperature derived from the release agent" in differential scanning calorimetry in the present invention, the peak temperature W ₍₁₎ p in the endothermic curve derived from the release agent observed in the first temperature rising process is 64 to From the viewpoint of the productivity of the electrostatic image developing toner, the temperature is preferably within the range of 100°C.

(1.2.2) Endothermic peak temperature of crystalline resin The “endothermic peak temperature of the crystalline resin” according to the present invention refers to the temperature during the first or second heating (heating process) in the differential scanning calorimetry described above. Refers to the endothermic peak temperature of the crystalline resin in the observed endothermic curve, among which the endothermic peak temperature of the crystalline resin in the endothermic curve observed during the first heating (temperature rising process) is C ₍₁₎ p (°C ).
In the "endothermic peak temperature of the crystalline resin" in differential scanning calorimetry in the present invention, the peak temperature C ₍₁₎ p of the endothermic curve of the crystalline resin observed in the first heating process is 60 to 85°C. is preferably within the range of , and more preferably within the range of 72 to 82°C.

The endothermic peak temperature W ₍₁₎ p (°C) derived from the releasing agent and the endothermic peak temperature C ₍₁₎ p (°C) of the crystalline resin observed in the first heating process in the differential scanning calorimetry. However, it is preferable to satisfy the relationship represented by the following formula (1b) from the viewpoint of improving the melting balance without forming mixed crystals of the release agent and the crystalline resin.
14≦W ₍₁₎ p−C ₍₁₎ p≦17 (1b)

By satisfying the relationship represented by the above formula (1b), it is possible to improve the low-temperature fixability by making the crystalline resin compatible with the binder resin, and to reduce the amount of bleeding of the release agent onto the image surface. can.
Furthermore, during image formation with toner, mixed crystals of the release agent and crystalline resin are not formed even when the toner is crystallized on the image, eliminating factors that hinder penetration of the varnish during varnishing. Improves varnishability.
In addition, since the crystal growth of the material that has already crystallized during the production of the toner can be moderately suppressed, the toner does not bleed out, and the productivity of the toner is improved.

(1.2.3) Softening Point Temperature The "softening point temperature" of the toner for electrostatic image development according to the present invention is the temperature at which the toner starts to soften and deform due to temperature rise.

The "softening point temperature measured by a heat flow evaluation device" of the toner for electrostatic charge image development according to the present invention is a temperature measured as follows.
(Method for measuring softening point temperature)
In the present invention, the softening point of the toner for electrostatic image development was measured using a thermal fluidity evaluation device (also referred to as a "thermal melt viscosity measuring device" or "flow tester") as follows.
Specifically, using a flow tester CFT-500D (manufactured by Shimadzu Corporation), a 1 cm ³ sample was heated at a temperature increase rate of 6 ° C./min, and a plunger (also referred to as a “piston”) was used to move 20 kg / A pressurized load of cm ² is applied, and a nozzle with a diameter of 1 mm and a length of 1 mm is extruded, thereby drawing a plunger descent amount (flow value)-temperature curve (also referred to as a "softening flow curve"). When the height of the S-shaped curve is h, the temperature corresponding to h/2 (the temperature at which half of the toner flows out) is the softening point temperature _Tf1/2 (also referred to as "1/2 method softening point"). bottom.

It is preferable that the softening point temperature Tf _1/2 according to the present invention is 90° C. or more because the meltability of the toner does not become too high and the fixation separation property becomes good.
It is preferable that the softening point temperature Tf _1/2 is 115° C. or less because the meltability of the toner does not become too low and the low-temperature fixability is improved.

As an embodiment of the present invention, the softening point temperature Tf _1/
2 (° C.) and the endothermic peak temperature C ₍₁₎ p (° C.) of the crystalline resin observed in the first heating process in the differential scanning calorimetry are represented by the following formula (3): It is preferable from the viewpoint of the melting balance between the electrostatic charge image developing toner and the crystalline resin to satisfy.
Tf _1/2 −C ₍₁₎ p≦48 (3)

The softening point temperature Tf _1/2 (°C) measured by the thermal flow evaluation device and the endothermic peak temperature W ₍₁₎ p derived from the release agent observed in the first temperature rising process in the differential scanning calorimetry. (° C.) preferably satisfies the relationship represented by the following formula (2b) from the viewpoint of the melting balance between the electrostatic image developing toner and the release agent.
11≦Tf _1/2 −W ₍₁₎ p≦30 (2b)

By satisfying the above formulas (3) and (2b), the toner for electrostatic charge image development, the crystalline resin, and the release agent have a good melting balance, the image becomes smooth, the gloss unevenness does not occur, and the separation is achieved. In-flight contamination by mold agent does not occur.

2. Effect of Mixed Crystals of Release Agent and Crystalline Resin on Toner Image Mixed crystals of the release agent and crystalline resin are formed when the melting point difference between the two disappears.
When the above mixed crystals are formed, a phenomenon is observed in which the sharp melting property and fixing separability of the toner are worse than expected.
In addition, when mixed crystals are formed, when the toner image is processed with varnish after the toner image is formed, the varnish is less likely to permeate into the toner image, resulting in deterioration of varnish processability.

In the present specification, the term "sharp meltability of toner" means that the difference between the melting start temperature and the melting end temperature in a DSC curve measured at a constant heating rate in differential scanning calorimeter measurement is small, and the peak of the DSC curve is Represents the state of being sharp.

(2.1) Method for confirming the state of existence of mixed crystals Confirmation of the state of existence of mixed crystals as to whether or not the mixed crystals are formed in the toner was performed by observing the cross section of the toner particles under the following conditions. .

(conditions)
Apparatus: Scanning transmission electron microscope "JSM-7401F" (manufactured by JEOL Ltd.)
Sample: section of toner particles stained with ruthenium tetroxide (RuO ₄ ) (section thickness: 60-100 nm)
Accelerating voltage: 30 kV
Magnification: 10000 times (bright field image)

(2.2) Method for Producing Sections of Toner Particles A method for producing sections of toner particles under the above (conditions) will be described below.

(Method for Producing Sections of Toner Particles)
After the toner is exposed to a ruthenium tetroxide (RuO ₄ ) vapor atmosphere for 10 minutes, it is dispersed in a photocurable resin “D-800” (manufactured by JEOL Ltd.) and then photocured to form blocks.
A microtome with diamond teeth is then used to cut flake samples of thickness 60-100 nm from the blocks and mounted on grids with support film for transmission electron microscopy.
A 5 cmφ plastic petri dish is covered with filter paper, and the grid with the section is placed thereon with the side on which the section is mounted facing up.

(2.3) Conditions for Ruthenium Tetroxide Dyeing Conditions for the ruthenium tetroxide dyeing in the above (method for producing sections of toner particles) are shown below.

(Ruthenium tetroxide staining conditions)
The dyeing conditions (time, temperature, concentration and amount of staining agent) are adjusted so that each resin can be distinguished when observed with a transmission electron microscope.
For example, 2 to 3 drops of 0.5% RuO ₄ staining solution are dropped at two points in the petri dish, and the dish is covered with a lid.

3. Structure of Electrostatic Image Developing Toner The electrostatic image developing toner of the present invention is an electrostatic image developing toner containing toner base particles containing at least a binder resin and a release agent, wherein the binder resin contains at least a crystalline resin, and W ₍₁₎ p (°C ), the endothermic peak temperature of the crystalline resin is C ₍₁₎ p (°C), and the softening point temperature measured by a heat flow evaluation device is Tf _1/2 (°C), the following formula (1a) and (2a) are satisfied.

(3.1) Toner Base Particles The toner base particles according to the present invention may contain other components such as other colorants, charge control agents and external additives in addition to the binder resin and release agent. .
In the present invention, "toner particles" refer to toner base particles to which an external additive is added, and aggregates of toner particles are referred to as "toner".
Generally, toner base particles can be used as toner particles as they are, but in the present invention, toner base particles to which an external additive is added are used as toner particles.
Further, in the following description, when there is no particular need to distinguish between toner base particles and toner particles, they may simply be referred to as "toner particles".
Details of each constituent material of the toner base particles according to the present invention will be described below.

(3.2) Binder Resin The binder resin contained in the toner base particles contained in the electrostatic image developing toner of the present invention contains at least a crystalline resin.
“Binder resin (also referred to as “binder resin”)” refers to internal additives (release agents, charge control agents, colorants, etc.) and external additives (silica, titanium oxide, etc.) contained in toner particles. ) and is used as a medium or matrix (mother) for dispersing and holding toner images, and has a function of adhering to a recording medium (for example, paper) during fixing processing of a toner image.
In the toner of the present invention, conventionally known binder resins such as crystalline resins and amorphous resins can be used as the binder resin.
The binder resin preferably contains at least a styrene-acrylic resin.
By containing the styrene-acrylic resin, it is possible to suppress excessive exudation of the release agent during fixing of the toner, improve fixation separability, and suppress contamination of the inside of the machine by the release agent.
In addition, other known resins may be contained within a range that does not impair the effects of the present invention.

(3.2.1) Crystalline Resin The crystalline resin according to the present invention refers to a resin having a clear endothermic peak instead of a stepwise endothermic change in the DSC of the crystalline resin or toner particles.
A clear endothermic peak specifically means a peak whose half width of the endothermic peak is within 15° C. when measured at a heating rate of 10° C./min in DSC.

The melting point (Tm) of the crystalline resin is more preferably in the range of 62 to 82° C. from the viewpoint of obtaining sufficient low-temperature fixability and high-temperature storage stability.
Here, in the present invention, the above-mentioned "melting point" means the endothermic peak temperature C ₍₁₎ p (° C.) of the crystalline resin observed in the first heating process in differential scanning calorimetry. do.

Crystalline resins are not particularly limited, but include polyolefin resins, polydiene resins, and polyester resins.
Among these, crystalline polyester resins are preferable from the viewpoint of ease of use, as well as sufficient low-temperature fixability and gloss uniformity can be obtained.

Also, the number average molecular weight (Mn) of the crystalline resin is preferably in the range of 2,500 to 5,000, more preferably in the range of 3,000 to 4,500.
The number average molecular weight (Mn) of the crystalline resin is preferably in the range of 3,000 to 12,500, more preferably in the range of 4,000 to 11,000, from the viewpoint of low-temperature fixability and gloss stability.
Further, the weight average molecular weight (Mw) of the crystalline resin is preferably in the range of 10000 to 100000, more preferably in the range of 15000 to 80000, and further preferably in the range of 20000 to 50000. preferable.

The crystalline resin is a hybrid crystalline polyester resin in which a crystalline polyester polymer segment and a vinyl resin polymer segment are combined to suppress bleeding out of the crystalline polyester in the toner for electrostatic charge image development. It is preferable from the viewpoint of
As described above, by suppressing the bleed-out, toner manufacturability is improved.

The content of the crystalline resin in the toner base particles is preferably in the range of 5 to 20% by mass from the viewpoint of achieving both good low-temperature fixability and transferability in a high-temperature, high-humidity environment.
When the content is 5% by mass or more, the formed toner image has sufficient low-temperature fixability.
Further, when the content is 20% by mass or less, transferability is sufficient.

(acid number)
From the viewpoint of productivity, the acid value of the crystalline resin is preferably within the range of 10 to 30 mgKOH/g.
When it is 10 mgKOH/g or more, the amount of carboxyl groups is sufficient to avoid emulsification. can be avoided, and as a result, generation of residue during fabrication can be prevented.

