JP4219872B2 - Toner, manufacturing method thereof, image forming method and apparatus, and process cartridge - Google Patents

Description

  The present invention relates to a toner technology used for electrophotography, electrostatic recording, electrostatic printing, and the like, and more specifically, a method for producing a toner having a stable particle size and a sharp particle size distribution, a toner obtained thereby, and The present invention relates to an image forming method and an image forming apparatus using the obtained toner.

In the developing process, a developer used in electrophotography, electrostatic recording, electrostatic printing, and the like is once attached to an image carrier such as a photoreceptor on which an electrostatic charge image is formed, and then transferred to a transfer process. After being transferred from the photosensitive member to a transfer medium such as transfer paper, the toner is fixed on the paper surface in a fixing step.
As a developer for developing an electrostatic charge image formed on the latent image holding surface of such a photoreceptor, a two-component developer composed of a carrier and a toner, and a magnetic toner or a non-magnetic toner that does not require a carrier These are known as dry toners. Conventionally, as dry toners used for such electrophotography, electrostatic recording, electrostatic printing, etc., a toner binder such as a styrene resin or a polyester resin is melt-kneaded together with a colorant and then finely pulverized. Is used.

  In order to obtain a high-quality and high-quality image, a method of reducing the particle diameter of the toner is generally adopted to improve the image quality and the like. However, when a production method based on a normal kneading and pulverizing method is used, the resulting toner particle shape is indefinite, and when used as a two-component developer, the toner particles are formed with a carrier in the developing portion of the image forming apparatus. When used as a one-component developer due to agitation stress, the toner is further pulverized due to stress due to contact between the developing roller and the toner supply roller, layer thickness regulating blade, friction charging blade, etc. Phenomena in which image quality deteriorates due to generation of ultrafine particles or a fluidizing agent embedded in the toner surface have occurred.

  In addition, the toner of irregular particle shape has poor fluidity as a powder, and it is necessary to increase fluidization, or the filling rate into the toner bottle is low, which is an obstacle to downsizing the apparatus. It has become. Therefore, the current situation is that the merit of reducing the particle size is not utilized. Further, in the production of toner particles by the pulverization method, there is a problem that there is a limit to the particle size obtained, and it is impossible to cope with further reduction in the particle size.

  Various spherical toner manufacturing methods have been devised in order to compensate for the disadvantages caused by such irregular particle shapes. For example, there are a polymer suspension method and an emulsification method as methods generally used. In the case of such a production method, an oil phase obtained by dissolving or dispersing a toner, such as a colorant such as a resin or a pigment, or a wax, in an organic solvent is emulsified into a toner size droplet in a water phase by mechanical emulsification means. Process is included.

In the case of a toner produced by a suspension method or an emulsification method, the emulsion is made into fine particles by shearing in the process of generating droplets of toner size, that is, in the emulsion retention region in the emulsification mechanism provided in the toner production apparatus. Droplets are generated while repeating the equilibrium reaction of coalescence of fine particles, and the particle size and particle size distribution are temporarily determined when the balance between fine particle and coalescence is balanced.
In this case, as a major factor that determines the particle size and particle size distribution of the toner, the shearing energy given to the raw material supplied by the emulsifier, the atomization by shearing, and the coalescence equilibrium reaction of the fine particles are performed. The total shear energy per unit flow rate of raw material feed (abbreviated as unit total energy) given during the period is considered.

  However, depending on the formulation of the toner composition, the equilibrium reaction rate of the microparticulation by shearing and the coalescence of the microparticles is different, so it cannot be controlled to make the conditions suitable, and the particle size (volume average particle size) in the emulsification process There has been a problem that a difference occurs in the particle size distribution. In order to deal with this, as a post-process, a method such as fine powder cutting, coarse powder cutting, etc. is adopted, and the method of adjusting the volume average particle size and particle size distribution of the toner to match the target value is used. However, there are problems such as complicated and time-consuming and worsening yield.

The following methods have been proposed as methods for improving the particle size and particle size distribution of toner particles.
For example, an agitation tank provided with an agitating blade in which the upper and lower adjacent stirring blades are arranged in advance in the rotational direction at an intersecting angle of less than 90 degrees with respect to the lower stirring blade. There has been proposed a method for producing a toner that has a sharp particle size distribution and no performance variation between the toner particles (see, for example, Patent Document 1).

  In addition, the particle size distribution after polymerization is sharpened by controlling the blade tip speed during the polymerization reaction, the depth from the surface of the stirring blade provided at the top, and the power required for stirring during the polymerization to a specific range. A method for producing a polymerization toner is proposed (for example, see Patent Document 2).

Alternatively, by setting the relationship between the liquid volume V (m ³ ) present in the granulation container and the use power P (kW) of the stirring device in the toner granulation step to be 15 <P / V <100, There has been proposed a method capable of efficiently producing a toner having a sharp particle size distribution (see, for example, Patent Document 3).

  However, all of the above methods are designed to control the shape and arrangement of the stirring blades and the stirring power so that the toner particles have a target value. In the present invention, which will be described later, one of the granulation mechanisms. It is hard to say that granulation takes into account the unifying behavior, which is regarded as an important factor. In other words, it is not controlled in consideration of the equilibrium reaction between the formation of fine particles by the addition of the shearing force and the coalescence of the fine particles. Therefore, it is not sufficient as a method for producing a toner having a more stable particle size and a sharp particle size distribution.

JP 2000-321821 A JP 2001-125309 A Japanese Patent Laid-Open No. 2002-91071

  The present invention has been made in view of the above prior art, and an easy manufacturing method of a toner having a stable particle size (volume average particle size) and a sharp particle size distribution, and a latent image obtained by the manufacturing method. It is an object of the present invention to provide a toner that can faithfully develop the toner and reproduce a high-quality full-color image, and an image forming method, a process cartridge, and an image forming apparatus using the toner.

  As a result of intensive studies, the present inventors have successfully controlled both the shearing conditions for finely divided particles and the coalescing conditions for the fine particles in the emulsification process of the oil phase and the aqueous phase when a toner having a small particle size is produced by an emulsification method. As a result, it has been found that a toner having a stable particle size and a sharp particle size distribution is obtained, and the above-mentioned problems are solved, and the present invention has been achieved. Hereinafter, the present invention will be specifically described.

That is, the present invention relates to a method for producing a toner for emulsifying an oil phase and an aqueous phase by an emulsification mechanism having an emulsifier equipped with at least a stirring blade and an emulsion liquid circulation path, which is used in an emulsification step of toner production. Because
The oil phase is a lysate or dispersion made of an organic phase containing at least a resin and a resin precursor,
And the stirring Reynolds number (stirring Re) calculated | required by following formula (1) at the time of stirring of the emulsion liquid with the said stirring blade is 3000 <= stirring Re <= 15000 ,
When the reference inner diameter of the main pipe constituting the emulsion circulation path is 1, the rate of change of the pipe inner diameter is in the range of 0.8 to 1.4,
In the toner production method, the flow energy loss (Eloss) of the emulsified liquid generated in the range of the inner diameter change of the main pipe is 20 to 82 J / kg .
Stirring Re = ρnd ² / μ (1)
(Wherein, ρ: density of emulsion (kg / m ³ ), n: rotation speed of stirring blade (rps), d: blade diameter (m) of stirring blade, μ: viscosity of emulsion (Pa · s) Is shown.)

Here, it is preferable that the resin and the resin precursor is the molecular weight of different polymers.

Here, it is preferable that the resin precursor is an isocyanate group-containing polyester prepolymer, and the resin is an unmodified polyester resin.

  Here, it is further preferable that the aqueous phase is an aqueous medium containing a solid fine particle dispersant.

In any of the above toner production methods, it is preferable that the shear energy (E) obtained by the following formula (2) generated by the rotation of the stirring blade is 400 or more and 2000 or less.
E = (n × 60) ³ × d ⁵ / Q (2)
(Where n is the rotational speed (rps) of the stirring blade, d is the blade diameter (m) of the stirring blade, and Q is the flow rate value (L / min) in the emulsion circulation path.)

Furthermore, in any one of the above toner production methods, the unit per raw material feed unit flow rate obtained by the following formula (3) received by the emulsion from the emulsifier while the emulsion circulates and stays in the emulsion circulation path. The total energy (e) is preferably 1 × 10 ⁶ or more and 5 × 10 ⁶ or less.
e = [(n × 60) ³ × d ⁵ × Q] / F ² (3)
(Where n is the number of revolutions of the stirring blade (rps), d is the blade diameter of the stirring blade (m), Q is the flow rate value in the emulsion circulation path (L / min), and F is the raw material feed rate (kg / min).)

  Furthermore, in any one of the above-described toner production methods, it is preferable that the flow rate (v) of the emulsion in the emulsion circulation path is 0.5 to 3 m / sec.

  In any one of the above toner production methods, it is preferable that an inner diameter (D) of a main pipe constituting the emulsion circulation path is 0.02 to 0.10 m.

