JP2010139696A - Toner and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner that has excellent durable stability performance even when low-temperature fixability is improved, and is capable of forming a high-quality image. <P>SOLUTION: The toner includes: toner particles having core particles containing a binding resin, a coloring agent, and wax, and a shell resin for covering the core particles; and inorganic fine particles that adhere to the toner particles. In the toner, the glass transition point (Tg1) is 25.0-60.0°C, A0 is 70.0% or lower, if A0 is taken as an aggregation degree at a temperature of 23.0°C and a humidity of 60% RH, and the difference between T1 and Tg1(T1-Tg1) is 5.0-40.0°C and a change rate α of the aggregation degree in T1 and T2 is 15.0-50.0 wherein α=ä98.0-(A0+10.0)}/(T2-T1), if T1(°C) is taken as the temperature at which the aggregation degree of the toner is A0+10.0%, and T2(°C) as the temperature at which the aggregation degree of the toner is 98.0% after the toner is left at rest for 72 hours. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner used in an electrophotographic method or a toner jet method and a method for producing the toner.

  The electrophotographic method has received various requests such as high image quality, small size and light weight of the apparatus, high speed, and energy saving. For that purpose, it is essential to improve the toner fixing performance. In particular, there is a demand for improvement in performance (hereinafter referred to as low-temperature fixing performance) capable of fixing toner onto a transfer material at a lower temperature.

  However, when the low-temperature fixing performance of the toner is improved, the performance of suppressing the aggregation of the toner during long-term storage (hereinafter referred to as anti-blocking performance) and the occurrence of image defects during a large amount of continuous printing or copying. Suppressing performance (hereinafter referred to as durability stability performance) tends to decrease.

  In the fixing process, after the toner on the transfer material adheres to the fixing member, the performance of suppressing the offset, which is a phenomenon that stains the transfer material by transferring the toner to the transfer material again (hereinafter referred to as offset resistance performance) Tends to decrease. After the image is formed, when the printed material is stored in a stacked manner, the toner of the printed material one sheet below is prevented from adhering to and contaminating the back surface of the upper printed material (hereinafter referred to as image storage performance). ) Tends to decrease.

  Furthermore, by forming a high-gloss image, the performance of improving the color development of the image (hereinafter referred to as gloss performance) and the performance of suppressing unevenness in the gloss of the image (hereinafter referred to as anti-smudge performance) Called) tends to decrease.

  For this reason, a toner that simultaneously satisfies these performances is desired.

  Patent Document 1 attempts to achieve both low-temperature fixing performance and anti-blocking performance of toner by coating the surface of toner particles having a low glass transition point (Tg) with resin fine particles having a Tg higher than that of the toner particles. Is. In Patent Document 2, core particles having a binder resin, a colorant, and a wax are coated with a shell layer formed by a seed polymerization method, so that both low-temperature fixing performance, anti-blocking performance, and durable stability performance of the toner are achieved. The aims.

  Patent Document 3 aims to improve the low-temperature fixing performance, anti-blocking performance, and durability stability performance of the toner by adding a polar resin to the toner having a vinyl resin.

JP 2004-226572 A JP 2007-171272 A JP 2007-322499 A

  However, there is a need for a toner that has a further improved low-temperature fixing performance compared with the toners of the above documents.

  An object of the present invention is to provide a toner capable of solving the above-described problems and a production method for producing the toner.

  That is, an object of the present invention is to provide a toner containing wax that has good anti-blocking performance and durability stability performance even when the low-temperature fixing performance is improved, and can form a high-quality image. To do.

The present invention includes at least toner particles having core particles containing a binder resin, a colorant, and a wax, a shell resin that covers the core particles, and inorganic fine particles attached to the surface of the toner particles. Toner,
The toner has a glass transition point (Tg1) measured by a differential scanning calorimeter (DSC) of 25.0 to 60.0 ° C., and the degree of aggregation at a temperature of 23.0 ° C. and a humidity of 60% is A0. Is equal to or less than 70.0%, and T1 (° C.) is a temperature at which the degree of aggregation of the toner after leaving the toner for 72 hours is A0 + 10.0%. When the temperature at which the degree of aggregation is 98.0% is T2 (° C.), the difference (T1−Tg1) between T1 (° C.) and Tg1 (° C.) is 5.0 to 40.0 ° C. The present invention relates to a toner in which the change rate α of the degree of aggregation at T2 = {98.0− (A0 + 10.0)} / (T2−T1) is 15.0 to 50.0.

Furthermore, the present invention comprises a step of forming a fine particle dispersion (1) of a shell resin in which the shell resin is dispersed in water in the form of fine particles;
It has a core particle containing a binder resin, a colorant, a wax, and other additives, a dispersion stabilizer such as an inorganic salt, and water, and the dispersion stabilizer is adsorbed on the surface of the core particle to be in water. Forming a dispersion (2) of core particles that forms a dispersed state;
The shell resin fine particle dispersion (1) is added to the core particle dispersion (2) to form a composite dispersion, and the shell is formed on the surface of the core particles using the dispersion stabilizer as a medium. A coating treatment step for forming a state in which fine particles of the resin for resin are adsorbed and coated on the surface of the core particles;
In the dispersion of the composite, heating and releasing the dispersion stabilizer existing as a medium from the medium state so that the core particles and the fine particles of the shell resin are in direct contact with each other to cover the core particles. Fixing process for forming toner particles by fixing resin fine particles on the core particle surface;
A drying step of collecting and drying the toner particles to form powder toner particles;
Mixing the toner particles and inorganic fine particles to form a toner,
The toner includes at least toner particles including core particles containing a binder resin, a colorant, and a wax, a shell resin that covers the core particles, and inorganic fine particles attached to the surface of the toner particles. The toner has a glass transition point (Tg1) of 25.0 to 60.0 ° C. by a differential scanning calorimeter (DSC), a cohesion degree at a temperature of 23.0 ° C. and a humidity of 60% as A0. The temperature at which the A0 is 70.0% or less and the degree of aggregation of the toner after leaving the toner for 72 hours is A0 + 10.0% is T1 (° C.), and the toner is left for 72 hours. When the temperature at which the degree of aggregation of the toner after this is 98.0% is T2 (° C.), the difference (T1−Tg1) between T1 (° C.) and Tg1 (° C.) is 5.0 to 40.0 ° C. And aggregation at T1 (° C.) and T2 (° C.) Rate of change α = {98.0- (A0 + 10.0)} / method for producing a toner, wherein (T2-T1) is a toner is 15.0 to 50.0.

  According to the present invention, at least a toner particle having a core particle containing a binder resin, a colorant, and a wax, a shell resin that coats the core particle, and an inorganic fine particle that adheres to the surface of the toner particle Even when the low-temperature fixing performance of the toner is improved, the toner has good anti-blocking performance and durability stability performance, and can form a high-quality image.

  In a toner having toner particles having core particles and a shell resin covering the core particles, and inorganic fine particles adhering to the surface of the toner particles, the low-temperature fixing performance of the toner is improved, and the anti-blocking performance is reduced. In order to suppress this, the toner has physical properties capable of suppressing a change in the degree of aggregation of the toner even when the toner is subjected to heat for a long time in a certain temperature range exceeding the glass transition point (Tg1) of the toner. I found it important. Furthermore, once the conditions for starting the change in the degree of aggregation of the toner are reached, a toner having physical properties with which the change in the degree of aggregation suddenly progresses, so that the toner can be fixed at a low temperature, with anti-blocking performance and durable stability. It was found that both of these can be achieved.

  The method for measuring the degree of aggregation of toner in the present invention will be described below.

When the true density of toner is ρ (g / cm ³ ), (2.0 × ρ) g of toner is weighed, and a 50 ml capacity plastic container (height 76 mm, bottom area 1134 mm ² (outer diameter 38 mm) polyethylene Into a cylindrical container made of, for example, 50 ml of a wide-mouthed plastic bottle (manufactured by Sun Platec Co., Ltd.). At this time, the toner layer is made almost horizontal in the plastic container. This is referred to as a toner in a plastic container.

  In the temperature range of 30.0 to 120.0 ° C., the toner in the plastic container is placed in a thermostatic chamber whose temperature is changed in increments of 10.0 ° C., and left for 72 hours. The plastic container is gently taken out from each thermostat and left to cool for 24 hours in an environment of temperature 23.0 ° C. and humidity 60% RH. Next, an iron plate having a length of 30 cm, a width of 30 cm, and a thickness of 1 cm is placed on the floor, and the plastic container is naturally dropped from a state in which the plastic container is kept at a height of 1 m to the iron plate. Using the toner thus treated, the degree of aggregation a (%) at each temperature is obtained by the method described later.

  In addition to the above, the same toner in a plastic container as described above is allowed to stand for 96 hours (72 hours + 24 hours) in an environment of temperature 23.0 ° C. and humidity 60% RH. Thereafter, in the same manner, the plastic container is naturally dropped from the state where the plastic container is kept vertical at the height of 1 m to the iron plate. Using this toner, the degree of aggregation A0 (%) in an environment of a temperature of 23.0 ° C. and a humidity of 60% RH is obtained by the method described later.

  In the degree of aggregation a (%) at each temperature measured as described above, the lowest temperature t (° C.) at which the degree of aggregation a (%) is 100.0% is determined.

  From this result, in order to obtain more detailed data, for the temperature range of 30.0 to t ° C., prepare a thermostatic bath in which the atmospheric temperature in the thermostatic bath is changed in increments of 2.0 ° C. The toner in a plastic container is placed in each thermostat and allowed to stand for 72 hours. Thereafter, in the same manner, the plastic container is gently taken out and left to stand for 24 hours under a temperature of 23.0 ° C. and a humidity of 60% RH for cooling. Next, the plastic container is naturally dropped from a state where the plastic container is kept vertical at a height of 1 m onto the iron plate. Using this toner, the degree of aggregation A (%) at each temperature is determined by the method described later.

  From the value obtained by this method, the atmosphere temperature T (° C.) in each thermostatic bath is plotted on the x axis, and the value A (%) of the aggregation degree at that time is plotted on the y axis T (° C.) (x axis). -A (%) (y-axis) graph is created. Each physical property value defined in the present invention is read from this graph.

  That is, a point of (A0 + 10.0)% is obtained on the y axis of the graph, and the value of the corresponding x axis is T1 (° C.). In addition, a 98.0% point is obtained on the y-axis of the graph, and the corresponding value on the x-axis is T2 (° C.). FIG. 1 shows the result of the above measurement using the toner prepared in Example 1.

As an apparatus for measuring the cohesion degree, for example, a device in which a digital display vibrometer “Digivibro MODEL 1332A” (manufactured by Showa Keiki Co., Ltd.) is connected to the side surface portion of a “powder tester” (manufactured by Hosokawa Micron Corporation). In order from the bottom, a sieve having an aperture of 38 μm (400 mesh), a sieve having an aperture of 75 μm (200 mesh), and a sieve having an aperture of 150 μm (100 mesh) are stacked, and this is set on the shaking table of the apparatus. The measurement is performed in the following manner at a temperature of 23.0 ° C. and a humidity of 60% RH.
(1) The vibration width of the vibration table is adjusted in advance so that the displacement value of the digital display vibrometer is 0.60 mm (peak-to-peak).
(2) Gently place the toner prepared by the above-described method on the uppermost sieve having a mesh size of 150 μm, and measure the mass of the toner.
(3) After vibrating the vibration table for 90 seconds, the mass of the toner remaining on each sieve is measured, and the degree of aggregation A (%) is calculated based on the following equation.
Aggregation degree (%) = {(sample mass (g) on a sieve having an opening of 150 μm) / 5 (g)} × 100
+ {(Sample mass on a sieve having an opening of 75 μm (g)) / 5 (g)} × 100 × 0.6
+ {(Sample mass (g) on a sieve having an opening of 38 μm) / 5 (g)} × 100 × 0.2

  When the above physical properties of a general toner are measured, the difference (T1−Tg1) (° C.) between the Tg1 (° C.) and the T1 (° C.) when the Tg of the toner by DSC is Tg1 (° C.) is It tends to be negative values such as −20 ° C. to −5 ° C. Further, the change rate α tends to be 10.0 or less. In this case, sufficient anti-blocking performance cannot be obtained in order to improve the low-temperature fixing performance of the toner.

  The toner of the present invention is a toner having core particles and a shell particle covering the core particles, wherein (T1-Tg1) (° C.) is 5.0 to 40.0 ° C. , Α is 15.0 to 50.0. When the (T1-Tg1) (° C.) is a positive value and 5.0 ° C. or higher, the toner has a shell resin having a Tg higher than the Tg of the core particles, and the core It shows that the particles and the shell resin are present in an incompatible state that can be detected by the physical property measurement of the present invention. Further, α being 15.0 or more means that the thickness of the coating layer of the shell resin is sufficiently thin, and the thickness of the coating layer of the shell resin is uniform over the entire surface of the toner particles. In addition, the uniformity of such a coating layer is uniform over the entire toner even when compared for each toner. That is, the above physical property values are considered to be physical property values that combine micro uniformity and macro uniformity with respect to the thickness of the coating layer of the shell resin covering the core particles.

  For example, in a toner having core particles and a shell resin that coats the core particles, when the surface of the core particles is not coated with the shell resin, or the thickness of the coating layer of the shell resin is In the case of non-uniformity, the T1 (° C.) tends to be a small value. This is probably because the toner is likely to agglomerate and fuse in portions that are not coated with the shell resin or in which the coating layer is particularly thin, and the degree of aggregation is likely to change even at low temperatures. Since T1 (° C.) is a small value, α is likely to be a small value. On the other hand, when the content of the shell resin contained in the toner is increased, the T2 (° C.) tends to increase and the α tends to decrease further. In such a case, the low-temperature fixing performance and gloss performance of the toner deteriorate. Further, since the shell resin is easily peeled off from the core particles, the durability stability performance of the toner tends to be lowered.

On the other hand, when the thickness of the coating layer made of the shell resin is sufficiently thin, the toner can exhibit the thermal melting characteristics equivalent to the core particles. This improves the low-temperature fixing performance and gloss performance of the toner. Moreover, since the thickness of the coating layer is thin, the coating layer is flexible, and the coating layer is difficult to break. Further, since the thickness of the coating layer is uniform over the entire surface of the toner particles, mechanical or thermal stress applied to the toner is dispersed throughout the coating layer, and the coating layer is difficult to break. As a result, the toner has excellent anti-blocking performance and durability stability performance.

  Further, the (T1-Tg1) (° C.) being 40.0 ° C. or lower and the α being 50.0 or lower indicate that the shell resin is sufficiently soft thermodynamically. As a result, it is possible to improve the low-temperature fixing performance, gloss performance, and durability stability performance of the toner while maintaining the toner's anti-blocking performance. If the softness of the resin for the shell is insufficient, the T1 tends to be a large value, so that the (T1−Tg1) (° C.) and the α are likely to be large. In this case, the low-temperature fixing performance and gloss performance of the toner are likely to deteriorate. Further, a thermodynamically hard resin is brittle and easily cracked, and when the difference in thermodynamic softness between the core particle and the shell resin becomes large, the coating layer easily breaks. It is considered that the stress received by the toner tends to concentrate on the thin coating layer made of the shell resin. In such a case, the coating layer is easily peeled off from the surface of the toner particles, and the durability stability performance of the toner is lowered.

  When the α is 15.0 to 50.0 and the (T1-Tg1) is less than 5.0 ° C., the film thickness of the coating layer made of the shell resin is uniform over the entire toner. It is considered that the softness between the core particle and the shell resin is thermodynamically close, or the shell resin is softer than the core particle. In such a case, the core particles and the shell resin are likely to be compatible with each other by external heat or the like, and the effect of shielding the core particles with the shell resin is likely to be reduced. Therefore, the toner's anti-blocking performance and image storage performance are likely to deteriorate. When the α is 15.0 to 50.0 and the (T1-Tg1) exceeds 40.0 ° C., the shell resin is considered to be thermodynamically too hard compared to the core particles. In such a case, when the coating layer made of the shell resin is thinned, the coating layer is easily broken, and the shell resin is easily peeled off from the surface of the toner particles. Therefore, the durability stability performance of the toner tends to decrease.

  On the other hand, when the (T1-Tg1) is 5.0 to 40.0 ° C. and the α is less than 15.0, the coating state of the shell resin contained in the toner is non-uniform and very It is thought that there are many cases. In such a case, the low-temperature fixing performance and gloss performance of the toner deteriorate. Further, since the mechanical stress applied to the toner tends to concentrate on the portion where the thickness of the coating layer by the shell resin is biased, the coating layer easily breaks from that portion. In such a case, the shell resin easily peels off from the surface of the toner particles, so that the durability stability performance of the toner is lowered. When (T1-Tg1) is 5.0 to 40.0 ° C. and α exceeds 50.0, the shell resin is too thermodynamically harder than the core particles, so the core particles and the shell Adhesiveness with resin for coating tends to be lowered. Further, since the shell resin is hard and brittle, the coating layer is easily broken when the coating layer made of the shell resin is thinned. In such a case, the shell resin easily peels off from the surface of the toner particles, so that the durability stability performance of the toner is lowered.

