JP7211008B2 - TONER, IMAGE FORMING APPARATUS, IMAGE FORMING METHOD, AND PROCESS CARTRIDGE - Google Patents

Description

The present invention relates to toners, image forming apparatuses, image forming methods, and process cartridges.

In recent years, toners are required to have low-temperature fixability for saving energy and heat-resistant storage stability that can withstand high temperature and high humidity during storage and transportation after production. In particular, power consumption during fixing accounts for most of the power consumption in the image forming process, so improvement of low-temperature fixability is very important.

In order to save energy, crystalline polyester is used as a binder resin for the purpose of lowering the glass transition temperature, thereby producing a toner that can be fixed at a lower temperature than before.
However, the use of crystalline polyester causes the toner to melt at a low temperature, which tends to deteriorate storage stability in high-temperature and high-humidity environments. In addition, the shape of the toner tends to change, which promotes the embedding of the external additive and deteriorates fluidity, which tends to cause system problems such as poor cleaning. Achieving both low-temperature fixability and storage stability and the cleaning process are major issues.

In order to solve such problems, a toner has been proposed in which non-spherical silica having a high spacer effect is used as an external additive of the toner to suppress the change in the amount of released silica (see, for example, Patent Document 1).

An object of the present invention is to provide a toner that suppresses the embedding of an external additive on the surface of the toner and has excellent low-temperature fixability, heat-resistant storage stability, durability, and cleanability.

The toner of the present invention as a means for solving the above-mentioned problems is a toner containing toner base particles containing a binder resin and a colorant, and an external additive,
The following conditions (a), (b), and (c) are satisfied, the external additive contains non-spherical silica, and the content of the non-spherical silica is 1.5 parts per 100 parts of the toner base particles. 5 parts to 2.
3.75 g of the toner is dispersed in 50 mL of a 0.5% by weight polyoxyalkylene alkyl ether dispersion in a 110 mL vial and subjected to ultrasonic vibration at 20 kHz and 750 watts for 1 minute. A toner, wherein the free amount B (% by mass) of all silica satisfies formula (4).
(a) The storage elastic modulus G'(50) of the toner at 50.degree. C. and the storage elastic modulus G'(90) of the toner at 90.degree.
G'(50)/G'(90)≧6.0×10 ² Expression (1)
(b) BET specific surface area Bt (m ² /g) of the toner and coverage Ct (%) at which the toner base particles are covered with all the external additives satisfy formula (2).
Bt−0.03×Ct≦1.60 Expression (2)
(c) the external additive contains at least coalesced particles;
The coalescent particles are non-spherical silica,
The coalesced particles are non-spherical secondary particles formed by coalescing primary particles,
A number average secondary particle diameter of the coalescent particles is 130 nm or more.
B>0.8 Expression (4)

According to the present invention, it is possible to provide a toner that suppresses the embedding of an external additive in the toner surface and has excellent low-temperature fixability, heat-resistant storage stability, durability, and cleanability.

FIG. 1 is a schematic diagram showing an example of the image forming apparatus of the present invention. FIG. 2 is a schematic diagram showing another example of the image forming apparatus of the present invention. 3 is a partially enlarged view of the image forming apparatus of FIG. 2. FIG. FIG. 4 is a schematic diagram showing an example of a process cartridge.

(toner)
The toner of the present invention contains toner base particles containing a binder resin and a colorant, and an external additive, and satisfies the following conditions (a), (b), and (c).
(a) The storage elastic modulus G'(50) of the toner at 50.degree. C. and the storage elastic modulus G'(90) of the toner at 90.degree.
G'(50)/G'(90)≧6.0×10 ² Expression (1)
(b) The BET specific surface area Bt (m ² /g) of the toner and the coverage Ct (%) at which the toner base particles are coated with the external additive satisfy formula (2).
Bt−0.03×Ct≦1.60 Expression (2)
(c) the external additive contains at least coalesced particles;
The coalesced particles are non-spherical secondary particles formed by coalescing primary particles,
A number average secondary particle size of the coalescent particles is 130 nm or more.

In the case of the toner described in Patent Document 1, since the contact area between the external additive and the toner is large, the external additive is buried on the toner surface, and the heat-resistant storage stability, durability, fluidity, and cleanability are deteriorated. is a problem.

As a result of extensive studies, the inventors of the present invention have found that a toner that satisfies all of the conditions (a), (b), and (c) has a small contact area between the toner base particles and the external additive, and is It has been found that the embedding of the external additive in the surface of the toner to be fixed at 100° C. can be suppressed.
Further, the present inventors have found that a toner that satisfies all of the conditions (a), (b), and (c) is excellent in low-temperature fixability, heat-resistant storage stability, durability, and cleanability.
Conditions (a), (b), and (c) will be described below.

The toner of the present invention satisfies condition (a). That is, the storage elastic modulus G'(50) of the toner at 50.degree. C. and the storage elastic modulus G'(90) of the toner at 90.degree.
G'(50)/G'(90)≧6.0×10 ² Expression (1)
A toner that satisfies the formula (1) can achieve a sharp melt property that enables both low-temperature fixability and heat-resistant storage stability of the toner to be at a high level.

If the toner does not satisfy the condition (a), that is, the toner that does not satisfy the formula (1), the sharp melt property of the toner is lowered, and high low-temperature fixability cannot be achieved.

The toner of the present invention satisfies condition (b). That is, the BET specific surface area Bt (m ² /g) of the toner and the coverage Ct (%) at which the toner base particles are coated with the external additive satisfy formula (2).
Bt−0.03×Ct≦1.60 Expression (2)
The toner that satisfies the formula (2) has a smaller surface area of the toner base particles and a smaller contact area with the external additive than the normal toner. Therefore, it is possible to suppress the embedding of the external additive on the surface of the toner that is fixed at a low temperature. In addition, high heat-resistant storage stability, durability, fluidity, and cleanability can be achieved.

In the case of a toner that does not satisfy the condition (b), that is, the toner that does not satisfy the formula (2), the contact area between the surface of the toner base particles and the external additive increases in the low-temperature fixation toner, and the external additive increases on the toner surface. The burial of the agent reduces heat-resistant storage stability, durability, fluidity, and cleanability.
In addition, since the external additive is buried, the surface area of the exposed toner base particles is increased, the adhesive force between the toner and between the toner and the photoreceptor or the transfer belt is increased, and heat-resistant storage stability, durability, and fluidity are further increased. , and the cleanability is reduced.

The process of deriving the formula (2) is as follows.
The BET specific surface area Bt of the toner is obtained as a value including the unevenness on the surface of the toner base particles and the unevenness on the surface of the external additive.
The amount of increase in the BET specific surface area of the toner with respect to the BET specific surface area of the toner base particles, where Ct% is the coverage of the toner coated with an external additive and having a BET specific surface area of about 20 m ² /g to 200 m ² /g. is approximately 0.03×Ctm ² /g. That is, when the relationship between the BET specific surface area Bt of the toner and the coverage Ct is graphed based on the measured values, the coefficient 0.03 included in the formula (2) is calculated.
Therefore, the BET specific surface area of the base particles can be estimated by setting the left side of Equation (2) to Bt−0.03×Ct.

The toner of the present invention satisfies condition (c). That is, the external additive contains at least coalesced particles, the coalesced particles are non-spherical secondary particles formed by coalescing primary particles, and the number average secondary particles of the coalesced particles The diameter is 130 nm or more.
Toner that satisfies condition (c) suppresses release and burial of external additives due to friction between toner particles and carriers. can do. In addition, high heat-resistant storage stability, durability, fluidity, and cleanability can be achieved.

In addition, when the toner does not satisfy the condition (c), that is, when the external additive has a spherical shape or a number average secondary particle diameter of the external additive is less than 130 nm, the external additive is buried, the heat-resistant storage stability, durability, fluidity, and cleanability are lowered.

Using a rocking mill, at a frequency of 700 rpm, 30 g of the developer containing the toner was stirred and mixed for 60 minutes, and the adhesive force A (gf) between deteriorated toner when compressed to 16 kg/cm ² was expressed by the following formula: (3) is preferably satisfied.
A<300 Expression (3)

In the case of the toner that satisfies the formula (3), the adhesiveness between toners and between the toner and the photoreceptor or transfer belt is low, so that heat-resistant storage stability, durability, fluidity, and cleanability can be improved.
In addition, by applying agitation processing using a rocking mill, it is possible to reproduce the liberation and burial of the external additive due to friction between toner particles and carrier in an actual machine. Further, by controlling the adhesive force between deteriorated toners, high quality can be ensured.

After stirring and mixing 30 g of developer containing the toner for 60 minutes using a rocking mill at a frequency of 700 rpm, the total energy is preferably 200 mJ or more and 350 mJ or less.

3.75 g of the toner was dispersed in 50 mL of a 0.5% by mass polyoxyalkylene alkyl ether dispersion in a 110 mL vial, and ultrasonic vibration was applied for 1 minute at 20 kHz and 750 watts. The liberated amount B (% by mass) preferably satisfies the formula (4).
B>0.8 Expression (4)

In the case of the toner that satisfies the above formula (4), the external additive is sufficiently liberated from the toner on the photoreceptor. can achieve sexuality.

<External Additives>
The toner contains an external additive.
The external additive contains at least coalesced particles and, if necessary, other components.

<<coalesced particles>>
The coalesced particles are non-spherical secondary particles formed by coalescing primary particles.
The coalescent particles have a number average secondary particle diameter of 130 nm or more.
Examples of the coalescent particles include non-spherical silica.

-Primary particles-
The average particle size (Da) of the primary particles is not particularly limited and can be appropriately selected depending on the intended purpose.
When the average particle size (Da) of the primary particles is 20 nm or more, the secondary particles function as a spacer, and the embedding of the external additive in the toner base particles due to external stress can be suppressed. When the average particle size (Da) of the primary particles is 150 nm or less, the external additive can be prevented from being liberated from the toner, and photoreceptor filming can also be prevented.

The average particle size (Da) of the primary particles can be measured based on the particle size of the primary particles in the secondary particles.
The average particle size (Da) of the primary particles can be measured, for example, as follows. First, after dispersing the secondary particles in an appropriate solvent such as tetrahydrofuran (THF), the solvent is removed on the substrate and dried to form a sample. Next, the obtained sample was observed with a field emission scanning electron microscope (FE-SEM, acceleration voltage: 5 kV or more and 8 kV or less, observation magnification: 8,000 times or more and 10,000 times or less). Measure the longest length of each primary particle. The number of particles to be measured is 100 or more and 200 or less. The average value of the longest length of the primary particles of the measured number of particles is calculated and taken as the average particle diameter of the primary particles.

-Secondary particles-
The secondary particles are non-spherical and are formed by coalescing primary particles.
The secondary particles have a number average particle diameter (number average secondary particle diameter) of 130 nm or more.
Examples of the secondary particles include non-spherical silica formed by coalescing primary particles of silica.

The non-spherical silica is secondary particles formed by coalescing primary particles of silica.
The non-spherical silica is not particularly limited as long as it is, for example, particles obtained by chemically bonding the primary particles with a treatment agent described later and secondary aggregation, and can be appropriately selected according to the purpose. It is preferably obtained by the method.

The average particle diameter (Db) of the secondary particles is not particularly limited, and can be appropriately selected according to the purpose. is particularly preferred.
When the average grain size is 80 nm or more, the function of the spacer effect is effectively achieved, and burying due to external stress can be suppressed. When the average particle diameter is 200 nm or less, the release from the toner is suppressed, and adhesion of the released silica to the photoreceptor is also suppressed, resulting in excellent filming resistance. Further, when the average particle diameter is 80 nm or more and 200 nm or less, it is advantageous in terms of suppressing burial in the toner and improving fluidity and transferability.

The average particle diameter (Db) of the secondary particles can be measured, for example, as follows. First, after dispersing the secondary particles in an appropriate solvent such as tetrahydrofuran (THF), the solvent is removed on the substrate and dried to form a sample. Next, the obtained sample is subjected to a field emission scanning electron microscope (FE-SEM, acceleration voltage: 5 kV or more and 8 kV or less, observation magnification: 8,000 times or more and 10,000 times or less). Measure the longest particle length. The number of particles to be measured is 100 or more and 200 or less. The average value of the longest length of the secondary particles of the measured number of particles is calculated and taken as the average particle size of the secondary particles.

- Degree of coalescence of secondary particles -
The degree of coalescence (G) of each secondary particle is the ratio of the particle size of the secondary particles to the average particle size of the primary particles contained in the secondary particles (particle size of secondary particles/average of primary particles particle size).
The particle size of the secondary particles and the average particle size of the primary particles are measured and calculated by the method described above.
The degree of coalescence (G) can be arbitrarily controlled by adjusting the primary particle size, the type and amount of the treatment agent to be described later, and the treatment conditions.

The average value of the degree of coalescence (G) of the secondary particles (particle size of secondary particles/average particle size of primary particles) is not particularly limited and can be appropriately selected depending on the purpose. .5 or more and 4.0 or less are preferable, and 2.0 or more and 3.0 or less are more preferable.
When the average value of the degree of coalescence (G) is 1.5 or more, the external additive is prevented from rolling and being buried in the concave portions of the surface of the toner base particles, resulting in excellent transferability. When the average value of the degree of coalescence (G) is 4.0 or less, the peeling of the external additive from the toner is suppressed, so that the carrier contamination causes a decrease in charging, damage to the photoreceptor, and deterioration over time. Image defects can also be suppressed.

The content of the secondary particles having a degree of coalescence of less than 1.3 is not particularly limited and can be appropriately selected according to the purpose. The following are preferred.
The secondary particles have a distribution in production, and the particles with the degree of coalescence of less than 1.3 are particles in which coalescence has not progressed, and exist in a nearly spherical state. . Therefore, it is difficult to function as an irregular shape additive that is characterized for suppressing burial.
The measurement of the content of the secondary particles with the degree of coalescence of less than 1.3 is performed by measuring the primary particles and the secondary particles of 100 or more and 200 or less secondary particles by the method described above. After that, the degree of coalescence of each secondary particle is calculated from the obtained measurement value, and the number of particles whose degree of coalescence is less than 1.3 is divided by the measured number.