In any one of the above-described toner manufacturing methods, the flow Reynolds number (flow Re) of the emulsion in the straight pipe portion of the main pipe constituting the emulsion circulation path, which is obtained by the following formula (4), is 500 or more. It is preferable that it is 4000 or less.
Flow Re = ρvD / μ (4)
(Where, ρ: density of emulsion (kg / m ³ ), v: flow rate of emulsion (m / s), D: inner diameter of main pipe (m), μ: viscosity of emulsion (Pa · s) Is shown.)

  Furthermore, in any of the above-described toner production methods, it is preferable that the surface roughness (Ra) of the inner surface of the main pipe constituting the emulsion circulation path satisfies Ra <0.8.

  Furthermore, in any one of the above-described toner production methods, it is preferable that the number of right-angle elbows is four or less when the main pipe constituting the emulsion circulation path has right-angle elbows. Here, when the main pipe has four or less right-angle elbows, the ratio (S) / (D) of the straight pipe section length (S) to the main pipe inner diameter (D) between the right-angle elbows is 10 The above is preferable.

  Furthermore, in the toner manufacturing method described in the headline, it is preferable that the shape of the emulsion circulation path is configured such that the emulsion is discharged to the next step without passing through the right angle elbow.

  In the toner manufacturing method described in the introduction, it is preferable that the main pipe diameter of the emulsion circulation path is configured so that the emulsion is discharged to the next step without passing through the different diameter pipe.

The present invention relates to a toner obtained by any one of the above-described toner manufacturing methods, wherein the toner has a volume average particle diameter (Dv) of 3 to 10 μm. .
Here, the value obtained by dividing the volume average particle diameter (Dv) of the toner by the number average particle diameter (Dn) is preferably 1.05 to 1.25.

  Furthermore, the present invention provides an image forming method in which an electrostatic latent image formed on a photoreceptor is developed with toner, and the toner development is transferred and fixed on a recording medium. The present invention relates to an image forming method.

  The present invention also provides a process cartridge that integrally supports at least one means selected from a photoconductor, a charging means, a developing means containing developer, and a cleaning means, and is detachable from the image forming apparatus main body. The toner used in the developer is a toner described in any of the above, and relates to a process cartridge.

  According to another aspect of the present invention, there is provided an image forming apparatus including a process cartridge which is detachably attached to the main body of the image forming apparatus, wherein the process cartridge is the process cartridge described above. The present invention relates to an image forming apparatus.

  According to the production method of the present invention, the structural conditions of the emulsification mechanism part constituting the granulation apparatus used in the emulsification step of toner production, the stirring conditions of the emulsion liquid, the circulation conditions of the emulsion liquid, and the discharge of the emulsion liquid from the emulsion mechanism part The conditions are specified, and both the shearing conditions for fine particle formation and the coalescence conditions for fine particles are suitably controlled, and the respective conditions are balanced to achieve a target stable particle size (volume average particle size). In addition, a toner having a sharp particle size distribution can be produced efficiently and easily. According to the production method of the present invention, a toner capable of faithfully developing a latent image and reproducing a high-quality full-color image can be obtained, and image formation with which a high-quality and high-quality image can be obtained by using such a toner. A method and a process cartridge and an image forming apparatus can be provided.

As described above, in the present invention, in the emulsification process in which the oil phase containing the toner composition and the aqueous phase are mixed and stirred, the equilibrium reaction between the formation of fine particles by applying shear force and the coalescence of the fine particles is repeated. Focusing on the process in which toner-sized droplets are generated and controlling both the shearing conditions for fine particle formation and the coalescence conditions for fine particles, it has a stable volume average particle size and a sharp particle size distribution. This makes it possible to efficiently and easily manufacture the toner having the toner.
Preferred embodiments of the present invention will be described below with reference to the drawings.

FIG. 1 is a schematic configuration diagram showing an example of a granulating apparatus used in an emulsification step of toner production according to the present invention. In FIG. 1, the emulsification mechanism unit 4 includes an emulsifier (PLHM) 2 and an emulsion liquid circulation path 3. That is, in the emulsification mechanism unit 4, the oil phase and the aqueous phase supplied from the supply tanks 17, 18, and 19 are mixed, and may be expressed as fine particles by applying a shear force (hereinafter referred to as fine particles by shearing). And droplets of toner size are generated while repeating the equilibrium reaction of coalescence of the fine particles. Here, the oil phase, lysates made of an organic phase containing at least a resin and a resin precursor or a dispersion (e.g., a resin, a colorant, lysates and releasing agent are dissolved in an organic solvent or dispersed dispersion) The aqueous phase is an aqueous medium containing a solid fine particle dispersant. For convenience of explanation, FIG. 1 shows a structure in which a right angle elbow 11 is provided in the main piping of the emulsion circulation path 3.

The oil phase in the present invention can contain a resin and a resin precursor , but in order to obtain good balance characteristics, for example, it is suitable to use two or more polymers having different molecular weights as the resin and the resin precursor. Yes.
As such a polymer, a polyester resin having good reproducibility of full-color images is particularly suitable. The polyester resin is composed of at least a modified polyester resin modified with a urea bond and an unmodified polyester resin not modified with a urea bond and having two or more resins having different molecular weights. This is preferable because a balance between storage stability and hot offset resistance can be achieved. The resin precursor is preferably an isocyanate group-containing polyester prepolymer, and the resin is preferably an unmodified polyester resin. Details of these resins will be described later. As the toner composition in the present invention, a resin used for a normal toner such as a styrene acrylic resin or a polyol resin can be used.
Hereinafter, a case where a modified polyester resin and an unmodified polyester resin are used as the toner composition in the production method of the present invention will be described as an example.

  In the embodiment of FIG. 1, an example is shown in which the resin raw material for the toner composition is divided and supplied to the A oil phase 7 and the B oil phase 8. Here, the A oil phase 7 is a resin (for example, an unmodified polyester resin), a colorant, a release agent dissolved in an organic solvent or a dispersed dispersion liquid (for example, a pre-form of the B oil phase 8). The B oil phase 8 is a solution in which a prepolymer having an isocyanate bond is dissolved in an organic solvent. The aqueous phase 9 is an aqueous medium containing a solid fine particle dispersant (for example, a solid resin fine particle dispersant). Details of each oil phase composition and water phase will be described later.

The A oil phase 7 and the B oil phase 8 are pre-stirred with an STM (static mixer) 10 before being mixed with the aqueous phase 9. The liquid after the pre-stirring is called an oil phase.
The oil phase mixed in STM 10 and the aqueous phase 9 are continuously fed to the emulsification mechanism unit 4 in a predetermined amount, and the emulsifier (PLHM) 2 provided in the path of the emulsion liquid circulation path 3 Emulsification is performed by receiving shearing force while stirring. Here, PLHM is an abbreviation for pipeline homomixer. The emulsified liquid is circulated and retained in the emulsified liquid circulation path 3 to form droplets having a suitable toner size. The emulsified liquid is discharged to the transfer pipe 5 and sent to the converging tank 6.
As described above, in order to obtain a toner having a stable fine particle size and a sharp particle size distribution, it is necessary to control the equilibrium reaction between the formation of fine particles by shearing and the coalescence of the fine particles. In other words, it is required that both the conditions for atomization and the conditions for coalescence are suitably defined. Hereinafter, these will be described in order.

First, as factors that are largely involved in the micronization, the stirring Reynolds number (stirring Re) at the time of emulsification, the shear energy (E), and the unit total energy per unit flow rate of raw material feed per unit flow (e ). The emulsification involves a polymerization reaction between the modified polyester resin (for example, a polyester prepolymer having an isocyanate group) and an extender (for example, an active hydrogen compound that undergoes an addition reaction with the prepolymer). The number of right-angle elbows should be considered when the main pipe constituting the emulsion circulation path 3 has a right-angle elbow.
Each condition provision and its basis are explained below.

[Fine particles]
The stirring Reynolds number (stirring Re) by the stirring blade of the emulsifier is obtained by the following formula (1), and the stirring Re during stirring of the emulsion is 3000 ≦ stirring Re ≦ 15000, more preferably 5000 ≦ stirring Re ≦ 15000. If this is the case, the entire fluid is disrupted macroscopically, and turbulent diffusion occurs.
Stirring Re = ρnd ² / μ (1)
(Wherein ρ is the density of the emulsion (kg / m ³ ), n is the number of revolutions of the stirring blade (rps), d is the blade diameter (m) of the stirring blade, and μ is the viscosity of the emulsion (Pa · s). Is shown.)

  That is, if the stirring Re is 3000 or more, more preferably 5000 or more, the molecules in the fluid are moved violently to increase the collision frequency, and shearing and coalescence reactions during emulsification become active, and coalescence after shearing. This is an advantageous state. Further, in the turbulent diffusion state, even high energy is transferred and transferred instantaneously, which is advantageous for fine particle formation and particle distribution control. On the other hand, if the stirring Re is less than 3000, turbulent diffusion does not occur, the collision frequency between molecules decreases, and the particles cannot be coalesced, which is disadvantageous for generating a sharp particle size distribution. End up. On the other hand, if it exceeds 15000, the emulsification system may be broken.