  The (T1-Tg1) is preferably 10.0 to 35.0 ° C, more preferably 10.0 to 25.0 ° C. Further, the (T1-Tg1) is particularly preferably 14.0 to 22.0 ° C. The α is preferably 16.0 to 46.0, and more preferably 18.0 to 42.0. Further, the α is particularly preferably 20.0 to 40.0.

  The (T1-Tg1) and the α are greatly influenced by the coating state of the shell resin on the toner particle surface and the coating amount. Further, it is also affected by the adhesion state of the interface between the core particles and the shell resin and the material of the shell resin. For this reason, it is controllable with the addition amount of a resin for shells, a composition, molecular weight, an acid value, and the kind and amount of other functional groups which the resin for shells has. It is also affected by the thermal properties of the core particles, so it can be controlled by the binder resin composition and molecular weight, wax type, molecular weight and addition amount, other additives, and the manufacturing process of coating the core particles with the shell resin. It is. Further, it can be controlled by the kind and amount of inorganic fine particles adhering to the toner particle surface and the particle diameter.

  The toner of the present invention is a toner having at least toner particles containing a binder resin, a colorant, and a wax, and inorganic fine particles adhering to the surface of the toner particles, and having a Tg1 (° C.) of 25.0 to 60.0 ° C. The Tg1 of 25.0 to 60.0 ° C. is preferable in terms of low-temperature fixing performance and image storage performance of the toner.

  If Tg1 is less than 25.0, the low-temperature fixing performance of the toner tends to be good, but sufficient image storage performance cannot be obtained. Further, the toner's anti-blocking performance, gloss performance, anti-offset performance and durability stability performance are likely to deteriorate. When Tg1 exceeds 60.0 ° C., the image storage performance of the toner tends to be good, but sufficient low-temperature fixing performance cannot be obtained. Further, the durability stability performance and the offset resistance performance of the toner are likely to be improved, but the gloss performance is likely to be deteriorated. In addition, the range of Tg1 is preferably 30.0 to 55.0 ° C, more preferably 33.0 to 50.0 ° C. Further, the Tg1 is particularly preferably 35.0 to 47.0 ° C.

  The Tg1 (° C.) is considered to be a value corresponding mainly to the glass transition point (° C.) of the binder resin that the core particles have. For this reason, it can be controlled by the composition, molecular weight, and molecular weight distribution of the binder resin contained in the core particles. Further, since it is also affected by the existence state such as compatibility / incompatibility between the binder resin and the wax, it can be controlled by the type and addition amount of the wax and the heating / cooling process in the process of producing the toner. The Tg1 (° C.) is also affected by the adhesion state at the interface between the core particle and the shell resin and the coating state of the shell resin on the toner particle surface. For this reason, the Tg1 (° C.) is the amount of addition, composition, molecular weight, acid value of the shell resin, the type and amount of other functional groups of the shell resin, and the core particles are covered with the shell resin. It can also be controlled by the manufacturing process.

  The toner of the present invention has an aggregation degree A0 (%) of 70.0% or less in an environment of a temperature of 23.0 ° C. and a humidity of 60% RH. A cohesion degree A0 (%) of 70.0% or less is preferable in terms of the durability and stability of the toner. In a toner having a core particle and a shell resin that coats the core particle, when the coating layer of the shell resin is thin, inorganic fine particles are easily embedded on the surface of the toner particle, and the A0 (%) becomes a large value. Prone. When the A0 (%) exceeds 70.0%, in the case of a toner having a small Tg1 (° C.) as in the present invention, the toner tends to stay on the toner carrier or the charging member, and the toner has stable durability. Performance decreases. This is presumably because the stress received by the toner in the developing device tends to increase and the coating layer made of the shell resin tends to break. In addition, as a range of A0 (%), it is more preferable that it is 30.0% or less, and it is further more preferable that it is 15.0% or less.

  On the other hand, if the A0 (%) is too small, the toner easily enters paper fibers, and the gloss performance of the toner may be reduced. In addition, when a large amount of inorganic fine particles adhering to the surface of the toner particles is contained in order to reduce the A0 (%), the low-temperature fixing performance of the toner tends to be lowered. Further, the additive is likely to be deposited on the toner carrier and the charging member, and the durability stability performance of the toner is likely to be lowered. From this viewpoint, the A0 (%) is preferably 0.3% or more, and more preferably 1.0% or more. From the above, the A0 (%) is preferably 0.3 to 70.0%, and more preferably 1.0 to 30.0%. Further, the A0 (%) is particularly preferably 1.0 to 15.0%.

  The A0 (%) can be controlled by the shape and particle diameter of the toner, the composition of the inorganic fine particles contained in the toner, the particle diameter, and the amount added. It can also be controlled by the coating state of the core particles with the shell resin.

  The T1 (° C.) is preferably 45.0 to 75.0 ° C. When the T1 (° C.) is 45.0 to 75.0 ° C., it is preferable from the viewpoint of compatibility of low-temperature fixing performance, anti-blocking performance, durability stability performance, image storage performance, and gloss resistance performance of the toner.

  When the T1 (° C.) is less than 45.0 ° C., the toner's anti-blocking performance, image storage performance, and anti-penetration performance may deteriorate. When T1 (° C.) exceeds 75.0 ° C., the low-temperature fixing performance, gloss performance, and durability stability performance of the toner tend to be lowered. The range of T1 (° C.) is more preferably 49.0 to 72.0 ° C., further preferably 50.0 to 70.0 ° C., and 52.0 to 68.0 ° C. It is particularly preferred.

  In the toner of the present invention, the T2 (° C.) is preferably 50.0 to 80.0 ° C. When the T2 (° C.) is 50.0 to 80.0 ° C., it is preferable from the viewpoint of compatibility of low-temperature fixing performance, anti-blocking performance, durability stability performance, image storage performance, and offset resistance performance of the toner.

  If the T2 (° C.) is less than 50.0 ° C., the toner image storage performance, anti-offset performance and anti-penetration performance may be deteriorated. When the T2 (° C.) exceeds 80.0 ° C., the low-temperature fixing performance and gloss performance of the toner are liable to deteriorate. In addition, the coating layer made of the shell resin may become brittle, and the durability stability performance of the toner may be reduced. The range of T2 (° C.) is more preferably 53.0 to 73.0 ° C., and particularly preferably 56.0 to 72.0 ° C.

  The T1 (° C.) and T2 (° C.) are greatly affected by the glass transition point (° C.) of the shell resin, the coating state of the shell resin on the toner particle surface, and the coating amount. For this reason, it is controllable with the addition amount of a resin for shells, a composition, molecular weight, an acid value, and the kind and amount of other functional groups which the resin for shells has. Moreover, it is controllable by the manufacturing process which coat | covers a core particle with resin for shells. Further, since it is also affected by the thermal characteristics of the core particles, it can be controlled by the binder resin composition, molecular weight and molecular weight distribution, wax type, molecular weight and addition amount, and other additives.

  In the toner of the present invention, when measuring the viscosity of the toner with a constant load capillary extruding rheometer, the temperature at which the viscosity is 5000 Pa · s is F1 (° C.) and the temperature at which the viscosity is 1000 Pa · s is F2 (° C.). F1 (° C.) is preferably 75.0 to 115.0 ° C., and the difference (F2−F1) between F1 (° C.) and F2 (° C.) is 8.0 to 40.0 ° C. Is preferred.

  When F1 (° C.) is 75.0 to 115.0 ° C., it is preferable in terms of low-temperature fixing performance, gloss performance, anti-offset performance, and anti-smudge performance of the toner. Further, when F1 (° C.) is in the low temperature region as described above, the toner is prevented from becoming brittle, and the durability stability performance of the toner is easily improved. In the toner having a thin coating layer made of the resin for shell, the coating layer is difficult to break, and therefore, the coating layer is difficult to peel off from the surface of the toner particles.

  Further, when the (F2-F1) is from 8.0 to 40.0 ° C., the gloss performance, penetration resistance, offset resistance performance, and image storage performance of the toner are further improved. When (F2-F1) has the wide temperature range as described above, the toner is prevented from becoming brittle, and the durability stability performance of the toner is easily improved. In the toner having a thin coating layer made of the resin for shell, the coating layer is difficult to break, and therefore, the coating layer is difficult to peel off from the surface of the toner particles.

  When the F1 (° C.) is less than 75.0 ° C., the gloss performance, anti-offset performance, and penetration resistance of the toner may deteriorate. When the F1 (° C.) exceeds 115.0 ° C., the low-temperature fixing performance and gloss performance of the toner may be deteriorated. Further, the toner tends to become brittle, and the durability stability performance of the toner may be reduced. In a toner having core particles and a shell resin that covers the core particles, the shell resin may be easily peeled off. In such a case, the durability stability performance of the toner tends to decrease.

  F1 (° C.) is more preferably 80.0 to 110.0 ° C., and further preferably 85.0 to 105.0 ° C.

  Further, when the (F2-F1) is less than 8.0 ° C., the offset resistance performance, gloss performance, penetration resistance, and image storage performance of the toner may be deteriorated. Further, the toner tends to become brittle, and the durability stability performance of the toner may be reduced. In a toner having core particles and a shell resin that covers the core particles, the shell resin may be easily peeled off. In such a case, the durability stability performance of the toner tends to decrease. When (F2-F1) exceeds 40.0 ° C., the low-temperature fixing performance and gloss performance of the toner may deteriorate.

  The (F2-F1) is more preferably at a temperature of 9.0 to 30.0 ° C, particularly preferably at a temperature of 10.0 to 22.0 ° C.

  The F1 and (F2-F1) are considered to be affected by the thermal properties of the core particles. Therefore, the composition can be controlled by the composition of the binder resin contained in the core particles, the molecular weight and the molecular weight distribution, the type of wax, the molecular weight and the added amount, and other additives. Further, it is also affected by the adhesion state of the interface between the core particle and the shell resin and the coating state of the shell resin on the toner particle surface. For this reason, said F1 and (F2-F1) are controllable with the addition amount of a resin for shells, a composition, molecular weight, an acid value, and the kind and quantity of the other functional group which the resin for shells has. It can also be controlled by a manufacturing process in which the core particles are coated with a shell resin.

  The amount of the shell resin contained in the toner is preferably 1.0 to 10.0% by mass with respect to the toner mass. This is preferable in terms of achieving both low-temperature fixing performance, blocking resistance performance, durability stability performance, offset resistance performance, image storage performance, and penetration resistance performance of the toner. When the amount of the shell resin contained in the toner is less than 1.0% by mass, the durability stability performance and image storage performance of the toner may be deteriorated. When the amount of the shell resin contained in the toner exceeds 10.0% by mass, the low-temperature fixability of the toner tends to be lowered. Further, when the amount of the shell resin is too large, the shell resin may be easily peeled off from the surface of the toner particles. In such a case, the durability stability performance of the toner decreases.

  The amount of the shell resin contained in the toner particles is more preferably 2.0 to 9.0% by mass, and particularly 3.0 to 6.0% by mass with respect to the toner mass. preferable.

  Further, in the toner of the present invention, when the glass transition point of the shell resin is Tg2 (° C.), the difference (Tg2−Tg1) between Tg2 and Tg1 is 10.0 to 50.0 ° C. preferable. When (Tg2−Tg1) is 10.0 to 50.0 ° C., it is preferable in terms of achieving both low-temperature fixing performance, anti-blocking performance, gloss performance, and durability stability performance of the toner. When the (Tg2-Tg1) is less than 10.0 ° C., the image storage performance and anti-blocking performance of the toner may be deteriorated. When the (Tg2-Tg1) exceeds 50.0 ° C., the low-temperature fixing performance and gloss performance of the toner are liable to deteriorate. In addition, the difference in thermal characteristics between the core particles and the shell resin becomes too large, and the shell resin may be easily peeled off from the toner particle surface. In this case, the durability stability performance of the toner decreases.

  The (Tg2-Tg1) is more preferably at a temperature of 15.0 to 45.0 ° C, particularly preferably at a temperature of 20.0 to 40.0 ° C. Furthermore, the (Tg2-Tg1) is particularly preferably at a temperature of 27.0 to 40.0 ° C.

  The toner of the present invention contains one or more fine particles selected from silica or titanium oxide as the inorganic fine particles contained in the toner, and the lower the content of the fine particles, the better the low-temperature fixability of the toner tends to be improved. . However, if the content is too small, the silica or titanium oxide tends to be embedded in the surface of the toner particles when the toner particles are thermally soft with the aim of improving the low-temperature fixing performance of the toner. Therefore, the content is preferably 0.50 to 3.00 mass% with respect to the total amount of toner. When the content is less than 0.50% by mass, the durability stability performance of the toner may be deteriorated. When the content exceeds 3.00% by mass, the low-temperature fixing performance and gloss performance of the toner may be deteriorated. In addition, the durability stability performance of the toner may be reduced. The content is more preferably 0.50 to 2.50% by mass, and particularly preferably 0.70 to 2.20% by mass.

  In addition, the inorganic fine particles of the toner have a primary particle number average particle diameter of 20.0 to 200.0 nm, which achieves both low-temperature fixing performance, anti-blocking performance, durability stability performance, and image storage performance of the toner. This is preferable. In the case of a toner having a core particle and a shell resin that coats the core particle, the surface of the thermally soft core particle is coated with the thermally hard shell resin. It is easy to be suppressed. For this reason, even if the number average particle diameter of the primary particles of the inorganic fine particles is small, good durability stability performance of the toner can be obtained, and the low-temperature fixing performance tends to be improved. On the other hand, if the number average particle diameter is too large, stress is easily concentrated on the contact between the inorganic fine particles and the shell resin due to the stress received by the toner from the member in the developing machine. For this reason, the shell resin is easily peeled off, and the durability stability performance of the toner may be lowered. For this reason, the number average particle diameter is more preferably 20.0 to 160.0 nm, and particularly preferably 20.0 to 120.0 nm.

In the present invention, the shell resin for covering the core particles, after the volume of the resin for the shell average particle diameter (D3 _s) is formed into a 5 to 500nm of the fine resin particles, it is preferable to coat the core particles. Further, the shell resin is preferably used as an aqueous dispersion of resin fine particles having the above-described particle diameter, and the core particles are preferably covered. By coating the shell resin on the surface of the core particles in the form of resin fine particles whose particle diameter is controlled in advance, it is possible to form the coating layer with the shell resin uniformly. Further, when the shell resin is used in the state of an aqueous dispersion of resin fine particles having the above particle diameter, the film thickness can be made more uniform even when compared between toner particles.

  In this way, the resin for the shell is made into resin fine particles, and the aqueous dispersion can be formed by a dispersion method in which the shell resin is diluted with a solvent, or heated and stirred or pressurized with water. it can. Further, it is also possible to form by a polymerization method in which a monomer as a raw material for a shell resin is dispersed in water and then polymerized to form resin fine particles.

  In the present invention, a preferable method for forming a toner having core particles having a binder resin, a colorant, and a wax, and a shell resin covering the core particles includes the following methods.

  (A) A step of forming a fine particle dispersion (1) of a shell resin in which the shell resin is dispersed in water in the form of fine particles. It has a core particle containing a binder resin, a colorant, a wax, and other additives, a dispersion stabilizer such as an inorganic salt, and water, and the dispersion stabilizer is adsorbed on the surface of the core particle to be in water. A step of forming a dispersion (2) of core particles that forms a dispersed state. The shell resin fine particle dispersion (1) is added to the core particle dispersion (2) to form a composite dispersion, and the shell is formed on the surface of the core particles using the dispersion stabilizer as a medium. A coating treatment step for forming a state in which fine particles of resin for resin are adsorbed and coated on the surface of the core particles. In the dispersion of the composite, heating and releasing the dispersion stabilizer existing as a medium from the medium state so that the core particles and the fine particles of the shell resin are in direct contact with each other to cover the core particles. Fixing process for forming toner particles by fixing resin fine particles on the surface of core particles. A drying step in which the toner particles are collected and dried to form powder toner particles. A method of forming a toner through a mixing step of mixing the toner particles and inorganic fine particles to form a toner.

  (B) A step of forming a fine particle dispersion (1) of the shell resin in which the shell resin is dispersed in water in the form of fine particles. A binder resin, a colorant, a wax, other additives, and a mixture containing an organic solvent are added to the aqueous dispersion (1) to form a composite dispersion. The binder resin, the colorant, the wax, The process of forming the dispersion liquid (3) of the complex which forms the state which the surface of the core particle which has an other additive and an organic solvent coat | covered the fine particle of the said resin for shells. Removing the organic solvent in the dispersion (3) to form toner particles; A drying step in which the toner particles are collected and dried to form powder toner particles. A method of forming a toner through a mixing step of mixing the toner particles and inorganic fine particles to form a toner.