[Method for measuring acid value]
The acid number is the mass in mg of potassium hydroxide (KOH) required to neutralize the acid contained in 1 g of sample. The acid value of the resin is measured by the following procedure according to JIS K0070-1966.

[Preparation of reagents]
A phenolphthalein solution is prepared by dissolving 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume) and adding ion-exchanged water to bring the total volume to 100 mL. 7 g of JIS special grade potassium hydroxide is dissolved in 5 mL of deionized water, and ethyl alcohol (95% by volume) is added to make 1 liter. Put in an alkali-resistant container so as not to touch carbon dioxide gas 3
After standing for days, it is filtered to prepare a potassium hydroxide solution. Orientation follows the description of JIS K0070-1966.

〔Main test〕
2.0 g of the pulverized sample is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene/ethanol (2:1) is added, and dissolved over 5 hours. Next, a few drops of the prepared phenolphthalein solution are added as an indicator, and titration is performed using the prepared potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.

[Blank test]
The same operation as in the main test is performed except that no sample is used (that is, only a mixed solution of toluene/ethanol (2:1) is used).

The acid value is calculated by substituting the titration results of the main test and the blank test into the following formula (1).
Formula (1) A = [(BC) x f x 5.6] / S
A: Acid value (mgKOH/g)
B: Amount of potassium hydroxide solution added during blank test (mL)
C: Amount (mL) of potassium hydroxide solution added during this test
f: factor of 0.1 mol/L potassium hydroxide ethanol solution S: mass of sample (g)

(3.2.2) Crystalline Polyester Resin It is preferable that the binder resin is a crystalline polyester resin from the viewpoint of promoting the crystallization of the release agent in the electrostatic image developing toner.
As described above, the adhesion of the release agent can be suppressed by promoting crystallization.
The crystalline polyester resin refers to a polyester resin among the crystalline resins described above.
A crystalline polyester resin is obtained by a polycondensation reaction between a divalent or higher carboxylic acid (polycarboxylic acid) and a divalent or higher alcohol (polyhydric alcohol).

(polycarboxylic acid)
Examples of polycarboxylic acids include dicarboxylic acids.
This dicarboxylic acid may be one or more, preferably an aliphatic dicarboxylic acid, and may further contain an aromatic dicarboxylic acid.
The aliphatic dicarboxylic acid is preferably linear from the viewpoint of enhancing the crystallinity of the crystalline polyester resin.

[Aliphatic dicarboxylic acid]
Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid. acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid (dodecanedioic acid), 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid, 1, 18-octadecanedicarboxylic acid, their lower alkyl esters and their acid anhydrides are included.
Among them, aliphatic dicarboxylic acids having 6 to 16 carbon atoms are preferred, and further aliphatic dicarboxylic acids having 10 to 14 carbon atoms are preferred from the viewpoint of easily obtaining the effect of both low-temperature fixability and transferability. is more preferred.

[Aromatic dicarboxylic acid]
Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4'-biphenyldicarboxylic acid.
Among them, terephthalic acid, isophthalic acid, and t-butylisophthalic acid are preferable from the viewpoint of availability and ease of emulsification.

[Content of dicarboxylic acid]
The content of the structural unit derived from the aliphatic dicarboxylic acid relative to the structural unit derived from the dicarboxylic acid in the crystalline polyester resin is preferably 50 mol% or more from the viewpoint of sufficiently ensuring the crystallinity of the crystalline polyester resin. , is more preferably 70 mol % or more, still more preferably 80 mol % or more, and particularly preferably 100 mol %.

(polyhydric alcohol)
Examples of the polyhydric alcohol component include diols.
Diols may be one or more, preferably aliphatic diols, and may further contain other diols.
From the viewpoint of increasing the crystallinity of the crystalline polyester resin, the aliphatic diol is preferably linear.

[Aliphatic diol]
Examples of said aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 - octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18 - Octadecanediol and 1,20-eicosanediol.
Among them, aliphatic diols having 2 to 120 carbon atoms are preferable, and aliphatic diols having 4 to 6 carbon atoms are more preferable, from the viewpoint of easily obtaining the effect of both low-temperature fixability and transferability. preferable.

[Other diols]
Examples of other diols include diols with double bonds and diols with sulfonic acid groups.
Specifically, examples of diols with double bonds include 2-butene-1,4-diol, 3-hexene-1,6-diol and 4-octene-1,8-diol.

[Content of aliphatic diol]
The content of the aliphatic diol-derived structural unit with respect to the diol-derived structural unit in the crystalline polyester resin is 50 mol % or more from the viewpoint of improving the low-temperature fixability of the toner and the glossiness of the finally formed image. is preferably 70 mol % or more, more preferably 80 mol % or more, and particularly preferably 100 mol %.

(Proportion of diol and dicarboxylic acid)
The ratio of the diol to the dicarboxylic acid in the monomer of the crystalline polyester resin is 2.0/[OH]/[COOH] in terms of the equivalent ratio of the hydroxy group [OH] of the diol to the carboxy group [COOH] of the dicarboxylic acid. It is preferably within the range of 1.0 to 1.0/2.0, more preferably within the range of 1.5/1.0 to 1.0/1.5, and 1.3/1 .0 to 1.0/1.3 is particularly preferred.

(Melting point of crystalline polyester resin)
The melting point (Tm) of the crystalline polyester resin is more preferably in the range of 62 to 82° C. from the viewpoint of obtaining sufficient low-temperature fixability and high-temperature storage stability.

The melting point of the crystalline polyester resin can be measured by the DSC measurement method described above.

(Weight average molecular weight and number average molecular weight of crystalline polyester resin)
Further, the weight average molecular weight (Mw) of the crystalline polyester resin is in the range of 5,000 to 50,000, and the number average molecular weight (Mn) is in the range of 2,000 to 10,000. It is preferable from the viewpoint of expression of gloss.

The weight average molecular weight (Mw) and number average molecular weight (Mn) can be obtained from the molecular weight distribution measured by gel permeation chromatography (GPC) as follows.

The sample was added to tetrahydrofuran (THF) to a concentration of 1 mg/mL, dispersed for 5 minutes using an ultrasonic disperser at room temperature, and then treated with a membrane filter having a pore size of 0.2 μm to remove the sample solution. Prepare.

Using a GPC apparatus HLC-8120GPC (manufactured by Tosoh Corporation) and a column "TSKguardcolumn + TSKgel SuperHZM-M triplet" (manufactured by Tosoh Corporation), while maintaining the column temperature at 40 ° C., THF as a carrier solvent is flowed at a flow rate of 0.2 mL / min. . 10 μL of the prepared sample solution is injected into the GPC device together with the carrier solvent, and the sample is detected using a refractive index detector (RI detector).
Then, the molecular weight distribution of the sample is calculated using a calibration curve measured using 10 points of monodisperse polystyrene standard particles.

(Synthesis of crystalline polyester resin)
The crystalline polyester resin can be synthesized by polycondensing (esterifying) the polyhydric carboxylic acid and polyhydric alcohol using a known esterification catalyst.

〔catalyst〕
One or more catalysts can be used to synthesize the crystalline polyester resin, examples of which include alkali metal compounds such as sodium and lithium; compounds containing Group 2 elements such as magnesium and calcium; aluminum and zinc. , manganese, antimony, titanium, tin, zirconium, germanium, and the like; phosphorous compounds; phosphoric acid compounds; and amine compounds.

Specifically, examples of tin compounds include dibutyltin oxide, tin octylate, tin dioctate and salts thereof.
Examples of titanium compounds include titanium alkoxides such as tetra-n-butyl titanate, tetraisopropyl titanate, tetramethyl titanate, tetrastearyl titanate; titanium acylates such as polyhydroxytitanium stearate; and titanium tetraacetylacetonate, titanium lactate, titanium Titanium chelates such as triethanolamine are included.
Examples of germanium compounds include germanium dioxide, and examples of aluminum compounds include oxides such as polyaluminum hydroxide, aluminum alkoxides and tributylaluminate.
Among the above compounds, tin compounds are preferred.

[Polymerization temperature]
The polymerization temperature of the crystalline polyester resin is preferably within the range of 150 to 250°C. Moreover, the polymerization time is preferably in the range of 0.5 to 10 hours. During the polymerization, the pressure inside the reaction system may be reduced as necessary.

(3.2.3) Amorphous resin One or more types of amorphous resins may be used. Examples of amorphous resins include vinyl resins, urethane resins, urea resins, and styrene/acrylic-modified polyester resins. Contains polyester resin.
Among them, from the viewpoint of easy control of thermoplasticity, it is preferable that the vinyl resin is contained as a main component in the binder resin, and the vinyl resin accounts for 50% or more of the total binder resin.

(Weight average molecular weight of amorphous resin)
The weight average molecular weight (Mw) of the amorphous resin is preferably in the range of 5,000 to 150,000, more preferably in the range of 10,000 to 70,000, from the viewpoint of easy control of its plasticity.

(3.2.4) Vinyl resin The vinyl resin is, for example, a polymer of a vinyl compound, and examples thereof include acrylic acid ester resin, styrene-acrylic acid ester resin and ethylene-vinyl acetate resin.
Among them, styrene-acrylic acid ester resin (styrene-acrylic resin) is preferable from the viewpoint of plasticity at the time of heat fixing.

(styrene/acrylic resin)
The amorphous resin contained as the binder resin preferably contains at least a styrene-acrylic resin from the viewpoint of suppressing excessive exudation of the release agent.
By suppressing the release agent from exuding excessively as described above, the fixing separation property of the toner is improved, and the effect of preventing contamination inside the machine is exhibited.

The styrene-acrylic resin is formed by addition polymerization of at least a styrene monomer and a (meth)acrylate monomer.
Styrene monomers include styrene represented by the structural formula CH ₂ ═CH—C ₆ H ₅ as well as styrene derivatives having known side chains and functional groups in the styrene structure.

[(Meth) acrylic acid ester monomer]
The (meth)acrylic acid ester monomer is an acrylic represented by CH(R _a )=CHCOOR _b (R _a represents a hydrogen atom or a methyl group, and R _b represents an alkyl group having 1 to 24 carbon atoms) In addition to acid esters and methacrylic esters, acrylic acid ester derivatives and methacrylic acid ester derivatives having known side chains and functional groups in the structure of these esters are also included.

Examples of (meth)acrylate monomers include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl Acrylic ester monomers such as acrylates and phenyl acrylates; , phenyl methacrylate, diethylaminoethyl methacrylate, and dimethylaminoethyl methacrylate.

In the present specification, "(meth)acrylic ester monomer" is a generic term for "acrylic ester monomer" and "methacrylic ester monomer", and one or both of them means.

For example, "methyl (meth)acrylate" means one or both of "methyl acrylate" and "methyl methacrylate".

The (meth)acrylic acid ester monomer may be one or more.
For example, forming a copolymer using a styrene monomer and two or more acrylic acid ester monomers, or forming a copolymer using a styrene monomer and two or more methacrylic acid ester monomers and the combination of styrene monomers with acrylate and methacrylate monomers to form copolymers.

[Styrene monomer]
Examples of styrene monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p- Included are tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene and pn-dodecylstyrene.