Further, when a shearing force by an emulsifier is applied to the oil phase and the water phase, oil droplets are generated in the water phase, and a so-called O / W type emulsified state is obtained. When generating this O / W type emulsified state, the shear energy (E) obtained by the following formula (2) generated by the stirring blade is in the range of 400 or more and 2000 or less, more preferably 700 or more and 1500 or less. , Oil droplets having a target particle diameter are generated.
E = (n × 60) ³ × d ⁵ / Q (2)
(In the formula, n represents the rotation speed (rps) of the stirring blade, d represents the blade diameter (m) of the stirring blade, and Q represents the flow rate value (L / min) in the emulsification circuit).

  On the contrary, if the shear energy (E) is less than 400, a poor emulsification state occurs due to insufficient shearing force, whereas if it exceeds 2000, the emulsification becomes unstable due to excessive shearing. As a result, an emulsified disintegration state is generated, resulting in coalescence of coarse particles. That is, the shear energy (E) greatly contributes to particle design, so-called particle control.

Furthermore, the unit total energy (e) per raw material feed unit flow rate obtained by the following formula (3) received by the emulsion from the emulsifier 2 while the emulsion is circulating and staying in the emulsion circulation path 3 is 1 X 10 ⁶ or more and 5 x 10 ⁶ or less are preferable, and 3 x 10 ⁶ or more and 5 x 10 ⁶ or less are more preferable.
e = [(n × 60) ³ × d ⁵ × Q] / F ² (3)
(Where, n is the rotation speed (rps) of the stirring blade, d is the blade diameter (m) of the stirring blade, Q is the flow rate value (L / min) in the emulsification circuit, and F is the feed rate of raw material (kg / min) )

Specifically, assuming that the shear energy given from the emulsifier 2 is P (= (n × 60) ³ × d ⁵ ), P per unit liquid flow rate of the raw material to be supplied by one shearing by the emulsifier. / F energy is added. The number of times that the circulated / retained emulsion is subjected to shearing until it is discharged from the emulsion circulation path 3 to the transfer pipe 5 is defined as Q / F. Therefore, the unit total energy (e) added before being discharged is And the above equation (3).
When the unit total energy (e) is defined within the above range, an appropriate shear and coalescence equilibrium reaction proceeds, which is advantageous in forming a sharp particle size distribution. On the contrary, if it is less than 1 × 10 ⁶ , it becomes a shearing advantageous state, and if it exceeds 5 × 10 ⁶ , it becomes a united advantageous state, so that it is difficult to form a sharp particle size distribution.

  Next, factors that are largely involved in the coalescence of the fine particles in the equilibrium reaction include the flow rate of the emulsion in the emulsion circulation path 3 (v), the inner diameter of the main pipe constituting the emulsion circulation path 3 (D), The flow Reynolds number (flow Re) of the emulsion in the straight pipe portion of the main pipe, the surface roughness (Ra) of the inner surface of the main pipe constituting the emulsion circulation path 3, the number of right-angle elbows 11, and between the right-angle elbows The ratio (S) / (D) of the straight pipe section length (S) and the main pipe inner diameter (D), the change rate of the pipe inner diameter, the flow energy loss (Eloss) of the emulsion, and the like. Each regulation condition is as follows.

[Unification]
The flow rate (v) of the emulsion in the emulsion circulation path 3 is in the range of 0.5 to 3 m / sec, preferably 1 to 2 m / sec.
The inner diameter (D) of the main pipe constituting the emulsion circulation path 3 is in the range of 0.02 to 0.10 m, preferably 0.02 to 0.05 m.

The flow Reynolds number (flow Re) obtained by the following formula (4) of the emulsion in the straight pipe portion of the main pipe constituting the emulsion circulation path 3 is 500 or more and 4000 or less, preferably 1000 or more and 2500 or less. Range.
Flow Re = ρvD / μ (4)
(Where, ρ: density of emulsion (kg / m ³ ), v: flow rate of emulsion (m / s), D: inner diameter of main pipe (m), μ: viscosity of emulsion (Pa · s) Is shown.)

  The surface roughness (Ra) of the inner surface of the main pipe constituting the emulsion circulation path 3 is in the range of Ra <0.8, preferably Ra <0.5.

In the case where the main pipe constituting the emulsion circulation path 3 has a right angle elbow, the number of right angle elbows is 4 or less, and preferably 0.
Further, when the main pipe has four or less right angle elbows, the ratio (S) / (D) of the pipe straight pipe length (S) to the main pipe inner diameter (D) between the right angle elbows is 10 or more. It is necessary to be.

When the reference inner diameter of the main pipe constituting the emulsified liquid circulation path 3 is 1, the change rate of the inner diameter of the pipe needs to be in the range of 0.8 to 1.4 . The range is more preferably 0.8 to 1.2.
The flow energy loss (Eloss) of the emulsified liquid generated in the range of the inner diameter change of the main pipe is 20 to 100 J / kg, preferably 20 to 82 J / kg, more preferably 20 to 50 J / kg.

When the above conditions are satisfied, a flow state suitable for unity is obtained, which is advantageous in sharpening the particle size distribution. On the contrary, if it is below the above-mentioned specified range, it will be close to a stationary state, will not be united, but will tend to agglomerate leading to particle coarsening. On the other hand, if it is above the specified range, the coalescence is suppressed and the existence probability of the fine particles remains high, and the next shear is applied, so that the target particle size cannot be achieved.
Furthermore, by defining the emulsion circulation path 3 as described above, local turbulence during circulation and retention, that is, a turbulent state can be suppressed, and the equilibrium reaction is not hindered. In addition, it is considered that the load fluctuation due to the viscosity change of the processing liquid, the suppression of cavitation during circulation, and the pressure fluctuation are hardly affected. On the other hand, if it exceeds the above-mentioned regulation, there will be many opportunities to receive local disturbance after shearing, and the collision frequency will be different, making it difficult to make the target particle size. The main pipe of the emulsion circulation path 3 is preferably one having no different diameter pipe.

[Conditions for discharging the emulsion from the emulsion circulation path]
Furthermore, in order to obtain toner mother particles having a stable particle size and a sharp particle size distribution, it is necessary to define conditions for discharging the emulsion from the emulsion circulation path 3 to the next step, that is, the transfer pipe 5. . That is, when the emulsified liquid is discharged from the emulsified liquid circulation path 3, the main pipe has a circulation path shape that can be discharged to the transfer pipe 5 without going through the right angle elbow, and can be discharged without going through the different diameter pipe. It is necessary to have a diameter.

  The balance between shear and coalescence was achieved by defining the conditions for discharging the emulsion whose particle size was temporarily determined when the balance between shearing and coalescence was achieved from the emulsion circulation path 3 as described above. While maintaining the equilibrium state, the process proceeds to the next step, and a toner having a target particle size and a sharp particle size distribution can be obtained.

[Toner particle size]
Next, when the above-described polyester resin is used as the toner composition, the volume average particle diameter (Dv) of the toner (dry toner) is set in the range of 3 to 10 μm, and the volume average particle diameter (Dv) is the number average particle. When the value divided by the diameter (Dn) is in the range of 1.05 to 1.25, it is excellent in all of heat-resistant storage, low-temperature fixability, and hot offset resistance, especially when used in full-color copying machines. In addition, the two-component developer is excellent in glossiness of the image, and even if the toner balance for a long time is performed, the fluctuation of the toner particle diameter in the developer is reduced, and the long-time stirring in the developing device is also good. And stable developability can be obtained.

  In addition, when used as a one-component developer, the toner particle diameter variation is reduced even when the balance of the toner is performed, and there is no filming of the toner on the developing roller, so that the toner is thinned. There is no fusion of toner to a member such as a blade. For this reason, good and stable developability and images can be obtained even in the long-term use of the developing device with stirring of the toner.

  In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there. Further, when the volume average particle diameter is smaller than the range of the present invention, in the case of the two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is reduced, or the one-component development is performed. When used as an agent, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are easily generated. These problems can be solved by using the resin described later as the toner composition in the present invention and applying the above production method.

  In addition, it is considered that the smaller the toner particle size, the less likely it is affected by load fluctuations due to changes in the viscosity of the processing liquid, suppression of cavitation during circulation, and pressure fluctuations. On the contrary, when the particle diameter of the toner is larger than the range of the present invention, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, In many cases, the variation of the particle size becomes large. It was also found that the same applies when Dv / Dn is greater than 1.25. Further, when Dv / Dn is smaller than 1.05, there are preferable aspects from the viewpoint of stabilizing the behavior of the toner and equalizing the charge amount, but the toner cannot be sufficiently charged or the cleaning property is deteriorated. I found that there was a case.

(Particle size distribution measurement method)
The particle size (volume average particle size) and particle size distribution of the toner were measured as follows.
A Coulter Multisizer III (manufactured by Coulter) was used as a measuring device, a personal computer (manufactured by IBM) was connected, and data analysis was performed using dedicated analysis software (manufactured by Coulter). The Kd value was set using standard particles of 10 μm, and the aperture current was set at an automatic setting. As the electrolytic solution, a 1% NaCl aqueous solution prepared using primary sodium chloride was used. In addition, ISOTON-II (manufactured by Coulter Scientific Japan) can be used.