  (C) A step of forming a fine particle dispersion (1) of a shell resin in which the shell resin is dispersed in water in the form of fine particles. A step of forming a fine particle dispersion (2) of the binder resin in which the binder resin is dispersed in water in the form of fine particles. Forming a colorant dispersion (3) in which the colorant is dispersed in water; Forming a wax dispersion (4) in which the wax is finely dispersed in water. A coagulation step in which a binder resin fine particle dispersion (2), a colorant dispersion (3), and a wax dispersion (4) are mixed and aggregated to form a core particle dispersion. A coating step in which a fine particle dispersion (1) of the resin for shell is added to the dispersion of the core particle, and the surface of the core particle is coated with the fine particle of the resin for the shell to form a dispersion of toner particles. A drying step in which the toner particles are collected and dried to form powder toner particles. A method of forming a toner through a mixing step of mixing the toner particles and inorganic fine particles to form a toner.

  Among them, in the method (A), the dispersion stabilizer is adsorbed uniformly on the surface of the core particles by interfacial chemistry. The fine particles of the shell resin are adsorbed by an electrical interaction between the dispersion stabilizer uniformly arranged on the surface of the core particles and the fine particles of the shell resin. Since the fine particles of the shell resin are adsorbed as long as the dispersion stabilizer and the fine particles of the shell resin can come into contact with each other, only one layer of the fine particles of the shell resin is closely packed on the surface of the core particles with the dispersion stabilizer as a medium. be able to. After forming this state, while removing only the dispersion stabilizer, the shell resin fine particles are fixed to the core particle surface, so that a coating layer having a uniform film thickness can be formed over all directions of the toner particle surface, In addition, the uniformity is considered to cover the entire toner. For this reason, even when the core particles have a certain particle size distribution, it is considered that a coating layer corresponding to the diameter of the shell resin fine particles is formed for both the large core particles and the small core particles.

In the step of forming the fine particle dispersion of the shell resin, the volume average particle diameter (D3 _s ) of the fine particles of the shell resin is preferably 15 to 150 nm. When the D3 _s is in the above range, even when the addition amount of the fine particles of the shell resin is reduced, the uniformity of the coating state of the shell resin on the surface of the toner particles, the uniformity of the film thickness of the coating layer, In addition, the uniformity of the covering state by the shell resin when compared with the whole toner becomes better. For this reason, the low-temperature fixing performance and durability stability performance of the toner are likely to become better.

Furthermore, the shell resin fine particles preferably have a zeta potential (Z _1s ) of −110.0 to −35.0 mV. The Z _1s is considered to be derived from the type and content of the acidic group of the shell resin and the particle diameter of the fine particles of the shell resin. When the Z _1s is in the above range, the adhesion between the core particles and the shell resin fine particles becomes better. Further, even when the amount of fine particles of the shell resin is reduced, the uniformity of the coating state of the shell resin on the surface of the toner particles, the uniformity of the film thickness of the coating layer, and the whole toner are compared. The uniformity of the coating state with the shell resin becomes better. When Z _1s is less than −110.0 mV (negatively large), the shell resin may be easily peeled off from the surface of the toner particles. In addition, the fine particles of the shell resin are hardly fixed on the surface of the toner particles, and the fine particles of the free shell resin may be produced as a by-product. In such a case, the durability stability performance of the toner tends to decrease. When Z _1s exceeds −35.0 mV (negatively small), the coating state of the shell resin on the toner particle surface tends to be biased, and the coating layer thickness tends to be non-uniform. In this case, the shell resin is easily peeled off from the surface of the toner particles, and the durability stability performance of the toner tends to be lowered.

The range of D3 _s is more preferably 15 to 100 nm, and particularly preferably 20 to 80 nm. Further, the range of Z _1s is more preferably −95.0 to −35.0 mV, and particularly preferably −85.0 to −45.0 mV.

Resin for the shell, acid value Av (Av _s) is 3.0 to 40.0 mgKOH / g, product of the Av _s and the _{D3 s (Av s × D3 s} ) is 200 to 1000 Is preferred. When the Av _s is 3.0 to 40.0 mgKOH / g, the acidic group derived from the acid value is likely to interact with the surface of the core particle, and the adhesion between the core particle and the shell resin is good. Easy to become. Further, when (Av _s × D3 _s ) is 200 to 1000, even when the amount of fine particles of the shell resin is reduced, the uniformity of the coating state of the shell resin on the surface of the toner particles, the coating layer The uniformity of the film thickness and the uniformity of the coating state by the shell resin when compared with the whole toner are improved.

When the Av _s is less than 3.0 mgKOH / g, D3 _s exceeds 150 nm, or (Av _s × D3 _s ) is less than 200, the coating state of the shell resin fine particles on the toner particle surface is It tends to be non-uniform, and the layer thickness of the shell resin coating layer tends to be non-uniform. In this case, the shell resin is easily peeled off from the surface of the toner particles, and the durability stability performance of the toner tends to be lowered. If the Av _s exceeds 40.0 mgKOH / g, when D3 _s is less than 20 nm, or, if it exceeds (Av _s × D3 _s) 4000, coverage of the shell doses resin for coating the core particle toner It tends to be uneven among particles. Also in this case, the shell resin is easily peeled off from the surface of the toner particles, and the durability stability performance of the toner tends to be lowered. When the coating amount is too large, the low-temperature fixing performance and gloss performance of the toner may be deteriorated. For this reason, the Av _s of the surface layer resin is more preferably 6.0 to 35.0 mgKOH / g, and particularly preferably 6.0 to 30.0 mgKOH / g. The (Av _s × D3 _p ) is more preferably 200 to 600.

Fine particles of the resin for the shell, the ratio between the D3 _s 10% particle diameter on a volume distribution _{(D3 s10) (D3 s /} D3 s10) of 1.0 to 10.0, low temperature fixation of the toner It is preferable from the viewpoint of performance and durability stability performance. Even if the addition amount of the fine particles of the resin for the shell is reduced, the uniformity of the coating state of the resin for the shell on the surface of the toner particles, the uniformity of the film thickness of the coating layer, and the shell for the whole toner are compared. The uniformity of the coating state with the resin becomes better. When the D3 _s / D3 _s10 exceeds 10.0, the coating amount of the shell dose resin that coats the core particles tends to be uneven among the toner particles. In this case, the shell resin is easily peeled off from the surface of the toner particles, and the durability stability performance of the toner tends to be lowered. When the coating amount is too large, the low-temperature fixing performance and gloss performance of the toner may be deteriorated. For this reason, (D3 _s / D3 _s10 ) is more preferably 1.0 to 5.0, and particularly preferably 1.0 to 4.0.

Also, fine particles of the resin for the shell, the low temperature is a toner ratio of the D3 _s 90% particle diameter on a volume distribution _{(D3 s90) (D3 s90 /} D3 s) is 1.0 to 10.0 It is preferable from the viewpoint of fixing performance and durability stability performance. Even if the addition amount of the fine particles of the resin for the shell is reduced, the uniformity of the coating state of the resin for the shell on the surface of the toner particles, the uniformity of the film thickness of the coating layer, and the shell for the whole toner are compared. The uniformity of the coating state with the resin becomes better. When the (D3 _s90 / D3 _s ) exceeds 10.0, the coating amount of the shell dose resin that coats the core particles tends to be uneven among the toner particles. In this case, the shell resin is easily peeled off from the surface of the toner particles, and the durability stability performance of the toner tends to be lowered. When the coating amount is too large, the low-temperature fixing performance and gloss performance of the toner may be deteriorated. Therefore, the (D3 _s90 / D3 _s ) is more preferably 1.0 to 6.0, and particularly preferably 1.0 to 4.0.

  The shell resin preferably includes a polyester having an alcohol having an ether bond as a divalent alcohol component. Specific examples of the dihydric alcohol having an ether bond include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3.3) -2,2-bis. (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2, Alkylene oxide adducts of bisphenol A such as 2-bis (4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane; diethylene glycol, triethylene glycol, dipropylene glycol, Polyethylene glycol, polypropylene glycol, polytetramethylene glycol It can be mentioned compounds represented by or following Formula 2; Lumpur, bisphenol derivative represented by the following formula 1.

（式中、Ｒはエチレンまたはプロピレン基を示し、ｘ，ｙはそれぞれ１以上の整数を示し、且つｘ＋ｙの平均値は２乃至１０を示す。）

(In the formula, R represents an ethylene or propylene group, x and y each represents an integer of 1 or more, and the average value of x + y represents 2 to 10.)

（式中、Ｒ’はエチレン、プロピレン、又は、ブチレン基を示す。）

(In the formula, R ′ represents ethylene, propylene, or a butylene group.)

  The shell resin is a polyester having an alcohol having an ether bond as a divalent alcohol component, which means that the toner has a low-temperature fixing performance, blocking resistance, durability stability, offset resistance, image storage performance, and resistance. This is preferable in terms of both penetration performance. Having many ether bonds in the main chain has moderate affinity with the core layer, so even when the amount of shell resin added is small, the coating state of the shell resin on the core particles tends to be more uniform. .

  Examples of the polyvalent carboxylic acid component used in combination with the dihydric alcohol include the following compounds.

  Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides; substituted with an alkyl group having 6 to 12 carbon atoms Succinic acid or anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof; n-dodecenyl succinic acid, isododecenyl succinic acid, trimellitic acid.

  The shell resin preferably has the following anionic hydrophilic functional groups. It is preferable that the shell resin has an anionic hydrophilic functional group in terms of achieving both low-temperature fixing performance, anti-blocking performance, durability stability performance, anti-offset performance, and penetration resistance of the toner. By having an anionic hydrophilic functional group, the affinity with the core layer is improved, and even when the addition amount of the shell resin is small, the coating state of the shell resin on the core particles tends to be more uniform.

  As the anionic hydrophilic functional group, a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, a metal salt thereof, or an alkyl ester can be used. Examples of the metal salt include alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as magnesium. Among them, from the viewpoint of the adhesion between the core particles and the shell resin and the uniformity of the covering state, it has a sulfonic acid group selected from sulfonic acid groups, alkali metal salts of sulfonic acid groups, and alkyl ester salts of sulfonic acid groups. Is preferred. Even when the addition amount of the shell resin is small, the coating state of the shell resin on the core particles tends to be particularly uniform.

  The shell resin preferably contains 0.10 to 4.00 mass% of sulfonic acid groups when the resin content is 100.00 mass%. When the content of the sulfonic acid group is 0.10 to 4.00 mass%, the toner has low-temperature fixing performance, blocking resistance performance, durability stability performance, offset resistance performance, image storage performance, and penetration resistance performance. It is preferable in terms of both. When the content of the sulfonic acid group is within the above range, even when the addition amount of the shell resin is small, the coating state of the shell resin on the core particles tends to be particularly uniform. When the content of the sulfonic acid group is less than 0.10% by mass, the coating state of the shell resin on the surface of the toner particles is likely to be biased, and the film thickness of the coating layer tends to be uneven. In this case, the shell resin is easily peeled off from the surface of the toner particles, and the durability stability performance of the toner tends to be lowered. When the content of the sulfonic acid group exceeds 4.00% by mass, the shell resin may be easily peeled off from the surface of the toner particles. In addition, the fine particles of the shell resin are hardly fixed on the surface of the toner particles, and the fine particles of the free shell resin may be produced as a by-product. In such a case, the durability stability performance of the toner tends to decrease. The content of the sulfonic acid group is preferably 0.20 to 3.00% by mass, and more preferably 0.40 to 2.00% by mass.

  The shell resin has a weight average molecular weight (Mw) of 3,000 to 300,000, such that the toner has low temperature fixing performance, blocking resistance performance, durability stability performance, gloss performance, offset resistance performance, image storage performance, and stain resistance. This is preferable from the viewpoint of compatibility of the loading performance. When the weight average molecular weight of the resin is less than 3000, the shell resin easily breaks in the developing machine, and the durability stability performance of the toner tends to decrease. In addition, the offset resistance performance, image storage performance, and anti-smudge performance of the toner may be reduced. When the weight average molecular weight of the resin exceeds 300,000, the low-temperature fixing performance and gloss performance of the toner may be deteriorated. The weight average molecular weight of the resin is preferably 4000 to 100,000, more preferably 5000 to 70000. The weight average molecular weight of the resin is particularly preferably 5000 to 50000.

  The shell resin has a number average molecular weight (Mn) of 2,000 to 100,000. The low-temperature fixing performance, blocking resistance performance, durability stability performance, gloss performance, offset resistance performance, image storage performance, and stain resistance of the toner. This is preferable from the viewpoint of compatibility of the loading performance. When the number average molecular weight of the resin is less than 2,000, the shell resin easily breaks in the developing machine, and the durability stability performance of the toner tends to decrease. In addition, the offset resistance performance, image storage performance, and anti-smudge performance of the toner may be reduced. When the number average molecular weight of the resin exceeds 100,000, the low-temperature fixing performance and gloss performance of the toner may be deteriorated. The number average molecular weight of the resin is preferably 2000 to 50000, and more preferably 3000 to 10,000.

  The shell resin has a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) of 1.20 to 50.0. It is preferable from the viewpoint of achieving both of stable durability performance, gloss performance, offset resistance performance, image storage performance, and penetration resistance performance. When the Mw / Mn of the resin is less than 1.20, the shell resin is easily broken in the developing machine, and the durability stability performance of the toner may be lowered. In addition, the offset resistance performance, image storage performance, and anti-smudge performance of the toner may be reduced. When the Mw / Mn of the resin exceeds 50.0, the low-temperature fixing performance and gloss performance of the toner may be deteriorated. The Mw / Mn of the resin is preferably 1.30 to 15.0, and more preferably 1.50 to 10.0.

  In the preferred method of forming the toner of the present invention described above, the following conditions are preferred when the method shown in (A) is used.

In the step of forming the core particle dispersion (2), the weight average particle diameter D4 _c of the core particles is 3.0 to 8.0 μm, and the number average particle diameter D1 _{c of the} core particles and the D4 _c The ratio (D4 _c / D1 _c ) is preferably 1.00 to 1.30. When the D4 _{c of the} core particle is less than 3.0 μm, when forming a coating layer with the shell resin, the toner particles tend to aggregate through the shell resin, and the durability stability performance of the toner is reduced. There is a case. If the D4 _c exceeds 8.0 .mu.m, may adhesion between core particles and the shell resin is lowered, surface shell resin is easily peeled off from the toner particles, the durability stability performance of the toner tends to decrease . Similarly, when (D4 _c / D1 _c ) exceeds 1.30, when forming the coating phase with the shell resin, the toner particles tend to aggregate through the shell resin, and the durability of the toner is stabilized. Performance may be degraded. In addition, (D4 _c / D1 _c ) is an index indicating the degree of particle size distribution, and is 1.00 when it is completely monodispersed. The larger the value is than 1.00, the larger the particle size distribution.

For the same reason as described above, the D4 _c is more preferably 3.0 to 7.0 μm, and further preferably 4.0 to 6.0 μm. Further, the (D4 _c / D1 _c ) is more preferably 1.00 to 1.25, and further preferably 1.00 to 1.20. The (D4 _c / D1 _c ) is particularly preferably 1.00 to 1.15.

In the step of forming the dispersion (2) of the core particles, the core particles have a dispersion stabilizer on the surface, and the zeta potential (Z _2c ) of the core particles is −15.0 mV or less (negatively large). And the difference between Z _2c and Z _1s (Z _2c −Z _1s ) is preferably 5.0 to 50.0 mV. The Z _2c is (a small negative) exceeding -15.0mV case, when forming the coating layer of the shell resin, among the toner particles are easily aggregated through the resin for the shell, the toner durability Stability performance may be reduced. When the (Z _2c -Z _1s ) is less than 5.0 mV, the coating state of the shell resin on the toner particle surface is likely to be biased, and the coating layer thickness tends to be non-uniform. In this case, the shell resin is easily peeled off from the surface of the toner particles, and the durability stability performance of the toner tends to be lowered. When the (Z _2c -Z _1s ) exceeds 50.0 mV, the shell resin may be easily peeled off from the surface of the toner particles. In addition, the fine particles of the shell resin are hardly fixed on the surface of the toner particles, and the fine particles of the free shell resin may be produced as a by-product. In such a case, the durability stability performance of the toner tends to decrease.

The Z _2c is more preferably -85.0 to -15.0 mV, and further preferably -70.0 to -20.0 mV. Particularly preferred Z _2c is −55.0 to −30.0 mV. The (Z _2c -Z _1s ) is more preferably 20.0 to 45.0 mV, and further preferably 25.0 to 45.0 mV. Particularly preferred (Z _2c -Z _1s ) is 30.0 to 45.0 mV.

  In the step of forming the core particle dispersion (2), the dispersion stabilizer of the core particles is preferably a poorly water-soluble inorganic salt selected from Ca, Mg, Ba, Zn, and Al. Since the coating state of the shell resin that coats the core particles becomes more uniform and can be uniformly dissolved by the addition of acid or alkali, the adhesion between the core particles and the shell resin is likely to be improved. Examples of particularly preferable inorganic salts include the following compounds.

  Multivalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; inorganic salts such as calcium metasuccinate, calcium sulfate and barium sulfate; Inorganic oxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite and alumina.