〔Content〕
From the viewpoint of controlling the plasticity of the styrene-acrylic resin, the content of structural units derived from styrene monomers in the styrene-acrylic resin is preferably in the range of 40 to 90% by mass.
Further, the content of structural units derived from (meth)acrylic acid ester monomers in the styrene-acrylic resin is preferably in the range of 10 to 60% by mass.

[Other monomers]
The styrene-acrylic resin may further contain structural units derived from monomers other than the styrene monomer and the (meth)acrylate monomer.
The other monomer is preferably a compound that forms an ester bond with a hydroxy group (--OH) derived from a polyhydric alcohol or a carboxy group (--COOH) derived from a polyvalent carboxylic acid.
That is, the styrene-acrylic resin is capable of undergoing addition polymerization with respect to the styrene monomer and the (meth)acrylic acid ester monomer, and a compound having a carboxy group or a hydroxy group (an amphoteric compound) is further polymerized. It is preferably a polymer consisting of

[Amphoteric compound]
Examples of amphoteric compounds include compounds having a carboxy group such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl esters, itaconic acid monoalkyl esters, 2-hydroxyethyl ( meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene Compounds with hydroxy groups such as glycol mono(meth)acrylates are included.

[Content of Structural Unit Derived from Amphoteric Compound]
The content of structural units derived from the amphoteric compound in the styrene-acrylic resin is preferably in the range of 0.5 to 20% by mass.

[Synthesis method]
The styrene-acrylic resin can be synthesized by a method of polymerizing monomers using a known oil-soluble or water-soluble polymerization initiator.
Examples of oil-soluble polymerization initiators include azo or diazo polymerization initiators and peroxide polymerization initiators.

[Azo or diazo polymerization initiator]
Examples of the azo or diazo polymerization initiators include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis ( cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile.

[Peroxide polymerization initiator]
Examples of peroxide polymerization initiators include benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2 ,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis-(4,4-t-butylperoxycyclohexyl)propane and tris-(t-butylperoxy)triazine.

[Water-soluble radical polymerization initiator]
Further, when synthesizing resin particles of a styrene-acrylic resin by an emulsion polymerization method, a water-soluble radical polymerization initiator can be used as the polymerization initiator.
Examples of water-soluble radical polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropane acetate, azobiscyanovaleric acid and its salts, and hydrogen peroxide.

(3.2.5) Hybrid Crystalline Polyester Resin As the crystalline polyester resin described above, a hybrid crystalline polyester resin (hereinafter also simply referred to as "hybrid resin") may be contained.

By containing the hybrid crystalline resin, the compatibility with the amorphous resin used in combination is improved, so that the low-temperature fixability of the toner is improved.
In addition, since the dispersibility of the crystalline resin in the toner is improved, bleeding out can be suppressed.

One or more hybrid resins may be used.
In addition, the hybrid resin may replace the entire amount of the crystalline polyester resin, or may be used in combination with a part of the crystalline polyester resin.

A hybrid resin is a resin in which a crystalline polyester polymer segment and an amorphous polymer segment are chemically bonded.
The crystalline polyester polymerized segment means a portion derived from the crystalline polyester resin.
That is, it means a molecular chain having the same chemical structure as the molecular chain constituting the crystalline polyester resin described above. Further, the amorphous polymer segment means a portion derived from the amorphous resin.
That is, it means a molecular chain having the same chemical structure as the molecular chain constituting the amorphous resin described above.

(Weight average molecular weight)
The preferred weight-average molecular weight (Mw) of the hybrid resin is preferably in the range of 5000 to 100000, more preferably in the range of 7000 to 50000, from the viewpoint of ensuring both sufficient low-temperature fixability and excellent long-term storage stability. Within the range of 8,000 to 20,000 is particularly preferred.
By setting the weight-average molecular weight (Mw) of the hybrid resin to 100,000 or less, sufficient low-temperature fixability can be obtained.
On the other hand, by setting the weight-average molecular weight (Mw) of the hybrid resin to 5000 or more, excessive progress of compatibility between the hybrid resin and the amorphous resin is suppressed during toner storage, and fusion between the toner particles is suppressed. It is possible to effectively suppress image defects caused by

(Crystalline polyester polymerization segment)
The crystalline polyester polymerized segment may be, for example, a resin having a structure obtained by copolymerizing the main chain of the crystalline polyester polymerized segment with other components, or the crystalline polyester polymerized segment may be copolymerized with the main chain composed of other components. It may also be a resin having a structure that is rounded.
The crystalline polyester polymerized segment can be synthesized from the polyhydric carboxylic acid and polyhydric alcohol described above in the same manner as the crystalline polyester resin described above.

The content of the crystalline polyester polymer segment in the hybrid resin is preferably in the range of 80 to 98% by mass, more preferably in the range of 90 to 95% by mass, from the viewpoint of imparting sufficient crystallinity to the hybrid resin. and more preferably in the range of 91 to 93% by mass.
The constituent components and the content of each polymer segment in the hybrid resin (or in the toner) can be determined by, for example, nuclear magnetic resonance (NMR) or methylation reaction pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). It can be specified by using a known analysis method such as.

The crystalline polyester polymerized segment preferably further contains a monomer having an unsaturated bond from the viewpoint of introducing a chemical bonding site with the amorphous polymerized segment into the segment.

A monomer having an unsaturated bond is, for example, a polyhydric alcohol having a double bond, examples of which include methylenesuccinic acid, fumaric acid, maleic acid, 3-hexenedioic acid, 3-octenedioic acid, and the like. Polyvalent carboxylic acids with double bonds; 2-butene-1,4-diol, 3-hexene-1,6-diol and 4-octene-1,8-diol are included.

The content of the structural unit derived from the unsaturated bond-containing monomer in the crystalline polyester polymerized segment is preferably in the range of 0.5 to 20% by mass.

The hybrid resin may be a block copolymer or a graft copolymer, but being a graft copolymer makes it easier to control the orientation of the crystalline polyester polymer segment, It is preferable from the viewpoint of imparting sufficient crystallinity to the resin, and it is more preferable that the crystalline polyester polymer segment is grafted with the amorphous polymer segment as the main chain.
That is, the hybrid resin is preferably a graft copolymer having the amorphous polymer segment as the main chain and the crystalline polyester polymer segment as the side chain.

A functional group such as a sulfonic acid group, a carboxyl group, or a urethane group may be further introduced into the hybrid resin.
The functional group may be introduced into the crystalline polyester polymer segment or into the amorphous polymer segment.

(amorphous polymer segment)
The amorphous polymer segment enhances affinity between the amorphous resin and the hybrid resin that constitute the binder resin.
As a result, the hybrid resin is more likely to be incorporated into the amorphous resin, further improving the charging uniformity of the toner.
The composition of the amorphous polymer segment in the hybrid resin (or in the toner) and its content can be specified by using known analysis methods such as NMR and methylation reaction Py-GC/MS. .

In addition, the amorphous polymer segment has a glass transition temperature (Tg ₁ ) observed in the first heating process of DSC in the range of 30 to 80 ° C., similar to the amorphous resin according to the present invention. It is preferably within the range of 40 to 65°C.
Note that the glass transition temperature (Tg ₁ ) can be measured by a known method (for example, DSC).

The amorphous polymer segment is preferably composed of the same type of resin as the amorphous resin contained in the binder resin, from the viewpoint of enhancing the affinity with the binder resin and enhancing the charging uniformity of the toner.
Such a form further improves the affinity between the hybrid resin and the amorphous resin.
In addition, "the same kind of resin" means resins having characteristic chemical bonds in the repeating units.

"Characteristic chemical bond" means the "polymer Classification”. Polyacrylics, polyamides, polyanhydrides, polycarbonates, polydienes, polyesters, polyhaloolefins, polyimides, polyimines, polyketones, polyolefins, polyethers, polyphenylenes, polyphosphazenes, polysiloxanes, polystyrenes, polysulfides, polysulfones, polyurethanes, polyureas , polyvinyl and other polymers.

In addition, when the resin is a copolymer, the “same type of resin” means that, in the chemical structure of a plurality of monomer species constituting the copolymer, when the monomer species having the chemical bond is used as a structural unit, the characteristic means resins having common chemical bonds.
Therefore, even if the properties exhibited by the resins themselves are different from each other, or even if the molar component ratios of the monomer species constituting the copolymer are different from each other, the same type Regarded as resin.

For example, a resin (or polymer segment) formed by styrene, butyl acrylate and acrylic acid and a resin (or polymer segment) formed by styrene, butyl acrylate and methacrylic acid have chemical bonds that constitute at least polyacrylic acid. Since these are the same type of resin.

To further illustrate, the resin (or polymerized segment) formed by styrene, butyl acrylate and acrylic acid and the resin (or polymerized segment) formed by styrene, butyl acrylate, acrylic acid, terephthalic acid and fumaric acid As a common chemical bond, it has at least a chemical bond that constitutes polyacryl.
They are therefore homogeneous resins.

Examples of amorphous polymerized segments include vinyl polymerized segments, urethane polymerized segments and urea polymerized segments.
Among them, vinyl polymerized segments are preferable from the viewpoint of easy control of thermoplasticity.
Vinyl polymerized segments may be synthesized in the same manner as the vinyl resins of the present invention.

The content of structural units derived from styrene monomers in the amorphous polymer segment is preferably within the range of 40 to 90% by mass from the viewpoint of facilitating control of the plasticity of the hybrid resin.
Also, from the same point of view, the content of structural units derived from (meth)acrylic acid ester monomers in the amorphous polymer segment is preferably within the range of 10 to 60% by mass.

Furthermore, it is preferable that the amorphous polymerized segment further contains the aforementioned amphoteric compound in the monomer from the viewpoint of introducing a chemical bonding site with the crystalline polyester polymerized segment into the amorphous polymerized segment.
The content of structural units derived from the amphoteric compound in the amorphous polymer segment is preferably in the range of 0.5 to 20% by mass.

From the viewpoint of imparting sufficient crystallinity to the hybrid resin, the content of the amorphous polymer segment in the hybrid resin is preferably in the range of 3 to 15% by mass, and in the range of 5 to 10% by mass. and more preferably in the range of 7 to 9% by mass.

(Method for producing hybrid resin)
The hybrid resin can be produced, for example, by the first to third production methods shown below.

[First manufacturing method]
The first production method is a method of producing a hybrid resin by carrying out a polymerization reaction to synthesize a crystalline polyester polymerized segment in the presence of an amorphous polymerized segment synthesized in advance.

In this method, first, the monomers (preferably vinyl monomers such as styrene monomers and (meth)acrylic acid ester monomers) constituting the above-described amorphous polymer segment are subjected to an addition reaction to form a non-crystalline polymer segment. Synthesize a crystalline polymerized segment.

Next, a polyhydric carboxylic acid and a polyhydric alcohol are polymerized in the presence of an amorphous polymerized segment to synthesize a crystalline polyester polymerized segment.

At this time, a hybrid resin is synthesized by subjecting a polyhydric carboxylic acid and a polyhydric alcohol to a condensation reaction, and by subjecting the amorphous polymer segment to an addition reaction of the polyhydric carboxylic acid or the polyhydric alcohol.

In the first method, it is preferable to incorporate into the crystalline polyester polymerized segment or the amorphous polymerized segment a site at which these polymerized segments can react with each other.