-Index for agitation of secondary particles-
The secondary particles are not particularly limited and can be appropriately selected according to the purpose. (adhesion force) is maintained and the durability of the toner is increased, and it is more preferable to satisfy the following formula (ii-1).
Nx/1,000×100≦30% Formula (ii)
Nx/1,000×100≦20% Formula (ii-1)
However, in the formulas (ii) and (ii-1), Nx is 0.5 g of the secondary particles and 49.5 g of the carrier in a 50 mL bottle at 67 Hz for 10 minutes. 1 shows the number of primary particles present singly in the region where 1,000 secondary particles are observed, when observed with a scanning electron microscope after stirring with .

When the cohesive force of the secondary particles is strong, the external additive in the toner cracks or collapses due to the load of a developing device or the like, and the number of particles that become primary particles decreases, suppressing the burial and rolling of the external additive. high transfer rate can be maintained over time.

When the cohesive force of the secondary particles is weak (when the ratio of the primary particles existing alone exceeds 30% with respect to 1,000 secondary particles), the external additive in the toner is The number of particles cracking or collapsing due to the load increases, the proportion of spherical primary particles increases, the external additive tends to move and bury, and it is difficult to maintain a high transfer rate over time. Become.
When the primary particles have an excessively small particle size (for example, less than 80 nm), the external additive tends to be buried in the toner base particles, and the external additive tends to roll into concave portions, which may make it impossible to maintain transferability and chargeability. be. When the primary particles are particles having an excessively large particle size (for example, more than 200 nm), the external additive is easily peeled off from the toner, resulting in image defects over time due to deterioration in charging due to carrier contamination and damage to the photoreceptor. There is fear.

In the formulas (ii) and (ii-1), the primary particles are not coalesced after the secondary particles are stirred under the stirring conditions using the mixing stirrer, Refers to particles that exist alone, including particles that have cracked or collapsed after the stirring and become primary particles, and particles that existed as the primary particles alone before the stirring, and the primary particles This includes particles that are not coalesced.
In the formulas (ii) and (ii-1), the shape of the primary particles is not particularly limited as long as the particles are not coalesced, and can be appropriately selected according to the purpose. It often exists in a substantially spherical state.

In the formulas (ii) and (ii-1), the method for confirming the presence of the primary particles is not particularly limited and can be appropriately selected depending on the purpose. A method of confirming that the particles exist alone by observing them with a SEM is preferred.
The method for measuring the average particle size of the primary particles is not particularly limited and can be appropriately selected according to the purpose. ,000 times or more and 10,000 times or less), and the average value of the particle size of the primary particles in the field of view is measured (the number of particles to be measured: 100 or more).

In the formulas (ii) and (ii-1), in the measurement of the number of the primary particles that exist alone with respect to 1,000 of the secondary particles, the particles are observed with a scanning electron microscope after the stirring. A particle existing alone is counted as one primary particle.
When a secondary particle formed by coalescence of a plurality of particles is confirmed by the scanning electron microscope, the secondary particle is counted as one secondary particle.
In the above formulas (ii) and (ii-1), as a method for measuring the number of the primary particles that exist alone with respect to 1,000 of the secondary particles, for example, the contours of the respective secondary particles and primary particles can be expressed by the number of primary particles per 1,000 secondary particles in the observation area when observed with the scanning electron microscope at a particle density and observation magnification that can be distinguished. As the observation area, for example, a plurality of arbitrary fields or areas in the scanning electron microscope, preferably a plurality of adjacent fields or areas, are appropriately selected so that the number of secondary particles to be observed is 1,000 or more. can be set.

The mixing stirrer is not particularly limited and can be appropriately selected depending on the purpose. For example, a rocking mill can be used. Examples of rocking mills include those manufactured by Seiwa Giken Co., Ltd.
The carrier is not particularly limited and can be appropriately selected according to the purpose. Ferrite powder is preferably used.
The 50 mL bottle is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include a commercially available glass bottle (manufactured by Nichiden Rika Glass Co., Ltd.).

- Particle size distribution index of secondary particles -
The particle size distribution index of the secondary particles is not particularly limited and can be appropriately selected according to the purpose. It is preferable that By using, as the secondary particles, particles having a sharp particle size distribution as represented by the following formula (iii), the toner can be particularly excellent in cleanability.
Db50/Db10≦1.20 Formula (iii)
However, in the formula (iii), Db50 is the particle size (nm) of the secondary particles on the horizontal axis, and the cumulative value (number %) of the secondary particles on the vertical axis. When the cumulative distribution is drawn from the small particle side, Db10 represents the particle size of the secondary particles at which the cumulative value is 50% by number, and Db10 is the particle size of the secondary particles at which the cumulative value is 10% by number. represents

The Db50 is, for example, represented by the cumulative distribution of the secondary particles when the particle diameter (nm) of the secondary particles is taken as the horizontal axis and the cumulative value (number %) of the secondary particles is taken as the vertical axis, If the measured number of secondary particles is 200, it means the 100th secondary particle, and if it is 150, it means the 75th secondary particle.

As a method for measuring Db50, for example, after dispersing the secondary particles in an appropriate solvent such as tetrahydrofuran (THF), a sample obtained by removing the solvent and drying on the substrate is subjected to a field emission scanning type The particle size of the secondary particles in the field of view is measured with an electron microscope (FE-SEM, acceleration voltage: 5 kV or more and 8 kV or less, observation magnification: 8,000 times or more and 10,000 times or less), and the cumulative value is 50. %, by measuring the particle size of the secondary particles.
The particle size of the secondary particles can be measured by measuring the longest length of the aggregated secondary particles (the number of particles to be measured: 100 or more and 200 or less).

The Db10 is represented by the cumulative distribution of the secondary particles, for example, when the particle size (nm) of the secondary particles is the horizontal axis and the cumulative value (number %) of the secondary particles is the vertical axis, If the measured number of secondary particles is 200, it means the 20th secondary particle, and if it is 150, it means the 15th secondary particle.

As a method for measuring Db10, for example, after dispersing the secondary particles in an appropriate solvent such as tetrahydrofuran (THF), a sample obtained by removing the solvent and drying on the substrate is subjected to a field emission scanning type The particle size of the secondary particles in the field of view is measured with an electron microscope (FE-SEM, acceleration voltage: 5 kV or more and 8 kV or less, observation magnification: 8,000 times or more and 10,000 times or less), and the cumulative value is 10. %, by measuring the particle size of the secondary particles.
The particle size of the secondary particles can be measured by measuring the longest length of aggregated particles (number of particles measured: 100 or more and 200 or less).

The "Db50/Db10" is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1.00 or more and 1.20 or less, more preferably 1.00 or more and 1.15 or less.
As the "Db50/Db10" approaches 1.00, the shape of the particle size distribution becomes sharper, the number of primary particles that are not coalesced, and the number of secondary particles that are coalesced but have a small particle size. is preferable in that the When the "Db50/Db10" is 1.20 or less, the particle size distribution of the secondary particles does not spread too much, and an increase in the number of particles with a small particle size can be suppressed. That is, "small particle size A" (particles that have not progressed coalescence and are present in the state of primary particles) and "small particle size particles B" (particles that have coalesced but are primary particles particles which themselves are of small particle size).
When the amount of the "small-diameter particles A" is small, the function as a non-spherical external additive is achieved and the burial resistance is excellent, so that the occurrence of abnormal images can be suppressed.
When the amount of the "small-diameter particles B" is small, the spacer effect can be achieved, the external stress can be reduced, and the embedding of the external additive in the toner base particles can be suppressed.

The method for reducing the "small particle size particles A" and the "small particle size particles B" is not particularly limited and can be appropriately selected according to the purpose. A method that removes small particles is preferred.

-Shape of secondary particles-
The shape of the secondary particles is not particularly limited as long as it has a non-spherical shape in which particles are coalesced, and can be appropriately selected according to the purpose. A non-spherical shape formed by coalescing may be mentioned.
By using the secondary particles, high fluidity of the toner is realized, and even when a load is applied to the toner such as being agitated in the developing device, the embedding and rolling of the external additive are suppressed. , it is possible to maintain a high transfer rate over time. In addition, the secondary particles maintain cohesive force (coalescing force) between particles even under constant stirring conditions, so that the durability of the toner is high.

The method for confirming that the primary particles are coalesced in the secondary particles is not particularly limited and can be appropriately selected depending on the purpose. A method of confirming by observing with a SEM is preferred.

-Method for producing secondary particles-
A method for producing the secondary particles is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include a sol-gel method and a dry method. Among these, the method of manufacturing by the sol-gel method is preferable.
Specifically, it is preferable to manufacture the secondary particles by mixing or firing the primary particles and the treatment agent described below to cause chemical bonding and secondary agglomeration to form the secondary particles. When synthesizing by the sol-gel method, secondary particles may be prepared by a one-step reaction in the presence of the treating agent.

The secondary particles produced by the sol-gel method are preferable in that the particle size control is easier than in the dry method, the particle size distribution is sharp, and the secondary particles are excellent in moisture adsorption. It is possible to suppress burial in the toner and separation from the toner due to excessively large particle diameter.
In addition, the secondary particles produced by the sol-gel method are porous, which dry silica does not have, and are thought to absorb moisture, so it is possible to reduce the effect of humidity on the polyester resin, suppress changes in shape, and improve storage stability. Expected.

--Processing agent--
The treating agent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include silane-based treating agents and epoxy-based treating agents. These may be used individually by 1 type, and may use 2 or more types together.
When the primary particles of silica are used, the Si—O—Si bond formed by the silane treatment agent is more resistant to heat than the Si—O—C bond formed by the epoxy treatment agent. A silane-based treatment agent is preferred in that it is stable against the surface. Moreover, you may use a processing aid (water, 1 mass % acetic acid aqueous solution, etc.) as needed.

---Silane treatment agent---
The silane-based treatment agent is not particularly limited and can be appropriately selected depending on the intended purpose. silane, dimethyldiethoxysilane, methyldimethoxysilane, methyldiethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, etc.); silane coupling agents (γ-aminopropyltoluethoxysilane, γ-glycidoxysilane, propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, methylvinyldimethoxysilane, etc.); vinyltrichlorosilane, dimethyl Dichlorosilane, methylvinyldichlorosilane, methylphenyldichlorosilane, phenyltrichlorosilane, N,N'-bis(trimethylsilyl)urea, N,O-bis(trimethylsilyl)acetamide, dimethyltrimethylsilylamine, hexamethyldisilazane, cyclic silazane and the like.

ただし、前記式（Ａ）中、Ｒは、アルキル基を示す。 The silane-based treatment agent chemically bonds the primary particles to form secondary aggregates, as described below.
When the silica primary particles are treated with the alkoxysilanes, the silane coupling agent, or the like as the silane-based treatment agent, as shown in the following formula (A), silanol groups bonded to the silica primary particles and the alkoxy groups bonded to the silane-based treatment agent react to form new Si--O--Si bonds through dealcoholization, resulting in secondary aggregation.
When the chlorosilanes are used as the silane-based treatment agent to treat the primary silica particles, the chloro groups of the chlorosilanes and the silanol groups bonded to the primary silica particles undergo a dehydrochlorination reaction to form new Si The silanol groups that bond to --O--Si form new Si--O--Si bonds due to dehydration reaction and undergo secondary aggregation. Further, when the chlorosilanes are used as the silane-based treatment agent to treat the primary silica particles, when water coexists in the system, the chlorosilanes first hydrolyze with water to form silanol groups, The silanol groups and the silanol groups bonded to the primary silica particles form new Si--O--Si bonds due to dehydration reaction, resulting in secondary aggregation.
When the silica primary particles are treated with silazanes as the silane-based treatment agent, the amino groups and the silanol groups bonded to the silica primary particles are deammonified to form new Si—O—Si bonds. secondary agglomeration.

However, in said formula (A), R shows an alkyl group.

--- Epoxy treatment agent ---
The epoxy-based treatment agent is not particularly limited and can be appropriately selected depending on the intended purpose. Bisphenol A novolac type epoxy resins, biphenol type epoxy resins, glycidylamine type epoxy resins, alicyclic epoxy resins and the like can be mentioned.

The epoxy-based treatment agent chemically bonds the primary silica particles to form secondary aggregates, as shown in the following formula (B). When the primary silica particles are treated with the epoxy treatment agent, the silanol groups bonded to the primary silica particles add the oxygen atoms of the epoxy group of the epoxy treatment agent and the carbon atoms bonded to the epoxy groups. As a result, a new Si—O—C bond is formed and secondary aggregation occurs.

The mixing mass ratio of the treating agent and the primary particles (primary particles: treating agent) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100:0.01 to 100:50. . The degree of coalescence tends to increase as the amount of the treating agent increases.

A method of mixing the processing agent and the primary particles is not particularly limited and can be appropriately selected depending on the intended purpose. When mixing, the treatment agent may be mixed after the primary particles are prepared, or the treatment agent may be coexisted when the primary particles are prepared, and prepared by a one-step reaction. You may

The temperature for calcining the treating agent and the primary particles is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100° C. or higher and 2,500° C. or lower. Note that the higher the firing temperature, the higher the degree of coalescence tends to be.

The baking time of the treating agent and the primary particles is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.5 hours or more and 30 hours or less.

The content of the external additive is not particularly limited and can be appropriately selected depending on the intended purpose. It is preferably 1.0 parts by mass or more and 4.0 parts by mass or less. When the content is 0.5 parts by mass or more, the coating rate of the external additive on the base particles is high, so that fluidity, heat-resistant storage stability, durability, and cleanability are excellent. When the content is 4.0 parts by mass or less, the amount of silica liberated on the photoreceptor can be reduced, so that the occurrence of abnormal images can be suppressed.

<<Other Ingredients>>
Other components in the external additive include, for example, primary particles.