  The core particles preferably contain styrene-acrylic resin as a main component, and further contain 2.0 to 20.0 parts by mass of polyester with respect to 100 parts by mass of the binder resin. When the core particles contain polyester, the uniformity of the inorganic salt adsorbed on the core particles is further improved. As a result, the uniformity of the film thickness of the shell resin covering the surface of the toner particles becomes better. In addition, the content of the polyester is more preferably 3.0 to 15.0 parts by mass, and further preferably 4.0 to 10.0 parts by mass.

  In the coating treatment step in the method shown in (A) above, when the fine particle dispersion of the shell resin is added to the aqueous dispersion of the core particles, the coating rate is lower when the addition rate of the fine particle dispersion of the shell resin is slower. It is preferable from the viewpoint of the uniformity of the state. The addition rate of the shell resin as a solid content is preferably 0.01 to 1.50 parts by mass / min from the viewpoint of achieving both low-temperature fixing performance, anti-blocking performance, and durability stability performance of the toner. When the addition rate of the shell resin is less than 0.01 parts by mass / minute, the coating state of the shell resin with the fine particles may be slightly uneven. In this case, the durability stability performance of the toner tends to decrease. When the addition rate of the shell resin exceeds 1.50 parts by mass / minute, the toner particles may melt by using the fine particles of the shell resin as a medium. In this case, the durability stability performance of the toner tends to decrease. The addition rate of the shell resin is more preferably 0.03 to 1.00 parts by mass / min, and further preferably 0.03 to 0.30 parts by mass / min.

  In the fixing treatment step in the method shown in (A) above, the heating temperature is such that the glass transition point of the core particles is Tg0 (° C.) and the glass transition point of the shell resin is Tg2 (° C.). It is preferable that the temperature is 2.0 ° C. or more higher than (° C.) and 1.0 ° C. or more lower than the Tg2 (° C.). The toner particles can be prevented from being fused to each other, and the fine particles of the resin for shell can be uniformly fixed on the surface of the core particles, so that the durability stability performance of the toner becomes better. The heating temperature is more preferably 8.0 ° C. or more higher than the Tg0 (° C.).

  In the fixing treatment step described above, it is also preferable to add a dispersion stabilizer such as a surfactant or the aforementioned poorly water-soluble inorganic salt in order to prevent the toner particles from fusing together. The addition amount is preferably 0.01 to 5.00 parts by mass with respect to 100 parts by weight of the toner particles. Examples of the surfactant that can be used include the following.

  Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and those having a fluoroalkyl group. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (carbon number 6 To 11) oxy] -1-alkyl (carbon number 3 to 4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6 to 8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11 to C20) carboxylic acid or metal salt thereof, perfluoroalkyl carboxylic acid (C7 to C13) or metal salt thereof, perfluoroalkyl (C4 to C12) sulfonic acid or metal salt thereof, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- 2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6 to 10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6 to 10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate etc. are mentioned. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Florad FC-93, FC-95, FC-98, FC -129 (manufactured by Sumitomo 3M Co., Ltd.); Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F-191, F-812, F- 833 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); 100, F150 (manufactured by Neos) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. Among these cationic surfactants, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, and perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (Asahi Glass Co., Ltd.); Florad FC-135 (Sumitomo 3M Co., Ltd.); Unidyne DS-202 (Daikin Industries Co., Ltd.), Megafuck F-150, F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products);

  In the fixing treatment step in the method shown in the above (A), as a method for releasing the dispersion stabilizer from the mediating state, an acid treatment step is performed in which the pH of the dispersion is reduced to 5.0 or less by adding hydrochloric acid. It is preferable. By dissolving the dispersion stabilizer such as a sparingly water-soluble inorganic salt in the acid treatment step, the fine particles of the shell resin can be uniformly fixed to all the core particles in the dispersion. The durability and stability of the toner is further improved.

  In the acid treatment step, when hydrochloric acid is added, a slower addition rate of hydrochloric acid is preferable from the viewpoint of the uniformity of the coating state. It is preferable that the addition rate of hydrochloric acid is 0.01 to 0.10 mol / hour from the viewpoint of achieving both low-temperature fixing performance, anti-blocking performance, and durability stability performance of the toner. If the addition rate of hydrochloric acid is less than 0.01 mol / hour, the shell resin may be easily peeled off from the toner particle surface. In this case, the durability stability performance of the toner tends to decrease. When the addition rate of hydrochloric acid exceeds 0.10 mol / hour, the toner particles tend to aggregate and fuse. In this case, the durability stability performance of the toner may deteriorate. The addition rate of the shell resin is more preferably 0.03 to 0.06 mol / hour.

  The heating temperature (heating step 1) in the fixing treatment step is a temperature equal to or lower than the Tg2 (° C) and (Tg0 + 2.0) to (Tg0 + 20.0) ° C compared to the Tg0 (° C). The temperature is preferably from the viewpoint of the durability stability performance of the toner. When the temperature is lower than Tg0 + 2.0 ° C., the shell resin is easily peeled off from the toner particle surfaces, and the durability stability performance of the toner is likely to be lowered. When the temperature exceeds Tg0 + 20.0 ° C., the coating efficiency on the surface of the core particles may be lowered, and a free shell resin may be by-produced. In this case, the durability stability performance and anti-blocking performance of the toner are likely to deteriorate. When the temperature exceeds Tg2 (° C.), the toner particles are likely to be fused with each other, and the durability stability performance of the toner tends to be lowered. The temperature is more preferably (Tg0 + 5.0) to (Tg0 + 15.0) ° C.

  When the aqueous dispersion of the core particles contains a hardly water-soluble inorganic salt as a dispersion stabilizer, it is preferable to have a step of setting the pH of the dispersion to 6.0 or higher after the acid treatment step. Furthermore, it has a step (heating step 2) of heating to a temperature of (Tg2-10.0) to (Tg2-0.5) ° C compared with Tg2 above the Tg0 (° C). Is preferred.

  By setting the pH to 6.0 or more, the inorganic salt can be reprecipitated outside the fine particles of the shell resin coated with the core particles. Furthermore, by having the process of heating to the said range, the adhesiveness of core particle and shell resin can be improved, and the durable stability performance of a toner becomes more favorable. If the pH is less than 6.0, the toner particles may be fused together, and the durability stability performance of the toner may deteriorate. When the temperature in the heating step 2 exceeds Tg2−0.5 ° C., the toner particles may be fused with each other to deteriorate the durability stability performance of the toner. When the temperature in the heating step 2 is lower than Tg2-10.0 ° C., the shell resin may be easily peeled off from the toner particle surface. The pH is more preferably 6.0 to 12.0, and further preferably 6.0 to 9.0. The temperature range of the heating step 2 is more preferably (Tg2-8.0) to (Tg2-1.0) ° C., and more preferably (Tg2-5.0) to (Tg2-1). 0.0) ° C. is preferable.

  The toner of the present invention contains 3.0 to 45.0% by mass of a tetrahydrofuran (THF) insoluble component obtained by a Soxhlet extraction method, and the THF soluble component contains 0.010 to 1% of a sulfur element derived from a sulfonic acid group. It is preferable to contain 000 mass%. In the present invention, the sulfonic acid group is considered to be a sulfonic acid group contained in the shell resin. According to the present invention, when the content of the sulfonic acid group is in the above range, the adsorptivity between the core particles and the shell resin is improved. For this reason, even if the addition amount of the resin for the shell contained in the toner is reduced, the physical property values specified in the present invention can be expressed well, and the durability stability performance and low-temperature fixing performance of the toner can be further improved. Can do. The sulfur element content is more preferably 0.050 to 0.500% by mass, and still more preferably 0.100 to 0.500% by mass. The content of the elemental sulfur is particularly preferably 0.100 to 0.300% by mass.

  When the content of the THF-insoluble component is less than 3.0% by mass, the shell resin may be easily embedded in the core particles. Further, the offset resistance performance and the image storage performance of the toner are likely to deteriorate. When the content of the THF-insoluble component exceeds 45.0% by mass, the shell resin may be easily peeled off from the toner particle surface. Further, the low-temperature fixing performance and gloss performance of the toner are liable to deteriorate. For this reason, the content of the THF-insoluble component is more preferably 6.0 to 35.0% by mass, and particularly preferably 8.0 to 25.0% by mass. The content of the THF-insoluble component can be controlled by the types and addition amounts of the binder resin and the crosslinking agent, toner production conditions, and the like.

  The THF soluble component contained in the toner preferably has a weight average molecular weight (Mw) in terms of polystyrene (St) by gel permeation chromatography (GPC) of 8,000 to 300,000. Moreover, it is preferable that the ratio (Mw / Mn) of the number average molecular weight (Mn) and Mw determined by the above measurement is 2.0 to 20.0. When the THF-soluble component has Mw and Mw / Mn in the above-described range, the low-temperature fixing performance, penetration resistance, and offset resistance performance of the toner are further improved. When the Mw is less than 8000, the durability stability performance, offset resistance performance and image stacking performance of the toner may be deteriorated. When the Mw exceeds 300,000, the low-temperature fixing performance and gloss performance of the toner may be deteriorated. Similarly, when the Mw / Mn is less than 2.0, the toner durability stability performance, anti-offset performance, and image stacking performance may deteriorate. When the Mw / Mn exceeds 20.0, the low-temperature fixing performance and gloss performance of the toner may be deteriorated. The Mw range is more preferably a molecular weight of 30,000 to 150,000, and particularly preferably a molecular weight of 50,000 to 150,000. The range of Mw / Mn is more preferably 2.0 to 10.0, and particularly preferably 3.0 to 8.0.

  In order to have the Mw and Mw / Mn within the above ranges, it is possible to control the type and amount of the crosslinking agent and polymerization initiator, the production conditions of the toner, and the like.

  The toner of the present invention preferably has an average circularity in the range of 0.945 to 0.995 by a flow type particle image analyzer. More preferably, it is 0.965 to 0.995, and particularly preferably 0.975 to 0.990. When the average circularity is less than 0.945, the toner particles are easily cracked from the concave and convex portions of the toner particles in the developing device, and the broken toner particles are deposited on the charging member and the like, and the durability and stability performance is deteriorated. It becomes easy. In the toner particles containing the shell resin as in the present invention, if the shell resin content is not uniform among the toner particles, the shell resin forms a concave portion or a convex portion of the toner particles and averages. The circularity tends to be a small value, and the shell resin is easily peeled off in the developing device. When the average circularity is larger than 0.995, the toner is easily packed in an excessively dense manner, and when the low temperature fixing performance is aimed at, the durability stability performance may be lowered.

  Further, the standard deviation of the circularity obtained by the above measurement is preferably 0.050 or less from the viewpoint of the durability stability performance of the toner. When the standard deviation exceeds 0.050, the shell resin easily peels off from the surface of the toner particles, and the durability stability performance of the toner tends to decrease. The standard deviation is more preferably 0.045 or less, and further preferably 0.040 or less.

  The toner of the present invention preferably has a content of particles of 2.0 μm or less in a number distribution by a flow type particle image analyzer of 20.0% by number or less. When the content of the particles exceeds 20% by number, the particles are accumulated in the charging member or the like in the developing device, and the durability and stability performance tends to be lowered. As in the toner to which the present invention can be applied, in the toner particles containing the shell resin, if the shell resin content is not uniform on the toner particle surface, the shell resin is detected as particles of 2 μm or less. The durability stability performance of the toner is likely to decrease. The content of the particles of 2.0 μm or less is more preferably 15.0% by number or less, further preferably 10.0% by number or less, and 5.0% by number or less. Particularly preferred.

  Next, materials that can be used for the toner of the present invention and a method for producing the same will be described.

  Specific examples of the monomer that can be used for the binder resin of the present invention include the following compounds.

  Examples of the vinyl monomer for producing the vinyl polymer include the following compounds.

  Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene and derivatives thereof such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated such as butadiene and isoprene Polyenes; vinyl chloride, vinyl chloride, vinyl bromide, fluoride Vinyl halides such as vinyl; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid-n-butyl, isobutyl methacrylate, methacrylic acid- α-methylene aliphatic monocarboxylic esters such as n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate; L-acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid Acrylic acid esters such as 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  Furthermore, the following compounds are mentioned.

  Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; unsaturated such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride Dibasic acid anhydride: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid Half-esters of unsaturated dibasic acids such as acid methyl half ester, fumaric acid methyl half ester and mesaconic acid methyl half ester; Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid; Acrylic acid, Methacrylic acid Α, β-unsaturated acids such as crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, and anhydrous α and β-unsaturated acids and lower fatty acids. A monomer having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof.

  Furthermore, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1) -Methylhexyl) Monomers having a hydroxy group such as styrene.

  In the toner of the present invention, the vinyl polymer unit of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds. Examples of diacrylate compounds linked by an alkyl chain include the following compounds. Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate and the above compounds The acrylate was replaced with methacrylate. Examples of the diacrylate compounds linked by an alkyl chain containing an ether bond include the following compounds. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds are replaced with methacrylate. Examples of diacrylate compounds linked by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacrylate and polyoxyethylene (4) -2. , 2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing acrylate of the above compound with methacrylate.

  Examples of the polyfunctional crosslinking agent include the following compounds.

  Pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds are replaced by methacrylate; triallyl cyanurate, triallyl trimellitate.

  The hybrid resin used in the present invention preferably contains a monomer component capable of reacting with both resin components in one or both of the vinyl polymer unit component and the polyester unit. Examples of the monomer constituting the polyester unit that can react with the vinyl polymer unit include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl polymer unit, those that can react with the polyester unit include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  As a method of obtaining a reaction product of a vinyl polymer unit and a polyester unit, a polymer containing a monomer component capable of reacting with each unit is present, and a polymerization reaction of one or both resins is performed. The method obtained by

  As a polymerization initiator used when manufacturing the vinyl polymer of this invention, the following compounds are mentioned, for example.

  2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2 , 2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyro Nitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone Ketone peroxides such as peroxide, acetylacetone peroxide, cyclohexanone peroxide, 2,2-bis (t-butyl) Peroxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumylper Oxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide Oxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxy -Bonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t- Butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl per Oxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxyhexahydroterephthalate, di-t-butyl peroxyazelate.

  The toner of the present invention contains one kind or two or more kinds of waxes. Examples of the wax that can be used in the present invention include the following compounds.

  Low molecular weight polyethylene, low molecular weight polypropylene, olefin copolymers, aliphatic hydrocarbon waxes such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; aliphatic hydrocarbon waxes Block copolymer; wax mainly composed of fatty acid ester such as carnauba wax and montanic acid ester wax; and deoxidized part or all of fatty acid ester such as deoxidized carnauba wax. Examples of the ester wax include behenyl behenate and stearyl stearate.

  Examples thereof include partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and the like.

  Particularly preferably used waxes are aliphatic hydrocarbon waxes such as paraffin wax, polyethylene, and Fischer-Tropsch wax that have a short molecular chain and little steric hindrance and excellent mobility.

  In the molecular weight distribution of the wax, the main peak is preferably in the region of molecular weight 350 to 2400, and more preferably in the region of molecular weight 400 to 2000. By giving such a molecular weight distribution, preferable thermal characteristics can be imparted to the toner.

  The wax content is preferably 3 to 30 parts by mass with respect to 100 parts by mass of the binder resin. In the toner of the present invention, a part of the wax contained in the toner is used as a plasticizer by being compatible with a binder resin when the toner is produced. Further, in the fixing step, a part of the wax contained in the toner is compatible with the binder resin and used as a plasticizer. For this reason, since all of the wax contained in the toner does not act as a release agent, it is preferable to contain more wax than usual. If the wax content is less than 3 parts by mass, the anti-offset performance tends to decrease. When the wax content exceeds 30 parts by mass, the endothermic amount of the wax in the fixing process becomes too large, and the low-temperature fixing performance tends to be lowered. The wax content of the toner of the present invention is more preferably 5 to 20 parts by mass, and particularly preferably 6 to 14 parts by mass.

  When the above physical properties are required, the extraction method is not particularly limited and any method can be used when the wax needs to be extracted from the toner.

  For example, a predetermined amount of toner is Soxhlet extracted with toluene, and after removing the solvent from the obtained toluene-soluble component, a chloroform-insoluble component is obtained.

  Thereafter, identification analysis is performed by IR method or the like.

  In addition, quantitative analysis is performed by DSC.

  Among these wax components, those having a maximum endothermic peak in the region of 60 to 140 ° C. in the DSC curve measured by a differential scanning calorimeter are preferable, and those having the maximum endothermic peak in the region of 60 to 90 ° C. Further preferred. By having the maximum endothermic peak in the above temperature range, it is possible to effectively exhibit releasability while greatly contributing to low-temperature fixing. If this maximum endothermic peak is less than 60 ° C., the self-aggregation force of the wax component becomes weak, and the offset resistance performance of the toner may be reduced. On the other hand, when the maximum endothermic peak exceeds 140 ° C., the low-temperature fixing performance of the toner tends to be lowered.

  The toner of the present invention may use a charge control agent.