Specifically, when synthesizing the amorphous polymerized segment, the amphoteric compound described above is used in addition to the monomers constituting the amorphous polymerized segment.
The amphoteric compound reacts with a carboxy group or a hydroxy group in the crystalline polyester polymerized segment, thereby chemically and quantitatively bonding the crystalline polyester polymerized segment with the amorphous polymerized segment.
Further, when synthesizing the crystalline polyester polymerized segment, the monomer may further contain the aforementioned compound having an unsaturated bond.

According to the first method, it is possible to synthesize a hybrid resin having a structure (graft structure) in which a crystalline polyester polymer segment is molecularly bonded to an amorphous polymer segment.

[Second manufacturing method]
The second production method is a method in which a crystalline polyester polymerized segment and an amorphous polymerized segment are separately formed, and these are combined to produce a hybrid resin.

In this method, first, a polyhydric carboxylic acid and a polyhydric alcohol are subjected to a condensation reaction to synthesize a crystalline polyester polymerized segment.
Separately from the reaction system for synthesizing the crystalline polyester polymerized segment, the amorphous polymerized segment is synthesized by addition-polymerizing the monomers constituting the amorphous polymerized segment described above.

At this time, it is preferable to incorporate into one or both of the crystalline polyester polymerized segment and the amorphous polymerized segment a site that allows the crystalline polyester polymerized segment and the amorphous polymerized segment to react with each other as described above.

Next, by reacting the synthesized crystalline polyester polymer segment and the amorphous polymer segment, a hybrid resin having a structure in which the crystalline polyester polymer segment and the amorphous polymer segment are molecularly bonded can be synthesized.

Further, when the reactive site is incorporated in neither the crystalline polyester polymerized segment nor the amorphous polymerized segment, in a system in which the crystalline polyester polymerized segment and the amorphous polymerized segment coexist, the crystallinity A method of introducing a compound having sites capable of binding to both the polyester polymer segment and the amorphous polymer segment may be adopted.
Thereby, a hybrid resin having a structure in which a crystalline polyester polymer segment and an amorphous polymer segment are molecularly bonded through the compound can be synthesized.

[Third manufacturing method]
A third production method is a method of producing a hybrid resin by conducting a polymerization reaction to synthesize an amorphous polymerized segment in the presence of a crystalline polyester polymerized segment.

In this method, first, a polyhydric carboxylic acid and a polyhydric alcohol are condensed and polymerized to synthesize a crystalline polyester polymerized segment.

Next, in the presence of the crystalline polyester polymerized segment, the monomers constituting the amorphous polymerized segment are polymerized to synthesize the amorphous polymerized segment.

At this time, as in the first production method, it is preferable to incorporate into the crystalline polyester polymerized segment or the amorphous polymerized segment a site at which these polymerized segments can react with each other.

By the method described above, a hybrid resin having a structure (graft structure) in which an amorphous polymer segment is molecularly bonded to a crystalline polyester polymer segment can be synthesized.

Among the first to third production methods, the first production method facilitates synthesis of a hybrid resin having a structure in which a crystalline polyester resin chain is grafted onto an amorphous resin chain, and can simplify the production process. Therefore, it is preferable.
In the first production method, since the amorphous polymerized segment is formed in advance and then the crystalline polyester polymerized segment is bonded, the orientation of the crystalline polyester polymerized segment tends to be uniform.

(3.3) Release agent (wax)
The release agent that constitutes the toner is not particularly limited, and any known release agent can be used.
Specifically, for example, polyolefin waxes such as polyethylene wax and polypropylene wax, branched hydrocarbon waxes such as microcrystalline wax, long-chain hydrocarbon waxes such as paraffin wax and Sasol wax, dialkyl waxes such as distearyl ketone, etc. Ketone wax, carnauba wax, montan wax, behenylbehenate, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecane Ester waxes such as diol distearate, tristearyl trimellitate, and distearyl maleate, and amide waxes such as ethylenediamine behenylamide and tristearylamide trimellitate.

The melting point of the release agent is preferably in the range of 60-100°C, more preferably in the range of 70-95°C.
By setting the melting point within the above range, the heat-resistant storage stability of the toner can be ensured, and stable toner image formation can be performed without causing cold offset or the like even when fixing is performed at a low temperature.
Here, in the present invention, the above-mentioned "melting point" refers to the endothermic peak temperature W ₍₁₎ p (°C) derived from the release agent observed in the first heating process in differential scanning calorimetry. and
The content of the release agent in the toner is preferably in the range of 1 to 30 mass %, more preferably in the range of 5 to 20 mass %.

(3.4) Other Components In the toner of the present invention, in addition to the essential components described above, if necessary, internal additives such as colorants, charge control agents, and crystal nucleating agents, inorganic fine particles, organic fine particles, An external additive such as a lubricant may be contained.

(coloring agent)
Carbon black, magnetic substances, dyes, pigments, etc. can be optionally used as colorants that can constitute the toner, and channel black, furnace black, acetylene black, thermal black, lamp black, etc. can be used as carbon black. be done.
Ferromagnetic metals such as iron, nickel, and cobalt, alloys containing these metals, compounds of ferromagnetic metals such as ferrite and magnetite, alloys that do not contain ferromagnetic metals but exhibit ferromagnetism by heat treatment, For example, alloys of the type called Heusler alloys such as manganese-copper-aluminum, manganese-copper-tin, chromium dioxide, and the like can be used.

Examples of black colorants include carbon black such as furnace black, channel black, acetylene black, thermal black and lamp black, and magnetic powder such as magnetite and ferrite.

Colorants for magenta or red include C.I. I. Pigment Red 2, 3, 5, 6, 7, 15, 16, 48:1, 53:1, 57:1, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 139, 144, 149, 150, 163, 166, 170, 177, 178, 184, 202, 206, 207, 209, 222, 238, 269 and the like.

Colorants for orange or yellow include C.I. I. Pigment Orange 31, 43, C.I. I. Pigment Yellow 12, 14, 15, 17, 74, 83, 93, 94, 138, 155, 162, 180, 185 and the like.

Further, as a colorant for green or cyan, C.I. I. Pigment Blue 2, 3, 15, 15:2, 15:3, 15:4, 16, 17, 60, 62, 66, C.I. I. Pigment Green 7 and the like.

These colorants may be used singly or in combination of two or more as required.

The amount of the colorant to be added is preferably in the range of 1 to 30% by mass, more preferably in the range of 2 to 20% by mass, based on the total toner, and a mixture thereof can also be used. and image color reproducibility can be ensured.

As for the size of the colorant, the volume average particle diameter is preferably in the range of 10 to 1000 nm, preferably in the range of 50 to 500 nm, and particularly preferably in the range of 80 to 300 nm.

(Charge control agent)
As the charge control agent, various known compounds such as nigrosine dyes, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, and metal salicylates can be used. .

The amount of the charge control agent to be added is usually in the range of 0.1 to 10% by mass, preferably in the range of 0.5 to 5% by mass, based on 100% by mass of the binder resin in the finally obtained toner particles. It is considered to be the amount that becomes

As for the size of the charge control agent particles, the number average primary particle diameter is preferably in the range of 10 to 1000 nm, preferably in the range of 50 to 500 nm, and particularly preferably in the range of 80 to 300 nm.

(Crystal nucleating agent)
"Crystal nucleating agent (nucleating agent)" is an additive that promotes the crystallization of crystalline polymers. It is an additive that can be expected to improve.
The crystal nucleating agent may be a compound capable of forming a crystal nucleating agent site, and is preferably an aliphatic monocarboxylic acid having 18 to 30 carbon atoms or an aliphatic monocarboxylic acid having 18 to 30 carbon atoms. Alcohol.
Specific examples include triacontanoic acid, arachidic acid, and arachidyl alcohol.
The crystal nucleating agent, which is an aliphatic monocarboxylic acid or an aliphatic monoalcohol, binds so as to block the terminal of the polyester polymer segment, and as a result, the crystal nucleus is attached to at least one terminal of the polyester polymer segment. It is preferable because it can form an agent site.

(external additive)
From the viewpoint of improving charging performance, fluidity, or cleanability of the toner, particles such as known inorganic fine particles or organic fine particles and a lubricant can be added to the surface of the toner particles as an external additive.

Preferable examples of inorganic fine particles include inorganic fine particles of silica, titania, alumina, strontium titanate, and the like.

These inorganic fine particles may be subjected to a hydrophobic treatment, if necessary.

As the organic fine particles, spherical organic fine particles having a number average primary particle diameter in the range of about 10 to 2000 nm can be used. Specifically, organic fine particles of homopolymers such as styrene and methyl methacrylate, and copolymers thereof can be used.

Lubricants are used for the purpose of further improving cleaning properties and transfer properties. Examples of lubricants include salts of zinc stearate, aluminum, copper, magnesium, calcium, etc., zinc oleate, Higher fatty acid metals such as salts of manganese, iron, copper, magnesium, etc., salts of zinc, copper, magnesium, calcium, etc. of palmitate, salts of zinc, calcium, etc. of linoleate, salts of zinc, calcium, etc. of ricinoleate salt. Various external additives may be used in combination.

The amount of the external additive to be added is preferably in the range of 0.1 to 10.0% by mass with respect to 100% by mass of the toner particles.

Examples of the method of adding the external additive include a method of adding using various known mixing devices such as a Turbular mixer, a Henschel mixer, a Nauta mixer, and a V-type mixer.

(3.5) Structure and Shape of Toner Particles (3.5.1) Core-Shell Structure Toner base particles can be used as they are in toner. The toner particles may have a multi-layered structure such as a core-shell structure including a shell layer covering the .
The shell layer may not cover the entire surface of the core particles, and the core particles may be partially exposed. The cross section of the core-shell structure can be confirmed by a known observation means such as a transmission electron microscope (TEM) or a scanning probe microscope (SPM).

In the case of the core-shell structure, the core particles and the shell layer can have different characteristics such as glass transition point, melting point, hardness, etc., and the toner particles can be designed according to the purpose. For example, a resin having a relatively high glass transition point (Tg) is aggregated and fused to the surface of a core particle containing a binder resin, a coloring agent, a release agent, etc. and having a relatively low glass transition point (Tg). , can form a shell layer. The shell layer preferably contains an amorphous resin.

(3.5.2) Particle Diameter of Toner Particles As for the particle diameter of toner particles, the volume-based median diameter (d ₅₀ ) is preferably in the range of 3 to 10 μm, more preferably in the range of 5 to 8 μm. is more preferable.
Within the above range, high reproducibility can be obtained even for extremely minute dot images of the 1200 dpi level.
The particle size of the toner particles can be controlled by adjusting the concentration of the aggregating agent used during production, the amount of the organic solvent added, the fusion bonding time, the composition of the binder resin, and the like.

For the measurement of the volume-based median diameter (d ₅₀ ) of the toner particles, a measuring device comprising Multisizer 3 (manufactured by Beckman Coulter, Inc.) connected to a computer system equipped with data processing software Software V3.51 is used. can be done.
Specifically, a measurement sample (toner) is added to a surfactant solution (for example, a surfactant solution obtained by diluting a neutral detergent containing a surfactant component with pure water 10 times for the purpose of dispersing toner particles). After the particles are blended together, ultrasonic dispersion is performed to prepare a toner particle dispersion.
This toner particle dispersion is pipetted into a beaker containing ISOTON II (manufactured by Beckman Coulter, Inc.) in a sample stand until the concentration indicated by the measuring device reaches 8%.
Here, by using this concentration, reproducible measured values can be obtained.
Then, in the measuring device, the measured particle count number is 25000, the aperture diameter is 100 μm, and the frequency value is calculated by dividing the measurement range of 2 to 60 μm into 256, and 50 from the larger volume integrated fraction. % particle size is given as volume-based median diameter (d ₅₀ ).