The primary particles are not particularly limited and can be appropriately selected depending on the purpose. Examples include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, Tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. inorganic fine particles, organic fine particles, and the like. These may be used individually by 1 type, and may use 2 or more types together.

<Toner base particles>
The toner base particles contain a binder resin and a colorant, preferably a release agent, and optionally other components.

<<Binder Resin>>
The toner base particles contain a binder resin.
Examples of the binder resin include polyester resins.
Examples of the polyester resins include amorphous polyester resins and crystalline polyester resins.
The binder resin preferably contains an amorphous polyester resin, and more preferably further contains a crystalline polyester resin.
As the amorphous polyester resin, a non-linear amorphous polyester resin is preferable.
When the toner base particles contain a component insoluble in tetrahydrofuran (THF), the component insoluble in THF preferably contains a non-linear amorphous polyester or a crystalline polyester.

<<<amorphous polyester resin>>>
The amorphous polyester resin is obtained by using a polyhydric alcohol component and a polycarboxylic acid component such as a polycarboxylic acid, a polycarboxylic acid anhydride, or a polycarboxylic acid ester.
As described above, the amorphous polyester resin is obtained by using a polyhydric alcohol component and a polycarboxylic acid component such as a polycarboxylic acid, a polycarboxylic anhydride, or a polycarboxylic acid ester. A modified polyester resin, for example, a prepolymer described later and a resin obtained by cross-linking and/or elongating the prepolymer, do not belong to the amorphous polyester resin.

-Polyhydric alcohol component-
The polyhydric alcohol component is not particularly limited and can be appropriately selected depending on the intended purpose. ethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane and other alkylene (carbon number: 2-3) oxide (average addition mole number: 1-10) adducts of bisphenol A, ethylene glycol, Propylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, or their alkylene (carbon number: 2-3) oxide (average addition mole number: 1-10) adducts, etc. mentioned. These may be used individually by 1 type, and may use 2 or more types together.

-Polyvalent carboxylic acid component-
The polyvalent carboxylic acid component is not particularly limited and can be appropriately selected depending on the intended purpose. Examples include substituted succinic acid, trimellitic acid, pyromellitic acid, anhydrides of these acids, and alkyl (carbon number: 1-8) esters of these acids.
Examples of the dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, and maleic acid.
Examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecenyl succinic acid and octyl succinic acid. These may be used individually by 1 type, and may use 2 or more types together.

It is preferable that at least a part of the amorphous polyester resin, a prepolymer described below, and a resin obtained by cross-linking and/or elongation reaction of this prepolymer are compatible with each other. By being compatible with each other, low-temperature fixability and high-temperature offset resistance can be improved. For this reason, the polyhydric alcohol component and the polycarboxylic acid component that constitute the amorphous polyester resin and the polyhydric alcohol component and the polycarboxylic acid component that constitute the prepolymer to be described later have similar compositions. preferable.

The molecular structure of the amorphous polyester resin can be confirmed by, for example, NMR measurement in solution or solid, X-ray structure diffraction, GC/MS, LC/MS, IR measurement, and the like.
As a simple detection method, in the infrared absorption spectrum (IR), amorphous polyester that does not have absorption based on δ _CH (out-of-plane bending vibration) of olefin at 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 A method of detecting as a resin can be mentioned.

The molecular weight of the amorphous polyester resin is not particularly limited and can be appropriately selected according to the purpose. It is preferable that the molecular weight (Mn) is 1,000 or more and 4,000 or less, and the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn) is 1.0 or more and 4.0 or less.
When the weight-average molecular weight (Mw) is 2,500 or more and the number-average molecular weight (Mn) is 1,000 or more, the toner has improved heat-resistant storage stability and resistance to stress such as agitation in the developing device.
When the weight-average molecular weight (Mw) is 10,000 or less and the number-average molecular weight (Mn) is 4,000 or less, an increase in viscoelasticity of the toner during melting is suppressed, and low-temperature fixability is improved.

The acid value of the amorphous polyester resin is not particularly limited and can be appropriately selected according to the purpose. preferable.
When the acid value is 1 mgKOH/g or more, the toner tends to be negatively charged, and the affinity between the toner and the paper is improved when the toner is fixed to the paper, so that the low-temperature fixability can be improved.
When the acid value is 50 mgKOH/g or less, it is possible to maintain charging stability, particularly charging stability against environmental fluctuations.

The hydroxyl value of the amorphous polyester resin is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 5 mgKOH/g or more.

The glass transition temperature (Tg) of the amorphous polyester resin is not particularly limited and can be appropriately selected depending on the intended purpose. preferable.
When the Tg is 40° C. or higher, the toner is excellent in heat-resistant storage stability and durability against stress such as agitation in a developing device. If the Tg is 70° C. or less, the viscoelasticity of the toner during melting is suppressed from increasing, and the low-temperature fixability is excellent.

The content of the amorphous polyester resin is not particularly limited and can be appropriately selected according to the intended purpose. Parts or more and 90 mass parts or less are more preferable.
When the content is 50 parts by mass or more, the dispersibility of the pigment and release agent in the toner is improved, and image fogging and distortion can be suppressed. When the content is 95 parts by mass or less, the content of the crystalline polyester does not become too small, and the low-temperature fixability can be maintained. When the content is 60 parts by mass or more and 90 parts by mass or less, it is advantageous in terms of excellent image quality, high stability, and low-temperature fixability.

<<<Crystalline Polyester Resin>>>
Crystalline polyester resins have constitutional units derived from saturated aliphatic diols.
As the saturated aliphatic diol, it is preferable to use an alcohol component containing a linear aliphatic diol having 2 to 8 carbon atoms. As a result, the crystalline polyester resin can be uniformly and finely dispersed inside the toner, thereby preventing the filming of the crystalline polyester resin, improving the stress resistance, and achieving excellent low-temperature fixing of the toner. sex can be achieved.

Since the crystalline polyester resin has high crystallinity, it exhibits a heat melting characteristic that exhibits a rapid viscosity drop near the fixing start temperature. By using the crystalline polyester resin having such properties in the toner, the toner exhibits excellent heat-resistant storage stability due to its crystallinity until just before the melting start temperature, and causes a rapid viscosity drop (sharp meltability) at the melting start temperature to cause fixation. As a result, a toner having both good heat-resistant storage stability and low-temperature fixability can be obtained. Good results are also obtained with respect to the mold release width (the difference between the minimum fixing temperature and the temperature at which hot offset occurs).

The crystalline polyester resin is obtained using a polyhydric alcohol component and a polycarboxylic acid component such as a polycarboxylic acid, a polycarboxylic anhydride, or a polycarboxylic acid ester.
As described above, the crystalline polyester resin is obtained by using a polyhydric alcohol component and a polycarboxylic acid component such as a polycarboxylic acid, a polycarboxylic anhydride, or a polycarboxylic acid ester. However, modified crystalline polyester resins, such as prepolymers described later and resins obtained by cross-linking and/or elongation reaction of the prepolymers, do not belong to the crystalline polyester resins.

-Polyhydric alcohol component-
The polyhydric alcohol component is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include diols and trihydric or higher alcohols.
Examples of the diols include saturated aliphatic diols.
Examples of the saturated aliphatic diols include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated aliphatic diols having 2 to 8 carbon atoms are more preferable.
When the saturated aliphatic diol is linear, the crystallinity of the crystalline polyester resin is high, and the melting point can be increased. When the number of carbon atoms in the main chain portion is 2 or more, the melting temperature is suppressed from becoming high in the case of polycondensation with an aromatic dicarboxylic acid, resulting in excellent low-temperature fixability. When the number of carbon atoms in the main chain portion is 8 or less, practical materials are readily available.

Examples of the saturated aliphatic diol 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, 1,14-eicosandecanediol, and the like. These may be used individually by 1 type, and may use 2 or more types together. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 - hexanediol is preferred.

Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. These may be used individually by 1 type, and may use 2 or more types together.

-Polyvalent carboxylic acid component-
Sebacic acid is preferred as the polyvalent carboxylic acid component. Moreover, if necessary, other divalent carboxylic acids and trivalent or higher carboxylic acids can be used together.
Examples of the divalent carboxylic acid include saturated aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as dibasic acids.
Examples of the saturated aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, speriric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid and the like.
Examples of aromatic dicarboxylic acids such as dibasic acids include phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid and mesaconic acid.
Further, anhydrides thereof and lower alkyl esters thereof are also included.

Examples of the tricarboxylic or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, anhydrides thereof, and and lower alkyl esters.

The polyvalent carboxylic acid component may contain a dicarboxylic acid component having a sulfonic acid group in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid. Furthermore, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid component having a double bond may be contained. These may be used individually by 1 type, and may use 2 or more types together.

The molecular structure of the crystalline polyester resin can be confirmed by, for example, NMR measurement in solution or solid, X-ray structure diffraction, GC/MS, LC/MS, IR measurement, and the like.
As a simple detection method, in the infrared absorption spectrum (IR), amorphous polyester that does not have absorption based on δ _CH (out-of-plane bending vibration) of olefin at 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 A method of detecting as a resin can be mentioned.

The melting point of the crystalline polyester resin is not particularly limited and can be appropriately selected according to the purpose, but is preferably 60°C or higher and lower than 80°C. When the melting point is 60° C. or higher, the crystalline polyester resin can be prevented from melting at a low temperature, and the heat resistant storage stability of the toner can be improved. When the melting point is less than 80° C., low-temperature fixability can be improved.
The melting point can be obtained, for example, from the endothermic peak value of a DSC chart in differential scanning calorimeter (DSC) measurement.

The molecular weight of the crystalline polyester resin is not particularly limited and can be appropriately selected according to the purpose. (Mn) is preferably 1,000 or more and 10,000 or less, and the ratio of weight average molecular weight to number average molecular weight (Mw/Mn) is preferably 1.0 or more and 10 or less.
When the crystalline polyester resin is dissolved in ortho-dichlorobenzene, the molecular weight of the crystalline polyester resin is the soluble portion in ortho-dichlorobenzene.
In GPC measurement, the content of the crystalline polyester having a number average molecular weight (Mn) of 1,000 or less is preferably 10% or less from the viewpoint of low-temperature fixability and heat-resistant storage stability.

The acid value of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the intended purpose. .
When the acid value is 5 mgKOH/g or more, the affinity between the recording medium such as paper and the resin and the low-temperature fixability are excellent. When the acid value is 45 mgKOH/g or less, high temperature offset resistance can be improved.

The hydroxyl value of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the intended purpose. 50 mgKOH/g or less is more preferable.

The content of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the intended purpose. More than 15 mass parts or less is more preferable.
When the content is 2 parts by mass or more, the sharp melt property of the crystalline polyester resin is high and the low-temperature fixability is excellent. When the content is 20 parts by mass or less, excellent heat-resistant storage stability can be obtained, and fogging of images can be suppressed. When the content is 5 parts by mass or more and 15 parts by mass or less, it is advantageous in terms of excellent image quality, high stability, and low-temperature fixability.

<<coloring agent>>
The toner base particles contain a colorant.
The coloring agent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow , yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G, R), tartrazine lake, quinoline yellow lake, anthrazane yellow BGL, isoindolinone yellow, red iron oxide, red lead, red lead, cadmium red, cadmium mercury red, antimony vermillion, permanent Red 4R, Para Red, Phise Red, Parachlororthonitroaniline Red, Risol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkanfast Thrubin B, Brilliant Scarlet G, Risol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine lake B, rhodamine lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue , alkali blue lake, peacock blue lake, victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue (RS, BC), indigo, ultramarine blue, navy blue, anthraquinone blue, fast violet B, methyl violet Lake, cobalt violet, manganese violet, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite g Examples include lean lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and litbon. These may be used individually by 1 type, and may use 2 or more types together.

The content of the coloring agent is not particularly limited and can be appropriately selected according to the intended purpose. Part by mass or less is more preferable.

The colorant can also be used as a masterbatch combined with a resin.
The resin to be used for producing the masterbatch or kneaded together with the masterbatch is not particularly limited and can be appropriately selected depending on the purpose. Polymers of styrene or its substitution; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer , styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-methacrylic acid Butyl copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile -Styrenic copolymers such as indene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, Polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used individually by 1 type, and may use 2 or more types together.

The masterbatch can be obtained by mixing the masterbatch resin and the colorant with high shearing force and kneading the mixture. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, in which an aqueous paste containing colorant water is mixed and kneaded with a resin and an organic solvent, the colorant is transferred to the resin side, and the water and organic solvent components are removed. Since the cake can be used as it is, there is no need to dry it, and it is preferably used. For mixing and kneading, a high-shear dispersing device such as a three-roll mill is preferably used.

<< Release agent >>
The toner base particles preferably contain a release agent.
The release agent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include release agents of waxes and waxes.
Examples of release agents for waxes and waxes include natural waxes and synthetic waxes.

Examples of the natural waxes include plant waxes, animal waxes, mineral waxes, and petroleum waxes.
Examples of the plant waxes include carnauba wax, cotton wax, Japan wax, and rice wax.
Examples of the animal waxes include beeswax and lanolin.
Examples of the mineral waxes include ozokerite and cersin.
Examples of the petroleum wax include paraffin wax, microcrystalline wax, petrolatum wax and the like.
Among these, paraffin wax and microcrystalline wax are preferred.

Synthetic waxes include, for example, synthetic hydrocarbon waxes, waxes containing esters, ketones, ethers, and the like.
Examples of the synthetic hydrocarbon wax include Fischer-Tropsch wax, polyethylene wax, polypropylene wax and the like.
Other synthetic waxes include, for example, fatty acid amide compounds, polyacrylate homopolymers or copolymers, and crystalline polymers having long alkyl groups in side chains.
Examples of the fatty acid amide compound include 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, and chlorinated hydrocarbons.
Examples of the polyacrylate homopolymer or copolymer include poly-n-stearyl methacrylate and poly-n-lauryl methacrylate, which are low-molecular-weight crystalline polymer resins, specifically n-stearyl acrylate. - A copolymer of ethyl methacrylate and the like. These may be used individually by 1 type, and may use 2 or more types together.
Among these, synthetic hydrocarbon waxes are preferred.