  As a specific measurement method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample is suspended is dispersed for about 1 to 3 minutes using an ultrasonic disperser, and the volume and number distribution of the toner is measured by 50,000 counts and the number of toners of 2 μm or more using a 100 μm aperture tube. And calculated. Then, the volume-based volume average particle diameter (Dv) obtained from the volume distribution according to the present invention and the number-based number average particle diameter (Dn) obtained from the number distribution were obtained. The closer the Dv / Dn is to 1.0, the sharper the particle size distribution.

Next, the toner composition contained in the oil phase, that is, the organic phase in the present invention will be described.
The organic phase may contain a resin and a resin precursor , but as described above, two or more polymers having different molecular weights suitable for obtaining a good balance property as the resin and the resin precursor, particularly a full-color image. An example of a polyester resin (combination of a modified polyester resin and an unmodified polyester resin) that is suitable for reproducing the above will be described below.

(Modified polyester resin)
The polyester resin contains a functional group derived from a monomer unit of acid and alcohol used as a raw material component and a bonding group other than an ester bond, or has a different structure in which a polyester resin is bonded by a covalent bond or an ionic bond. A resin containing a resin component is defined as a modified polyester resin.

  Examples of the modified polyester resin include a resin obtained by modifying the terminal of the polyester resin with a bond other than an ester bond. Specifically, it is reacted with an acid group at the terminal of the polyester resin or a compound that reacts with a hydroxyl group (for example, an isocyanate compound), a functional group such as an isocyanate group is introduced, and this functional group is reacted with an active hydrogen compound. In this way, a resin whose end is modified or subjected to an extension reaction can be mentioned. Examples of such a modified polyester resin include urea-modified polyester and urethane-modified polyester.

  In addition, a reactive group such as a double bond is introduced into the polyester main chain, radical polymerization is introduced therefrom, a carbon-carbon bond graft component is introduced into the side chain, or double bonds are bridged together. (For example, styrene-modified, acrylic-modified polyester, etc.).

 Further, a resin component having a different structure is copolymerized in the main chain of the polyester resin or reacted with a carboxyl group or a hydroxyl group at the terminal, for example, a silicone resin having a carboxyl group, a hydroxyl group, an epoxy group, or a mercapto group at the terminal And those copolymerized with (eg, silicone-modified polyester). Hereinafter, typical modified polyester resins will be described in detail.

(Urea-modified polyester resin)
Examples of the polyester modified with a urea bond (urea-modified polyester resin) (i) include a reaction product of a polyester prepolymer (A) having an isocyanate group and an amine (B). Polyester prepolymer (A) having an isocyanate group is a polycondensate of polyol (1) and polycarboxylic acid (2), and a polyester having an active hydrogen group and further reacted with polyisocyanate (3). Etc.

  Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred.

  Diol (1-1) includes alkylene glycol (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (Eg, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (eg, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenol (For example, bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxides of the above alicyclic diols (for example, ethylene oxide, propylene oxide, Chi alkylene oxide, etc.) adducts, alkylene oxide of the bisphenols (e.g., ethylene oxide, propylene oxide, and the like butylene oxide, etc.) adducts.

  Among the above, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

  As the trivalent or higher polyol (1-2), a trihydric or higher polyhydric aliphatic alcohol (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); Phenols (for example, trisphenol PA, phenol novolak, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or higher polyphenols and the like.

  Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred.

  Examples of the dicarboxylic acid (2-1) include alkylene dicarboxylic acids (for example, succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (for example, maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (for example, phthalic acid) , Isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

  Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (for example, trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (For example, methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) and the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (eg, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate); alicyclic polyisocyanates (eg, isophorone diisocyanate, cyclohexylmethane diisocyanate). Aromatic diisocyanates (eg, tolylene diisocyanate, diphenylmethane diisocyanate, etc.); aromatic aliphatic diisocyanates (eg, α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; Blocked with a phenol derivative, oxime, caprolactam or the like; and combinations of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5/1, the low-temperature fixability deteriorates. When the equivalent ratio [NCO] / [OH] is less than 1/1, the urea content in the modified polyester becomes low, and the hot offset resistance deteriorates.

  The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

 The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned.

  Examples of the diamine (B1) include aromatic diamines (eg, phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane); alicyclic diamines (eg, 4,4′-diamino-3,3′dimethyldicyclohexylmethane). , Diamine cyclohexane, isophorone diamine, etc.); and aliphatic diamines (eg, ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.

  Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.

  Examples of the B1-B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1-B5 amines and ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). . Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester resin (i) can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (for example, diethylamine, dibutylamine, butylamine, laurylamine, and the like), and those obtained by blocking them (for example, ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. Here, in the formula of the amino group [NHx], x is 1 or 2, and the main body is 2. When [NCO] / [NHx] exceeds 2/1 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates.

  In the present invention, the urethane bond may be contained together with the urea bond in the polyester modified with the urea bond, that is, the urea-modified polyester resin (i). The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

  The urea-modified polyester resin (i) in the present invention is produced by a one-shot method or a prepolymer method. The weight average molecular weight of the urea-modified polyester resin (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester is not particularly limited when the unmodified unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. . The number average molecular weight is usually 20000 or less, preferably 1000 to 10000, more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

(Unmodified polyester resin)
In the present invention, not only the urea-modified polyester resin (i) but also a polyester (abbreviated as an unmodified polyester resin) (ii) not modified with a urea bond as a toner binder component together with (i). Can be made. By using (ii) in combination, low-temperature fixability and glossiness when used in a full-color device are improved.

  Examples of (ii) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (i) above, and preferred ones are also the same as (i). The unmodified polyester resin (ii) is not limited to a so-called unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance.

  Accordingly, the polyester component (i) and (ii) preferably have similar compositions. When (ii) is contained, the weight ratio of (i) and (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. If the weight ratio of (i) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (ii) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 30000, low-temperature fixability will deteriorate. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (ii) is usually 1-30, preferably 5-20. By having an acid value, it tends to be negatively charged.

  In the present invention, the glass transition point (Tg) of the resin as the toner binder is usually 50 to 70 ° C., preferably 55 to 65 ° C. If it is less than 50 ° C., the heat resistant storage stability of the toner is deteriorated, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the urea-modified polyester resin (i), the dry toner of the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with known polyester-based toners.

As the storage elastic modulus of the resin as the toner binder, the temperature (TG ′) at which 10000 dyne / cm ² (10 ³ N / m ² ) is obtained at a measurement frequency of 20 Hz is usually 100 ° C. or higher, preferably 110 to 200 ° C. . If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner binder, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or lower, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, from the viewpoint of achieving both low temperature fixability and hot offset resistance, TG ′ is preferably higher than Tη. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

(Coloring agent)
As the colorant used as the toner composition in the present invention, all known dyes and pigments can be used.
Examples of such a colorant 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, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Pang Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faise Red, Parachlor Ortho Nitro Aniline red, resource Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol 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, claw Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridiane, emerald green, pigment green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anne Traquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used.
The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the whole toner composition.

  The colorant used as the toner composition in the present invention can also be used in the form of a master batch that is previously combined with a resin. In addition to the modified and unmodified polyester resins mentioned above, the styrene copolymer (for example, polystyrene, poly p-chlorostyrene, polyvinyltoluene) can be used as the binder resin to be kneaded with the masterbatch or the masterbatch. Styrene and substituted polymers thereof such as styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene -Methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethylketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene- Maleic acid copolymer, styrene-maleic acid ester copolymer, etc.), polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, Polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, etc. Or they can be mixed and used.

  The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under high shearing force. In producing this master batch, an organic solvent can be used to enhance the interaction between the colorant and the resin. Further, a method of mixing and kneading an aqueous colorant paste containing water together with a resin and an organic solvent, transferring the colorant to the resin side, and removing water and organic solvent components, a so-called flushing method is also preferably used. This method is advantageous because the wet cake of the colorant can be used as it is and does not need to be dried. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
Wax may be included as a release agent used as a toner composition in the present invention.
As the wax used in the present invention, known waxes can be used, for example, polyolefin wax (for example, polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (for example, paraffin wax, sasol wax, etc.); Examples thereof include carbonyl group-containing waxes. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (for example, carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1 , 18-octadecanediol distearate, etc.); polyalkanol esters (eg, tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (eg, ethylenediamine dibehenyl amide); polyalkylamides (eg, Trimellitic acid tristearyl amide, etc.); and dialkyl ketones (eg, distearyl ketone, etc.). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.

  The melting point of the wax used as the toner composition in the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps (5 to 1000 mPa · s), more preferably 10 to 100 cps (10 to 100 mPa · s) as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps (1000 mPa · s) have a poor effect of improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

(Charge control agent)
Furthermore, a charge control agent may be contained as necessary in the toner composition of the present invention. As the charge control agent, all known ones can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts ( Examples include fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, metal salts of salicylic acid and salicylic acid derivatives.

  Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP 1415 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary Copy charge PSY VP 2038 of ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex 147 (manufactured by Nippon Carlit), copper phthalocyanine, perylene, quinacrid And azo pigments, and other polymer compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

  The amount of the charge control agent used is determined primarily by the type of resin for the binder, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents and release agents can be melt-kneaded together with the masterbatch and the resin, and of course, they may be added when dissolved and dispersed in an organic solvent.