(3.5.3) Average Circularity of Toner Particles Toner particles preferably have an average circularity in the range of 0.930 to 1.000 from the viewpoint of enhancing the stability of chargeability and low-temperature fixability. , 0.950 to 0.995.
If the average circularity is within the above range, individual toner particles are less likely to be crushed.
As a result, it is possible to suppress the contamination of the triboelectrification imparting member, stabilize the chargeability of the toner, and improve the image quality of the formed image.

The average circularity of toner particles can be measured using FPIA-2100 (manufactured by Sysmex).
Specifically, the sample (toner) to be measured is soaked in an aqueous solution containing a surfactant, and ultrasonically dispersed for 1 minute to disperse the sample.
After that, FPIA-2100 (manufactured by Sysmex) is used to perform imaging at an appropriate density of 3,000 to 10,000 HPF detections under the measurement conditions of HPF (high magnification imaging) mode.
If the HPF detection number is within the above range, reproducible measured values can be obtained.
From the photographed particle image, the circularity of each toner particle is calculated according to the following formula (I), and the circularity of each toner particle is added and divided by the total number of toner particles to obtain the average circularity.
Formula (I):
Circularity = (perimeter of a circle having the same projected area as the particle image)/(perimeter of the projected particle image)

4. Method for producing toner for developing an electrostatic charge image The method for producing a toner for developing an electrostatic charge image of the present invention is a method for producing the toner for developing an electrostatic charge image of the present invention, comprising: The step of producing particles includes a step of adding a crystalline resin fine particle dispersion to an amorphous resin fine particle dispersion and growing toner particles at a temperature equal to or higher than the melting point of the crystalline resin.
As a result, a toner having the desired thermophysical properties described above can be obtained.
As the above production method, for example, an emulsion polymerization aggregation method or an emulsion aggregation method can be suitably employed.

The emulsion polymerization aggregation method, which is preferably used in the method for producing the toner according to the present invention, comprises a dispersion liquid of fine particles of a binder resin produced by an emulsion polymerization method (hereinafter also referred to as “fine binder resin particles”), and a coloring agent. fine particles (hereinafter also referred to as "colorant fine particles") dispersion and a release agent dispersion such as wax, and the toner particles are aggregated until they have a desired particle size. In this method, toner particles are produced by performing shape control by fusing.

Further, in the emulsion aggregation method preferably used as a method for producing the toner according to the present invention, a binder resin solution dissolved in a solvent is added dropwise to a poor solvent to form a fine resin particle dispersion, and the resin fine particle dispersion and the colorant dispersion are prepared. and a dispersion liquid of a release agent such as wax, and the toner particles are aggregated until they have a desired diameter, and the binder resin fine particles are fused to control the shape to produce toner particles. The method.
Either production method can be applied to the toner of the present invention.

An example of the method for producing the toner of the present invention using an emulsion polymerization aggregation method is shown below.
(1) A step of preparing a dispersion in which fine particles of a colorant are dispersed in an aqueous medium (2) A dispersion in which fine particles of a binder resin, optionally containing an internal additive, are dispersed in an aqueous medium (3) a step of preparing a dispersion of fine binder resin particles by emulsion polymerization; (4) a dispersion of fine particles of a coloring agent and a dispersion of fine binder resin particles; (5) Filtering off the toner base particles from the dispersion system (aqueous medium) of the toner base particles and adding a surfactant or the like. (6) Drying the toner base particles (7) Adding an external additive to the toner base particles

When the toner is produced by the emulsion polymerization aggregation method, the fine binder resin particles obtained by the emulsion polymerization method may have a multi-layered structure of two or more layers composed of binder resins having different compositions.
For the binder resin fine particles having such a structure, for example, those having a two-layer structure, a resin particle dispersion is prepared by an emulsion polymerization treatment (first-stage polymerization) according to a conventional method, and the polymerization is initiated in this dispersion. It can be obtained by adding an agent and a polymerizable monomer and subjecting this system to polymerization treatment (second-stage polymerization).

Toner particles having a core-shell structure can also be obtained by an emulsion polymerization aggregation method.
Specifically, toner particles having a core-shell structure are prepared by aggregating, associating, and fusing binder resin fine particles for core particles and coloring agent fine particles to form core particles.
Next, fine binder resin particles for the shell layer are added to the core particle dispersion, and the fine binder resin particles for the shell layer are aggregated and fused to the surface of the core particles to form a shell layer covering the surface of the core particles. can be obtained by

Further, an example of a case where a pulverization method is used as a method for producing the toner of the present invention is shown below.
(1) A step of mixing a binder resin, a colorant and, if necessary, an internal additive with a Henschel mixer or the like. (2) A step of kneading the obtained mixture while heating it with an extrusion kneader or the like. A step of coarsely pulverizing the kneaded material with a hammer mill or the like, and then further pulverizing with a turbo mill pulverizer or the like. Step of forming toner base particles (5) Step of adding an external additive to the toner base particles

It should be noted that the embodiments to which the present invention can be applied are not limited to the above-described embodiments, and can be modified as appropriate without departing from the gist of the present invention.

5. Developer The electrostatic charge image developing toner of the present invention can be used as a magnetic or non-magnetic one-component developer, but may be mixed with a carrier and used as a two-component developer.
When the toner is used as a two-component developer, magnetic particles made of conventionally known materials such as metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead are used as the carrier. Ferrite particles are particularly preferred.

As the carrier, a coated carrier in which the surfaces of magnetic particles are coated with a coating agent such as a resin, or a dispersion type carrier in which magnetic fine powder is dispersed in a binder resin may be used.
The volume-based median diameter (d ₅₀ ) of the carrier is preferably in the range of 20 to 100 μm, more preferably in the range of 25 to 80 μm.
The volume-based median diameter (d ₅₀ ) of the carrier can be measured, for example, with a laser diffraction particle size distribution analyzer HELOS (manufactured by SYMPATEC) equipped with a wet disperser.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these. In the examples, "parts" or "%" are used, but "mass parts" or "mass%" are indicated unless otherwise specified.

A. Preparation of crystalline resin fine particle dispersion (A.1) Preparation of crystalline resin [Preparation of crystalline resin (1a)]
A raw material monomer (1a-1) for the following addition polymerizable resin (styrene/acrylic resin) segment containing both reactive monomers and 4 parts by mass of di-t-butyl peroxide as a radical polymerization initiator were placed in a dropping funnel. .

<Raw material monomer (1a-1)>
Styrene 20.0 parts by mass n-Butyl acrylate 8 parts by mass Acrylic acid 1.75 parts by mass

In addition, a raw material monomer (1a-2) for the following polycondensation resin (crystalline polyester resin) segment is placed in a four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and heated to 170 ° C. and dissolved.

<Raw material monomer (1a-2)>
Sebacic acid (acid) 412.6 parts by mass 1,6-hexanediol (alcohol) 152.6 parts by mass

Then, the above monomers (1a-1) and (1a-2) are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction tube, and the inside of the reaction vessel is replaced with dry nitrogen gas to obtain a mixed solution. got

0.4 parts by mass of Ti(On-Bu) ₄ was added to the resulting mixed solution, the temperature was raised to 235° C., and the reaction was carried out under normal pressure (101.3 kPa) for 5 hours. 8 kPa) under 1
A reaction liquid was obtained by performing a time reaction.

After cooling the obtained reaction solution to 200° C., the crystalline resin (1a ) was made.

[Preparation of crystalline resin (2a)]
A raw material monomer (2a-1) for the following addition polymerizable resin (styrene/acrylic resin) segment containing both reactive monomers and 4 parts by mass of di-t-butyl peroxide as a radical polymerization initiator were placed in a dropping funnel. .

<Raw material monomer (2a-1)>
Styrene 20.0 parts by mass n-Butyl acrylate 8 parts by mass Acrylic acid 1.75 parts by mass

In addition, a raw material monomer (2a-2) for the following polycondensation resin (crystalline polyester resin) unit is placed in a four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and heated to 170 ° C. and dissolved.

<Raw material monomer (2a-2)>
Tetradecane diacid (acid) 412.6 parts by mass 1,4-butanediol (alcohol) 152.6 parts by mass

Then, the above monomers (2a-1) and (2a-2) are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction tube, and the inside of the reaction vessel is replaced with dry nitrogen gas to obtain a mixed solution. got

0.4 parts by mass of Ti(On-Bu) ₄ was added to the resulting mixed solution, the temperature was raised to 235° C., and the reaction was carried out under normal pressure (101.3 kPa) for 5 hours. A reaction liquid was obtained by performing the reaction for 1 hour under a pressure of 8 kPa).

After cooling the resulting reaction solution to 200° C., the reaction was carried out under reduced pressure (20 kPa) so that the acid value calculated by the above-described measuring method would be 20.0 mgKOH/g.

[Preparation of crystalline resin (3a)]
A raw material monomer (3a-1) for the following addition polymerizable resin (styrene/acrylic resin) unit containing both reactive monomers and 4 parts by mass of di-t-butyl peroxide as a radical polymerization initiator were placed in a dropping funnel. .

<Raw material monomer (3a-1)>
Styrene 20.0 parts by mass n-Butyl acrylate 8 parts by mass Acrylic acid 1.75 parts by mass

In addition, a raw material monomer (3a-2) for the following polycondensation resin (crystalline polyester resin) unit is placed in a four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and heated to 170 ° C. and dissolved.

<Raw material monomer (3a-2)>
Sebacic acid (acid) 412.6 parts by mass 1,12-dodecanediol (alcohol) 152.6 parts by mass

Then, the above monomers (3a-1) and (3a-2) are placed in a reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas introduction tube, and the inside of the reaction vessel is replaced with dry nitrogen gas to obtain a mixed solution. got

0.4 parts by mass of Ti(OBu) ₄ was added to the resulting mixed solution, the temperature was raised to 235° C., and the reaction was continued under normal pressure (101.3 kPa) for 5 hours and then under reduced pressure (8 kPa) for 1 hour. A reaction liquid was obtained by carrying out.
After cooling the resulting reaction solution to 200° C., the reaction was carried out under reduced pressure (20 kPa) so that the acid value calculated by the above-described measuring method would be 20.0 mgKOH/g.

[Preparation of crystalline resin (4a)]
A raw material monomer (4a-1) for the polycondensation resin (crystalline polyester resin) unit described below is placed in a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen gas introduction tube, and the reaction vessel is filled with dry nitrogen gas. replaced.

<Raw material monomer (4a-1)>
Tetradecanedioic acid (acid) 280 parts by mass 1,4-butanediol (alcohol) 105 parts by mass

0.4 parts by mass of Ti(On-Bu) ₄ was added to the resulting mixed solution, the temperature was raised to 235° C., and the reaction was carried out under normal pressure (101.3 kPa) for 5 hours. A reaction liquid was obtained by performing the reaction for 1 hour under a pressure of 8 kPa).

After cooling the resulting reaction solution to 200° C., the reaction was carried out under reduced pressure (20 kPa) so that the acid value calculated by the above-described measuring method was 21.4 mgKOH/g.