Hydrocarbon wax having a melting point of 60° C. or more and less than 95° C. is preferable as the release agent. A synthetic hydrocarbon wax having a melting point of 60° C. or more and less than 95° C. can effectively act as a release agent between the fixing roller and the toner interface. Even without it, the high temperature offset resistance can be improved.
In particular, the synthetic hydrocarbon wax has almost no compatibility with the polyester resin and can function independently of each other. It is preferable because it is less likely to be damaged.

The melting point of the release agent is not particularly limited and can be appropriately selected according to the purpose, but is preferably 60°C or higher and lower than 95°C. When the melting point of the release agent is 60° C. or higher, the melting of the release agent at low temperatures can be suppressed, and the heat-resistant storage stability of the toner can be improved. If the melting point of the release agent is less than 95° C., the release agent melts more when heated during fixing, and sufficient offset properties can be obtained.

The content of the release agent is not particularly limited and can be appropriately selected according to the purpose. 8 parts by mass or less is more preferable.
When the content is 2 parts by mass or more, high-temperature offset resistance and low-temperature fixability during fixing are excellent. When the content is 10 parts by mass or less, heat-resistant storage stability is improved, and fogging of images can be suppressed. When the content is 3 parts by mass or more and 8 parts by mass or less, it is advantageous in terms of improving image quality and fixing stability.

<<Other Ingredients>>
Other components in the toner base particles are not particularly limited and can be appropriately selected depending on the intended purpose. Examples include charge control agents, magnetic materials, cleaning improvers, fluidity improvers, and the like.

-Polymer having a site capable of reacting with an active hydrogen group-containing compound-
The polymer having a site capable of reacting with the active hydrogen group-containing compound (sometimes referred to as "prepolymer") is not particularly limited and can be appropriately selected depending on the purpose. For example, polyol resin , polyacrylic resins, polyester resins, epoxy resins, derivatives thereof, and the like. These may be used individually by 1 type, and may use 2 or more types together.
Among these, polyester resins are preferable from the viewpoint of high fluidity and transparency when melted.

Examples of the site of the prepolymer that can react with the active hydrogen group-containing compound include an isocyanate group, an epoxy group, a carboxyl group, and a functional group represented by —COCl. These may be used individually by 1 type, and may use 2 or more types together.
Among these, an isocyanate group is preferred.

The prepolymer is not particularly limited and can be appropriately selected according to the intended purpose. A polyester resin having an isocyanate group or the like capable of forming a urea bond is preferred from the viewpoint of ensuring good mold releasability and fixability even in the absence of a release oil coating mechanism.

-Compound containing active hydrogen group-
The active hydrogen group-containing compound acts as an elongation agent, a cross-linking agent, etc. when a polymer having a site capable of reacting with the active hydrogen group-containing compound undergoes elongation reaction, cross-linking reaction, etc. in an aqueous medium.

The active hydrogen group is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), amino group, carboxyl group and mercapto group. These may be used individually by 1 type, and may use 2 or more types together.

The active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the purpose. In some cases, amines are preferable because they can be polymerized by extension reaction, cross-linking reaction, or the like with the polyester resin.
The amines are not particularly limited and can be appropriately selected depending on the intended purpose. are mentioned. These may be used individually by 1 type, and may use 2 or more types together.
Among these, diamines and mixtures of diamines and a small amount of trivalent or higher amines are preferred.

The diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aromatic diamines, alicyclic diamines, and aliphatic diamines.
The aromatic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane and the like.
The alicyclic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. be done.
The aliphatic diamine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include ethylenediamine, tetramethylenediamine, hexamethylenediamine and the like.

The trivalent or higher amine is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.

The aminoalcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine, hydroxyethylaniline, and the like.
The aminomercaptan is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aminoethylmercaptan and aminopropylmercaptan.

The amino acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.
The blocked amino group is not particularly limited and can be appropriately selected depending on the intended purpose. Examples include ketimine compounds and oxazolizone compounds.

The polyester resin containing an isocyanate group (hereinafter sometimes referred to as "polyester prepolymer having an isocyanate group") is not particularly limited and can be appropriately selected depending on the purpose. A reaction product of a polyester resin having an active hydrogen group obtained by polycondensation of a carboxylic acid and a polyisocyanate, and the like.

The polyol is not particularly limited and can be appropriately selected depending on the intended purpose. These may be used individually by 1 type, and may use 2 or more types together.
Among these, diols and mixtures of diols and a small amount of trihydric or higher alcohol are preferred.

The diol is not particularly limited and can be appropriately selected depending on the intended purpose. - alkylene glycol such as hexanediol; diol having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc. alicyclic diols; alicyclic diols to which alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide are added; bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenols, ethylene oxide, propylene oxide, Alkylene oxide adducts of bisphenols such as those to which alkylene oxides such as butylene oxide are added; and the like.
The number of carbon atoms in the alkylene glycol is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 2 to 12 carbon atoms.
Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms are preferred. is more preferred.

The trihydric or higher alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. and oxide adducts.
The trihydric or higher aliphatic alcohol is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and sorbitol.
The trihydric or higher polyphenols are not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include trisphenol PA, phenol novolak, cresol novolak and the like.
Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.
When the diol and the trihydric or higher alcohol are mixed and used, the mass ratio of the trihydric or higher alcohol to the diol is not particularly limited and can be appropriately selected depending on the purpose. % or more and 10 mass % or less is preferable, and 0.01 mass % or more and 1 mass % or less is more preferable.

The polycarboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. be done. These may be used individually by 1 type, and may use 2 or more types together.
Among these, dicarboxylic acids and mixtures of dicarboxylic acids and a small amount of trivalent or higher polycarboxylic acids are preferred.

The dicarboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include divalent alkanoic acid, divalent alkenoic acid, and aromatic dicarboxylic acid.
The divalent alkanoic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid and sebacic acid.
The divalent alkenoic acid is not particularly limited and can be appropriately selected depending on the purpose, but divalent alkenoic acid having 4 to 20 carbon atoms is preferable. The divalent alkenoic acid having 4 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include maleic acid and fumaric acid.
The aromatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose, but an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable. The aromatic dicarboxylic acid having 8 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid and naphthalenedicarboxylic acid.

The trivalent or higher carboxylic acid is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include trivalent or higher aromatic carboxylic acids.
The trivalent or higher aromatic carboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, but a trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms is preferable. The trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include trimellitic acid and pyromellitic acid.

As the polycarboxylic acid, any acid anhydride or lower alkyl ester of a dicarboxylic acid, a trivalent or higher carboxylic acid, or a mixture of a dicarboxylic acid and a trivalent or higher carboxylic acid can be used.
The lower alkyl ester is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include methyl ester, ethyl ester and isopropyl ester.
When the dicarboxylic acid and the trivalent or higher carboxylic acid are mixed and used, the mass ratio of the trivalent or higher carboxylic acid to the dicarboxylic acid is not particularly limited, and can be appropriately selected depending on the purpose. , preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.01% by mass or more and 1% by mass or less.

When polycondensing the polyol and the polycarboxylic acid, the equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid is not particularly limited and can be appropriately selected according to the purpose. It is preferably 2 or less, more preferably 1 or more and 1.5 or less, and particularly preferably 1.02 or more and 1.3 or less.

The content of the polyol-derived structural unit in the polyester prepolymer having an isocyanate group is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5% by mass or more and 40% by mass or less. , more preferably 1% by mass or more and 30% by mass or less, and particularly preferably 2% by mass or more and 20% by mass or less.
When the content is 0.5% by mass or more, high-temperature offset resistance is improved, and both heat-resistant storage stability and low-temperature fixability of the toner can be achieved. When the content is 40% by mass or less, the low-temperature fixability can be improved.

The polyisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. , oxime, caprolactam and the like.

The aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate and the like.

The alicyclic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.

The aromatic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. diphenyl, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 4,4'-diisocyanato-3-methyldiphenylmethane, 4,4'-diisocyanato-diphenyl ether and the like.

The araliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include α,α,α',α'-tetramethylxylylene diisocyanate.
The isocyanurates are not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include tris(isocyanatoalkyl)isocyanurate and tris(isocyanatocycloalkyl)isocyanurate. These may be used individually by 1 type, and may use 2 or more types together.

When the polyisocyanate is reacted with a polyester resin having a hydroxyl group, the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is not particularly limited and can be appropriately selected according to the purpose. 1 or more and 5 or less are preferable, 1.2 or more and 4 or less are more preferable, and 1.5 or more and 3 or less are especially preferable. When the equivalent ratio is 1 or more, offset resistance is improved. When the equivalent ratio is 5 or less, low-temperature fixability is improved.

The content of the polyisocyanate-derived structural unit in the polyester prepolymer having an isocyanate group is not particularly limited and can be appropriately selected depending on the purpose. It is preferably 1% by mass or more and 30% by mass or less, and particularly preferably 2% by mass or more and 20% by mass or less. When the content is 0.5% by mass or more, high temperature offset resistance is improved. When the content is 40% by mass or less, low-temperature fixability is improved.

The average number of isocyanate groups per molecule of the polyester prepolymer having an isocyanate group is not particularly limited and can be appropriately selected depending on the purpose. is more preferable, and 1.5 or more and 4 or less is particularly preferable. When the average number is 1 or more, the molecular weight of the urea-modified polyester resin is not too low, and high temperature offset resistance is improved.

The mass ratio of the polyester prepolymer having an isocyanate group to the polyester resin containing 50 mol% or more of the propylene oxide adduct of a bisphenol in the polyhydric alcohol component and having a specific hydroxyl value and acid value is particularly limited. However, it is preferably 5/95 or more and 25/75 or less, more preferably 10/90 or more and 25/75 or less. When the mass ratio is 5/95 or more, high temperature offset resistance is improved. When the mass ratio is 25/75 or less, low-temperature fixability and image glossiness are improved.

- Charge control agent -
The charge control agent is not particularly limited and can be appropriately selected depending on the intended purpose. Alkoxy-based amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus elements or compounds, tungsten elements or compounds, fluorine-based activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. are mentioned. These may be used individually by 1 type, and may use 2 or more types together.

Commercially available products may be appropriately used as the charge control agent. Examples of the commercially available products include nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal. Complex E-84, phenolic condensate E-89 (manufactured by Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd. ), LRA-901, boron complex LR-147 (manufactured by Nihon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other high-grade compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts. Examples include molecular compounds. These may be used individually by 1 type, and may use 2 or more types together.

The content of the charge control agent is not particularly limited and can be appropriately selected according to the intended purpose. 2 parts by mass or more and 5 parts by mass or less is more preferable. When the content is 0.1 parts by mass or more, the effect of the main charge control agent is excellent. When the content is 10 parts by mass or less, the chargeability of the toner is not too high, the effect of the main charge control agent is excellent, and the electrostatic attractive force with the developing roller is maintained. In addition, the fluidity of the developer is improved, and the image density is also excellent.
These charge control agents can be dissolved and dispersed after being melted and kneaded together with the masterbatch and resin. Alternatively, they can be directly added to an organic solvent during dissolution and dispersion, or they can be fixed on the toner surface after toner particle preparation. You may let

－Magnetic materials－
The magnetic material is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include iron powder, magnetite, and ferrite. Among these, white ones are preferable in terms of color tone.

- Cleanability improver -
The cleaning property improver is not particularly limited as long as it is an agent added to the toner to remove the developer remaining on the photoreceptor or the primary transfer medium after transfer, and may be appropriately selected according to the purpose. Examples thereof include zinc stearate, calcium stearate, fatty acid metal salts such as stearic acid, polymethyl methacrylate fine particles, polystyrene fine particles and the like produced by soap-free emulsion polymerization.
The volume-average particle diameter of the polymer fine particles is not particularly limited and can be appropriately selected depending on the intended purpose.

- Fluidity improver -
A fluidity improver is an agent that performs surface treatment to increase hydrophobicity and prevent deterioration of fluidity and charging characteristics even under high humidity conditions. silane coupling agents having alkyl groups, organic titanate-based coupling agents, aluminum-based coupling agents, silicone oils, modified silicone oils, and the like.
The fluidity improver may be surface-treated with silica, titanium oxide, etc. In this case, it is preferable to use hydrophobic silica, hydrophobic titanium oxide, or the like.

[Physical properties of toner]
A hydroxyl value can be measured, for example, using a method based on JIS K0070-1966.
Specifically, first, 0.5 g of a sample is accurately weighed into a 100 mL volumetric flask, and 5 mL of an acetylation reagent is added thereto. After heating in a hot bath at 100±5° C. for 1 to 2 hours, the flask is removed from the hot bath and allowed to cool. Further, water is added and shaken to decompose acetic anhydride. Next, in order to completely decompose the acetic anhydride, the flask is again heated in the hot bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent.
Furthermore, using a potentiometric automatic titrator DL-53 Titrator (manufactured by Mettler Toledo) and an electrode DG113-SC (manufactured by Mettler Toledo), the hydroxyl value was measured at 23 ° C., and analysis software LabX Light Version 1.00 Analyze using .000. A mixed solvent of 120 mL of toluene and 30 mL of ethanol is used for calibration of the apparatus.
At this time, the measurement conditions are as follows.

-Measurement condition-
Stir
Speed [%] 25
Time[s] 15
EQP titration
Titan/Sensor
Titrant CH3ONa
Concentration [mol/L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE(set) [mV] 8.0
dV (min) [mL] 0.03
dV(max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt[s] 1.0
t (min) [s] 2.0
t(max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No.
Tendency None
Termination
at maximum volume [mL] 10.0
at potential no
at slope no
After number EQPs Yes
n=1
comb. Termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for revaluation No

The acid value of the toner is not particularly limited and can be appropriately selected according to the intended purpose. More than 40 mgKOH/g or less is preferable.
When the acid value is 0.5 mgKOH/g or more, the dispersion stability due to base during production is improved, and the production stability is improved. When the acid value is 40 mgKOH/g or less, the elongation reaction and/or the cross-linking reaction proceed sufficiently when the prepolymer is used, and the high temperature offset resistance is improved.