  Examples of the charge control agent for controlling the toner particles to be negatively charged include the following.

  Organometallic compound, chelate compound, monoazo metal compound, acetylacetone metal compound, urea derivative, metal-containing salicylic acid compound, metal-containing naphthoic acid compound, quaternary ammonium salt, calixarene, silicon compound, nonmetal carboxylic acid compound and derivatives thereof .

  Further, as the charge control agent for controlling the toner particles to be positively charged, for example, the following charge control agent can be used.

  Modified products with nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof And these lake pigments, triphenylmethane dyes and these lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide) ), Metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin borate Diorgano tin borate such as theft. These can be used alone or in combination of two or more. Among these, a charge control agent such as a nigrosine-type quaternary ammonium salt is particularly preferably used.

  The charge control agent is preferably contained in an amount of 0.01 to 20 parts by weight, more preferably 0.5 to 10 parts by weight per 100 parts by weight of the binder resin in the toner particles.

  The toner particles of the present invention contain a colorant. As the black colorant, carbon black, a magnetic material, or a color toned to black using a yellow / magenta / cyan colorant shown below is used.

  As the colorant for cyan toner, magenta toner, and yellow toner, for example, the following colorants can be used.

  As the yellow colorant, compounds represented by monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used as pigments. Specifically, the following pigments are preferably used.

  C. I. Pigment Yellow 3, 7, 10, 12 to 15, 17, 23, 24, 60, 62, 73, 74, 75, 83, 93 to 95, 99, 100, 101, 104, 108 to 111, 117, 120, 123, 128, 129, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168 to 177, 179, 180, 181, 183, 185, 191: 1, 191, 192, 193, 199, 214.

  Examples of the dye system include C.I. l. Solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. Disperse Yellow 42, 64, 201, 211 can be mentioned.

  As the magenta colorant, monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, the following colorants are mentioned. C. I. Pigment Red 2, 3, 5 to 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19 and the like can be exemplified.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds can be used. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

  As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

  These colorants can be used alone or mixed and further used in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 0.4 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  The polyester that the core particles have together with the styrene-acrylic resin preferably includes a polyester having an alcohol having an ether bond as a divalent alcohol component. Specific examples of the dihydric alcohol having an ether bond include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3.3) -2,2-bis. (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2, Alkylene oxide adducts of bisphenol A such as 2-bis (4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane; diethylene glycol, triethylene glycol, dipropylene glycol, Polyethylene glycol, polypropylene glycol, polytetramethylene glycol It can be mentioned compounds represented by or following Formula 2; Lumpur, bisphenol derivative represented by the following formula 1.

（式中、Ｒはエチレンまたはプロピレン基を示し、ｘ，ｙはそれぞれ１以上の整数を示し、且つｘ＋ｙの平均値は２乃至１０を示す。）

(In the formula, R represents an ethylene or propylene group, x and y each represents an integer of 1 or more, and the average value of x + y represents 2 to 10.)

（式中、Ｒ’はエチレン、プロピレン、又は、ブチレン基を示す。）

(In the formula, R ′ represents ethylene, propylene, or a butylene group.)

  That the resin for the shell is a polyester having an alcohol having an ether bond as a divalent alcohol component is compatible with low-temperature fixing performance, blocking resistance, durability stability performance, offset resistance performance, and image storage performance of the toner. This is preferable. Having many ether bonds in the main chain has moderate affinity with the core layer, so even when the amount of shell resin added is small, the coating state of the shell resin on the core particles tends to be more uniform. .

  Examples of the polyvalent carboxylic acid component used in combination with the dihydric alcohol include the following compounds.

  Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides; substituted with an alkyl group having 6 to 12 carbon atoms Succinic acid or anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof; n-dodecenyl succinic acid, isododecenyl succinic acid, trimellitic acid.

  Among them, in particular, a bisphenol derivative represented by the above chemical formula 1 and an alkyl diol having 2 to 6 carbon atoms are used as a diol component, and it consists of a divalent carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof. Carboxylic acid components (for example, fumaric acid, maleic acid, maleic acid, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, alkyl dicarboxylic acids having 4 to 10 carbon atoms, and acid anhydrides of these compounds) As the acid component, polyester obtained by polycondensation of these is preferable as a toner because it has good charging characteristics.

  The toner particles of the present invention contain a magnetic material and can be used as a magnetic toner. In this case, the magnetic material can also serve as a colorant. In the present invention, examples of the magnetic material include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel. Or alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof. .

  These magnetic materials preferably have an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount to be contained in the toner is 20 to 200 parts by mass, particularly preferably 40 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

  The magnetic material has a coercive force (Hc) of 1.59 to 23.9 kA / m (20 to 300 oersted), saturation magnetization (σs) of 50 to 200 emu / g when 796 kA / m (10 koersted) is applied. A magnetic material having a remanent magnetization (σr) of 2 to 20 emu / g is preferable.

  In the toner of the present invention, one or more inorganic fine particles selected from silica and titanium oxide or one or more inorganic fine particles selected from hydrophobic silica and titanium oxide are externally added to the toner particles as a fluidity improver. It is preferable to be mixed. For example, titanium oxide fine particles, silica fine particles, and alumina fine particles are preferably added and used, and silica fine particles are particularly preferably used.

The inorganic fine powder used in the toner of the present invention has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, and particularly in the range of 50 to 400 m ² / g gives good results. Is preferable.

  Furthermore, the toner of the present invention may have an external additive other than the fluidity improver mixed with the toner particles as necessary.

For example, for the purpose of improving the cleaning property, it is one of preferable modes to further add fine particles having a primary particle size exceeding 30 nm (preferably having a specific surface area of less than 50 m ² / g) to the toner particles. More preferably, it is one or more inorganic fine particles or organic fine particles selected from silica and titanium oxide having a primary particle size of 50 nm or more (preferably having a specific surface area of less than 30 m ² / g) and a nearly spherical shape. For example, spherical silica fine particles, spherical polymethylsilsesquioxane fine particles, and spherical resin fine particles are preferably used.

  Further, other additives shown below can also be added in small amounts as developability improvers.

  Lubricant powder such as fluororesin powder, zinc stearate powder, polyvinylidene fluoride powder; or abrasive such as cerium oxide powder, silicon carbide powder, strontium titanate powder; anti-caking agent; or, for example, carbon black powder, zinc oxide powder, Conductivity imparting agent such as tin oxide powder; organic fine particles with reverse polarity and one or more inorganic fine particles selected from silica and titanium oxide. These additives can also be used after the surface is hydrophobized. It is.

  The external additive as described above may be used in an amount of 0.1 to 5 parts by mass (preferably 0.1 to 3 parts by mass) with respect to 100 parts by mass of the toner.

  When the core particles used in the toner of the present invention are produced by a pulverization method, a known method can be used. For example, components such as a binder resin, a release agent and a charge control agent, and other additives are sufficiently mixed in a mixer such as a Henschel mixer or a ball mill. Thereafter, the mixture is melt-kneaded using a heat kneader such as a heating roll, a kneader, and an extruder to mutually melt the resins. Toner particles are obtained by a multi-step process in which other toner materials such as magnetite are dispersed or dissolved, cooled, solidified, and pulverized, followed by classification and surface treatment with resin fine particles. A toner can be obtained by adding and mixing fine powder or the like to the obtained toner particles as necessary. Either the classification or the surface treatment may be performed first. In the classification step, it is preferable to use a multi-division classifier from the viewpoint of production efficiency.

  The pulverization step can be performed using a known pulverizer such as a mechanical impact type or a jet type. In order to obtain a developer having a specific circularity according to the present invention, it is preferable to further pulverize by applying heat or to add a mechanical impact in an auxiliary manner. Further, a hot water bath method in which finely pulverized (classified as necessary) toner particles are dispersed in hot water, a method of passing in a hot air stream, or the like may be used.

  As a method of applying a mechanical impact force, for example, there is a method using a mechanical impact type pulverizer such as a kryptron system manufactured by Kawasaki Heavy Industries, Ltd. or a turbo mill manufactured by Turbo Industry. Alternatively, a method may be used in which toner particles are pressed against the inside of the casing by centrifugal force with blades rotating at high speed, and mechanical impact force is applied to the toner particles by force such as compression force or friction force. As such an apparatus, for example, a mechano-fusion system manufactured by Hosokawa Micron Corporation, a hybridization system manufactured by Nara Machinery Co., Ltd., or the like can be used.

  Further, the toner of the present invention is a method of atomizing a molten mixture into air using a disk or a multi-fluid nozzle to obtain substantially spherical toner particles, or a water-based organic insoluble in a polymer that is soluble in a monomer. It can be manufactured using a dispersion polymerization method in which toner particles are directly generated using a solvent. Furthermore, a method for producing toner particles using an emulsion polymerization method typified by a soap-free polymerization method in which toner particles are produced by direct polymerization in the presence of a water-soluble polar polymerization initiator, a dissolution suspension method, an emulsification Manufacture is also possible by agglomeration.

  A particularly preferred production method is a suspension polymerization method obtained by directly polymerizing a polymerizable monomer in an aqueous medium.

  In the production of toner particles by the suspension polymerization method, in general, a polymerizable monomer, a colorant, a wax, a charge control agent, a cross-linking agent, etc. are uniformly distributed by a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser. Dissolve or disperse in The monomer composition thus obtained is suspended in an aqueous medium containing a dispersion stabilizer. At this time, the particle size distribution of the obtained toner particles becomes sharper by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired toner particle size at a stretch. The polymerization initiator may be added in advance to the monomer composition, or may be added after the monomer composition is suspended in an aqueous medium.

  After the suspension, stirring may be performed using an ordinary stirrer to such an extent that the particle state is maintained and the floating / sedimentation of the particles is prevented. In the present invention, the pH is preferably 4 to 10.5 when suspended. If the pH is less than 4, the toner may have a wide particle size distribution. On the other hand, if the pH exceeds 10.5, the charging performance of the toner may deteriorate.

  In the suspension polymerization method, known surfactants and organic / inorganic dispersants can be used as dispersion stabilizers. Among these, inorganic dispersants can be preferably used because their stability is not easily lost even when the reaction temperature is changed. Examples of such inorganic dispersants include the following compounds.

  Multivalent metal phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; inorganic salts such as calcium metasuccinate, calcium sulfate and barium sulfate; Inorganic oxides such as calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite and alumina.

  These inorganic dispersants are preferably used alone or in combination of two or more, with respect to 100 parts by weight of the polymerizable monomer. When aiming at a more finely divided toner having an average particle diameter of 5 μm or less, 0.001 to 0.1 parts by mass of a surfactant may be used in combination. The surfactant that can be used is the same as described above.

  When these inorganic dispersants are used, they may be used as they are, but in order to obtain finer particles, it is preferable to produce the inorganic dispersant in an aqueous medium. Specifically, for example, in the case of tricalcium phosphate, it is possible to produce a poorly water-soluble tricalcium phosphate by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution with high-speed stirring. Distribution becomes possible. The inorganic dispersant can be almost completely removed by dissolving with an acid or alkali after completion of the polymerization.

  In the polymerization step, the polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. When the polymerization is performed within this temperature range, the binder resin and the wax are phase-separated with the progress of the polymerization, and a toner in which the wax is encapsulated is obtained. It is also preferable to raise the reaction temperature to 90 to 150 ° C. at the end of the polymerization reaction.

  The toner of the present invention can be used as a one-component developer, and can also be used as a two-component developer having a toner and a carrier.

When used as a two-component developer, it is used as a developer in which the toner of the present invention and a carrier are mixed. The carrier is composed of an element selected from iron, copper, zinc, nickel, cobalt, manganese, and chromium element alone or a composite ferrite. As the shape of the carrier, there are a sphere or a substantially spherical shape, a flat shape or an indeterminate shape, any of which can be used. Among them, the carrier is preferably a magnetic carrier having a resin component on the surface and a true density of 2.5 to 4.2 g / cm ³ .

The carrier combined with the toner of the present invention is not particularly limited as long as it is the above magnetic carrier. For example,
(1) A magnetic substance-containing resin carrier containing a resin component on the surface of a magnetic substance-containing resin carrier core in which the magnetic substance is dispersed in the resin. (2) A resin is impregnated with a porous magnetic substance (including porous ferrite). And a resin impregnated carrier.

  (1) The magnetic substance-containing resin carrier will be described.

  As a method for producing the core of the magnetic substance-containing resin carrier, there is a method obtained by polymerizing monomers constituting the resin in the presence of the magnetic substance.

  At this time, as monomers used for polymerization, in addition to vinyl monomers, bisphenols and epichlorohydrin for forming epoxy resins; phenols and aldehydes for forming phenol resins; urea resins are formed Urea and aldehydes for forming; melamine and aldehydes for forming melamine resin are used.

  Phenol resin is preferable as the resin for forming the magnetic substance-containing resin carrier used in the present invention. As phenols for producing the phenol resin, m-cresol, p-tert-butylphenol, o-, in addition to phenol, are used. Examples thereof include compounds having a phenolic hydroxyl group such as alkylphenols such as propylphenol, resorcinol, and bisphenol A, and halogenated phenols in which a benzene nucleus or alkyl group is partially or entirely substituted with a chlorine atom or a bromine atom. Of these, phenol (hydroxybenzene) is more preferable.

  Examples of aldehydes for producing the phenol resin include formaldehyde and furfural in the form of either formalin or paraaldehyde. Of these, formaldehyde is particularly preferable.

  The molar ratio of aldehydes to phenols is preferably 1 to 4, particularly preferably 1.2 to 3. If the molar ratio of aldehydes to phenols is less than 1, the strength of the particles produced may be weakened. On the other hand, if the molar ratio of aldehydes to phenols is greater than 4, unreacted aldehydes remaining in the aqueous medium after the reaction may increase.

  Examples of the basic catalyst used for polycondensation of phenols and aldehydes include those used in the production of ordinary resol type resins. Examples of such basic catalysts include aqueous ammonia, hexamethylenetetramine, and alkylamines such as dimethylamine, diethyltriamine, and polyethyleneimine. The molar ratio of these basic catalysts to phenols is preferably 0.02 to 0.30.

In the magnetic substance-containing resin carrier core, the magnetic substance is preferably magnetite fine particles or magnetic ferrite fine particles containing at least an iron element. Further, in order to adjust the magnetic properties of the carrier, a part of the magnetic material contained in the magnetic material-containing resin carrier may be replaced with a nonmagnetic inorganic compound. It is more preferable that the nonmagnetic inorganic compound is hematite (α-Fe ₂ O ₃ ) fine particles in order to make the dispersibility in the carrier uniform and adjust the magnetic properties and true density of the carrier. A nonmagnetic inorganic compound has a specific resistance value larger than that of a magnetic substance.

  The number average particle size of the magnetic material is preferably 0.02 to 2 μm from the viewpoint of making the state of the carrier particle surface uniform. The nonmagnetic inorganic compound preferably has a number average particle diameter of 0.05 to 5 μm, and the nonmagnetic inorganic compound has a particle diameter of 1.1 times or more larger than that of the magnetic substance. It is preferable for increasing the surface resistance value.

  The amount of the magnetic material used for the magnetic substance-containing resin carrier core is 70 to 95% by mass (more preferably 80 to 92% by mass) with respect to the magnetic substance-containing resin carrier core. It is preferable for reducing the density and sufficiently securing the mechanical strength.

  Further, the magnetic substance is contained in an amount of 30 to 99% by mass with respect to the total amount of the magnetic substance and the nonmagnetic inorganic compound in the magnetic substance-containing resin carrier core. It is preferable to adjust to prevent carrier adhesion and to adjust the specific resistance value of the magnetic substance-containing resin carrier core.

  As a method for producing a magnetic substance-containing resin carrier core using a phenol resin, for example, in an aqueous medium containing phenols, aldehydes, and a magnetic substance, phenols and aldehydes are polymerized in the presence of a basic catalyst. Thus, a magnetic substance-containing resin carrier core can be obtained. When a magnetic substance-containing resin carrier core is manufactured by this method, the average circularity is easily adjusted to the above range, and this method is a preferable manufacturing method.

  As another method for manufacturing the above-mentioned magnetic material-containing resin carrier core, a vinyl-based or non-vinyl-based thermoplastic resin, a magnetic material, and other additives are sufficiently mixed by a mixer, and then heated rolls, kneaders, extensibles. There is a method in which a magnetic material-containing resin carrier core is obtained by melting and kneading using a kneader such as a ruder, cooling this, and then crushing and classifying. At this time, it is preferable to thermally or mechanically spheroidize the obtained magnetic substance-containing resin carrier core and use it as a magnetic substance-containing resin carrier core.

  The surface of the carrier core is preferably coated with a coating resin from the viewpoint of imparting charge to the toner and releasability. As the coating resin, an insulating resin is preferably used. The insulating resin that can be used in this case may be a thermoplastic resin or a thermosetting resin.

  The following resin is mentioned as an example of a thermoplastic resin.