Then, the pressure in the reactor was gradually released to return to normal pressure, and then 20.3 parts by mass of stearic acid was added as a crystal nucleating agent and reacted under normal pressure at a temperature of 200° C. for 1.5 hours.
Thereafter, the pressure in the reactor was reduced to 5 kPa or less at 200° C., and the reaction was carried out for 2.5 hours to obtain a crystalline resin (4a).
The crystalline resin (4a) had an acid value of 21.4 mgKOH/g.

[Production of crystalline resin (5a)]
A reaction vessel equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube is charged with the raw material monomer (5a-1) for the polycondensation resin (crystalline polyester resin) unit described below, and the reaction vessel is filled with dry nitrogen gas. replaced.

<Raw material monomer (5a-1)>
Sebacic acid (acid) 280 parts by mass 1,6-hexanediol (alcohol) 105 parts by mass 1,4-butanediol (alcohol) 105 parts by mass

0.4 parts by mass of Ti(On-Bu) ₄ was added to the resulting mixed solution, the temperature was raised to 235° C., and the reaction was carried out under normal pressure (101.3 kPa) for 5 hours. A reaction liquid was obtained by performing the reaction for 1 hour under a pressure of 8 kPa).

After cooling the resulting reaction solution to 200° C., the reaction was carried out under reduced pressure (20 kPa) so that the acid value calculated by the above-described measuring method was 21.4 mgKOH/g.

Then, the pressure in the reactor was gradually released to return to normal pressure, and then 20.3 parts by mass of stearic acid was added as a crystal nucleating agent and reacted under normal pressure at a temperature of 200° C. for 1.5 hours.
After that, the pressure in the reactor was reduced to 5 kPa or less at 200° C., and the reaction was carried out for 2.5 hours to obtain a crystalline resin (5a).
The crystalline resin (5a) had an acid value of 21.4 mgKOH/g.

(A.2) Preparation of crystalline resin fine particle dispersion [Preparation of crystalline resin fine particle dispersion (1A)]
174.3 parts by mass of the crystalline resin (1a) and 102 parts by mass of methyl ethyl ketone are placed in a reaction vessel, stirred at 75° C. for 30 minutes to dissolve, and 3.1 parts by mass of a 25% by mass sodium hydroxide aqueous solution is added. A lysate was obtained by

The above solution was placed in a reaction vessel equipped with a stirrer, and 375 parts by mass of water warmed to 70° C. was added dropwise for 70 minutes while stirring.
The liquid in the container became cloudy during the dropwise addition, and an emulsified liquid (1a) in a uniformly emulsified state was obtained after the entire amount was dropped.

While the above emulsion was kept at 70° C., the pressure was reduced to 15 kPa (150 mbar) using a diaphragm vacuum pump "V-700" (manufactured by BUCHI), and the mixture was stirred for 3 hours to remove methyl ethyl ketone by distillation. .
Then, the mixture was cooled at a cooling rate of 6° C./min to prepare a crystalline resin fine particle dispersion (1A) in which fine particles of the crystalline resin (1a) were dispersed.

The volume average particle diameter of the crystalline resin (1a) in the crystalline resin fine particle dispersion (1A) was measured using a particle size distribution analyzer (laser diffraction particle size distribution analyzer “LA-750 (manufactured by HORIBA)”). As a result, the volume average particle size of the crystalline resin (1a) was 202 nm.

[Preparation of Crystalline Resin Fine Particle Dispersions (2A) to (5A)]
Crystalline resin fine particle dispersion liquid (2A) to crystalline resin fine particle dispersion liquid (2A) to crystalline resin fine particle dispersion liquid (2A) to (5A) was prepared.

(A.3) Styrene/Acrylic Modified Crystalline Polyester Composition Ratios and Melting Points Table I shows the composition ratios and melting points of the styrene/acrylic modified crystalline polyesters in the crystalline resin fine particle dispersions (1A) to (5A).
The styrene/acrylic-modified crystalline polyester composition ratio in Table I is, for example, the total mass (29.75 parts by mass) of the raw material monomer (1a-1) and the raw material monomer when producing the crystalline resin (1a). This value was calculated from the total mass (565.2 parts by mass) of (1a-2), and the other crystalline resins (2a) to (5a) were also calculated in the same manner.
In addition, as described above, in the present invention, the “melting point” is the endothermic peak temperature C ₍₁₎ p (° C.) of the crystalline resin observed in the first heating process in differential scanning calorimetry. , and the "melting point" in Table I is the above C ₍₁₎ p (°C).

B. Preparation of Amorphous Resin Particle Dispersion [Preparation of Amorphous Resin Particle Dispersion (1)]
(First stage polymerization)
8 parts by mass of sodium dodecyl sulfate and 3000 parts by mass of ion-exchanged water were charged into a 5 L reaction vessel equipped with a stirring device, a temperature sensor, a cooling pipe and a nitrogen introduction device, and stirred at a stirring speed of 230 rpm under a nitrogen stream. The temperature was raised to 80°C.

After raising the temperature, a solution obtained by dissolving 10 parts by mass of potassium persulfate in 200 parts by mass of ion-exchanged water is added, the liquid temperature is raised to 80° C. again, and the following raw material monomer (1b-1) mixture is added over 1 hour. Dripped.

<Raw material monomer (1b-1)>
Styrene 480.0 parts by mass n-Butyl acrylate 250.0 parts by mass Methacrylic acid 68.0 parts by mass

After the mixture was dropped, the material monomer (1b-1) was polymerized by heating and stirring at 80° C. for 2 hours to prepare a vinyl resin fine particle dispersion (S1) of the first-stage polymerization liquid. .

(Second-stage polymerization)
1100 parts by mass of ion-exchanged water and the vinyl resin fine particle dispersion (S1) prepared by the first-stage polymerization (first-stage polymerization liquid) was charged and heated to 87°C.

After that, a mixed liquid obtained by dissolving the following raw material monomer (1b-2), a chain transfer agent and a release agent at 85° C. was dispersed for 10 minutes using a mechanical disperser CLEARMIX (manufactured by M Technic Co., Ltd.) having a circulation path. to prepare a dispersion containing emulsified particles (oil droplets).
The above dispersion liquid was added to the above 5 L reaction vessel, a polymerization initiator solution prepared by dissolving 5.5 parts by mass of potassium persulfate in 103 parts by mass of ion-exchanged water was added, and the system was heated at 87°C for 1 hour. Polymerization was carried out by heating and stirring over a period of time to prepare a vinyl resin fine particle dispersion (S1').

<Raw material monomer (1b-2)>
Styrene 253 parts by mass 2-ethylhexyl acrylate 107.3 parts by mass Methacrylic acid 39.2 parts by mass

<Chain transfer agent>
n-octyl-3-mercaptopropionate 4.45 parts by mass

<Release agent>
Behenic acid behenate 120.0 parts by mass

(Third stage polymerization)
A solution obtained by dissolving 7.4 parts by mass of potassium persulfate in 157.9 parts by mass of deionized water was further added to the vinyl resin fine particle dispersion (S1') obtained by the second stage polymerization.

Furthermore, under the temperature condition of 84° C., a mixed solution of the following raw material monomer (1b-3) and a chain transfer agent was added dropwise over 90 minutes.

<Raw material monomer (1b-3)>
Styrene 335.0 parts by mass n-Butyl acrylate 211.0 parts by mass Methacrylic acid 44.0 parts by mass n-Octyl-3-mercaptopropionate 8.1 parts by mass

After completion of the dropwise addition, polymerization was carried out by heating and stirring for 2 hours, followed by cooling to 28° C. to obtain Amorphous Resin Fine Particle Dispersion (1).

[Preparation of Amorphous Resin Fine Particle Dispersions (2) to (12)]
A vinyl-based resin fine particle dispersion (S1) was prepared in the same manner as in the preparation of the amorphous resin fine particle dispersion (1) until the first stage polymerization.
In the steps after the second-stage polymerization, resin fine particle dispersion liquid (1) was prepared except that each raw material monomer, chain transfer agent, and release agent were changed as shown in Table II to 289 parts by mass of the first-stage polymerization liquid. Resin fine particle dispersions (2) to (12) were prepared in the same manner as above.

C. Preparation of colorant fine particle dispersion 420 parts by mass of copper phthalocyanine (C.I. Pigment Blue 15:3) was gradually added to a solution of 226 parts by mass of sodium dodecyl sulfate added to 1600 parts by mass of ion-exchanged water while stirring. .

A colorant fine particle dispersion (P1) was prepared by dispersing using a stirring device Clearmix (manufactured by M Technic Co., Ltd., "Clearmix" is a registered trademark of the company).

The volume-based median diameter of the colorant particles in the colorant fine particle dispersion (P1) was measured to be 110 nm.

D. Preparation of each toner (D.1) Toner (1)
(D.1.1) Preparation of Toner Particles (1) 480 parts by mass (in terms of solid content) of the amorphous resin fine particle dispersion (1) and 350 parts by mass of the amorphous resin fine particle dispersion (1) were added to a reaction vessel equipped with a stirrer, a temperature sensor and a cooling pipe. Ion-exchanged water was added in parts by mass.

At room temperature (25° C.), a 5 mol/L sodium hydroxide aqueous solution was added to adjust the pH to 10.
Further, 36.4 parts by mass (in terms of solid content) of the colorant fine particle dispersion (P1) was added, and 80 parts by mass of a 50% by mass magnesium chloride aqueous solution was added with stirring at 30°C over 10 minutes, A dispersion was obtained.

After the obtained dispersion was allowed to stand for 5 minutes, the temperature was raised to 82° C. over 60 minutes. was added over 20 minutes, the stirring speed was adjusted so that the particle size growth rate was 0.01 μm / min, and the volume-based median diameter measured by Coulter Multisizer 3 (manufactured by Coulter Beckmann) was It was grown to 6.0 μm.

Next, an aqueous solution prepared by dissolving 80 parts by mass of sodium chloride in 300 parts by mass of ion-exchanged water was added to stop the growth of the particle size.
Next, the mixture is stirred at 82° C. to allow the particles to fuse together until the average circularity of the toner particles reaches 0.970, and then cooled at a rate of temperature drop of 0.5° C./min or more to reduce the liquid temperature to 30° C. or less. lowered the temperature.
Next, solid-liquid separation was performed, and the dehydrated toner cake was redispersed in ion-exchanged water, and the operation of solid-liquid separation was repeated three times for washing.
After washing, the toner particles (1) were prepared by drying at 35° C. for 24 hours.

(D.1.2) Preparation of Toner (1) 100 parts by mass of the obtained toner particles (1), 0.6 parts by mass of hydrophobic silica particles (number average primary particle diameter: 12 nm, degree of hydrophobicity: 68), 1.0 parts by mass of hydrophobic titanium oxide particles (number average primary particle size: 20 nm, degree of hydrophobicity: 63) and 1.0 parts by mass of sol-gel silica (number average primary particle size = 110 nm) were mixed in a Henschel mixer (Nippon Coke (manufactured by Kogyo Co., Ltd.) at a rotary blade peripheral speed of 35 mm/sec and 32° C. for 20 minutes.
After mixing, coarse particles were removed using a sieve with an opening of 45 μm to obtain Toner (1).