The acid value can be measured using a method based on JIS K0070-1992.
Specifically, first, 0.5 g of a sample (0.3 g of ethyl acetate solubles) is added to 120 mL of toluene and dissolved by stirring at 23° C. for about 10 hours. Next, 30 mL of ethanol is added to obtain a sample solution. If the sample does not dissolve, use a solvent such as dioxane or tetrahydrofuran. Furthermore, using a potentiometric automatic titrator DL-53 Titrator (manufactured by Mettler Toledo) and an electrode DG113-SC (manufactured by Mettler Toledo), the acid value was measured at 23 ° C., and analysis software LabX Light Version 1.00 Analyze using .000. A mixed solvent of 120 mL of toluene and 30 mL of ethanol is used for calibration of the apparatus.
At this time, the measurement conditions are the same as those for the hydroxyl value described above.

The acid value can be measured as described above. Specifically, it is titrated with a pre-standardized 0.1N potassium hydroxide/alcohol solution, and from the titration amount, the acid value [mgKOH/g] = The acid value is calculated by titration amount [mL]×N×56.1 [mg/mL]/sample mass [g] (where N is the factor of 0.1N potassium hydroxide/alcohol solution).

The glass transition temperature (Tg) of the toner is not particularly limited and can be appropriately selected according to the purpose. Above 65°C is preferable, and above 50°C and below 60°C is more preferable.
Thereby, low-temperature fixability, heat-resistant storage stability and high durability can be obtained. When the Tg1st is 45° C. or higher, blocking in the developing machine and filming on the photoreceptor can be suppressed. When the Tg1st is less than 65° C., the low-temperature fixability is improved.

In the DSC measurement of the toner, the glass transition temperature (Tg2nd) calculated in the second temperature rise is preferably 20°C or higher and lower than 40°C. When the Tg2nd is 20° C. or higher, blocking in the developing machine and filming on the photoreceptor can be suppressed. When the Tg2nd is 40° C. or less, low-temperature fixability is improved.

The melting point and glass transition temperature (Tg) can be measured using, for example, a DSC system (differential scanning calorimeter) (“DSC-60” manufactured by Shimadzu Corporation).
Specifically, the melting point and glass transition temperature of the target sample can be measured by the following procedure.
First, about 5.0 mg of a target sample is placed in an aluminum sample container, the sample container is placed on a holder unit, and set in an electric furnace. Next, it is heated from 0° C. to 150° C. at a heating rate of 10° C./min in a nitrogen atmosphere. Then, it is cooled from 150 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min, and further heated to 150 ° C. at a temperature increase rate of 10 ° C./min. ) to measure the DSC curve.
From the obtained DSC curve, using the analysis program "endothermic shoulder temperature" in the DSC-60 system, select the DSC curve at the time of the first heating, and obtain the glass transition temperature of the target sample at the first time of heating. can be done. In addition, the "endothermic shoulder temperature" can be used to select the DSC curve at the time of the second temperature rise, and the glass transition temperature of the target sample at the time of the second temperature rise can be obtained.
Also, from the obtained DSC curve, using the analysis program "endothermic peak temperature" in the DSC-60 system, select the DSC curve at the time of the first heating, and obtain the melting point of the target sample at the first time of heating. can be done. Also, using the "endothermic peak temperature", the DSC curve at the time of the second temperature rise can be selected, and the melting point of the target sample at the time of the second temperature rise can be obtained.

When toner is used as the target sample, the glass transition temperature during the first heating can be defined as Tg1st, and the glass transition temperature during the second heating can be defined as Tg2nd.
The melting point, Tg, of each component at the time of the second heating can be taken as the melting point, Tg, of each target sample.

The volume-average particle diameter of the toner is not particularly limited and can be appropriately selected according to the intended purpose. . When the volume average particle diameter is 3 μm or more, the particles are easily scraped off by the blade in the cleaning portion, and thus the cleaning property is excellent. When the volume average particle diameter is 7 μm or less, the transfer efficiency is improved, resulting in excellent image quality.
The toner preferably contains 1% by number or more and 10% by number or less of a component having a volume average particle diameter of 2 μm or less.
In the toner, the ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less.

The volume-average particle diameter (D4) and number-average particle diameter (Dn) of the toner and their ratio (D4/Dn) are determined using, for example, Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). can be measured by Coulter Multisizer II was used in the present invention. The measurement method is described below.
First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) is added as a dispersant to 100 mL to 150 mL of the electrolytic aqueous solution. Here, the electrolytic aqueous solution is a 1 mass % NaCl aqueous solution prepared using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 mg to 20 mg of the measurement sample is added. The electrolytic aqueous solution in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toner particles or toner are measured by the measuring device using a 100 μm aperture as an aperture. , to calculate the volume distribution and the number distribution. From the obtained distribution, the volume average particle size (D4) and number average particle size (Dn) of the toner can be obtained.

2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 25.40 μm to less than 32.00 μm; 32.00 μm to less than 40.30 μm using 13 channels, targeting particles with a particle size of 2.00 μm to less than 40.30 μm.

(Toner manufacturing method)
The method for producing the toner is not particularly limited and can be appropriately selected according to the intended purpose. Granulation is preferably carried out by dispersing an oil phase containing a colorant in an aqueous medium.
An example of such a method for producing the toner includes a known dissolution suspension method.
Further, as another example of the method for producing the toner, a method produced by an elongation reaction and/or a cross-linking reaction between the active hydrogen group-containing compound and a polymer having a site capable of reacting with the active hydrogen group-containing compound (hereinafter referred to as , sometimes referred to as an "adhesive substrate"), while forming the toner base particles is shown below. In such a method, preparation of an aqueous medium, preparation of an oil phase containing a toner material, emulsification or dispersion of the toner material, removal of an organic solvent, and the like are carried out.

The toner base particles are prepared by dissolving or dispersing at least a binder resin and a release agent in an organic solvent, adding the resulting solution or dispersion to an aqueous phase, and removing the organic solvent from the resulting dispersion. At least the binder resin precursor and the release agent are dissolved or dispersed in an organic solvent, and the resulting solution or dispersion is added to the aqueous phase to obtain the binder resin precursor. is crosslinked or extended, and the organic solvent is removed.

-Preparation of aqueous medium (aqueous phase)-
The aqueous medium can be prepared, for example, by dispersing the resin particles in the aqueous medium. The amount of the resin particles added to the aqueous medium is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 0.5% by mass or more and 10% by mass or less. The resin particles are not particularly limited and can be appropriately selected according to the intended purpose. Examples thereof include surfactants, poorly water-soluble inorganic compound dispersants, and polymeric protective colloids. These may be used individually by 1 type, and may use 2 or more types together. Among these, surfactants are preferred.

The aqueous medium is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include water, water-miscible solvents, and mixtures thereof. These may be used individually by 1 type, and may use 2 or more types together. Among these, water is preferred.
The water-miscible solvent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include alcohols, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones and the like.
Examples of the alcohol include methanol, isopropanol, ethylene glycol, and the like.
Examples of the lower ketones include acetone and methyl ethyl ketone.

-Preparation of oil phase-
The oil phase containing the toner material is prepared by adding the active hydrogen group-containing compound, the polymer having a site capable of reacting with the active hydrogen group-containing compound, the crystalline polyester resin, and the amorphous It can be carried out by dissolving or dispersing a toner material containing the polyester resin, the releasing agent, the hybrid resin, the coloring agent, and the like.

The organic solvent is not particularly limited and can be appropriately selected depending on the intended purpose, but an organic solvent having a boiling point of less than 150° C. is preferable because it is easy to remove.
The organic solvent having a boiling point of less than 150° C. is not particularly limited and can be appropriately selected depending on the intended purpose. , 1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like. These may be used individually by 1 type, and may use 2 or more types together.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferred, and ethyl acetate is more preferred.

-Emulsification or dispersion-
The emulsification or dispersion of the toner material can be performed by dispersing the oil phase containing the toner material in the aqueous medium. Then, when emulsifying or dispersing the toner material, the active hydrogen group-containing compound and the polymer having a site capable of reacting with the active hydrogen group-containing compound undergo an elongation reaction and/or a cross-linking reaction to form an adhesive substrate. Generate.

The adhesive substrate comprises, for example, an oil phase containing a polymer having reactivity with active hydrogen groups, such as a polyester prepolymer having an isocyanate group, together with a compound containing an active hydrogen group such as amines, and an aqueous medium. The oil phase containing the toner material may be emulsified or dispersed in an aqueous medium, and the two may be subjected to an elongation reaction and/or a cross-linking reaction in an aqueous medium. may be produced by emulsifying or dispersing both in an aqueous medium and subjecting them to an elongation reaction and/or crosslinking reaction in an aqueous medium, and after emulsifying or dispersing an oil phase containing a toner material in an aqueous medium, It may be produced by adding a compound having a hydrogen group and subjecting both to an elongation reaction and/or a cross-linking reaction from the particle interface in an aqueous medium. In addition, when the elongation reaction and/or cross-linking reaction is performed from the particle interface, the urea-modified polyester resin is preferentially formed on the surface of the generated toner, and the concentration gradient of the urea-modified polyester resin can be provided in the toner.

The reaction conditions (reaction time, reaction temperature) for producing the adhesive substrate are not particularly limited, and an active hydrogen group-containing compound and a polymer having a site capable of reacting with the active hydrogen group-containing compound can be appropriately selected according to the combination of
The reaction time is not particularly limited and can be appropriately selected according to the purpose, but is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours.
The reaction temperature is not particularly limited and can be appropriately selected depending on the intended purpose.

The method for stably forming a dispersion containing a polymer having a site capable of reacting with an active hydrogen group-containing compound such as a polyester prepolymer having an isocyanate group in the aqueous medium is not particularly limited. For example, an oil phase prepared by dissolving or dispersing a toner material in a solvent is added to an aqueous medium phase, and the method is dispersed by shearing force.

The disperser for the dispersion is not particularly limited and can be appropriately selected according to the purpose. , an ultrasonic disperser, and the like.
Among these, a high-speed shear type disperser is preferable because the particle size of the dispersion (oil droplets) can be controlled to 2 μm to 20 μm.
When the high-speed shear type disperser is used, the conditions such as rotation speed, dispersion time, and dispersion temperature can be appropriately selected according to the purpose.

The rotation speed is not particularly limited and can be appropriately selected according to the purpose, but is preferably 1,000 rpm or more and 30,000 rpm or less, more preferably 5,000 rpm or more and 20,000 rpm or less.
The dispersion time is not particularly limited and can be appropriately selected according to the purpose.
The dispersion temperature is not particularly limited and can be appropriately selected according to the intended purpose. In general, the higher the dispersion temperature, the easier the dispersion.

The amount of the aqueous medium used in emulsifying or dispersing the toner material is not particularly limited and can be appropriately selected according to the intended purpose. 000 parts by mass or less is preferable, and 100 parts by mass or more and 1,000 parts by mass or less is more preferable.
When the amount of the aqueous medium used is 50 parts by mass or more, the toner is excellent in the dispersed state, and toner base particles having a predetermined particle size can be obtained. It is excellent in production cost in the usage-amount of the said aqueous medium being 2,000 mass parts or less.

When emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets, forming a desired shape, and sharpening the particle size distribution. .
The dispersant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include surfactants, poorly water-soluble inorganic compound dispersants, polymeric protective colloids, and the like. These may be used individually by 1 type, and may use 2 or more types together.
Among these, surfactants are preferred.

The surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, and the like. can be used.
The anionic surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters. Among these, those having a fluoroalkyl group are preferred.

A catalyst can be used for the elongation reaction and/or the cross-linking reaction when producing the adhesive substrate.
The catalyst is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include dibutyltin laurate and dioctyltin laurate.

-Removal of organic solvent-
The method for removing the organic solvent from the dispersion such as the emulsified slurry is not particularly limited and can be appropriately selected according to the purpose. A method of evaporating the organic solvent, a method of spraying the dispersion into a dry atmosphere to remove the organic solvent in the oil droplets, and the like can be mentioned.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, and further classified. The classification may be carried out by removing fine particles in a liquid using a cyclone, decanter, centrifugation, or the like, or may be carried out after drying.

The obtained toner base particles may be mixed with particles such as the external additive and the charge control agent. At this time, by applying a mechanical impact force, it is possible to suppress detachment of particles such as the external additive from the surface of the toner base particles.
The method for applying the mechanical impact force is not particularly limited and can be appropriately selected according to the purpose. The mixture is put into the chamber and accelerated to collide the particles with each other or against a suitable collision plate.
The apparatus used in the above method is not particularly limited and can be appropriately selected according to the purpose. apparatus with lowered pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

(Developer)
The developer related to the present invention contains at least the toner described above, and optionally other components such as a carrier that are appropriately selected.
Therefore, it is possible to stably form a high-quality image with excellent transferability, chargeability, and the like. The developer may be a one-component developer or a two-component developer. Two-component developers are preferred because of their improved performance.

When the developer is used as a one-component developer, even if the toner balance is performed, the variation in the particle size of the toner is small, and the filming of the toner on the developing roller and members such as blades that thin the toner layer. There is little fusion of toner to the toner, and good and stable developability and images can be obtained even during long-term agitation in the developing device.

When the developer is used as a two-component developer, even if the toner balance is maintained over a long period of time, the toner particle size fluctuates little, and good and stable developability and images can be obtained even during long-term agitation in the developing device. can get.

When the toner is used in a two-component developer, it may be used by being mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and can be appropriately selected depending on the intended purpose. The following are more preferred.

<Carrier>
The carrier is not particularly limited and can be appropriately selected depending on the intended purpose, but preferably has a core material and a resin layer covering the core material.