  Polystyrene; Acrylic resin such as polymethyl methacrylate and styrene-acrylic acid copolymer; Styrene-butadiene copolymer; Ethylene-vinyl acetate copolymer; Polyvinyl chloride; Polyvinyl acetate; Polyvinylidene fluoride resin; Fluorocarbon resin; Fluorocarbon resin; solvent-soluble perfluorocarbon resin; polyvinyl alcohol; polyvinyl acetal; polyvinyl pyrrolidone; petroleum resin; cellulose derivatives such as cellulose, cellulose acetate, cellulose nitrate, methylcellulose, hydroxymethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose; novolak resin; low molecular weight Polyethylene; saturated alkyl polyester resin; polyethylene terephthalate, polybutylene terephthalate, poly Aromatic polyester resins such Reto; polyamide resin; polyacetal resin; polycarbonate resins; polyether sulfone resins; polysulfone resin; polyphenylene sulfide resins; polyether ketone resins.

  Examples of thermosetting resins include phenolic resins, modified phenolic resins, maleic resins, alkyd resins, epoxy resins, acrylic resins, unsaturated polyesters obtained by polycondensation of maleic anhydride, terephthalic acid and polyhydric alcohols, urea Resin, melamine resin, urea-melamine resin, xylene resin, toluene resin, guanamine resin, melamine-guanamine resin, acetoguanamine resin, gliptal resin, furan resin, silicone resin, polyimide, polyamideimide resin, polyetherimide resin, polyurethane resin Is mentioned.

  The above-mentioned resins can be used alone or in combination. In addition, a curing agent or the like can be mixed with a thermoplastic resin and cured for use. As a particularly preferable form, it is preferable to use a resin having a higher release property for a toner having a small particle diameter and containing a release agent.

  Furthermore, the coat resin may contain particles having conductivity and particles having charge controllability. Such a coating resin is preferably coated on the carrier core by an appropriate method, either alone or by adding conductive particles or charge controllable particles to the monomer forming the resin. These particles are preferably contained from the viewpoint of providing a soft and quick charge to a toner having a small particle size and having a low-temperature fixability.

The conductive particles preferably have a specific resistance of 1 × 10 ⁸ Ωcm or less, and more preferably have a specific resistance of 1 × 10 ⁶ Ωcm or less. Specifically, the conductive particles are preferably particles containing at least one kind of particles selected from carbon black, magnetite, graphite, zinc oxide, and tin oxide. In particular, as the particles having conductivity, carbon black having good conductivity is preferable in terms of improving the charge imparting property (rise of charge amount) to the toner.

  It is preferable that the conductive particles have a number average particle size of 1 μm or less in order to prevent the particles from falling off from the carrier and to function as a uniform conductive site.

  The particles having charge controllability include organometallic complex particles, organometallic salt particles, chelate compound particles, monoazo metal complex particles, acetylacetone metal complex particles, hydroxycarboxylic acid metal complex particles, and polycarboxylic acid. Examples include metal complex particles and polyol metal complex particles. A charge control agent dispersed in the toner particles may be used, but use of resin particles having a functional group or inorganic particles treated with a treatment agent having a functional group improves the charge imparting property to the toner. It is preferable for this purpose.

  Specific examples of the particles having charge controllability include polymethyl methacrylate resin particles, polystyrene resin particles, melamine resin particles, phenol resin particles, nylon resin particles, silica particles, titanium oxide particles, And particles containing at least one kind of particles selected from alumina particles. Further, in the case of inorganic particles, it is preferable to use them after being treated with various coupling agents in order to develop charge controllability and conductivity.

  The particles having charge control properties preferably have a number average particle diameter of 0.01 to 1.50 μm from the viewpoint of functioning as a uniform charging site.

  The coating amount of the coating resin on the carrier core is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the carrier core, thereby improving the charge imparting property to the toner and the durability of the magnetic carrier. Preferred above. The blending amount of the conductive particles and the charge controllable particles is preferably 0.1 to 30 parts by mass in total with respect to 100 parts by mass of the coating resin.

  When the conductive particles or the charge controllable particles are added in an amount exceeding 30 parts by mass, the particles are difficult to disperse in the coating resin, and the particles may be detached from the magnetic carrier. In particular, when carbon black is added, the toner may be contaminated with carbon black or the member may be contaminated as the durability increases.

  (2) The resin-impregnated carrier will be described.

  The core of the resin-impregnated carrier is manufactured using a porous magnetic material. Examples of porous magnetic materials include Ca—Mg—Fe ferrite, Li—Fe ferrite, Mn—Mg—Fe ferrite, Ca—Be—Fe ferrite, Mn—Mg—Sr—Fe ferrite, Li -Ferrite magnetic bodies of iron-based oxides such as -Mg-Fe-based ferrite and Li-Rb-Fe-based ferrite are included. Ferrites of iron-based oxides can be obtained by mixing metal oxides, carbonates, nitrates, and the like in a wet or dry manner and calcining to obtain a desired ferrite composition. The obtained iron oxide ferrite is pulverized to submicron. To the pulverized ferrite, 20 to 50% by mass of water for adjusting the particle size is added to the ferrite, and 0.1 to 10% by mass of, for example, polyvinyl alcohol (molecular weight 500 to 10,000) is added as a binder, and pores are further added. A slurry is prepared by adding 0.5 to 15% by mass of a metal carbonate such as calcium carbonate for controlling the density.

  The slurry can be granulated using a spray dryer or the like to obtain a porous magnetic material. Here, the particle size of the porous magnetic material can be controlled by appropriately adjusting the viscosity of the slurry and the size of the nozzle of the spray dryer.

  A resin-impregnated carrier can be produced by impregnating the core of the resin-impregnated carrier thus produced with a coat resin. Any coating resin may be used. For example, the resin used in the magnetic substance-containing resin carrier can be used.

  The carrier used for the two-component developer and the replenishment developer of the present invention has a 50% particle size (D50) of 15 to 70 μm based on volume distribution. The thickness is preferably 20 to 70 μm, more preferably 25 to 60 μm. When the 50% particle size (D50) based on the volume distribution of the magnetic carrier is within this range, an image with good dot reproducibility can be obtained over a long period of time without fogging. When the 50% particle size (D50) based on the volume distribution of the carrier is less than 15 μm, the fluidity of the carrier is lowered, and the durability stability performance of the toner may be lowered. If it exceeds 70 μm, the carrier particle size is large, so that the density of the magnetic brush becomes rough and the graininess of the image may become rough.

  The particle size of the carrier can be within the above range by classification with an air classifier (Elbow Jet Lab EJ-L3, manufactured by Nippon Steel Mining Co., Ltd.) or the like.

  A method for measuring the 50% particle size (D50) based on the volume distribution will be described later.

The true density of the carrier is 2.5 to 4.2 g / cm ³ , preferably 2.7 to 4.1 g / cm ³ , more preferably 3.0 to 4.0 g / cm ³ . Since the true density of the carrier is small, the phenomenon that the toner and the carrier deteriorate in the developing machine is suppressed.

  Furthermore, when a two-component development method is used in which a developer for replenishment containing toner and a carrier is developed while being replenished to the developer, and the excess carrier inside the developer is discharged from the developer as needed. Since the specific gravity difference between the carrier and the toner is small, the excess carrier is pumped up to the developer recovery port, and the excess carrier in the developing device can be effectively discharged. For this reason, high image quality can be maintained over a long period of time.

  A method for measuring the true density of the carrier will be described later.

The magnetization strength of the carrier is preferably 40 to 70 Am ² / kg under a magnetic field of 1000 / 4π (kA / m). When the carrier is within this range, an image with good dot reproducibility can be obtained over a long period of time. When the intensity of magnetization of the carrier is less than 40 kAm ² / kg, it is easy to be developed on the photosensitive drum at the time of development, and carrier adhesion may occur. When the magnetization intensity of the carrier exceeds 70 kAm ² / kg, the stress on the developer between the regulating blade 9 and the developing sleeve 8 increases, and the carrier may be deteriorated.

  A method for measuring the magnetization intensity will be described later.

  The carrier preferably contains 90% by number or more of particles having an average circularity of 0.85 to 0.95 and a circularity of 0.80 or more. The average circularity is preferably 0.87 to 0.93, more preferably 0.88 to 0.92. The average circularity is a coefficient representing the shape of the roundness of the particle, and is obtained from the maximum diameter of the particle and the measured particle projected area. An average circularity of 1.00 indicates a perfect sphere (perfect circle), and a smaller numerical value indicates an elongated or irregular shape.

  When the average circularity of the carrier is 0.85 to 0.95, it has sufficient carrier strength, excellent chargeability to the toner, and hardly adheres to the toner and toner components, and has excellent durability. . When the average circularity is less than 0.85, it means that the particles have an irregular shape. In this case, the charge imparting property to the toner may be deteriorated. Further, when the average circularity of the carrier exceeds 0.95, the specific surface area of the carrier becomes small, and the chargeability of the toner may be lowered.

  A method for measuring the average circularity of the carrier will be described later.

  When toner and carrier are mixed and used as a two-component developer in the developing device, the mixing ratio of toner and carrier should be 0.02 to 0.35 parts by mass with respect to 1 part by mass of carrier. Is preferable, 0.04 to 0.25 parts by mass is more preferable, and 0.05 to 0.20 parts by mass is particularly preferable. If the amount is less than 0.02 parts by mass, the image density may decrease. If the amount exceeds 0.35 parts by mass, fog and in-flight scattering may occur.

<Measurement of polystyrene equivalent molecular weight by gel permeation chromatography (GPC)>
In the present invention, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the maximum value (Mp) of the molecular weight distribution by GPC are values determined by the following methods.

A sample to be measured is placed in tetrahydrofuran (THF) and left at room temperature for 24 hours. This is filtered with a disposable filter for high performance liquid chromatograph (HPLC) “Mysholy disk H-25-5” (manufactured by Tosoh Corporation) to obtain a sample solution. Using this sample solution, measurement is performed under the following conditions. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using the following standard sample is used. Polymer Laboratories standard polystyrene Easy PS-1 (Molecular weights 750,000, 841700, 148000, 28500, 2930, and molecular weights 256,000, 320,000, 59500, 9920, 580) and PS-2 (Molecular weights 377400, 96000, 19720) , 4490, 1180 and mixtures of molecular weights 188700, 46500, 9920, 2360, 580). An RI (refractive index) detector is used as the detector.

<Measurement of the content of THF-soluble or insoluble components in the toner and the resin used>
It is measured by the Soxhlet extraction method shown below.

Cylindrical filter paper (for example, Toyo Filter Paper No. 86R can be used) is vacuum-dried at a temperature of 40 ° C. for 24 hours and then left in an environment adjusted to a temperature and humidity of 25 ° C. and 60% RH for 3 days. . About 2.0 g of the sample to be measured is weighed on the cylindrical filter paper, and the weight of the sample at this time is defined as W1 (g). Using a Soxhlet extractor, 200 ml of THF is used as a solvent, and extraction is performed in an oil bath at a temperature of 90 ° C. for 24 hours. Thereafter, the cylindrical filter paper is gently taken out and vacuum-dried at a temperature of 40 ° C. for 24 hours. After leaving this in an environment adjusted to a temperature of 25 ° C. and a humidity of 60% RH for 3 days, the amount of solid content remaining on the cylindrical filter paper is weighed, and this is defined as W2 (g). The content of the THF soluble component or insoluble component is calculated from the following formula.
Content of THF-insoluble component of sample (mass%) = (W2 / W1) × 100
Content (mass%) of THF soluble component of sample = 100− (W2 / W1) × 100

  As a sample for measuring the X-ray fluorescence of the THF-soluble component, a solution obtained by distilling off the solvent of the solution extracted by the Soxhlet extractor to recover the resin component and drying in a vacuum at 40 ° C. for 24 hours is used.

<Measurement of Toner and Resin Used, Glass Transition Point (Tg), Melting Point (Tm), Endothermic Amount of Maximum Endothermic Peak, and Measurement of Its Half-width>
In the present invention, the glass transition point (Tg), the temperature of the maximum endothermic peak, the endothermic amount, and the half-value width thereof are measured using a differential scanning calorimeter (DSC). Specifically, for example, Q1000 (manufactured by TA Instruments) can be used as the DSC. As a measuring method, 4 mg of a sample is precisely weighed on an aluminum pan, and an empty aluminum pan is used as a reference pan, and measurement is performed in a nitrogen atmosphere with a modulation amplitude of 1.0 ° C. and a frequency of 1 / min. The measurement temperature was held at 0 ° C. for 10 minutes, and then a reversing heat flow curve obtained by scanning from 0 ° C. to 200 ° C. at a heating rate of 1 ° C./min was used as a DSC curve, and the midpoint method was used. To obtain Tg. The glass transition point determined by the midpoint method is the glass transition point at the intersection of the baseline before the endothermic peak and the baseline after the endothermic peak in the DSC curve at elevated temperature and the rising curve. (See FIG. 2).

  The measurement of the maximum endothermic peak temperature, endothermic amount, and half-value width of the toner is based on the extrapolation of the baseline before the endothermic peak in the reversing heat flow curve obtained by the same measurement as above. In the region surrounded by the endothermic peak and the straight line connecting the extrapolated line of the baseline after the end of the endothermic peak and the point where the endothermic peak is in contact with the endothermic peak, the temperature at which the endothermic peak reaches its maximum value The maximum endothermic peak temperature. When two or more maximum values exist in the peak, the temperature at the maximum value where the length of the connected straight line and the maximum value is long in the enclosed region is set as the temperature of the maximum endothermic peak. Even when two or more of the enclosed regions exist independently, the temperature at the maximum value where the length between the straight line and the maximum value connected in the same manner as described above is long is set as the temperature of the maximum endothermic peak. In addition, the half-value width of the maximum endothermic peak is a point at which the maximum endothermic peak specified above is ½ of the length between the straight line and the maximum value connected in the same manner as described above, and a temperature lower than the maximum value. The temperature width of the line connecting the DSC curve on the side is the half-value width of the maximum endothermic peak.

  In the reversing heat flow curve obtained by the above measurement, the endothermic amount is the point where the endothermic peak departs from the extrapolation line of the baseline before the endothermic peak, the extrapolation line of the baseline after the end of the endothermic peak, and the The endothermic amount (J / g) is obtained from the area (integrated value of the melting peak) of the region surrounded by the straight line connecting the points where the endothermic peak contacts and the endothermic peak. In the case where two or more of the enclosed regions are present independently, they are summed to obtain an endothermic amount.

<Measurement of acid value of resin>
The acid value of the resin is determined as follows. Basic operation conforms to JIS-K0070.

  The number of mg of potassium hydroxide required to neutralize free fatty acids, resin acid groups and the like contained in 1 g of a sample is referred to as an acid value, and is measured by the following method.

(1) Reagent (a) Preparation of solvent As a sample solvent, an ethyl ether-ethyl alcohol mixture (1 + 1 or 2 + 1) or a benzene-ethyl alcohol mixture (1 + 1 or 2 + 1) is used. These solutions are neutralized with a 0.1 mol / liter potassium hydroxide ethyl alcohol solution using phenolphthalein as an indicator immediately before use.
(B) Preparation of phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 v / v%).
(C) Preparation of 0.1 mol / liter potassium hydroxide-ethyl alcohol solution Dissolve 7.0 g of potassium hydroxide in as little water as possible and add ethyl alcohol (95 v / v%) to make 1 liter. Filter after standing for days. The standardization is performed according to JISK 8006 (basic matters concerning titration during the reagent content test).

(2) Operation Weigh correctly 1 to 20 g of sample, add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well until the sample is completely dissolved. In the case of a solid sample, dissolve it by heating on a water bath. After cooling, this was titrated with a 0.1 mol / liter potassium hydroxide-ethyl alcohol solution, and the neutralization end point was reached when the indicator was slightly red for 30 seconds.

(3) Calculation formula The acid value is calculated by the following formula.

A = B × f × 5.661 / S
A: Acid value (mgKOH / g)
B: 0.1 mol / liter-amount of potassium hydroxide ethyl alcohol solution used (ml)
f: 0.1 mol / liter-factor of potassium hydroxide ethyl alcohol solution S: sample (g)

  The hydroxyl value of the resin is determined as follows. Basic operation conforms to JIS-K0070.

  When 1 g of a sample is acetylated by a specified method, the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group is referred to as a hydroxyl value and is measured by the following method.

(1) Preparation of Reagent (a) Acetylation Reagent 25 ml of acetic anhydride is placed in a 100 ml volumetric flask, pyridine is added to make a total volume of 100 ml, and shaken sufficiently. (In some cases, pyridine may be added). The acetylating reagent should be kept in brown bottles away from moisture, carbon dioxide and acid vapors.
(B) Preparation of phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 v / v%).
(C) Preparation of 0.2 mol / L Potassium Hydroxide-Ethyl Alcohol Solution Dissolve 35 g of potassium hydroxide in as little water as possible and add 1 liter of ethyl alcohol (95 v / v%) to 2 to 3 days Filter after standing. The orientation is performed according to JISK 8006.