(Drop formation in aqueous media)
Next, formation of droplets by emulsification in an aqueous medium will be described.
As described above, in the emulsification step in the toner production of the present invention, the oil phase and the aqueous phase are continuously mixed and emulsified by the emulsification mechanism unit including the emulsifier equipped with the stirring blade and the emulsion liquid circulation path. Toner size droplets are formed and granulated. After granulation, the emulsion is sent to the next step, and toner base particles are formed through steps such as solvent removal, filtration, washing, and drying.
As described above, the aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (eg, methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (eg, methyl cellosolve), lower ketones (eg, acetone, methyl ethyl ketone, etc.), and the like. It is done.

  The resin as the toner binder used for the toner composition is preferably a polyester resin as described above, but can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, the polyisocyanate (3) is reacted with this at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group.

In the production method of the present invention, as shown in FIG. 1, an oil phase (A in which an unmodified polyester resin, a colorant, and a release agent are dissolved in an organic solvent or a dispersed dispersion and an extender are mixed. A solution prepared by dissolving an oil phase 7) and a prepolymer (A) having an isocyanate bond in an organic solvent is divided into a separately prepared oil phase (B oil phase 8) and polymerized in the emulsifying mechanism 4 It is emulsified continuously as the reaction proceeds.
By this polymerization reaction, a polyester (modified polyester resin) (i) modified with a urea bond is obtained. The polyester (unmodified polyester resin) (ii) not modified with a urea bond can be obtained in the same manner as the above polyester having a hydroxyl group. In addition, when making (3) react and when making (A) and (B) react, a solvent can be used.

  Usable solvents include aromatic solvents (eg, toluene, xylene, etc.), ketones (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (eg, ethyl acetate, etc.), amides (eg, dimethyl) Inactive to isocyanate (3) such as formamide, dimethylacetamide, etc.) and ethers (eg, tetrahydrofuran, etc.).

The oil phase containing the toner composition is made low in viscosity to enable emulsification, and, for example, the boiling point that is easy when the modified polyester resin (i) or the prepolymer (A) is dissolved and later removed. Is preferably a volatile organic solvent having a temperature of less than 100 ° C.
Examples of such solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid. Ethyl, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are preferable. In addition, the toner shape can be further adjusted by using a solvent that can be dissolved in an aqueous medium such as alcohol or water. The amount of solvent used is usually 10 to 900 parts with respect to 100 parts of the toner composition.

A high-speed shearing disperser is preferably used as an emulsifier equipped with a stirring blade disposed in the emulsification mechanism for dispersing and emulsifying the oil phase in an aqueous medium. As the high-speed shearing disperser, for example, commercially available apparatuses such as Ebara Milder (manufactured by Ebara Seisakusho Co., Ltd.) and TK Pipeline Homomixer (manufactured by Special Machine Industries Co., Ltd.) can be used.
When a high-speed shearing disperser is used, the number of rotations is suitable for the conditions of fine particle formation and coalescence, such as the stirring Reynolds number (stirring Re) and the shearing energy (E) when stirring the emulsion. It is adjusted to become.
As a rotation speed, it is 1000-30000 rpm normally, for example, Preferably it is 5000-20000 rpm. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 10 to 98 ° C. Higher temperatures are preferred in that the dispersion of the modified polyester resin (i) or the prepolymer (A) having an isocyanate bond has a low viscosity and is easily dispersed.

  The amount of the aqueous medium used for emulsification in the emulsification mechanism is usually 50 to 2000 parts by weight based on 100 parts of the oil phase toner composition containing urea-modified polyester (i) and prepolymer (A). The amount is preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and droplet particles having a predetermined particle size cannot be obtained. If it exceeds 20000 parts by weight, it is not economical.

(Solid fine particle dispersant)
In the present invention, the solid fine particle dispersant to be dispersed in the aqueous medium is a solid that is hardly soluble in water in the aqueous medium, and is preferably fine particles having an average particle diameter of 0.01 to 1 μm. Such solid fine particle dispersants include inorganic solid fine particle dispersants and organic solid fine particle dispersants.
Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
More preferably, tricalcium phosphate, calcium carbonate, colloidal titanium oxide, colloidal silica, hydroxyapatite, or the like can also be used. In particular, hydroxyapatite synthesized by reacting sodium phosphate and calcium chloride in water under a basic condition is preferable.

Examples of organic solid fine particle dispersants include low molecular weight organic compound microcrystals and polymer fine particles, for example, monomers having carboxyl groups such as methacrylic acid obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization. Polymerized polystyrene or polymer particles of methacrylic acid ester or acrylic acid ester copolymer, polycondensation resin such as silicone, benzoguanamine, nylon, or thermosetting resin can be used.
As described above, the solid fine particle dispersant is dispersed in advance in the aqueous medium, but other dispersants can be used in combination to adjust the adsorptivity of the solid fine particle dispersant to the droplets.

  After adjusting the solid fine particle dispersant in water, an inorganic substance that can be dissolved in an acid such as tricalcium phosphate is partially dissolved in advance by adding a necessary amount of hydrochloric acid or the like. The addition amount of the acid is preferably 0.01% to 10%, more preferably 0.1% to 5% of the amount capable of completely dissolving the inorganic substance.

  When a solid fine particle dispersant that can be dissolved in alkali such as polymer fine particles copolymerized with methacrylic acid having a carboxyl group is used, a necessary amount of a base such as sodium hydroxide is added and partially dissolved. The amount of alkali added is preferably 0.01% to 10%, more preferably 0.1% to 5% of the amount capable of completely dissolving the inorganic substance.

  Other dispersants added as needed during emulsification include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, etc. Cation surfactants of quaternary ammonium salts such as alkyltrimethylammonium salt, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid Nonionic surfactants such as amide derivatives and polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium beta Amphoteric surfactants such as.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 31- [omega-fluoroalkyl (C6-C11) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) mono-N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid and metal salt, Perfluoroalkyl carboxylic acids (C7 to C13) and their metal salts, perfluoroalkyl (C4 to C12) sulfonic acids and their metal salts, perfluorooctane sulfonic acid diethanolamide, N-propyl-N mono (2 hydroxy) Til) perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate Examples include esters.

  Commercially available materials can be used as the surfactant having the fluoroalkyl group. For example, as trade names, Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-l29 (Sumitomo 3M Co., Ltd.), Unidyne DS 101, DS-102, (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-l0, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF 1102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

Examples of the cationic surfactant include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6 1 C10) sulfonamidopropyltrimethylammonium salt, benza Examples thereof include a ruconium salt, a benzethonium chloride, a pyridinium salt, and an imidazolinium salt.
For example, as a trade name, Surflon S-21 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries Co., Ltd.), MegaFuck F-150, F-824 (Dainippon) Ink Co., Ltd.), Xtop EF-l32 (manufactured by Tochem Products), Footage F 1300 (manufactured by Neos), and the like.

The stabilization of the dispersed droplets may be controlled by a polymeric protective colloid. For example, (meth) acrylic monomer containing acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or hydroxyl group (For example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, acrylate 3- Chloro-2-hydroxypropyl, methacrylic acid 3-chloro-2-monohydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate , N-methylol acrylamide, N-methylol methacrylamide, etc.), vinyl alcohol or ethers with vinyl alcohol (for example, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc.), or containing vinyl alcohol and carboxyl group Esters (eg, vinyl acetate, vinyl propionate, vinyl butyrate), acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinylviridine, vinyl Homopolymers or copolymers such as those having a nitrogen atom such as pyrrolidone, vinylimidazole, ethyleneimine, or a heterocyclic ring thereof, polyoxyethylene, polyoxy Lopylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxy Polyoxyethylenes such as ethylene nonylphenyl ester, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.
When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, after the elongation and / or cross-linking reaction, it is better to dissolve and wash away the remaining solid fine particle dispersant. From the aspect, it is preferable.

  The emulsified liquid (emulsified dispersion) formed into toner-sized droplets in the emulsification step is transferred to the next step. Then, the organic solvent in the emulsified dispersion is removed. In order to remove the organic solvent from the emulsified dispersion, a method of gradually elevating the temperature of the entire system and completely evaporating and removing the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion may be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form fine particles that become a toner base, and the aqueous dispersant may be removed by evaporation. Is possible. As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Toner base particles having sufficient target quality can be obtained by a short time treatment such as a spray dryer, belt dryer or rotary kiln.

  The resulting dried toner base particles are mixed with different particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles to form composite particles, or mechanical impact on the composite particles By applying a force, it is possible to prevent the detachment of the foreign particles from the particle surface by immobilizing or fusing the surface.

  Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

(Dry toner manufacturing method)
After the toner base particles and the different particles are mixed and processed, inorganic fine particles such as hydrophobic silica fine powder are added and mixed as an external additive for further preparation as a dry toner, that is, a developer. Further, developability and transferability may be improved.
For mixing external additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to control the internal temperature. In order to change the load history applied to the external additive, the external additive may be added in the middle or gradually. Of course, you may change the rotation speed of a mixer, rolling speed, time, temperature, etc. A strong load may be given first, then a relatively weak load, and vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, a Henschel mixer, and the like.