-core material-
The material of the core material is not particularly limited and can be appropriately selected according to the purpose. . From the viewpoint of securing image density, a highly magnetized material such as iron powder of 100 emu/g or more and magnetite of 75 emu/g or more and 120 emu/g or less is preferable. In addition, a low magnetization material such as a copper-zinc system having a content of 30 emu/g or more and 80 emu/g or less is preferable because it can reduce the impact of the standing developer on the photoreceptor and is advantageous for high image quality. . These may be used individually by 1 type, and may use 2 or more types together.

The volume average particle diameter of the core material is not particularly limited and can be appropriately selected depending on the intended purpose. When the volume-average particle size is 10 μm or more, the amount of fine powder in the carrier is not too large, and a decrease in magnetization per particle can be suppressed, so scattering of the carrier can also be suppressed. When the volume average particle diameter is 150 μm or less, a decrease in specific surface area can be suppressed, and toner scattering can also be suppressed. Also, in full-color printing with many solid portions, the reproducibility of the solid portions can be maintained.

-Resin layer-
The material of the resin layer is not particularly limited and can be appropriately selected depending on the intended purpose. Vinylide, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene, vinylidene fluoride and fluoro group and fluoroterpolymers such as copolymers of monomers having no , and silicone resins. These may be used individually by 1 type, and may use 2 or more types together.

Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin and epoxy resin.
Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral.
Examples of the polystyrene resin include polystyrene and styrene-acrylic copolymers.
Examples of the polyhalogenated olefin include polyvinyl chloride.
Examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate.

The resin layer may contain conductive powder or the like, if necessary.
The conductive powder is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include metal powder, carbon black, titanium oxide, tin oxide and zinc oxide.
The average particle size of the conductive powder is preferably 1 μm or less. An average particle size of 1 μm or less is advantageous in terms of electrical resistance control.

As a method for forming the resin layer, for example, a silicone resin or the like is dissolved in a solvent to prepare a coating solution, the coating solution is applied to the surface of the core material, dried, and then baked. is mentioned.

The coating method is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include dip coating, spray coating, and brush coating.
The solvent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, butyl cellosolve acetate and the like.
The baking may be performed by an external heating method or an internal heating method. Specific examples include a method using a fixed electric furnace, a fluidized electric furnace, a rotary electric furnace, a burner furnace, and the like, and a method using microwaves.

The content of the resin layer in the carrier is not particularly limited and can be appropriately selected depending on the intended purpose, but is preferably 0.01% by mass or more and 5.0% by mass or less. When the content is 0.01% by mass or more, a uniform resin layer can be formed on the surface of the core material. When the content is 5.0% by mass or less, the resin layer does not become too thick and fusion between carriers is suppressed, so that the uniformity of carriers can be improved.

<Toner storage unit>
A toner containing unit in the present invention means a unit having a function of containing toner and containing toner. Here, examples of the toner storage unit include a toner storage container, a developing device, and a process cartridge.
A toner container is a container containing toner.
A developing device means a device having a means for storing and developing toner.

(process cartridge)
The process cartridge of the present invention is detachably mounted on various image forming apparatuses. It has at least developing means for forming a toner image. Incidentally, the process cartridge of the present invention may further have other means as required.
The developing means includes at least a developer accommodating section that accommodates the developer of the present invention, and a developer carrier that carries and conveys the developer accommodated in the developer accommodating section. The developing means may further have a regulating member or the like for regulating the thickness of the developer to be carried.

To provide high-definition, high-quality images excellent in offset resistance, charging stability, stress resistance, and scumming resistance over a long period of time by mounting the toner storage unit on an image forming apparatus and forming images. It is possible to form high-quality, high-definition images having long-term image stability by making use of the characteristics of the toner that can be used.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention has at least an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and further has other means as necessary.
The image forming method of the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming means, and the developing step can be performed by the developing means. and the other steps can be preferably performed by the other means.

More preferably, the image forming apparatus of the present invention comprises: an electrostatic latent image carrier; electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier; Developing means having toner for developing the electrostatic latent image formed on the electrostatic latent image on a recording medium with toner to form a toner image; It includes transfer means for transferring onto the surface of the recording medium, and fixing means for fixing the toner image transferred onto the surface of the recording medium.
Further, the image forming method of the present invention more preferably comprises an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier; a developing step of developing an electrostatic latent image with toner to form a toner image; a transferring step of transferring the toner image formed on the electrostatic latent image carrier onto a surface of a recording medium; and a fixing step of fixing the toner image transferred to the surface of the medium.

The toner is used in the developing means. Preferably, the toner image is formed by using a developer containing the toner and, if necessary, other components such as a carrier.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier (hereinafter also referred to as "photoreceptor") are not particularly limited, and can be appropriately selected from known ones. , inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine.

<Electrostatic latent image forming means>
The electrostatic latent image forming means is not particularly limited as long as it is means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples include means having at least a charging member for charging the surface of the electrostatic latent image carrier and an exposure member for imagewise exposing the surface of the electrostatic latent image carrier.

<Development means>
The developing means is not particularly limited as long as it is a developing means equipped with toner that develops the electrostatic latent image formed on the electrostatic latent image bearing member to form a visible image. can be selected as appropriate.

<Cleaning Means>
The image forming apparatus of the present invention preferably has cleaning means.
As described above, the toner of the present invention is excellent in cleanability. Therefore, by applying the toner to the image forming apparatus having the cleaning means, the cleanability is improved in the following points.
・By controlling the adhesion force between toner particles, the fluidity of the toner is controlled and the cleanability is improved.
・By controlling the properties of degraded toner, it is possible to maintain excellent cleaning quality even under harsh conditions such as longer life and high temperature and humidity.
・External additive release amount B (% by mass) satisfies the above-described formula (4), so that the external additive is sufficiently released from the toner on the photoreceptor, so that the external additive accumulates at the cleaning blade nip portion. A high cleanability can be achieved by forming a layer (dam layer).

The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. Magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

<Other means>
Examples of the other means include transfer means, fixing means, static elimination means, recycling means, control means, and the like.

Next, one aspect of implementing a method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG.

FIG. 1 shows an example of the image forming apparatus of the present invention. A color image forming apparatus 100A shown in FIG. It comprises an exposure device 30 as exposure means, a developing device 40 as the development means, an intermediate transfer body 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means. .

The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of the arrow by means of three rollers 51 arranged inside and stretched thereon. Some of the three rollers 51 also function as transfer bias rollers capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer body 50 . A cleaning device 90 having a cleaning blade is arranged near the intermediate transfer member 50 . Further, in the vicinity of the intermediate transfer member 50, there is a transfer roller 80 as the transfer means capable of applying a transfer bias for transferring (secondary transfer) the developed image (toner image) onto the transfer paper P as the recording medium. , are arranged to face the intermediate transfer member 50 . Around the intermediate transfer body 50 , a corona charger 52 for imparting electric charge to the toner image on the intermediate transfer body 50 is arranged so that the photoreceptor 10 and the intermediate transfer body 50 are in contact with each other in the rotation direction of the intermediate transfer body 50 . It is arranged between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper P. As shown in FIG.

Around the photosensitive drum 10, a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M and a cyan developing unit 45C are arranged directly facing each other. The black developing unit 45K includes a developer container 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. The developing belt 41 is an endless belt and is rotatably stretched around a plurality of belt rollers, and a part of the developing belt 41 is in contact with the electrostatic latent image carrier 10 .

In the color image forming apparatus 100A shown in FIG. 1, for example, the charging roller 20 uniformly charges the photosensitive drum 10. As shown in FIG. The exposure device 30 imagewise exposes the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51 and further transferred onto the transfer paper P (secondary transfer). As a result, a transfer image is formed on the transfer paper P. FIG. Toner remaining on the photoreceptor 10 is removed by the cleaning device 60 , and the charge on the photoreceptor 10 is temporarily removed by the charge removal lamp 70 .

FIG. 2 shows another example of the image forming apparatus of the present invention. An image forming apparatus 100B shown in FIG.
An endless belt-shaped intermediate transfer member 50 is provided in the center of the copying apparatus main body 150 . The intermediate transfer member 50 is stretched around support rollers 14, 15 and 16 and is rotatable clockwise in FIG. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is arranged near the support roller 15 . A tandem type in which four yellow, cyan, magenta, and black image forming means 120 are arranged facing each other along the conveying direction of the intermediate transfer body 50 stretched between the support rollers 14 and 15. A developing device 120 is arranged. In the vicinity of the tandem type developing device 120, the exposure device 21, which is the exposure member, is arranged. A secondary transfer device 22 is arranged on the side of the intermediate transfer member 50 opposite to the side where the tandem type developing device 120 is arranged. In the secondary transfer device 22, the secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. It is possible. In the vicinity of the secondary transfer device 22, a fixing device 25, which is the fixing means, is arranged. The fixing device 25 includes an endless fixing belt 26 and a pressure roller 27 pressed against the fixing belt 26 .
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper is arranged near the secondary transfer device 22 and the fixing device 25 to form images on both sides of the transfer paper. .

Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the document is set on the contact glass 32 of the scanner 300 by opening the automatic document feeder 400, and then the automatic document feeder is operated. Close 400.

When a start switch (not shown) is pressed, when a document is set on the automatic document feeder 400, the document is conveyed and moved onto the contact glass 32, and then set on the contact glass 32. Immediately after this, the scanner 300 is driven. Then, the first running body 33 and the second running body 34 run. At this time, the light from the light source is irradiated by the first traveling member 33, and the reflected light from the surface of the document is reflected by the mirror of the second traveling member 34, and is received by the reading sensor 36 through the imaging lens 35, resulting in a color image. A document (color image) is read to obtain black, yellow, magenta, and cyan image information.

Then, each image information of black, yellow, magenta, and cyan is supplied to each image forming means 120 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 . forming means). Then, each image forming means forms black, yellow, magenta, and cyan toner images. That is, each image forming means 120 (image forming means for black, image forming means for yellow, image forming means for magenta, and image forming means for cyan) in the tandem type developing device 120 is static as shown in FIG. an electrostatic latent image carrier 10 (a black electrostatic latent image carrier 10K, a yellow electrostatic latent image carrier 10Y, a magenta electrostatic latent image carrier 10M, and a cyan electrostatic latent image carrier 10C); A charging device 20 which is the charging means for uniformly charging the electrostatic latent image carrier 10, and an imagewise exposure of the electrostatic latent image carrier 10 corresponding to each color image based on each color image information (FIG. 3). medium, L), an exposure device for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and an exposure device for forming the electrostatic latent image on each color toner (black toner, yellow toner, magenta toner); , and cyan toner) to form a toner image of each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, A cleaning device 63 and a static eliminator 64 are provided. Each image forming unit 120 can form each monochromatic image (a black image, a yellow image, a magenta image, and a cyan image) based on the respective color image information. The black image, the yellow image, the magenta image and the cyan image thus formed are transferred onto an intermediate transfer member 50 which is rotationally moved by support rollers 14, 15 and 16, respectively. A black image formed on the top, a yellow image formed on the electrostatic latent image carrier 10Y for yellow, a magenta image formed on the electrostatic latent image carrier 10M for magenta, and an electrostatic latent image carrier for cyan. The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200 , one of the paper feed rollers 142 is selectively rotated to feed a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143 . The sheet is separated one by one by a separation roller 145 and sent to a paper feed path 146, conveyed by a conveying roller 147, guided to a paper feed path 148 in the main body 150 of the copying machine, and stopped by being abutted against a registration roller 49. be done. Alternatively, the sheet (recording paper) on the manual feed tray 54 is fed out by rotating the paper feed roller 142 , separated one by one by the separation roller 145 , put into the manual feed path 53 , and stopped by hitting the registration roller 49 . . Although the registration roller 49 is generally grounded and used, it may be used with a bias applied to remove paper dust from the sheet. Then, the registration rollers 49 are rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50 , and a sheet (recording paper) is placed between the intermediate transfer member 50 and the secondary transfer device 22 . , and the secondary transfer device 22 transfers (secondary transfer) the composite color image (color transfer image) onto the sheet (recording paper). By doing so, a color image is transferred and formed on the sheet (recording paper). The intermediate transfer member cleaning device 17 cleans residual toner on the intermediate transfer member 50 after image transfer.

The sheet (recording paper) on which the color image is transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25. In the fixing device 25, the composite color image (color image) is applied by heat and pressure. A transferred image) is fixed on the sheet (recording paper). After that, the sheet (recording paper) is switched by a switching claw 55 and discharged by a discharge roller 56 to be stacked on a paper discharge tray 57 . Alternatively, the sheet is switched by the switching claw 55, reversed by the sheet reversing device 28, and led to the transfer position again. be done.

FIG. 4 shows an example of the process cartridge of the present invention. This process cartridge 110 has a photosensitive drum 10 , a corona charger 52 , a developer 40 , a transfer roller 80 and a cleaning device 90 .

Examples of the present invention will be described below, but the present invention is not limited to these examples. "Parts" means "parts by mass" unless otherwise specified. "%" represents "% by mass" unless otherwise specified.

For each toner, "viscoelasticity of toner G'(50), G'(90)", "BET specific surface area Bt", "coverage Ct", "adhesive force A between deteriorated toner", and "external additive free amount B" were measured.

[Toner Viscoelasticity G′(50), G′(90)]
The obtained toner is molded into pellets with a diameter of 8 mm and a thickness of 1 mm to 2 mm, fixed on a parallel plate with a diameter of 8 mm, stabilized at 40° C., frequency of 1 Hz (6.28 rad/s), distortion The storage elastic modulus at 50°C and 90°C was measured by raising the temperature to 200°C at a rate of 2.0°C/min at an amount of 0.1% (strain amount control mode).
The storage elastic modulus was measured using a dynamic viscoelasticity measuring device (device name: ARES, manufactured by TA Instruments).