(2) Operation 0.5 to 20 g of a sample is correctly weighed in a round bottom flask, and 5 ml of an acetylating reagent is correctly added thereto. Put a small funnel over the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at a temperature of 95-100 ° C. and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, a cardboard disk with a round hole in it is put on the base of the neck of the flask. After 1 hour, the flask is removed from the bath, and after cooling, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride. To complete further decomposition, the flask was again heated in a glycerin bath for 10 minutes, allowed to cool, then the funnel and flask wall were washed with 5 ml of ethyl alcohol, and 0.2 mol / liter of phenolphthalein solution was used as an indicator. Titrate with potassium hydroxide ethyl alcohol solution. A blank test is performed in parallel with this test. In some cases, a KOH-THF solution may be used as an indicator.

(3) Calculation formula The hydroxyl value is calculated by the following formula.

A = {(BC) × f × 28.05 / S} + D
A: Hydroxyl value (mgKOH / g)
B: Amount of use of 0.5 mol / liter-potassium hydroxide ethyl alcohol solution in the blank test (ml)
C: Amount used of 0.5 mol / liter-potassium hydroxide ethyl alcohol solution in this test (ml)
f: Factor of 0.5 mol / liter-potassium hydroxide ethyl alcohol solution S: Sample (g)
D: Acid value (mgKOH / g)

<Measurement of average circularity of toner, standard deviation of circularity, and content of particles of 2 μm or less>
It is measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation).

  A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

  For the measurement, the above-mentioned flow type particle image analyzer equipped with “UPlanApro” (magnification 10 times, numerical aperture 0.40) as an objective lens is used, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. It was used. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.

  In the measurement, automatic focus adjustment is performed using standard latex particles (eg, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.985 to 200.0 μm.

  Further, the content of particles of 2 μm or less was determined from the number% of the number of particles having an equivalent circle diameter of less than 1.985 μm determined by the above measurement with respect to the total number of particles.

<Toner particle size measurement>
Specifically, the weight average particle diameter D4 (μm) and the number average particle diameter D1 (μm) of the toner can be measured by the following methods.

  As the apparatus, a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electric resistance method equipped with an aperture tube of 100 μm is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Note that the measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, dedicated software was set up as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and the Kd value is “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. A predetermined amount of ion-exchanged water is placed in a water tank of an ultrasonic disperser, and about 2 ml of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. When the graph / volume% is set with the dedicated software, the “average diameter” on the “analysis / volume statistics (arithmetic average)” screen is the weight average particle diameter (D4), and the graph / number% is set. The “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Measurement of sulfur element content derived from sulfonic acid group contained in THF-soluble component, sulfonic acid group content contained in resin for shell, silica contained in toner, and titanium oxide content>
Measurement was performed using wavelength-dispersed fluorescent X-ray “Axios advanced” (manufactured by PANalytical). About 3 g of the sample was put in a vinyl chloride ring for measuring 27 mm and pressed at 200 kN to mold the sample. The amount of sample used and the thickness of the molded sample were measured, and the above content was determined as an input value for content calculation. Analysis conditions and analysis conditions are shown below.

Analytical conditions / quantitative method: fundamental parameter method / analytical elements: for each element from boron B to uranium U in the periodic table / measurement atmosphere: vacuum / measurement sample: solid / collimator mask diameter: 27 mm
・ Measurement conditions: An automatic program set in advance to the optimum excitation conditions for each element was used. ・ Measurement time: Approx. 20 minutes.

Analysis / analysis program: UniQuant5
-Analysis conditions: Oxide morphology-Balance component: CH ₂
・ Other values used were recommended general values

<Measurement of toner viscosity using a constant load capillary tube rheometer>
A method for measuring the viscosity of the toner using the constant load capillary extrusion rheometer in the present invention will be described. As an apparatus, for example, a flow characteristic evaluation apparatus “Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) is used, and measurement is performed under the following conditions.
Sample: When the true density of toner is ρ, (1.0 × ρ) g of toner is weighed, and this is measured with a pressure molding machine under a load of 200 kgf (1960 N) under a normal temperature and normal pressure environment. A sample is molded by pressing for one minute, and is molded into a cylindrical shape having a diameter of about 10 mm and a height of about 10 mm.
・ Cylinder pressure: 9.81 × 10 ⁵ (Pa)
Measurement mode: Temperature rising method Temperature rising rate: 4.0 ° C./min Heating time: 5.0 minutes Die: Die length 1.0 mm, Die diameter 0.5 mm, and die surface is mirror polished Use die and measurement environment: Temperature 23 ° C Humidity 60%
Measurement start temperature: 25.0 ° C
From the graph of the temperature-viscosity curve obtained by the above measurement, the temperature at which the viscosity becomes 5000 Pa · s and the temperature at which the viscosity becomes 1000 Pa · s are read and set as values of F1 (° C.) and F 2 (° C.), respectively.

<Measurement of particle size of fine particles of resin for shell>
The volume average particle diameter (D3 _s ), the 10% particle diameter (D3 _s10 ), and the 90% particle diameter (D3 _s90 ) of the resin fine particles for the shell are, for example, MICROTRAC UPA MODEL: 9232 (Leeds and Northrup) ) Can be measured. The measurement conditions are as shown below.
Particle Material: Latex
Transparent Particles: Yes
SPECIAL PARTITICLES: Yes
Particle Refractive Index: 1.59
Fluid: water

<Measurement method of primary particle size of inorganic fine particles>
The number average primary particle size of the inorganic fine powder is determined by taking a photograph of the toner magnified (100,000 times) with a scanning electron microscope (S4700, Hitachi, Ltd.) and an X-ray microanalyzer attached to the scanning electron microscope ( XMA) and the like are measured against a photograph of a toner on which the elements contained in the inorganic fine powder are mapped. About 100 particles from the photographed images, when the longest side of the primary particles was a and the shortest side was b, it was determined as (a + b) / 2, and the number average value was used as the primary particle diameter.

<Carrier volume distribution standard 50% particle size (D50) and average circularity>
The 50% particle size (D50) and average circularity based on the volume distribution of the carrier are measured as follows using, for example, a multi-image analyzer (manufactured by Beckman Coulter).

  A solution obtained by mixing about 1% NaCl aqueous solution and glycerin at 50% by volume: 50% by volume is used as the electrolytic solution. Here, the NaCl aqueous solution may be prepared using primary sodium chloride, and may be, for example, ISOTON (registered trademark) -II (manufactured by Coulter Scientific Japan). Glycerin may be a special grade or first grade reagent.

  To the electrolytic solution (about 30 ml), 0.1 to 1.0 ml of a surfactant (preferably alkylbenzenesulfone hydrochloric acid) is added as a dispersant, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is dispersed for about 1 minute with an ultrasonic disperser to obtain a dispersion.

Using a 200 μm aperture and a 20 × lens as the aperture, the equivalent circle diameter and circularity are calculated under the following measurement conditions.
Average luminance within measurement frame: 220 to 230
Measurement frame setting: 300
SH (threshold): 50
Binarization level: 180

  The electrolytic solution and the dispersion are put in a glass measuring container, and the concentration of carrier particles in the measuring container is set to 5 to 10% by volume. Stir the contents of the glass measuring container at the maximum stirring speed. The sample suction pressure is 10 kPa. If the carrier specific gravity is large and sedimentation tends to occur, the measurement time is 15 to 30 minutes. In addition, the measurement is interrupted every 5 to 10 minutes to replenish the sample solution and the electrolyte solution-glycerin mixed solution.

  The number of measurements is 2000. After the measurement is finished, the main body software removes a defocused image, aggregated particles (multiple simultaneous measurements), etc. on the particle image screen.

The circularity and equivalent circle diameter of the carrier are calculated by the following formula.
Circularity = (4 × Area) / (MaxLength2 × π)
Circle equivalent diameter = √ (4 · Area / π)

  Here, “Area” is the projected area of the binarized carrier particle image, and “MaxLength” is defined as the maximum diameter of the carrier particle image. The equivalent circle diameter is represented by the diameter of a perfect circle when “Area” is the area of the perfect circle. The equivalent circle diameter is divided into 256 parts of 4 to 100 μm, and is used logarithmically on a volume basis. Using this, the 50% particle size (D50) based on volume distribution is obtained. The average circularity is obtained by adding the circularity of each particle and dividing by the total number of particles.

<Measurement of true density of toner and carrier>
The true density of the toner and carrier can be measured by a method using a gas displacement pycnometer. The measurement principle is that a shut-off valve is provided between a sample chamber (volume V1) having a constant volume and a comparison chamber (volume V2), and after measuring the mass (M0 (g)), the sample is put into the sample chamber. The sample chamber and the comparison chamber are filled with an inert gas such as helium, and the pressure at that time is P1. Close the shut-off valve and add inert gas only to the sample chamber. The pressure at that time is P2. The shutoff valve is opened, and the pressure in the system when the sample chamber and the comparison chamber are connected is P3. The volume (V0 (cm ³ )) of the sample can be obtained by the following formula A. The following formula B, can be obtained toner, the true density of the carrier ρ a (g / cm ^3).
V0 = V1- [V2 / {(P2-P1) / (P3-P1) -1}] (Formula A)
ρ = M0 / V0 (Formula B)

As the above method, in the present invention, measurement was performed using a dry automatic densitometer Accupic 1330 (manufactured by Shimadzu Corporation). At this time, a 10 cm ³ sample container is used, and as a sample pretreatment, helium gas purge is performed 10 times at a maximum pressure of 19.5 psig (134.4 kPa). Thereafter, as a pressure equilibrium judgment value as to whether or not the pressure in the container has reached equilibrium, the pressure fluctuation in the sample chamber is set to 0.0050 psig / min as a guide. Start and automatically measure true density. The measurement is performed 5 times, and the average value is obtained to obtain the true density (g / cm ³ ).

<Measurement of magnetization of carrier>
The magnetization strength of the carrier contained in the replenishment developer of the present invention can be determined by a vibrating magnetic field type magnetic property device VSM (Vibrating sample magnetometer), a direct current magnetization property recording device (BH tracer), or the like. . Preferably, it can be measured with an oscillating magnetic field type magnetic property apparatus. Examples of the oscillating magnetic field type magnetic property apparatus include an oscillating magnetic field type magnetic property automatic recording apparatus BHV-30 manufactured by Riken Denshi Co., Ltd. Using this, it can be measured by the following procedure. A cylindrical plastic container is packed sufficiently densely, while an external magnetic field of 1000 / 4π (kA / m) (1000 oersted) is created, and the magnetization moment of the carrier filled in the container is measured in this state. . Further, the actual mass of the carrier filled in the container is measured to determine the magnetization strength (Am ² / kg) of the carrier.

  EXAMPLES Hereinafter, although a manufacture example and an Example demonstrate this invention concretely, these do not limit this invention at all.

(Example of production of resin 1 for shell)
The following raw materials were put in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, reacted at 260 ° C. under normal pressure for 8 hours, cooled to 240 ° C., and reduced in pressure to 1 mmHg over 1 hour. The reaction was further continued for 3 hours to obtain a polyester having a sulfonic acid group.

(Alcohol monomer)
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (BPA-PO): 110 parts by mass Polyoxyethylene (2.2) -2,2-bis (4-hydroxy Phenyl) propane (BPA-EO): 34 parts by mass / ethylene glycol: 60 parts by mass

(Acid monomer)
-Terephthalic acid: 80 parts by mass-Isophthalic acid: 70 parts by mass-Trimellitic anhydride: 5 parts by mass-5-Sodium sulfoisophthalic acid: 3.7 parts by mass

(catalyst)
Tetrabutyl titanate: 0.3 part by mass

  In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 100 parts by mass of the polyester, 50 parts by mass of methyl ethyl ketone, and 50 parts by mass of tetrahydrofuran were placed and heated to 75 ° C. while stirring. To this, 300 parts by mass of 75 ° C. water was added and stirred for 1 hour. After heating to 90 ° C. and stirring for 3 hours and 95 ° C. for 2 hours, the mixture was cooled to 30 ° C. to obtain an aqueous dispersion of shell resin 1.

  The particle diameter measurement of the aqueous dispersion of the resin for shell 1 and the zeta potential measurement were performed. Further, the aqueous dispersion of the resin for shell 1 was put in an aluminum petri dish, dried for 3 days with a hot air dryer at 40 ° C., and further solidified by drying for 1 day with a vacuum dryer at 40 ° C. Using this, measurement of the glass transition point (Tg) by DSC, measurement of the content of the sulfonic acid group, measurement of Mw of the THF-soluble component, measurement of Mw / Mn, and measurement of the content of the THF-insoluble component were performed. Table 2 shows the physical properties of the shell resin 1 obtained by the measurement.

(Production example of shell resins 2 to 5)
Except as shown in Table 1, aqueous dispersions of shell resins 2 to 5 were obtained in the same manner as in Shell resin production example 1. The physical properties of the shell resins 2 to 5 were measured in the same manner as in Production Example 1 of the shell resin. These physical properties are shown in Table 2.

(Production example 1 of polar resin)
The following raw materials were put in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, reacted at 260 ° C. under normal pressure for 8 hours, cooled to 240 ° C., and reduced in pressure to 1 mmHg over 1 hour. The reaction was further continued for 3 hours to obtain a polar resin.

(Alcohol monomer)
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (BPA-PO): 110 parts by mass Polyoxyethylene (2.2) -2,2-bis (4-hydroxy Phenyl) propane (BPA-EO): 51 parts by mass Ethylene glycol: 56 parts by mass

(Acid monomer)
-Terephthalic acid: 74 parts by mass-Isophthalic acid: 79 parts by mass-Trimellitic anhydride: 5 parts by mass

(catalyst)
Tetrabutyl titanate: 0.3 part by mass The physical properties of the polar resin are as follows: DSC Tg is 69.4 ° C., Mw is 23600, Mw / Mn is 2.51, and THF-insoluble component content is 1.8% by mass. Met.

(Production example of aqueous dispersion of core particle 1)
Styrene: 65 parts by mass n-butyl acrylate: 35 parts by mass Pigment Blue 15: 3: 6 parts by mass Aluminum salicylate compound: 1 part by mass (Bontron E-88: manufactured by Orient Chemical Co., Ltd.)
Divinylbenzene: 0.024 parts by mass Polar resin obtained in the above polar resin production example: 2.5 parts by mass Wax: 8 parts by mass (HNP-10: Nippon Seiwa Co., Ltd.)
A mixture of monomers consisting of was prepared. 15 mm ceramic beads were put in this, and dispersed for 2 hours using an attritor to obtain a monomer composition.

450 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution was added to 700 parts by mass of ion-exchanged water and heated to 70 ° C. The mixture was stirred at 10,000 rpm using a TK type homomixer (manufactured by Tokushu Kika Kogyo). To this, 68 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was added to obtain an aqueous dispersion containing calcium phosphate.

  9.5 parts by mass of a 70% toluene solution of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, which is a polymerization initiator, was added to the monomer composition, and this was dispersed in the dispersion. It was put into the system. The granulation process was performed for 3 minutes while maintaining 12000 revolutions / minute with the high-speed stirring device. Then, the stirrer was changed from the high-speed stirrer to the propeller stirring blade, and polymerization was performed at 150 rpm for 10 hours. After cooling to 30 ° C., an aqueous dispersion of core particles 1 was obtained.

  A part of the aqueous dispersion was taken out, and hydrochloric acid was added dropwise while stirring the aqueous dispersion at 150 rpm, so that the pH of the aqueous dispersion was 1.5. After stirring as it was for 2 hours, filtration and washing with water were repeated three times. This was dried for 1 day in a vacuum dryer at 40 ° C., and the core particles 1 were taken out.

  About core particle 1, Tg was measured by DSC. Moreover, the particle diameter and the zeta potential were measured using the aqueous dispersion of the core particle 1. The physical properties of these core particles 1 are shown in Table 3.

(Production example of aqueous dispersion of core particles 2 to 4)
Except having changed the addition amount of the material shown in Table 3, it carried out similarly to the manufacture example of the aqueous dispersion of the core particle 1, and obtained the aqueous dispersion of the core particles 2-4.

  With respect to the aqueous dispersions of the core particles 2 to 4, the physical properties of the core particles 2 to 4 were measured in the same manner as in the production example of the aqueous dispersion of the core particles 1. Table 3 shows the physical properties of the core particles 2 to 4.

<Example 1>
(Coating process)
About 1 aqueous dispersion of the said core particle, solid-liquid ratio was calculated | required from the mass of solid content with respect to the mass of an aqueous dispersion.

  Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 1040 parts by mass of the aqueous dispersion of core particles 1 (content of core particles: 100 parts by mass) was added and stirred at 150 rpm. . While maintaining stirring, 20 parts by mass of the aqueous dispersion of shell resin 1 obtained in the production example of shell resin 1 (content of shell resin: 5 parts by mass) was 0.5 parts by mass / min. The aqueous dispersion of the composite was formed by dropping at a rate of.

(Fixing process)
While maintaining the stirring, the aqueous dispersion of the composite was heated, set to a temperature of Tg0 + 10.0 (° C.) of the core particle 1, and stirred for 2 hours (heating step 1).