  In order to further adjust the shape of the obtained toner, a toner material composed of a toner binder and a colorant is melt-kneaded and then finely pulverized and then mechanically adjusted using a hybridizer, mechanofusion, etc. The so-called spray drying method is a method in which a toner material is dissolved and dispersed in a solvent in which the toner binder is soluble, and then the solvent is removed using a spray drying apparatus to obtain a spherical toner. Moreover, although the method of making it spherical by heating in an aqueous medium is mentioned, it is not limited to this.

(External additive)
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used.
The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight.

Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, Examples thereof include diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
Other polymer fine particles, for example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, methacrylate ester, acrylate ester copolymer, polycondensation system such as silicone, benzoguanamine, nylon, thermosetting Examples thereof include polymer particles made of a resin.

  Such a fluidizing agent performs surface treatment to improve hydrophobicity, and can prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. It is done.

  Examples of the cleaning property improver used to remove the developer remaining on the photoreceptor after transfer and the primary transfer medium include fatty acid metal salts (for example, zinc stearate, calcium stearate, stearic acid, etc.), soap-free emulsion polymerization, etc. Polymer fine particles produced by the above (for example, polymethyl methacrylate fine particles, polystyrene fine particles, etc.). The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

(Carrier for two components)
When the toner obtained by the production method of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier, and the carrier to toner content ratio in the developer is 100 parts by weight of the carrier. 1 to 10 parts by weight of toner is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used.

  Examples of the carrier coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resin such as vinyl chloride, polyester resin such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexa Fluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro such as terpolymers of emission and non-fluoride monomers including, and silicone resins.

Moreover, you may make conductive powder etc. contain in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used.
The conductive powder preferably has an average particle size of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance. The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

  By using the toner of the present invention in an image forming method in which an electrostatic latent image formed on a photoreceptor is developed with toner, and the toner development is transferred and fixed on a recording medium, the latent image is particularly faithfully reproduced. It can be developed to reproduce high-quality full-color images.

In addition, the toner of the present invention is integrally supported by at least one means selected from a photosensitive member, a charging means, a developing means containing developer, and a cleaning means, and is detachable from the main body of the image forming apparatus. By using it as a toner used as a developer for a process cartridge, in particular, an electrostatic latent image formed on a photosensitive member is faithfully developed, and a high-quality full-color image can be reproduced.
Furthermore, by mounting the process cartridge on an image forming apparatus, maintenance can be simplified, high reliability and high quality image formation can be achieved.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to this. Hereinafter, a part shows a weight part. Examples 1 to 4 correspond to reference examples in the present invention.

(Example 1)
Using an agglomeration apparatus having the same configuration as in FIG. 1 described in the above embodiment, an oil phase (a mixture of A and B oil phases) and an aqueous phase are mixed to form an emulsified dispersion and granulated. . The A oil phase, the B oil phase, and the aqueous phase were prepared and granulated as follows, and then solvent removal, filtration, washing, and drying were performed to obtain toner base particles.
First, raw materials such as an unmodified polyester resin, a master batch (MB), and a ketimine made of a low-molecular polyester necessary for the preparation of [A oil phase] were prepared.

<Synthesis of unmodified polyester resin comprising low molecular weight polyester>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 529 parts of bisphenol A propylene oxide 3-mole adduct, 208 parts terephthalic acid, 46 parts adipic acid and dibutyl 2 parts of tin oxide was added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg, and then 44 parts of trimellitic anhydride was added to the reaction vessel at 180 ° C. and normal pressure. Was reacted for 2 hours to obtain [Non-modified Polyester Resin 1] comprising a low-molecular polyester. [Unmodified Polyester Resin 1] had a number average molecular weight of 2500, a weight average molecular weight of 6700, a Tg of 43 ° C., and an acid value of 25. [Non-modified polyester resin 1] refers to a polyester that is defined in the detailed description and is not modified with a so-called urea bond.

<Synthesis of master batch>
1200 parts of water, 540 parts of carbon black (Printex35: manufactured by Dexa) and 1200 parts of polyester resin are added and mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). After cooling, the mixture was pulverized with a pulverizer to obtain [Masterbatch 1]. Carbon black has DBP oil absorption = 42 ml / 100 mg and pH = 9.5.

<Synthesis of ketimine>
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418. Ketimine serves as an extender for the polyester prepolymer having an isocyanate group of the following B oil phase.

[Preparation of oil phase A (black)]
Using the [unmodified polyester resin 1], [masterbatch 1], and [ketimine compound 1] prepared above, an A oil phase (black) was prepared as follows.
In a container in which a stir bar and a thermometer are set, 378 parts of [unmodified polyester resin 1], 110 parts of Carnauba WAX, 22 parts of CCA (salicylic acid metal complex E-84: Orient Chemical Industry), and 947 parts of ethyl acetate are charged and stirred. The temperature was raised to 80 ° C., kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour. Next, 500 parts of [Masterbatch 1] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1]. 1324 parts of the obtained [Raw Material Solution 1] was transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Corporation), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads were added. Carbon black and WAX were dispersed under the conditions of 80% by volume filling and 3 passes. Next, 1324 parts of a 65% ethyl acetate solution of [Unmodified Polyester Resin 1] was added and passed once with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1]. The solid content concentration of [Pigment / WAX Dispersion 1] (130 ° C., 30 minutes) was 50%). [Pigment / WAX Dispersion 1] 749 parts and [Ketimine Compound 1] 2.9 parts are put in a container and mixed with a homodisper (made by Tokushu Kika) for 1 minute at 5,000 rpm [A oil phase (black) 1] was prepared.

<Synthesis of polyester prepolymer having isocyanate group>
Next, a polyester prepolymer having an isocyanate group necessary for the preparation of [B oil phase] was prepared.
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. for 8 hours at normal pressure, and further reacted for 5 hours at a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.
Next, 410 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate were added to a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Prepolymer 1] was obtained. [Prepolymer 1] had a free isocyanate weight% of 1.53%. This is designated as [B oil phase 1].

<Preparation of aqueous phase>
Next, [Aqueous Phase] was prepared as follows.
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries), 83 parts of styrene, 83 parts of methacrylic acid, When 110 parts of butyl acrylate and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes, a white emulsion was obtained. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to give a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). An aqueous dispersion [fine particle dispersion 1] was obtained. The volume average particle diameter of [fine particle dispersion 1] measured by LA-920 was 105 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The resin content had a Tg of 59 ° C. and a weight average molecular weight of 150,000. 83 parts of this [fine particle dispersion 1], 990 parts of water, 37 parts of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7: manufactured by Sanyo Chemical Industries) and 90 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

[Granulation by emulsification]
[A oil phase (black) 1], [B oil phase 1] [water phase 1] obtained above were fed from each raw material supply tank in FIG. 1 to the emulsification mechanism unit 4 for emulsification. The A oil phase 1 and the B oil phase 1 are mixed in advance in the static mixer (STM) 10 and then mixed with the aqueous phase 1. The mixing ratio of A oil phase 1, B oil phase 1 and water phase at the time of emulsification is 60.4 parts of A oil phase, 7.4 parts of B oil phase, and 101.6 parts of water phase in terms of parts by weight. . The conditions in the emulsifier 2 and the emulsion liquid circulation path 3 constituting the emulsification mechanism unit 4 are as follows.
<Emulsification conditions>
Stirring Reynolds number (stirring Re): 5118, Shear energy (E): 1813, Unit total energy (e): 4.0 × 10 ⁶ , Emulsion flow rate in emulsion circulation path (v): 1.89 m / s, flow Reynolds number (flow Re) in the pipe: 851, flow energy loss (Eloss) of the emulsion: 125 J / kg, number of right angle elbows: 4, inner diameter of the main pipe constituting the emulsion circulation path (D ): 0.0225 m, surface roughness of inner surface of main pipe (Ra): 0.5, rate of change of inner diameter of main pipe constituting emulsified liquid circulation path: 1.0 to 1.2, straight pipe between right angle elbow Pipe length (S) / main pipe inner diameter (D): 20, Emulsion discharge condition: via right angle elbow.
After continuously emulsifying under the above-mentioned constitution conditions and granulated into toner-sized droplets, the emulsified liquid was transferred to the next step and processed as described below to obtain a toner.

That is, the desolvation step of the organic solvent contained in the emulsion transferred to the next step was performed by the following method. The temperature of the emulsified liquid was raised to 45 ° C., and the organic solvent was removed at an outer peripheral end peripheral speed of 10.5 m / s under atmospheric pressure (101.3 kPa). The solvent removal time required 20 hours. After removing the solvent, it was filtered, washed and dried to obtain toner base particles.
Next, 100 parts of the obtained base particles and 0.25 part of a charge control agent (Bontron E-84: manufactured by Orient Chemical Co., Ltd.) were charged into a Q-type mixer (Mitsui Mining Co., Ltd.), and the peripheral speed of the turbine blades was adjusted to 50 m. The cycle was set to / sec, operated for 2 minutes and stopped for 1 minute, 5 cycles were performed, and the total processing time was 10 minutes. Furthermore, 0.5 part of hydrophobic silica (H2000: manufactured by Clariant Japan) was added, the peripheral speed was set to 15 m / sec, and the cycle of mixing for 30 seconds and resting for 1 minute was performed 5 cycles. Further, 0.5 part of hydrophobic silica and 0.5 part of hydrophobized titanium oxide were mixed with a Henschel mixer, and coarse particles were removed with a screen having an opening of 37 μm. The toner of Example 1 (black toner) Got.