[BET specific surface area Bt]
After weighing 1.0 g of the obtained toner in a sample cell, it was vacuum-dried for 24 hours using a pretreatment smartprep (manufactured by Shimadzu Corporation) to remove impurities and moisture from the surface of the toner. Next, after the pretreated toner was set in an automatic specific surface area/pore size distribution measuring device, the relationship between the nitrogen gas adsorption amount and the relative pressure was determined, and the BET specific surface area Bt was determined by the BET multipoint method.
The BET specific surface area Bt was measured using an automatic specific surface area/pore size distribution measuring device (device name: TriStar 3000, manufactured by Shimadzu Corporation).

[Coverage Ct]
The obtained toner was observed using a field emission scanning electron microscope (SEM, device name: MERILIN, manufactured by SII Nanotech) to obtain a secondary electron image of the toner. At this time, a conductive tape was used as the substrate, the toner was made to appear brighter than the substrate, and the contrast was selected and acquired so that there would be no dark areas and white areas in the entire image. Next, the obtained image was read with image editing/processing software (GIMP for Windows, registered trademark), and the portions judged to be external additives by visual inspection were filled with black (R: 0, G: 0, B: 0). rice field. Next, a binarization process was performed to obtain an area ratio A of the portion painted in black with respect to the entire image. Further, the original image read by GIMP for Windows was subjected to binarization processing with a moderate brightness threshold value to obtain the area ratio B of the projected toner image to the entire image. Next, the ratio (A/B) of the external additive area to the projected toner image was obtained. (A/B) was similarly obtained for 50 toners, and the average value was taken as Ct.
The SEM measurement conditions were as follows.
・Acceleration voltage: 3.0 kV
・WD (Working Distance): 10.0mm

[Adhesion A between deteriorated toner]
Using a rocking mill (apparatus name: RM-05S, manufactured by Seiwa Giken Co., Ltd.), 30 g of the developer was stirred and mixed for 60 minutes at a vibration frequency of 700 rpm to deteriorate the developer. Next, using a powder bed compression/tensile property measuring device (device name: Agrobot, manufactured by Hosokawa Micron Corporation), a certain amount of powder was filled in a cylindrical cell divided into upper and lower halves under the following measurement conditions, and 16 kg. / cm ² , the upper cell is lifted, and from the strength when the powder layer is broken, the height (distance) at the time of compression, and the volume, the adhesive force A between the deteriorated toner (compression Adhesive force) was calculated.
-Measurement condition-
・Sample amount: 6g
・Environmental temperature: 23℃
・Humidity: 60%
・Cell inner diameter: 25mm
・Cell temperature: 25°C
・Spring wire diameter: 1.0mm
・Compression speed: 0.1 mm/second ・Compression stress: 16 kg/cm ²
・Compression holding time: 60 seconds ・Tension speed: 0.01 mm/second

[External additive release amount B]
In a 500 mL beaker, 10 g of polyoxyalkylene alkyl ether (trade name: Noigen ET-165, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 300 mL of pure water were placed and dispersed by ultrasonication for 1 hour to obtain dispersion A. After that, Dispersion A was transferred to a 2 L volumetric flask, the volume was increased, and dissolved by applying ultrasonic waves for 1 hour to obtain Dispersion B containing 0.5% polyoxyalkylene alkyl ether.
Next, 50 mL of Dispersion B was poured into a 110 mL screw tube, and 3.75 g of sample toner was added. Dispersion liquid C was obtained by stirring for 30 to 90 minutes until the screw tube became familiar with dispersion liquid B. At this time, the rotation was made as small as possible to prevent foaming. After sufficiently dispersing the toner, an ultrasonic homogenizer (apparatus name: VCX750, manufactured by SONICS & Materials, Inc., 20 kHz, 750 W) was used to make the vibrating part penetrate 2.5 cm into liquid C, and at an output energy of 40%, 1 A liquid D was prepared by applying ultrasonic vibration for a minute.
Liquid D was placed in a 50 mL centrifuge tube and centrifuged at 2,000 rpm for 2 minutes to obtain a supernatant and a precipitate. While rinsing the precipitate with 60 mL of pure water, it was poured into a separate funnel, and the washing water was removed by suction filtration.
The precipitate after filtration was placed in the mini cup again, 60 mL of pure water was poured into the mini cup, and the mixture was stirred five times with a spatula handle. At this time, the mixture was not stirred too vigorously. The washing water was removed by suction filtration again, and the toner remaining on the filter paper was collected and dried in a constant temperature bath at 40° C. for 8 hours. 3 g of the toner obtained after drying was made into a diameter of 3 mm and a thickness of 2 mm by an automatic pressure molding machine (device name: T-BRB-32, manufactured by Maekawa, load: 6.0 t, pressure time: 60 seconds). It was pellet-molded and treated as a sample toner.
The initial sample toner, which was not subjected to the above treatment, was similarly formed into pellets having a diameter of 3 mm and a thickness of 2 mm to prepare sample toner before treatment.
Quantitative analysis was performed using a fluorescent X-ray device (device name: ZSX-100e, manufactured by Rigaku Corporation) to measure the number of silica particles in the pellet-molded sample toner. The calibration curve used was prepared in advance with sample toners containing 0.1 part, 1 part and 1.8 part of silica per 100 parts of toner.
After that, the external additive release amount B (% by mass) from the toner was calculated according to the following formula.
Free amount of external additive B (% by mass)=[Silica content (parts) of sample toner before treatment−Silica content (parts) of sample toner after treatment]/Sample toner before treatment (parts)×100

(Production Example 1-1)
<Synthesis of crystalline polyester resin 1>
Sebacic acid and 1,2-ethylene glycol were charged into a reaction vessel equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple. At this time, the molar ratio of hydroxyl groups to carboxyl groups was set to 0.9, and 500 ppm of titanium tetraisopropoxide was added to all monomers. Next, after reacting at 180° C. for 10 hours, the temperature was raised to 200° C. and reaction was continued for 3 hours. Further, the reaction was carried out under a reduced pressure of 8.3 kPa for 2 hours to obtain a crystalline polyester resin 1. The crystalline polyester resin 1 had a melting point of 73° C. and a weight average molecular weight of 20,000.

(Production Example 1-2)
<Synthesis of crystalline polyester resin 2>
Crystalline polyester resin 2 was obtained in the same manner as in [Synthesis of crystalline polyester resin 1] except that 1,6-hexanediol was used instead of 1,2-ethylene glycol. The crystalline polyester resin 2 had a melting point of 67° C. and a weight average molecular weight of 25,000.

(Production Example 1-3)
<Synthesis of crystalline polyester resin 3>
A crystalline polyester resin 3 was obtained in the same manner as in [Synthesis of crystalline polyester resin 1] except that 1,10-decanediol was used instead of 1,2-ethylene glycol. The crystalline polyester resin 3 had a melting point of 62° C. and a weight average molecular weight of 28,000.

(Production Example 2-1)
<Synthesis of amorphous polyester resin 1>
Into a 5 L four-necked flask equipped with a nitrogen inlet, a dehydrator, a stirrer and a thermocouple were charged 1427.5 g of bisphenol A propylene oxide side 2 molar adduct, 20.2 g of trimethylolpropane, 512.7 g of terephthalic acid, and 119.9 g of adipic acid was added and reacted at 230° C. under normal pressure for 10 hours, and further reacted under reduced pressure of 10 mmHg to 15 mmHg for 5 hours. The mixture was reacted under pressure for 3 hours, and an amorphous polyester resin 1 was obtained.
The amorphous polyester resin 1 had a weight average molecular weight of 10,000, a number average molecular weight of 2,900, a Tg of 57.5°C, and an acid value of 20 mgKOH/g.

(Production Example 3-1)
<Preparation of crystalline polyester resin dispersion liquid 1>
100 parts of the crystalline polyester resin 1 and 200 parts of ethyl acetate were placed in a 2 L metal container, dissolved by heating at 75° C., and then rapidly cooled in an ice water bath at a rate of 27° C./min. 500 mL of glass beads (diameter: 3 mm) were added to this, and pulverization was carried out for 10 hours with a batch-type sand mill apparatus (manufactured by Campehapio) to obtain a crystalline polyester resin dispersion liquid 1.

(Production Example 3-2)
<Preparation of crystalline polyester resin dispersion liquid 2>
A crystalline polyester resin dispersion 2 was obtained in the same manner as in Production Example 3-1, except that the crystalline polyester resin 1 was replaced with the crystalline polyester resin 2 in Production Example 3-1.

(Production Example 3-3)
<Preparation of Crystalline Polyester Resin Dispersion 3>
A crystalline polyester resin dispersion 3 was obtained in the same manner as in Production Example 3-1, except that the crystalline polyester resin 1 was replaced with the crystalline polyester resin 3 in Production Example 3-1.

(Example 1)
-Preparation of oil phase-
--Synthesis of prepolymer--
682 parts of bisphenol A ethylene oxide 2 mol adduct, 81 parts of bisphenol A propylene oxide 2 mol adduct, 283 parts of terephthalic acid and 22 parts of trimellitic anhydride were placed in a reaction vessel equipped with a condenser, stirrer and nitrogen inlet tube. , and 2 parts of dibutyltin oxide were added, reacted at 230° C. under normal pressure for 8 hours, and further reacted under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate polyester 1]. [Intermediate polyester 1] had a weight average molecular weight of 9,500, a number average molecular weight of 2,100, a Tg of 55°C, an acid value of 0.5 mgKOH/g, and a hydroxyl value of 51 mgKOH/g.
Next, 410 parts of [intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen inlet tube, and reacted at 100° C. for 5 hours [ Prepolymer 1] was obtained. The free isocyanate mass % of [Prepolymer 1] was 1.53%.

--Synthesis of ketimine--
170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stirring rod and a thermometer, and reacted at 50° C. for 5 hours to obtain [Ketimine Compound 1]. [Ketimine compound 1] had an amine value of 418 mgKOH/g.

--Synthesis of masterbatch (MB)--
1,200 parts of water, 540 parts of carbon black (trade name: Printex 35, manufactured by Dexsa, DBP oil absorption: 42 mL/100 mg, pH: 9.5), and 1,200 parts of amorphous polyester resin were added, and Henschel Mixed with a mixer (manufactured by Nippon Coke Industry Co., Ltd.). After kneading the mixture at 150° C. for 30 minutes using two rolls, the mixture was rolled, cooled, and pulverized with a pulperizer to obtain [Masterbatch 1].

--Preparation of wax dispersion--
50 parts of paraffin wax (trade name: HNP-9, manufactured by Nippon Seiro Co., Ltd., hydrocarbon wax, melting point: 75 ° C., SP value: 8.0%) as release agent 1 in a container equipped with a stirring rod and a thermometer. 8) and 450 parts of ethyl acetate were added, the temperature was raised to 80° C. while stirring, and the temperature was maintained at 80° C. for 5 hours. After that, it was cooled to 30° C. in 1 hour, and using a bead mill (trade name: Ultra Visco Mill, manufactured by Aimex), the liquid feeding speed was 1 kg/hour, the disk peripheral speed was 6 m/second, and the diameter was 0.5 mm. 80% by volume of zirconia beads were filled, and dispersion was performed under the condition of 3 passes to obtain [wax dispersion liquid 1].

[Wax dispersion 1] 500 parts, [Prepolymer 1] 200 parts, [Crystalline polyester resin dispersion 2] 500 parts, [Amorphous polyester resin 1] 750 parts, [Masterbatch 1] 100 parts, and curing 2 parts of [ketimine compound 1] as an agent were placed in a container and mixed at 5,000 rpm for 60 minutes with a device name: TK Homomixer (manufactured by Primix Co., Ltd.) to obtain [oil phase 1].

-Synthesis of organic fine particle emulsion (fine particle dispersion)-
Into a reaction vessel equipped with a stirring rod and a thermometer, 683 parts of water, sodium salt of methacrylic acid ethylene oxide adduct sulfate ester (trade name: Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.), 138 parts of styrene, methacrylic 138 parts of acid and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to give a white emulsion. This was heated to raise the temperature in the system to 75° C. and reacted for 5 hours. Further, 30 parts of a 1% aqueous solution of ammonium persulfate was added, and the mixture was aged at 75° C. for 5 hours to give an aqueous dispersion of a vinyl resin (copolymer of sodium salt of styrene-methacrylic acid-ethylene oxide methacrylic acid adduct sulfate ester) [fine particles]. Dispersion 1] was obtained. [Fine particle dispersion liquid 1] was measured with an apparatus name: LA-920 (manufactured by HORIBA), and the volume average particle diameter was 0.14 μm. A portion of [fine particle dispersion liquid 1] was dried to isolate the resin component.

-Preparation of aqueous phase-
990 parts of water, 83 parts of [fine particle dispersion 1], 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (trade name: Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.) 37 parts, and 90 parts of ethyl acetate are mixed. Stir to obtain a milky white liquid. This was designated as [aqueous phase 1].

－Emulsification/Desolvation－
1,200 parts of [aqueous phase 1] was added to the container containing the [oil phase 1], and mixed with a TK homomixer at a rotation speed of 13,000 rpm for 20 minutes to obtain [emulsified slurry 1].
[Emulsified slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30° C. for 8 hours, and then aged at 45° C. for 4 hours to obtain [dispersed slurry 1].

－Washing・Heat treatment・Drying－
After filtering 100 parts of [dispersion slurry 1] under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 100 parts of a 10% sodium hydroxide aqueous solution was added to the filter cake of (1), mixed with a TK homomixer (rotation speed: 12,000 rpm for 30 minutes), and filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): 300 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (12,000 rpm for 10 minutes), and then filtered.
The above operations (1) to (4) were performed twice in total.
(5): Add 100 parts of ion-exchanged water to the filter cake of (4), mix with a TK homomixer at 12,000 rpm for 10 minutes, heat-treat at 50°C for 4 hours, and then filter. Cake 1] was obtained.
(6): [Filtration cake 1] was dried at 45° C. for 48 hours in a circulating dryer and sieved with a mesh having an opening of 75 μm to obtain [Toner base particles 1].