(D.1.3) Production of two-component developer Toner (1) and a ferrite carrier coated with acrylic resin and having a volume average particle diameter of 32 μm are added so that the concentration of toner (1) becomes 6% by mass. and mixed.
Through the above steps, a two-component developer containing toner (1) was produced.

(D.2) Toners (2), (3), (5)-(11), (13)-(18)
Except for changing the resin fine particle dispersion, the crystalline resin fine particle dispersion, and the composition ratio of the amorphous resin and the crystalline resin as shown in Table III in the preparation of the toner (1) and the two-component developer containing it. prepared toners (2), (3), (5) to (11), (13) to (18) and two-component developers containing them in the same manner.

(D.3) Toner (4)
(D.3.1) Production of amorphous polyester resin (1b) Raw material monomer (1b-1) for the following vinyl resin, raw material monomer having a substituent that reacts with both the amorphous polyester resin and the vinyl resin, and polymerization A mixed solution containing 16.0 parts by mass of di-t-butyl peroxide as an initiator was put into the dropping funnel.

<Raw material monomer (1b-1)>
Styrene 80.0 parts by mass n-butyl acrylate 20.0 parts by mass

<Raw material monomer having a substituent that reacts with both the amorphous polyester resin and the vinyl resin>
Acrylic acid 10.0 parts by mass

In addition, raw material monomer (1b-2) for the following amorphous polyester resin was placed in a four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and heated to 170° C. to dissolve.

<Raw material monomer (1b-2)>
Bisphenol A ethylene oxide 2 mol adduct 50.2 parts by mass Bisphenol A propylene oxide 2 mol adduct 249.8 parts by mass Terephthalic acid 120.1 parts by mass Dodecenylsuccinic acid 46.0 parts by mass

Under stirring, the mixed solution in the dropping funnel was dropped into the four-necked flask over 90 minutes, aged for 60 minutes, and then unreacted raw material monomers were removed under reduced pressure (8 kPa).

After that, 0.4 parts by mass of Ti(OBu) ₄ was added as an esterification catalyst, the temperature was raised to 235°C, and the reaction was carried out under normal pressure (101.3 kPa) for 5 hours, and further under reduced pressure (8 kPa). The reaction was carried out at for 1 hour.

Then, the mixture was cooled to 200° C., reacted under reduced pressure (20 kPa), and then desolubilized to prepare an amorphous polyester resin (1b).
The obtained amorphous polyester resin (1b) had a weight average molecular weight (Mw) of 24000 and an acid value of 18.2 mgKOH/g.

(D.3.2) Preparation of Amorphous Polyester Resin Fine Particle Dispersion (1B) 108 parts by mass of the obtained amorphous polyester resin (1b) and 64 parts by mass of methyl ethyl ketone were placed in a reaction vessel and heated at 70°C. A solution was obtained by stirring for 30 minutes and dissolving.

3.4 parts by mass of a 25% by mass sodium hydroxide aqueous solution was added to the above solution, which was placed in a reaction vessel equipped with a stirrer, and 210 parts by mass of water warmed to 70°C was added for 70 minutes while stirring. was mixed dropwise over a period of time.
The liquid in the container became cloudy during the dropping, and an emulsion in a uniformly emulsified state was obtained after the entire amount was dropped.

The particle size of the oil droplets in the above emulsified liquid was measured using a laser diffraction particle size distribution analyzer "LA-750 (HORI
BA)”, the volume average particle diameter was 90 nm.

Next, while the emulsion is kept at 70° C., it is stirred under a reduced pressure of 15 kPa (150 mbar) for 3 hours using a diaphragm vacuum pump “V-700” (manufactured by BUCHI) to remove methyl ethyl ketone by distillation. Then, an amorphous polyester resin fine particle dispersion (1B) was prepared.

As a result of measurement with the particle size distribution analyzer, the volume average particle diameter of the amorphous polyester resin (1b) in the amorphous polyester resin fine particle dispersion (1B) was 94 nm.

(D.3.3) Production of Toner Particles (4) 486 parts by mass (in terms of solid content) of the fine resin particle dispersion (6) and 350 parts by mass of Ion-exchanged water was added.
At room temperature (25° C.), a 5 mol/L sodium hydroxide aqueous solution was added to adjust the pH to 10.

Further, 36.4 parts by mass (in terms of solid content) of the colorant fine particle dispersion (P1) was added, and 80 parts by mass of a 50% by mass magnesium chloride aqueous solution was added with stirring at 30°C over 10 minutes, A dispersion was obtained.

After the obtained dispersion was allowed to stand for 5 minutes, the temperature was raised to 82° C. over 60 minutes. The volume-based median diameter measured by Coulter Multisizer 3 (manufactured by Coulter Beckmann) was 6.00 μm/min. It was grown to 0 μm.

Next, 60 parts by mass of the amorphous polyester resin fine particle dispersion (1B) (in terms of solid content) was added over 30 minutes. An aqueous solution dissolved in 300 parts by mass was added to stop the particle size growth.

Next, the mixture is stirred at 82° C. to allow the particles to fuse together until the average circularity of the toner particles reaches 0.970, and then cooled at a rate of temperature drop of 0.5° C./min or more to reduce the liquid temperature to 30° C. or less. lowered the temperature.

Next, solid-liquid separation was performed, and the dehydrated toner cake was redispersed in ion-exchanged water, and the operation of solid-liquid separation was repeated three times for washing.
After washing, the toner particles (4) were prepared by drying at 35° C. for 24 hours.

(D.3.4) Production of Toner (4) To 100 parts by mass of toner particles (4) obtained, 0.6 parts by mass of hydrophobic silica particles (number average primary particle diameter: 12 nm, degree of hydrophobicity: 68) was added. , 1.0 parts by mass of hydrophobic titanium oxide particles (number average primary particle size: 20 nm, degree of hydrophobicity: 63) and 1.0 parts by mass of sol-gel silica (number average primary particle size = 110 nm) were added, and a Henschel mixer was added. (manufactured by Nippon Coke Kogyo Co., Ltd.) at a rotary blade peripheral speed of 35 mm/sec and 32° C. for 20 minutes.
After mixing, coarse particles were removed using a sieve with an opening of 45 μm to prepare Toner (4).

(D.3.5) Preparation of two-component developer Toner (4) and a ferrite carrier coated with acrylic resin and having a volume average particle diameter of 32 μm are added and mixed so that the toner particle concentration becomes 6% by mass. bottom.
A two-component developer containing toner (4) was produced through the above steps.

(D.4) Toner (12)
(D.4.1) Preparation of release agent particle dispersion (W1)

FNP-0090 (release agent, melting point 89 ° C.) 100 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Neogen RK) 10 parts by mass Ion-exchanged water 400 parts by mass

The above materials were mixed, heated to 80° C. and thoroughly dispersed using an IKA Ultra Turrax T50.
Thereafter, after dispersion treatment using a pressure-discharging Gaulin homogenizer, ion-exchanged water was added to the dispersion to adjust the solid content to 15% to prepare a release agent particle dispersion (W1).
The volume-based median diameter of the release agent particles in this dispersion was measured with a laser diffraction particle size distribution analyzer LA-750 (manufactured by HORIBA) and found to be 220 nm.

(D.4.2) Preparation of Toner Particles (12) 340.81 parts by mass of amorphous polyester resin dispersion (1B) (in terms of solid content) was added to a reaction vessel equipped with a stirrer, temperature sensor and cooling pipe. 48.44 parts by mass of release agent dispersion (W1) (in terms of solid content) and 2000 parts by mass of ion-exchanged water were added.

At room temperature (25° C.), a 5 mol/L sodium hydroxide aqueous solution was added to adjust the pH to 10.
Further, 7 parts by mass of the colorant fine particle dispersion (P1) (in terms of solid content) was added, and a solution obtained by dissolving 60 parts by mass of magnesium chloride in 60 parts by mass of ion-exchanged water was stirred at 30°C for 10 minutes. was added.

After standing for 3 minutes, the temperature was raised to 80° C. over 60 minutes, and after reaching 80° C., 43.25 parts by mass (calculated as solid content) of the crystalline resin fine particle dispersion (5A) was added over 20 minutes to obtain a particle size. The stirring speed was adjusted so that the growth rate of 0.01 μm/min, and the growth was continued until the volume-based median diameter measured by Coulter Multisizer 3 (manufactured by Coulter Beckman) reached 6.0 μm.

Next, an aqueous solution prepared by dissolving 190 parts by mass of sodium chloride in 760 parts by mass of deionized water was added to stop the growth of the particle size.

Then, the mixture was heated and stirred at 80° C. to promote fusion of the toner particles until the average circularity of the toner particles reached 0.970.

After that, the temperature was raised to 50° C. over 30 minutes while stirring, and a heat treatment step was performed for 3 hours.
After that, it was cooled to lower the liquid temperature to 30°C or less.

Next, solid-liquid separation was performed, and the dehydrated toner cake was redispersed in ion-exchanged water, and the operation of solid-liquid separation was repeated three times for washing.
After washing, the toner particles (12) were obtained by drying at 40° C. for 24 hours.

(D.4.3) Preparation of Toner (12) 100 parts by mass of toner particles (12) obtained, 0.6 parts by mass of hydrophobic silica particles (number average primary particle diameter: 12 nm, degree of hydrophobicity: 68), Hydrophobic titanium oxide particles (number average primary particle size: 2
0 nm, degree of hydrophobicity: 63) 1.0 parts by mass and 1.0 parts by mass of sol-gel silica (number average primary particle size = 110 nm) are added, and the Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.) is used to rotate the blade circumference. Mixed for 20 minutes at a speed of 35 mm/sec and 32°C.
After that, coarse particles were removed using a sieve with an opening of 45 μm to prepare Toner (12).

(D.4.4) Preparation of two-component developer Toner (12) and a ferrite carrier coated with an acrylic resin and having a volume average particle diameter of 32 μm are added and mixed so that the toner particle concentration becomes 6% by mass. bottom.
A two-component developer containing toner (12) was produced through the above steps.

E. Examples and Comparative Examples Toner No. The types of dispersions of amorphous resins and crystalline resins in (1) to (18) are shown in Table III.
The evaluation results shown in Table IV were obtained using each release agent, crystalline resin and toner shown in Table III.
Each evaluation method and evaluation criteria are shown below.

(Measurement of thermophysical properties of each release agent and crystalline resin by differential scanning calorimetry)
Thermophysical properties of each release agent and crystalline resin were measured by differential scanning calorimetry according to the following procedure.

5 mg of the sample to be measured (each release agent and crystalline resin) was placed in an aluminum pan KITNO. B0143013, set in a sample holder of a thermal analysis device "Diamond DSC (manufactured by PerkinElmer)", and during the first heating (heating process), 0 ° C. to 100 at a heating rate of 10 ° C./min The temperature is raised to ° C. and held at 100 ° C. for 1 minute, and the endothermic peak temperature derived from each release agent in the endothermic curve obtained at that time is W ₍₁₎ p (° C.) and the endothermic peak temperature of the crystalline resin C _{( 1)} p (°C) was measured.
After that, the temperature was lowered from 100° C. to 0° C. at a rate of 10° C./min for cooling, and the temperature of 0° C. was maintained for 1 minute.
Then, during the second heating (heating process), the temperature was raised from 0° C. to 100° C. at a rate of 10° C./min and held at 100° C. for 1 minute.
An empty aluminum pan was used as a reference.