  The emulsification conditions in the toner production are shown in Table 1 below, divided into droplet micronization factors and coalescence factors. The discharge conditions for the emulsion are also shown in Table 1. The emulsified particle diameter (Dv, Dv / Dn) and toner base particle diameter (abbreviated as toner particle diameter) (Dv, Dv / Dn) are shown in Table 2 below. Table 2 also describes the evaluation results of the following fine line reproducibility.

[Evaluation of fine line reproducibility]
The toner of Example 1 was used as a developer, and this was stored in a remodeling machine excluding the fixing oil part of an intermediate transfer type commercial color copying machine (IMAGIO COLOR 5000: manufactured by Ricoh Co., Ltd.) and evaluated for fine line reproducibility. did.
The evaluation was performed using a 6000 paper manufactured by Ricoh Co., Ltd., and the printing ratio was 7%. Compare the original 10th image and the 30,000th image thin line portion of the running image with the original, observe it with an optical microscope at a magnification of 100x, and evaluate it in five levels while comparing the line missing state with the step sample. did. In the evaluation of 1 to 5, 5 represents the best state. This is the level where there is no problem. The results are shown in Table 2.

(Example 2)
Except that the emulsification conditions in Example 1 were changed to the following, the emulsion was continuously emulsified in the same manner and granulated into toner-sized droplets, and then the emulsified liquid was transferred to the next step, followed by solvent removal, filtration and washing. Then, drying treatment was performed to obtain toner base particles, and the same treatment as in Example 1 was performed to obtain the toner of Example 2.
<Emulsification conditions>
Stirring Reynolds number (stirring Re): 13269, shear energy (E): 655, unit total energy (e): 2.6 × 10 ⁶ , flow rate of emulsion in the emulsion circulation path (v): 1.92 m / s, flow Reynolds number in the pipe (flow Re): 4608, flow energy loss (Eloss) of the emulsion: 152 J / kg, number of right angle elbows: 5, inner diameter of the main pipe constituting the emulsion circulation path (D ): 0.12 m, surface roughness (Ra) of inner surface of main pipe: 0.91, rate of change of inner diameter of main pipe constituting emulsified liquid circulation path: 1.4, length of straight pipe section between right angle elbows (S ) / Main pipe inner diameter (D): 5, Emulsion discharge condition: Via right angle elbow.

As in Example 1, the micronization factors and coalescence factors for the emulsification conditions are shown in Table 1 below. Emulsion discharge conditions are also listed in Table 1. The emulsified particle size and toner particle size are shown in Table 2 below.
Similar to Example 1, the results of evaluating fine line reproducibility using the toner of Example 2 as a developer are shown in Table 2 below.

(Example 3)
Except that the emulsification conditions in Example 2 were changed to the following, the emulsion was continuously emulsified in the same manner and granulated into toner-sized droplets, and then the emulsified liquid was transferred to the next step, followed by solvent removal, filtration and washing. Then, a drying process was performed to obtain toner base particles, and the same processing as in Example 2 was performed to obtain the toner of Example 3.
<Emulsification conditions>
Eloss flow energy loss (Eloss): 130 J / kg, right angle elbow number: 3.

As in Example 1, the micronization factors and coalescence factors for the emulsification conditions are shown in Table 1 below. Emulsion discharge conditions are also listed in Table 1. The emulsified particle size and toner particle size are shown in Table 2 below.
As in Example 1, the results of evaluating fine line reproducibility using the toner of Example 3 as a developer are shown in Table 2 below.

(Example 4)
Except that the emulsification conditions in Example 3 were changed to the following, the emulsion was continuously emulsified in the same manner and granulated into toner-sized droplets, and then the emulsified liquid was transferred to the next step, followed by solvent removal, filtration and washing. Then, drying treatment was performed to obtain toner base particles, and the same treatment as in Example 3 was performed to obtain the toner of Example 4.
<Emulsification conditions>
Flow energy loss (Eloss) of the emulsified liquid: 98 J / kg, inner diameter (D) of the main pipe constituting the emulsified liquid circulation path: 0.053 m.

As in Example 1, the micronization factors and coalescence factors for the emulsification conditions are shown in Table 1 below. Emulsion discharge conditions are also listed in Table 1. The emulsified particle size and toner particle size are shown in Table 2 below.
Similar to Example 1, the results of evaluating fine line reproducibility using the toner of Example 4 as a developer are shown in Table 2 below.

(Example 5)
Except that the emulsification conditions in Example 4 were changed to the following, the emulsion was continuously emulsified in the same manner and granulated into toner-sized droplets, and then the emulsified liquid was transferred to the next step, followed by solvent removal, filtration and washing. Then, drying treatment was performed to obtain toner base particles, and the same treatment as in Example 4 was performed to obtain the toner of Example 5.
<Emulsification conditions>
Flow energy loss (Eloss) of the emulsified liquid: 82 J / kg, surface roughness (Ra) of inner surface of main pipe: 0.5.

As in Example 1, the micronization factors and coalescence factors for the emulsification conditions are shown in Table 1 below. Emulsion discharge conditions are also listed in Table 1. The emulsified particle size and toner particle size are shown in Table 2 below.
As in Example 1, Table 2 shows the results of evaluation of fine line reproducibility using the toner of Example 5 as a developer.

(Example 6)
Except that the emulsification conditions in Example 5 were changed to the following, the emulsion was continuously emulsified in the same manner and granulated into toner-sized droplets, and then the emulsified liquid was transferred to the next process, followed by solvent removal, filtration and washing. Then, drying treatment was performed to obtain toner base particles, and the same processing as in Example 5 was performed to obtain the toner of Example 6.
<Emulsification conditions>
Flow energy loss (Eloss) of the emulsion: 70 J / kg, Rate of change of the inner diameter of the main pipe constituting the emulsion circulation path: 1.0.

As in Example 1, the micronization factors and coalescence factors for the emulsification conditions are shown in Table 1 below. Emulsion discharge conditions are also listed in Table 1. The emulsified particle size and toner particle size are shown in Table 2 below.
As in Example 1, Table 2 shows the results of evaluation of fine line reproducibility using the toner of Example 6 as a developer.

(Example 7)
Except that the emulsification conditions in Example 6 were changed to the following, the emulsion was continuously emulsified in the same manner and granulated into toner-sized droplets, and then the emulsified liquid was transferred to the next process, followed by solvent removal, filtration and washing. Then, drying treatment was performed to obtain toner base particles, and the same treatment as in Example 6 was performed to obtain the toner of Example 7.
<Emulsification conditions>
Flow energy loss (Eloss) of the emulsified liquid: 61 J / kg, pipe straight pipe length between right angle elbows (S) / main pipe inner diameter (D): 10.2.

As in Example 1, the micronization factors and coalescence factors for the emulsification conditions are shown in Table 1 below. Emulsion discharge conditions are also listed in Table 1. The emulsified particle size and toner particle size are shown in Table 2 below.
As in Example 1, Table 2 shows the results of evaluation of fine line reproducibility using the toner of Example 7 as a developer.

(Example 8)
Except that the emulsification conditions in Example 7 were changed to the following, the emulsion was continuously emulsified in the same manner and granulated into toner-sized droplets, and then the emulsified liquid was transferred to the next step, followed by solvent removal, filtration and washing. Then, drying treatment was performed to obtain toner base particles, and the same processing as in Example 7 was performed to obtain the toner of Example 8.
<Emulsification conditions>
Emulsion fluid energy loss (Eloss): 42 J / kg, Emulsion fluid discharge conditions: No right angle elbow.

As in Example 1, the micronization factors and coalescence factors for the emulsification conditions are shown in Table 1 below. Emulsion discharge conditions are also listed in Table 1. The emulsified particle size and toner particle size are shown in Table 2 below.
As in Example 1, Table 2 shows the results of evaluation of fine line reproducibility using the toner of Example 8 as a developer.

(Comparative Example 1)
Except that the emulsification conditions in Example 1 were changed to the following, the emulsion was continuously emulsified in the same manner and granulated into toner-sized droplets, and then the emulsified liquid was transferred to the next step, followed by solvent removal, filtration and washing. Then, a drying process was performed to obtain toner base particles, and the same processing as in Example 1 was performed to obtain a toner of Comparative Example 1.
<Emulsification conditions>
Stirring Reynolds number (stirring Re): 1866, Shear energy (E): 241, Unit total energy (e): 2.8 × 10 ⁵ , Emulsion flow rate in emulsion circulation path (v): 2.12 m / s, flow Reynolds number (flow Re) in the pipe: 954, flow energy loss (Eloss) of the emulsion: 95 J / kg, number of right angle elbows: 3, inner diameter of the main pipe constituting the emulsion circulation path (D ): 0.0225 m, surface roughness of the inner surface of the main pipe (Ra): 0.72, change rate of the inner diameter of the main pipe constituting the emulsion circulation path: 1.0, pipe straight pipe length between right angle elbows (S ) / Main pipe inner diameter (D): 11.5, Emulsified liquid discharge condition: Without right angle elbow.