Using a Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd.), 100 parts of toner base particles, 0.8 parts of non-spherical hydrophobic silica having an average particle diameter of 140 nm, and A toner of Example 1 was obtained by mixing 1.0 part of hydrophobic titanium oxide of 20 nm.

(Example 2)
A toner of Example 2 was obtained in the same manner as in Example 1, except that the non-spherical hydrophobic silica was changed from 0.8 parts to 1.2 parts.

(Example 3)
In Example 1, except that [Crystalline polyester resin dispersion 1] was changed to [Crystalline polyester resin dispersion 2], and the non-spherical hydrophobic silica was changed from 0.8 parts to 1.5 parts. Toner of Example 3 was obtained in the same manner as above.

(Example 4)
In Example 1, except that [Crystalline polyester resin dispersion 1] was changed to [Crystalline polyester resin dispersion 3], and the non-spherical hydrophobic silica was changed from 0.8 parts to 1.5 parts. Toner of Example 4 was obtained in the same manner as above.

(Example 5)
Except that in Example 1, the non-spherical hydrophobic silica having an average particle size of 140 nm was changed to the non-spherical hydrophobic silica having an average particle size of 130 nm, and the non-spherical hydrophobic silica was changed from 0.8 parts to 1.5 parts. A toner of Example 5 was obtained in the same manner as in Example 1.

(Example 6)
A toner of Example 6 was obtained in the same manner as in Example 1, except that the non-spherical hydrophobic silica was changed from 0.8 parts to 2.0 parts.

(Comparative example 1)
Except that in Example 1, the non-spherical hydrophobic silica with an average particle size of 140 nm was replaced with the non-spherical hydrophobic silica with an average particle size of 120 nm, and the non-spherical hydrophobic silica was changed from 0.8 parts to 1.5 parts. obtained a toner of Comparative Example 1 in the same manner as in Example 1.

(Comparative example 2)
A toner of Comparative Example 2 was obtained in the same manner as in Example 1 except that the non-spherical hydrophobic silica having an average particle diameter of 140 nm in Example 4 was replaced with spherical hydrophobic silica having an average particle diameter of 140 nm.

(Comparative Example 3)
A toner of Comparative Example 3 was obtained in the same manner as in Example 1, except that in Example 4, the non-spherical hydrophobic silica having an average particle diameter of 140 nm was replaced with spherical hydrophobic silica having an average particle diameter of 60 nm.

(Comparative Example 4)
In Example 1, the non-spherical hydrophobic silica having an average particle diameter of 140 nm was replaced with spherical hydrophobic silica having an average particle diameter of 60 nm, and the hydrophobic silica was changed from 0.8 parts to 1.5 parts. A toner of Comparative Example 4 was obtained in the same manner as in Example 1.

(Comparative Example 5)
The toner of Comparative Example 5 was prepared in the same manner as in Example 1 except that the heat treatment time was changed to 2 hours and the non-spherical hydrophobic silica was changed from 0.8 parts to 1.5 parts. Obtained.

(Comparative Example 6)
The toner of Comparative Example 6 was prepared in the same manner as in Example 1 except that the heat treatment time was changed to 15 minutes and the non-spherical hydrophobic silica was changed from 0.8 parts to 1.5 parts. Obtained.

(Comparative Example 7)
In Example 1, [Crystalline polyester resin dispersion 1] was changed from 500 parts to 0 parts, [Amorphous polyester resin 1] was changed from 750 parts to 1,250 parts, and non-spherical hydrophobic silica was changed to 0.5 parts. A toner of Comparative Example 7 was obtained in the same manner as in Example 1, except that the amount was changed from 8 parts to 1.5 parts.

-Production of developer-
In the developer, the [carrier] used in combination with the toner is a silicone resin solution ⁽ SR2411 , Toray Dow Corning Silicone Co., Ltd.) 200 parts and carbon black (Ketjen Black EC-DJ600, manufactured by Lion Akzo Co., Ltd.) 3 parts are dispersed in toluene. After covering the surface of the core material, it was obtained by firing in an electric furnace at 300° C. for 2 hours. The carrier used had a relatively sharp particle size distribution and an average particle size of 30 μm to 60 μm.

0.9 part of each toner and 12 parts of carrier were mixed and stirred to prepare a developer.

Next, the developers including the toners of Examples 1 to 6 and Comparative Examples 1 to 7 were evaluated for "low temperature fixability", "heat resistant storage stability", "durability" and "cleanability". The results are shown in Tables 1 and 2 below.

<Low temperature fixability>
Paper (trade name: Type 6200 paper, manufactured by Ricoh Co., Ltd.) was modified from a copying machine (device name: Imagio MF2200, manufactured by Ricoh Co., Ltd.) using a Teflon (registered trademark) roller as a fixing roller. (manufactured) was tested for duplication. The cold offset temperature (minimum fixing temperature) was obtained by changing the fixing temperature, and the "low temperature fixability" was evaluated based on the following evaluation criteria.
The evaluation conditions for the lowest fixing temperature were paper feeding linear velocity: 120 mm/sec to 150 mm/sec, surface pressure: 1.2 kgf/cm ² , and nip width: 3 mm.
-Evaluation criteria-
◎: less than 115 ° C. ○: 115 ° C. or more and less than 125 ° C. △: 125 ° C. or more and less than 135 ° C. ×: 135 ° C. or more

<Heat-resistant storage stability>
10 g of toner was filled in a 50 mL glass container, tapped sufficiently until there was no change in the apparent density of the obtained toner powder, and the container was capped. After leaving it in a constant temperature bath at 50°C for 24 hours, it was cooled to 24°C, the penetration was measured by a penetration test (JIS K2235-1991), and the "heat resistant storage stability" was evaluated based on the following evaluation criteria. .
It should be noted that the higher the penetration, the better the heat-resistant storage stability. Those having a penetration of less than 15 mm are highly likely to cause problems in use.
-Evaluation criteria-
◎: Penetration of 25 mm or more ○: Penetration of 20 mm or more and less than 25 mm △: Penetration of 15 mm or more and less than 20 mm ×: Penetration of less than 15 mm

<Durability>
Including toner in a digital full-color multifunction machine (device name: Imagio MP C5000, manufactured by Ricoh Co., Ltd.) in a low-temperature, low-humidity environment (10°C, 15% RH) and a high-temperature, high-humidity environment (27°C, 80% RH). After each developer was filled, 500,000 sheets of an image having an image area ratio of 5% were copied. Next, after printing the entire solid image, the image was visually observed, and "durability" was evaluated based on the following evaluation criteria.
-Evaluation criteria-
A: No streak-like color loss O: Slight streak-like color loss (less than 5% of the solid image area)
Δ: Thin streak-like color loss occurs (5% or more and less than 10% of the solid image area)
x: A large amount of streak-like light color loss occurs (at least 10% of the solid image area), or streak-like dark color loss occurs.

<Cleanability>
A digital full-color multifunction machine (device name: Imagio MP C5000, manufactured by Ricoh Co., Ltd.) was charged with each developer containing toner, and then a solid image of A4 size with a toner adhesion amount of 1.0 mg/cm ² was copied. The time of copying 1,000 sheets is defined as the initial stage, and the time of copying 100,000 sheets is defined as elapsed time. Next, in each case, after the toner remaining on the photoreceptor that passed through the cleaning means was transferred to white paper with a scotch tape (manufactured by Sumitomo 3M), a reflection densitometer (apparatus name: RD514, manufactured by Gretag Macbeth) was used. was used to measure the reflection density, and the "cleanability" was evaluated based on the following evaluation criteria.
-Evaluation criteria-
◎: Difference in reflection density between initial stage and aging is less than 0.01 ○: Difference in reflection density between initial stage and aging is 0.01 or more and less than 0.025 △: Difference in reflection density between initial stage and aging is 0.025 or more and less than 0.05 ×: The difference in reflection density between the initial stage and the elapsed time is 0.05 or more.

As shown in Tables 1 and 2, the toners of Examples 1 to 6 were excellent in all of low-temperature fixability, heat-resistant storage stability, durability, and cleanability. In addition, toner viscoelasticity G'(50), G'(90), BET specific surface area Bt, coverage Ct, silica shape, silica particle size, adhesive force A between deteriorated toner, and external additive release amount B are controlled. As a result, low-temperature fixability, heat-resistant storage stability, durability, and cleanability could be improved.

On the other hand, since the toner of Comparative Example 1 is non-spherical hydrophobic silica having an average particle diameter of 120 nm, the heat-resistant storage stability, durability, and cleanability are deteriorated.
Since the toner of Comparative Example 2 was spherical hydrophobic silica, the heat-resistant storage stability, durability, and cleanability were deteriorated.
Since the toner of Comparative Example 3 is spherical hydrophobic silica having an average particle diameter of 60 nm, the heat-resistant storage stability, durability, and cleanability were deteriorated.
The toner of Comparative Example 4 is spherical hydrophobic silica having an average particle diameter of 60 nm, has an adhesive force A between deteriorated toners of 302 gf, and has a free external additive amount B of 0.77% by mass. , durability, and cleanability decreased.
In the toner of Comparative Example 5, the formula (2) (Bt−0.03×Ct) of the condition (b) was 1.68, the adhesive force A between deteriorated toners was 310 gf, and the external additive release amount B was Since it was 0.68% by mass, heat-resistant storage stability, durability, and cleanability were lowered.
The toner of Comparative Example 6 had a formula (2) (Bt−0.03×Ct) of condition (b) of 3.20, an adhesive force A between deteriorated toners of 405 gf, and an external additive release amount B of Since it was 0.41% by mass, heat-resistant storage stability, durability, and cleanability were lowered.
In the toner of Comparative Example 7, the formula (1) (G'(50)/G'(90)) of the condition (a) is 5.0×10 ² and the formula (2) (Bt −0.03×Ct) was 2.50, and the free amount B of the external additive was 0.52% by mass, so that the low-temperature fixability, durability, and cleanability were lowered.

Embodiments of the present invention are, for example, as follows.
<1> A toner containing toner base particles containing a binder resin and a colorant, and an external additive,
The toner is characterized by satisfying the following conditions (a), (b) and (c).
(a) The storage elastic modulus G'(50) of the toner at 50.degree. C. and the storage elastic modulus G'(90) of the toner at 90.degree.
G'(50)/G'(90)≧6.0×10 ² Expression (1)
(b) The BET specific surface area Bt (m ² /g) of the toner and the coverage Ct (%) at which the toner base particles are coated with the external additive satisfy formula (2).
Bt−0.03×Ct≦1.60 Expression (2)
(c) the external additive contains at least coalesced particles;
The coalesced particles are non-spherical secondary particles formed by coalescing primary particles,
A number average secondary particle diameter of the coalescent particles is 130 nm or more.
<2> 3.75 g of the toner was dispersed in 50 mL of a 0.5% by mass polyoxyalkylene alkyl ether dispersion in a 110 mL vial, and ultrasonic vibration was applied at 20 kHz and 750 watts for 1 minute. The toner according to <1> above, wherein the external additive free amount B (% by mass) satisfies the formula (4).
B>0.8 Expression (4)
<3> an electrostatic latent image carrier;
electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
a developing means provided with toner for developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a toner image;
a transfer means for transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
fixing means for fixing the toner image transferred onto the surface of the recording medium;
The image forming apparatus is characterized in that the toner is the toner according to any one of <1> to <2>.
<4> The image forming apparatus according to <3>, further comprising cleaning means for removing toner remaining on the electrostatic latent image carrier.
<5> an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier;
a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a toner image;
a transfer step of transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
a fixing step of fixing the toner image transferred onto the surface of the recording medium;
An image forming method, wherein the toner is the toner according to any one of <1> to <2>.
<6> an electrostatic latent image carrier;
Developing means comprising a toner for developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner according to any one of <1> to <2> to form a toner image; ,
A process cartridge characterized by comprising:

The toner according to any one of <1> to <2>, the image forming apparatus according to any one of <3> to <4>, the image forming method according to <5>, and <6>. According to the process cartridge described in 1., it is possible to solve the above-mentioned conventional problems and achieve the object of the present invention.

JP 2014-178528 A

Claims (5)

A toner comprising toner base particles containing a binder resin and a colorant, and an external additive,
The following conditions (a), (b), and (c) are satisfied, the external additive contains non-spherical silica, and the content of the non-spherical silica is 1.5 parts per 100 parts of the toner base particles. 5 parts to 2.
3.75 g of the toner is dispersed in 50 mL of a 0.5% by weight polyoxyalkylene alkyl ether dispersion in a 110 mL vial and subjected to ultrasonic vibration at 20 kHz and 750 watts for 1 minute. A toner, wherein the free amount B (% by mass) of all silica satisfies formula (4).
(a) The storage elastic modulus G'(50) of the toner at 50.degree. C. and the storage elastic modulus G'(90) of the toner at 90.degree.
G'(50)/G'(90)≧6.0×10 ² Expression (1)
(b) BET specific surface area Bt (m ² /g) of the toner and coverage Ct (%) at which the toner base particles are covered with all the external additives satisfy formula (2).
Bt−0.03×Ct≦1.60 Expression (2)
(c) the external additive contains at least coalesced particles;
The coalescent particles are non-spherical silica,
The coalesced particles are non-spherical secondary particles formed by coalescing primary particles,
A number average secondary particle diameter of the coalescent particles is 130 nm or more.
B>0.8 Expression (4) an electrostatic latent image carrier;
electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
a developing means provided with toner for developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a toner image;
a transfer means for transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
fixing means for fixing the toner image transferred onto the surface of the recording medium;
An image forming apparatus, wherein the toner is the toner according to claim 1 . 3. An image forming apparatus according to claim 2, further comprising cleaning means for removing toner remaining on said electrostatic latent image carrier. an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier;
a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with toner to form a toner image;
a transfer step of transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium;
a fixing step of fixing the toner image transferred onto the surface of the recording medium;
An image forming method, wherein the toner is the toner according to claim 1 . an electrostatic latent image carrier;
Developing means provided with toner for developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner according to claim 1 to form a toner image;
A process cartridge characterized by comprising:

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