  While maintaining stirring, 0.2 mol / liter of hydrochloric acid was added dropwise to the aqueous dispersion of the above composite, and the pH of the aqueous dispersion was adjusted to 1.6 over 3 hours (acid treatment step).

  Further, while maintaining stirring, a 1 mol / liter aqueous sodium hydroxide solution was added to the aqueous dispersion of the composite to adjust the pH of the aqueous dispersion to 7.0. It heated to Tg2-2.0 (degreeC) of the resin 1 for shells, and stirring was continued for 2 hours (heating process 2).

(Drying process)
After cooling to 20 ° C., filtration and washing with water were repeated three times, the toner particles 1 were obtained by drying for 1 day in a vacuum dryer maintained at 35 ° C.

(Mixing process)
Next, a mixture consisting of the following was mixed with a Henschel mixer to obtain toner 1.
The above mentioned toner particles 1: 100 parts by mass _{· n-C 4 H 9 Si} (OCH 3) 3 treated with hydrophobic titanium oxide (BET specific surface area: 120m ² / g): 0.9 parts by mass of hexamethyldisilazane Hydrophobic silica treated with silicone oil after treatment (BET specific surface area of 180 m ² / g): 0.9 parts by mass Using the toner 1, the physical properties shown in Tables 5 and 6 were measured. The toner 1 was evaluated as described later. The physical properties of Toner 1 are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.

<Examples 2 to 7>
In Example 1, the amount of raw materials used, the addition rate of the shell resin aqueous dispersion, the heating step 1, the acid treatment step, the heating step 2, and the external addition step were changed to the conditions shown in Table 4 In the same manner as in Example 1, toners 2 to 7 were obtained. In the same manner as in Example 1, the physical properties of the toners 2 to 7 were measured and evaluated. The physical properties of each toner are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.

<Comparative Examples 1 and 2>
In Example 1, the amount of raw materials used, the addition rate of the shell resin aqueous dispersion, the heating step 1, the acid treatment step, the heating step 2, and the external addition step were changed to the conditions shown in Table 4 In the same manner as in Example 1, toners 8 and 9 were obtained. In the same manner as in Example 1, the physical properties of the toners 8 and 9 were measured and evaluated. The physical properties of Toners 8 and 9 are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.

<Comparative Example 3>
In Example 1, the amount of raw materials used, the addition rate of the shell resin aqueous dispersion, the heating step 1, the heating step 2, and the external addition step were changed to the conditions shown in Table 4, and the acid treatment step was not performed. A toner 10 was obtained in the same manner as Example 1 except for the above. The physical properties of the toner 10 were measured and evaluated. The physical properties of the toner 10 are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.

<Comparative example 4>
Styrene: 65 parts by mass n-butyl acrylate: 35 parts by mass Pigment Blue 15: 3: 6 parts by mass Aluminum salicylate compound: 1 part by mass (Bontron E-88: manufactured by Orient Chemical Co., Ltd.)
Divinylbenzene: 0.024 parts by mass Polar resin obtained in the production example of polar resin: 5.0 parts by mass Wax: 8 parts by mass (HNP-10: Nippon Seiwa Co., Ltd.)
A mixture of monomers consisting of was prepared. 15 mm ceramic beads were put in this, and dispersed for 2 hours using an attritor to obtain a monomer composition.

450 parts by mass of a 0.1 mol / liter Na ₃ PO ₄ aqueous solution was added to 700 parts by mass of ion-exchanged water and heated to 70 ° C. The mixture was stirred at 10,000 rpm using a TK type homomixer (manufactured by Tokushu Kika Kogyo). To this, 68 parts by mass of a 1.0 mol / liter CaCl ₂ aqueous solution was added to obtain an aqueous dispersion containing calcium phosphate.

  9.5 parts by mass of a 70% toluene solution of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, which is a polymerization initiator, was added to the monomer composition, and this was dispersed in the dispersion. It was put into the system. The granulation process was performed for 3 minutes while maintaining 12000 revolutions / minute with the high-speed stirring device. Then, the stirrer was changed from the high-speed stirrer to the propeller stirring blade, and polymerization was performed at 150 rpm.

When 5 hours had elapsed, seed polymerization was performed by the following steps.
Styrene: 8.39 parts by mass (83.9% by mass)
N-butyl acrylate: 1.43 parts by mass (14.3% by mass)
・ Methacrylic acid: 0.18 parts by mass (1.8% by mass)
In the reaction vessel, a mixture of the above compounds and 2,2′-azobis (2-methyl-N- (2-hydroxyethyl) propionamide (VA-086) Wako Pure Chemical Industries dissolved in 35 parts by mass of ion-exchanged water. (Manufactured by Kogyo Co., Ltd.): 0.1 parts by mass of each were dropped simultaneously over 30 minutes, and polymerization was continued for 5 hours.

  After cooling to 30 ° C., hydrochloric acid was added dropwise while stirring the aqueous dispersion at 150 rpm, so that the pH of the aqueous dispersion was 1.5. After stirring as it was for 2 hours, filtration and washing with water were repeated three times. This was dried in a vacuum dryer at 35 ° C. for 1 day to obtain toner particles.

  The toner 11 was obtained through the external addition step in the same manner as in Example 1. The physical properties of the toner 11 were measured and evaluated. The physical properties of Toner 11 are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.

<Comparative Example 5>
In Comparative Example 4, the addition amount of styrene was 55 parts by mass, the addition amount of n-butyl acrylate was 45 parts by mass, the addition amount of the polar resin obtained in the polar resin production example was 30.0 parts by mass, and seed polymerization was performed. A toner 12 was obtained in the same manner as in Comparative Example 4 except that the polymerization was carried out for 10 hours without performing this step, and the external addition step was changed to the conditions shown in Table 4. The physical properties of the toner 12 were measured and evaluated. The physical properties of the toner 12 are shown in Tables 5 and 6, and the evaluation results are shown in Table 7.

<Evaluation method of anti-blocking performance>
5 g of toner was weighed into a 100 ml polycup, placed in a warm air dryer adjusted to 50 ° C. and a room adjusted to 25 ° C., and allowed to stand for 1 week. The fluidity of the toner when the polycup was gently taken out and rotated slowly was compared between the toner left at 50 ° C. and the toner left at 25 ° C., and evaluated visually.

Evaluation criteria A of anti-blocking performance: The fluidity of the toner that is allowed to stand at 50 ° C. is equivalent to that of the toner that is allowed to stand at 25 ° C. (the anti-blocking performance is excellent)
B: Although the fluidity of the toner standing at 50 ° C. is slightly inferior to that of the toner standing at 25 ° C., the fluidity gradually recovers with the rotation of the polycup (good anti-blocking performance). )
C: Toner standing at 50 ° C. shows agglomerated and fused lump (poor anti-blocking performance)
D: Toner left at 50 ° C. does not flow (particularly anti-blocking performance is inferior)

<Evaluation method for low-temperature fixing performance, offset resistance performance, penetration resistance performance, and color gamut performance>
Using a commercially available color laser printer (LBP-5400, manufactured by Canon), the toner in the cyan cartridge was taken out and filled with the toner, and the cartridge was mounted on the cyan station. Next, an unfixed toner image (0.5 mg / cm ² ) having a length of 2.0 cm and a width of 15.0 cm is placed on the image receiving paper (Canon office planner 64 g / m ² ) from the upper end with respect to the sheet passing direction. A 0.0 cm portion and a 2.0 cm portion from the lower end were formed. Next, the fixing unit removed from the commercially available color laser printer (LBP-5400, manufactured by Canon) was remodeled so that the fixing temperature and process speed could be adjusted, and a fixing test for unfixed images was performed using this. Under normal temperature and humidity, the process speed was set to 280 mm / sec, and the toner image was fixed at each temperature while changing the set temperature every 10 ° C. in the range of 120 ° C. to 240 ° C. According to the following evaluation criteria, low-temperature fixing performance, offset resistance performance, gloss performance, and penetration resistance performance were evaluated.

[Evaluation criteria for low-temperature fixing performance]
A: No low temperature offset occurs at 120 ° C or higher, and toner does not peel off even when rubbed with a finger (low temperature fixing performance is particularly excellent)
B: Low temperature offset does not occur at 130 ° C or higher, and toner does not peel off even when rubbed with a finger (low temperature fixing performance is good)
C: Low temperature offset does not occur at 140 ° C or higher, and toner does not peel off even when rubbed with a finger (low temperature fixing performance is at a level where there is no problem)
D: Low temperature offset does not occur at 150 ° C or higher, and toner does not peel off even when rubbed with a finger (low temperature fixing performance is slightly inferior)
E: Low temperature offset does not occur above 160 ° C, and toner does not peel off even when rubbed with a finger (low temperature fixing performance is inferior)

[Evaluation criteria for anti-offset performance]
A: No high temperature offset occurs in a temperature range higher by 50 ° C. than the minimum temperature at which no low temperature offset occurs B: No high temperature offset occurs in a temperature range higher than the minimum temperature at which no low temperature offset occurs by 40 ° C. C: Low temperature offset occurs High temperature offset does not occur in a temperature range higher than the lowest temperature by 30 ° C. or higher D: No high temperature offset occurs in a temperature range higher than the lowest temperature by which a low temperature offset does not occur E: 10 ° C. lower than the lowest temperature at which a low temperature offset does not occur High temperature offset does not occur at higher temperature range

[Gross performance evaluation criteria]
About the fixed image in which the low temperature offset and the high temperature offset did not occur, using a handy gloss meter gloss meter PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.), the measurement was performed under the condition of an incident angle of light of 75 °. evaluated.
A: The maximum glossiness of the solid image portion is 45 or more (the gloss performance is particularly excellent).
B: The maximum glossiness of the solid image portion is 40 or more and less than 45 (excellent gloss performance)
C: The maximum glossiness of the solid image portion is 35 or more and less than 40 (the gloss performance is a normal level)
D: The maximum glossiness of the solid image portion is 30 or more and less than 35 (the gloss performance is slightly inferior)
E: The maximum glossiness of the solid image portion is less than 30 (gross performance is inferior)

<Evaluation of image storage performance>
In the evaluation of the gloss performance, the following evaluation was performed on the fixing paper of the image having the highest glossiness. The image was placed on 500 sheets of unused paper of the same type with the image portion of the fixing paper facing downward. Furthermore, 500 sheets of the same kind of unused paper were placed on the fixing paper, and the fixing paper was sandwiched. This was left still in a 40 degreeC thermostat. After leaving still for 2 days, each was taken out from the thermostat. The manner in which the toner of the fixing paper adheres to unused paper in contact with the image portion of the fixing paper was evaluated according to the following criteria.
A: No adhesion of toner from the fixing paper is observed (image storage performance is particularly excellent)
B: Very little toner adheres to the image area (excellent image storage performance)
C: Slight toner adhesion to the area of the image area (image storage performance is at a normal level)
D: Toner adheres to the entire area of the image area, but the color of the adhered area is light (image storage performance is slightly inferior)
E: Dark parts are seen on unused paper, and clear toner adhesion is observed (the image storage performance is inferior)

<Evaluation of durability and stability>
A commercially available color laser printer (LBP-5400, manufactured by Canon Inc.) was used to take out the toner from the cyan cartridge, and 60 g of the toner was filled therein. The cartridge was mounted on a cyan station, and solid images were continuously printed on image receiving paper (Canon office planner 64 g / m ² ). When the toner in the cartridge became 40 g or less, the operation of adding 20 g of toner and performing continuous printing in the same manner was repeated. The durability stability performance was evaluated according to the following evaluation criteria.

(Evaluation criteria for durability and stability)
A: The solid image density becomes less than 1.5 after the added amount of toner is added four times. (Excellent durability and stability)
B: After adding the toner three times, the solid image density becomes less than 1.5. (Durable and stable performance is good)
C: After adding the toner twice, the solid image density becomes less than 1.5. (Durable and stable performance is normal level)
D: After adding toner once, the solid image density becomes less than 1.5. (Stable durability performance is slightly inferior)
E: The solid image density is less than 1.5 without adding toner. (The durability stability performance is inferior)

It is a figure which shows the result of having measured T1, T2 and (alpha) prescribed | regulated by this invention about the toner produced in Example 1. FIG. It is a figure which shows the method of measuring the glass transition point Tg (degreeC) and melting | fusing point Tm (degreeC) of the toner, resin, and wax by DSC.

Claims (8)

A toner having at least core particles containing a binder resin, a colorant, and a wax, toner particles having a shell resin covering the core particles, and inorganic fine particles attached to the surface of the toner particles. ,
The toner has a glass transition point (Tg1) measured by a differential scanning calorimeter (DSC) of 25.0 to 60.0 ° C., and the aggregation degree at a temperature of 23.0 ° C. and a humidity of 60% RH is A0. Toner after A0 is 70.0% or less, T1 (° C.) is the temperature at which the degree of aggregation of the toner after leaving the toner for 72 hours is A0 + 10.0%, and the toner is left for 72 hours When the temperature at which the degree of aggregation of 98.0% becomes T2 (° C.), the difference (T1−Tg1) between T1 (° C.) and Tg1 (° C.) is 5.0 to 40.0 ° C., and T1 A toner having a change rate α of aggregation degree at (° C.) and T2 (° C.) α = {98.0− (A0 + 10.0)} / (T2−T1) is 15.0 to 50.0.   The viscosity of the toner is F1 (° C.) when the viscosity is 5000 Pa · s and the temperature at which the viscosity is 1000 Pa · s is F 2 (° C.) in the viscosity measurement with a constant load capillary tube rheometer. 2 is from 75.0 to 115.0 ° C., and the difference (F2−F1) between the F1 (° C.) and the F2 (° C.) is 8.0 to 40.0 ° C. The toner described in 1.   The toner has a shell resin in an amount of 1.0 to 10.0% by mass with respect to the toner mass, and when the glass transition point of the shell resin is Tg2 (° C), the Tg2 and the Tg1 (° C) The toner according to claim 1, wherein a difference (Tg2−Tg1) with respect to the toner is 10.0 to 50.0 ° C.   The toner contains 3.0 to 45.0 mass% of a tetrahydrofuran (THF) insoluble component contained in the toner, and the THF soluble component contains 0.010 to 1.000 mass of sulfur element derived from a sulfonic acid group. The toner according to claim 1, wherein the toner is contained in a percentage.   2. The toner according to claim 1, wherein the toner contains one or more fine particles selected from silica or titanium oxide as inorganic fine particles in an amount of 0.50 to 3.00 mass% based on the total amount of the toner. The toner according to any one of 4 to 4.   6. The toner according to claim 1, wherein the shell resin contained in the toner contains 0.10 to 4.00% by mass of a sulfonic acid group. In the toner, the volume average particle diameter (D3 _s ) of the fine particles of the shell resin _{contained in the} toner is 15 to 150 nm, and the ratio of the volume distribution 10% particle diameter (D3 _s10 ) to the D3 _s (D3 _s). The toner according to claim 1, wherein / D3 _s10 ) is 1.0 to 10.0. Forming a fine particle dispersion (1) of the shell resin in which the shell resin is dispersed in water in the form of fine particles;
It has a core particle containing a binder resin, a colorant, a wax, and other additives, a dispersion stabilizer such as an inorganic salt, and water, and the dispersion stabilizer is adsorbed on the surface of the core particle to be in water. Forming a dispersion (2) of core particles that forms a dispersed state;
The shell resin fine particle dispersion (1) is added to the core particle dispersion (2) to form a composite dispersion, and the shell is formed on the surface of the core particles using the dispersion stabilizer as a medium. A coating treatment step for forming a state in which fine particles of the resin for resin are adsorbed and coated on the surface of the core particles;
In the dispersion of the composite, heating and releasing the dispersion stabilizer existing as a medium from the medium state so that the core particles and the fine particles of the shell resin are in direct contact with each other to cover the core particles. Fixing process for forming toner particles by fixing resin fine particles on the core particle surface;
A drying step of collecting and drying the toner particles to form powder toner particles;
A mixing step of mixing the toner particles and inorganic fine particles to form the toner according to claim 1,
The toner includes at least toner particles including core particles containing a binder resin, a colorant, and a wax, a shell resin that covers the core particles, and inorganic fine particles attached to the surface of the toner particles. The toner has a glass transition point (Tg1) of 25.0 to 60.0 ° C. by a differential scanning calorimeter (DSC), a cohesion degree at a temperature of 23.0 ° C. and a humidity of 60% as A0. The temperature at which the A0 is 70.0% or less and the degree of aggregation of the toner after leaving the toner for 72 hours is A0 + 10.0% is T1 (° C.), and the toner is left for 72 hours. The difference between T1 (° C.) and Tg1 (° C.) (T1−Tg1) is 5.0 to 40.0 ° C., where T2 (° C.) is the temperature at which the degree of aggregation of the toner is 98.0%. And aggregation at T1 (° C.) and T2 (° C.) Method for producing a toner, wherein the rate of change α = {98.0- (A0 + 10.0)} / (T2-T1) is a toner is 15.0 to 50.0.

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