As in Example 1, the micronization factors and coalescence factors for the emulsification conditions are shown in Table 1 below. Emulsion discharge conditions are also listed in Table 1. The emulsified particle size and toner particle size are shown in Table 2 below.
As in Example 1, Table 2 shows the results of evaluation of fine line reproducibility using the toner of Comparative Example 1 as a developer.

(Comparative Example 2)
Except that the emulsification conditions in Example 1 were changed to the following, the emulsion was continuously emulsified in the same manner and granulated into toner-sized droplets, and then the emulsified liquid was transferred to the next step, followed by solvent removal, filtration and washing. Then, a drying process was performed to obtain toner base particles, and the same processing as in Example 1 was performed to obtain a toner of Comparative Example 2.
<Emulsification conditions>
Stirring Reynolds number (stirring Re): 2710, Shear energy (E): 508, Unit total energy (e): 3.1 × 10 ⁵ , Emulsion flow rate in emulsion circulation path (v): 2.7 m / s, flow Reynolds number (flow Re) in the pipe: 1215, flow energy loss (Eloss) of the emulsion: 160 J / kg, number of right-angle elbows: 5, inner diameter of the main pipe constituting the emulsion circulation path (D ): 0.0225 m, surface roughness of the inner surface of the main pipe (Ra): 0.92 , change rate of the inner diameter of the main pipe constituting the emulsion circulation path: 1.5 , pipe straight pipe length between right angle elbows (S ) / Main pipe inner diameter (D): 10.2, Emulsion discharge condition: Via different diameter pipe (1D → 1.2D).

As in Example 1, the micronization factors and coalescence factors for the emulsification conditions are shown in Table 1 below. Emulsion discharge conditions are also listed in Table 1. The emulsified particle size and toner particle size are shown in Table 2 below.
As in Example 1, Table 2 shows the results of evaluation of fine line reproducibility using the toner of Comparative Example 2 as a developer.

It has been found that good evaluation results can be obtained when Dv and Dv / Dn satisfy the specified values as a result of the above thin line reproducibility test.
That is, it can be seen from the test results that there is the following tendency.
In the experiment, the emulsion particle diameter (volume average particle diameter) Dv = 3.82 μm of the embodiment 1 is all around the emulsion particle diameter Dv = 6 μm. From this, it is considered that there is no significant difference in the influence of the particle size because the ability of the micronization factor is almost the same. However, the particle size distribution (Dv / Dn) varies depending on the fluctuation of the value of the coalescence behavior factor, and the particle size distribution is improved as the coalescence behavior factor that falls within a predetermined range, that is, a value within the specified range, increases. In addition, as a discharge condition, when passing through a right angle elbow or a different diameter pipe, it is confirmed that the particle size distribution of the toner particle size tends to be slightly worse than the emulsified particle size. In Example 8 in which all of the micronization factor and the coalescence behavior factor are within the specifications, the sharpest particle size distribution is obtained, and the image evaluation is also good as 5.0. On the other hand, in Comparative Example 1, since the stirring Re and the shear energy (E) are outside the specified ranges, the emulsified particle size itself tends to be coarse. In Comparative Example 2, since the shear energy (E) is within the specified range, the particle size is a target value, but there is a coalescence factor that is outside the specified range, so the particle size distribution is deteriorated, and the image Evaluation results are also poor.

It is a schematic block diagram which shows an example of the granulation apparatus used for the emulsification process of toner manufacture in this invention.

Explanation of symbols

1 Granulator 2 Emulsifier (PLHM)
3 Emulsified liquid circulation path 4 Emulsifying mechanism 5 Transfer piping 6 Converging tank 7 A oil phase 8 B oil phase 9 Water phase 10 STM (static mixer)
11 Right angle elbow 12 Elbow 17 A Oil phase supply tank 18 B Oil phase supply tank 19 Water phase supply tank

Claims (19)

A method for producing a toner for emulsifying an oil phase and an aqueous phase by an emulsification mechanism having an emulsifier equipped with at least a stirring blade and an emulsion liquid circulation path, which is used in an emulsification step of toner production,
The oil phase is a lysate or dispersion made of an organic phase containing at least a resin and a resin precursor,
And the stirring Reynolds number (stirring Re) calculated | required by following formula (1) at the time of stirring of the emulsion liquid with the said stirring blade is 3000 <= stirring Re <= 15000 ,
When the reference inner diameter of the main pipe constituting the emulsion circulation path is 1, the rate of change of the pipe inner diameter is in the range of 0.8 to 1.4,
A toner production method, wherein a flow energy loss (Eloss) of an emulsified liquid generated in a range of an inner diameter change of the main pipe is 20 to 82 J / kg .
Stirring Re = ρnd ² / μ (1)
(Wherein, ρ: density of emulsion (kg / m ³ ), n: rotation speed of stirring blade (rps), d: blade diameter (m) of stirring blade, μ: viscosity of emulsion (Pa · s) Is shown.) Method for producing a toner according to claim 1, wherein the resin and the resin precursor is the molecular weight of different polymers. The resin precursor is an isocyanate group-containing polyester prepolymer,
The toner production method according to claim 1 , wherein the resin is an unmodified polyester resin.   The toner production method according to claim 1, wherein the aqueous phase is an aqueous medium containing a solid fine particle dispersant. The toner production method according to claim 1, wherein a shear energy (E) obtained by the following formula (2) generated by rotation of the stirring blade is 400 or more and 2000 or less.
E = (n × 60) ³ × d ⁵ / Q (2)
(Where n is the rotational speed (rps) of the stirring blade, d is the blade diameter (m) of the stirring blade, and Q is the flow rate value (L / min) in the emulsion circulation path.) While the emulsion circulates and stays in the emulsion circulation path, the unit total energy (e) per raw material feed unit flow rate obtained by the following equation (3) received by the emulsion from the emulsifier is 1 × 10 ^6. The toner production method according to claim 1, wherein the toner production amount is 5 × 10 ⁶ or less.
e = [(n × 60) ³ × d ⁵ × Q] / F ² (3)
(Where n is the number of revolutions of the stirring blade (rps), d is the blade diameter of the stirring blade (m), Q is the flow rate value in the emulsion circulation path (L / min), and F is the raw material feed rate (kg / min).)   The toner production method according to claim 1, wherein a flow rate (v) of the emulsion in the emulsion circulation path is 0.5 to 3 m / sec.   The toner manufacturing method according to claim 1, wherein an inner diameter (D) of a main pipe constituting the emulsion liquid circulation path is 0.02 to 0.10 m. The flow Reynolds number (flow Re) obtained by the following formula (4) of the emulsion in the straight pipe portion of the main pipe constituting the emulsion circulation path is 500 or more and 4000 or less. The method for producing a toner according to any one of 1 to 8.
Flow Re = ρvD / μ (4)
(Where, ρ: density of emulsion (kg / m ³ ), v: flow rate of emulsion (m / s), D: inner diameter of main pipe (m), μ: viscosity of emulsion (Pa · s) Is shown.)   The toner manufacturing method according to claim 1, wherein a surface roughness (Ra) of an inner surface of a main pipe constituting the emulsion liquid circulation path satisfies Ra <0.8.   The method for producing a toner according to claim 1, wherein the number of right-angle elbows is four or less when the main pipe constituting the emulsion circulation path has right-angle elbows.   When the main pipe has four or less right-angle elbows, the ratio (S) / (D) of the straight pipe section length (S) to the main pipe inner diameter (D) between the right-angle elbows is 10 or more. The method for producing a toner according to claim 11, wherein:   The method for producing a toner according to claim 1, wherein the emulsion circulation path is configured such that the emulsion is discharged to the next step without passing through the right-angle elbow.   The toner manufacturing method according to claim 1, wherein the main pipe diameter of the emulsion liquid circulation path is configured such that the emulsion liquid is discharged to the next step without passing through the different diameter pipe. A toner obtained by the method for producing a toner according to any one of claims 1-14, toner the toner of volume average particle diameter (Dv) is characterized by a 3 to 10 [mu] m. The toner according to claim 15 , wherein a value obtained by dividing the volume average particle diameter (Dv) of the toner by the number average particle diameter (Dn) is 1.05 to 1.25. 17. An image forming method in which an electrostatic latent image formed on a photoreceptor is developed with toner, and the toner development is transferred and fixed on a recording medium. The toner is the toner according to claim 15 or 16. An image forming method. A process cartridge that integrally supports at least one member selected from a photosensitive member, a charging unit, a developing unit containing developer, and a cleaning unit, and is detachable from the main body of the image forming apparatus; The process cartridge according to claim 15 or 16 , wherein the toner used for the developer is the toner according to claim 15 or 16 . 19. An image forming apparatus having a process cartridge which is detachably attached to an image forming apparatus main body, wherein the process cartridge is the process cartridge according to claim 18 .

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