(Measurement of softening point temperature by thermal fluid evaluation device)
Using a flow tester CFT-500D (manufactured by Shimadzu Corporation), while heating a 1 cm ³ sample at a heating rate of 6° C./min, a pressure of 20 kg/cm ² is applied by a plunger (also referred to as a “piston”). A load is applied to push out a nozzle with a diameter of 1 mm and a length of 1 mm, thereby drawing a plunger descent amount (flow value)-temperature curve (also referred to as a "softening flow curve"), and measuring the height of the S-shaped curve. When the height is h, the temperature corresponding to h/2 (the temperature at which half of the toner flows out) is the softening point temperature _Tf1/2 (also referred to as "1/2 method softening point").

(E.1) Toner Manufacturability After the toners (1) to (18) in Examples and Comparative Examples were produced, the surface of the toner particles was observed by the following method to determine whether the desired particle size and circularity were produced. , and the toner manufacturability was evaluated according to the following evaluation criteria.

(Method for Observing Surface of Toner Particles)
Toner particles, a small amount of neutral detergent, and pure water are added to a beaker, mixed well, and filtered through a mesh of 1 μm, which is repeated three times to remove external additive particles, and to remove the surface of the toner base particles. expose.
After that, the toner is fixed in one layer on a sample stand for electron microscope observation with a carbon tape.
The above toner was measured and photographed under the following conditions using a transmission electron microscope "JSM-7401F" (manufactured by JEOL Ltd.) to determine whether or not the crystalline material was bleeding out from the toner.

〔conditions〕
Measurement mode: SE mode, LEI
Accelerating voltage: 1.0 kV
Emission Current: 20 μA
Working Distance: 8mm
Magnification: ×10000
Data size: 1280×1024

(Evaluation criteria)
〇 Can be manufactured without problems without bleeding out of crystalline materials.
△ Bleed out of crystalline material, but can be manufactured without problems.
× Bleeding out of crystalline material occurred, and the desired grain size and degree of circularity were not achieved, and there was a problem in manufacturing.

(E.2) Low-temperature fixability evaluation As an image forming apparatus, a commercially available full-color multifunction machine "AccurioPress C3080 (manufactured by Konica Minolta)" was modified so that the surface temperature of the upper fixing belt and the lower fixing roller can be changed. The above-described two-component developer of each color was sequentially loaded.
A test was performed in which a solid image with a toner adhesion amount of 11.3 g/m ² was output on A4 (basis weight 90 g/m ² ) plain paper at a fixing temperature of 100 to 200°C, and the fixing temperature was changed in increments of 5°C. I did it repeatedly.
The lowest fixing temperature at which image staining due to fixing offset is not visually confirmed was defined as the lowest fixing temperature, and the low-temperature fixability was evaluated according to the following evaluation criteria.

(Evaluation criteria)
⊚ Minimum fixation temperature of less than 135°C (excellent low-temperature fixability of toner).
○ Minimum fixation temperature is 135° C. or more and less than 145° C. (good low-temperature fixability of toner).
Δ Minimum fixation temperature is 145° C. or more and less than 155° C. (low temperature fixability of toner is good).
× Minimum fixation temperature: 155° C. or higher (cannot be used due to poor low-temperature fixability of toner).

(E.3) Evaluation of Fixing Separability As an image forming apparatus, a commercially available color multifunction machine AccurioPress C3080 (manufactured by Konica Minolta) was modified so that the surface temperatures of the upper fixing belt and the lower fixing roller can be changed. A two-component developer of each color was loaded sequentially.
The above apparatus was modified so that the fixing temperature, toner adhesion amount, and system speed can be freely set.
OK Top Coat +85 g/m ² (manufactured by Oji Paper Co., Ltd.) was used as evaluation paper.
The temperature (U.O. avoidance temperature + 25°C), which is 25°C higher than the temperature at which underoffset does not occur (U.O. avoidance temperature), is defined as the temperature of the upper fixing belt, and the lower fixing roller is set to 90°C. , and each solid image (deposited amount: 8.0 g/m ² ) was printed by changing the edge margin amount.
The smaller the value of the separable leading edge margin, the better the separation performance.
In addition, evaluation was implemented in the normal temperature normal humidity environment (NN environment: 25 degreeC, 50 %RH).
In addition, it means that the smaller the separable leading edge margin, the better the thin paper separability.

(Evaluation criteria)
A: The value of the separable leading edge margin is 0 mm or more and 2 mm or less.
◯: The value of the separable leading edge margin is greater than 2 mm and 4 mm or less.
Δ: The value of the separable leading edge margin is greater than 4 mm and 6 mm or less.
x: The value of the separable leading edge margin is greater than 6 mm.

(E.4) Release agent adhesion evaluation In a commercially available color multifunction machine AccurioPress C3080 (manufactured by Konica Minolta), the fixing device was set at a surface temperature of the upper fixing belt in the range of 140 to 220 ° C. and the surface of the lower fixing roller. It was modified so that the temperature could be changed in the range of 120-200°C.
Each developer was sequentially loaded into this remodeled machine, and under normal temperature and normal humidity (temperature 20° C., humidity 50% RH), A4 (basis weight 157 g/m ² ) gloss coated paper was coated with a toner adhesion amount of 8.0%. A solid image of 0 g/m ² was formed and fixed.
The fixing speed during the fixing process was 460 mm/sec, and the fixing temperature (the surface temperature of the fixing belt) was the under-offset temperature +35°C.

The state of adhesion of wax to the conveying roller after printing 100 sheets was visually evaluated according to the following evaluation criteria, and ranked on a 10-point scale.

(Evaluation criteria)
Ranks 10 to 9: No adhesion of wax was observed (accepted).
Ranks 8 to 7: Wax adhesion is slightly observed, but there is no problem in quality (acceptance).
Ranks 6 to 5: Adhesion of wax is confirmed, but at a practical level (acceptable).
Ranks 4 to 1: Wax adhesion was confirmed and the level was not practical (failed).

(E.5) Gloss Unevenness A commercially available color multifunction machine AccurioPress C3080 (manufactured by Konica Minolta Co., Ltd.) was used with the fixing device under pressure in the nip region and the surface temperature of the fixing heat roller (fixing roller) within the range of 100 to 210 ° C. and the process speed (nip time) was changed, and each developer made from each toner was loaded.

For each developer produced from the toner, in an environment of normal temperature and normal humidity (temperature 20° C., humidity 50% RH), A3 size coated paper Esprit C 209 g / m ² (manufactured by Nippon Paper Industries Co., Ltd.) A fixing experiment for outputting an image for gloss memory evaluation (alphabet output image) with a toner adhesion amount of 8 g/m ² was conducted under conditions of a fixing device nip pressure of 238 kPa and a nip time of 25 milliseconds (process speed of 480 mm/s). , the set fixing temperature was changed from 160° C. to 200° C. by 10° C., and this was repeated.
Gloss unevenness was evaluated according to the following evaluation criteria.
In addition, if it is ○ in the following evaluation criteria, it is practical.

(Evaluation criteria)
◯: No gloss unevenness occurs (practically possible).
x: Gloss unevenness occurs (unpractical).

(E.6) Evaluation of varnish wettability In a commercially available color multifunction machine AccurioPress C3080 (manufactured by Konica Minolta), coated paper of 157 g/m ² was selected as the paper type, and each developer was sequentially loaded. A solid image with a toner adhesion amount of 8.0 g/m ² was formed on A4 (basis weight 157 g/m ² ) gloss coated paper under an environment of temperature 20° C. and humidity 50% RH, and fixed.
On this image, a varnish coater (Digi UV Coater manufactured by BN Technologies) was used to set the coating conditions to a speed of 30 m/min and a coating thickness of about 5 μm. A layered image was produced.
The varnish layer of each evaluation image obtained was visually observed, and the wettability of the varnish was evaluated according to the following evaluation criteria.

(Evaluation criteria)
◎ Zero pinholes of 0.1mm size in each 10cm x 10cm.
〇 No more than 2 pinholes of 0.1mm size in each 10cm x 10cm.
△ 3 to 10 or less 0.1 mm pinholes in each 10 cm x 10 cm.
There are 11 or less pinholes of 0.1mm size or pinholes with a size of 0.1mm or more in each of ×10cm×10cm.

[summary]
From the above, it can be seen that the examples are comprehensively superior to the comparative examples in the evaluation results of toner manufacturability, low-temperature fixability, fixation separability, release agent adhesion, gloss unevenness and varnish coverage.

Claims (10)

A toner for electrostatic charge image development containing toner base particles containing at least a binder resin and a release agent,
the binder resin contains at least a crystalline resin,
W ₍₁₎ p (° C.) is the endothermic peak temperature derived from the release agent observed in the first temperature rising process in the differential scanning calorimetry of the toner for developing an electrostatic charge image, and the endothermic peak of the crystalline resin is When the temperature is C ₍₁₎ p (°C) and the softening point temperature measured by the thermal flow evaluation device is Tf _1/2 (°C), the relationship represented by the following formulas (1a) and (2a) is obtained. A toner for developing an electrostatic charge image, which is characterized by:
11≦W ₍₁₎ p−C ₍₁₎ p≦23 (1a)
5≦Tf _1/2 −W ₍₁₎ p≦36 (2a) The softening point temperature Tf _1/2 (° C.) measured by the heat flow evaluation device and the endothermic peak temperature C ₍₁₎ p( °C) satisfies the relationship represented by the following formula (3).
Tf _1/2 −C ₍₁₎ p≦48 (3) The endothermic peak temperature W ₍₁₎ p (°C) derived from the release agent and the endothermic peak temperature C ₍₁₎ p (°C) of the crystalline resin observed in the first temperature rising process in the differential scanning calorimetry. ) satisfies the relationship represented by the following formula (1b).
14≦W ₍₁₎ p−C ₍₁₎ p≦17 (1b) The softening point temperature Tf _1/2 (°C) measured by the thermal flow evaluation device and the endothermic peak temperature W ₍₁₎ p derived from the release agent observed in the first temperature rising process in the differential scanning calorimetry. 4. The toner for electrostatic charge image development according to any one of claims 1 to 3, wherein (°C) satisfies the relationship represented by the following formula (2b).
11≦Tf _1/2 −W ₍₁₎ p≦30 (2b) 5. The endothermic peak temperature Wp ₍₁₎ (° C.) derived from the release agent is in the range of 64 to 100 (° C.). Toner for electrostatic charge image development. 6. The softening point temperature Tf _1/2 (° C.) measured by the thermohydraulic evaluation device is in the range of 90 to 115 (° C.). 3. The toner for electrostatic charge image development described in . 7. The toner for electrostatic charge image development according to any one of claims 1 to 6, wherein the crystalline resin contains a crystalline polyester. 8. The crystalline resin according to any one of claims 1 to 7, wherein the crystalline resin is a hybrid crystalline polyester resin in which a crystalline polyester polymer segment and a vinyl resin polymer segment are combined. A toner for developing an electrostatic charge image as described above. 9. The electrostatic image developing toner according to claim 1, wherein the binder resin contains at least styrene-acrylic resin. A method for producing the toner for developing an electrostatic charge image according to any one of claims 1 to 9, comprising:
The step of producing the toner particles includes a step of adding a crystalline resin fine particle dispersion to an amorphous resin fine particle dispersion and allowing the toner particles to grow at a temperature equal to or higher than the melting point of the crystalline resin. A method for producing a toner for electrostatic charge image development.