JP6914772B2 - Magnetic carrier, two-component developer, replenisher developer, and image forming method - Google Patents

Description

The present invention relates to a magnetic carrier, a two-component developer, a supplementary developer used in an image forming method for visualizing an electrostatic charge image using an electrophotographic method, and an image forming method using the same. It is a thing.

Conventionally, in the electrophotographic image forming method, an electrostatic latent image is formed on an electrostatic latent image carrier by various means, and toner is adhered to the electrostatic latent image to form the electrostatic latent image. The method of developing is common. In this development, a two-component developing method is widely used in which carrier particles called magnetic carriers are mixed with toner, triboelectrically charged, an appropriate amount of positive or negative charge is given to the toner, and the charge is developed as a driving force. It has been adopted.
The two-component developing method can impart functions such as stirring, transporting, and charging of the developer to the magnetic carrier, so that the division of functions with the toner is clear, and therefore, there are advantages such as good controllability of the developer performance. There is.

On the other hand, in recent years, due to technological evolution in the field of electrophotographic photography, it has become more and more strict to have high-definition and stable image quality as well as high speed and long life of the device. In order to meet such demands, higher performance of magnetic carriers is required.
One of them has been proposed to reduce the density fluctuation in long-term use and further reduce the tint fluctuation in the case of full color (see Patent Document 1). This carrier is characterized in that the magnetic core material is made uneven and the unevenness is exposed even if the magnetic core material is coated with the resin. As a result, the above-mentioned problems will be improved, but in the recent demand for high-speed copying, the specific gravity of the magnetic carrier particles is heavy and the toner is loaded, so that the life of the developer is shortened and the image quality is high. Further improvement was required for the ability to follow changes in the environment and changes in the environment.
Under such circumstances, a proposal has been made to use a porous magnetic core having pores inside the magnetic core and having a reduced specific gravity (see Patent Documents 2 to 8).

Japanese Unexamined Patent Publication No. 4-93954 Japanese Unexamined Patent Publication No. 2012-173375 Japanese Unexamined Patent Publication No. 2006-337579 JP-A-2009-175666 Japanese Unexamined Patent Publication No. 2011-158830 Japanese Patent No. 4898959 Japanese Unexamined Patent Publication No. 2015-7758 Japanese Patent No. 6031708

The magnetic carriers of Patent Documents 2 to 8 have improved problems such as the life of the developer, white spots, and roughness.
However, in the market, especially in the field of on-demand printers, there is an increasing demand for stable acquisition of high-quality images with less fog and density unevenness in the image plane and less carrier adhesion even in long-term use. .. There is an urgent need to develop a magnetic carrier that satisfies such requirements, a two-component developer, and an image forming method using the same.
An object of the present invention is to provide a magnetic carrier that solves the above problems.
Specifically, it is an object of the present invention to provide a magnetic carrier that suppresses fog of an image and uneven density in the image plane, and can stably obtain a high-quality image even after long-term use.

By using a porous magnetic core and using a magnetic carrier having a resin abundance of a particle cross section as shown below, the present inventors suppress image fog, uneven density in the image plane, and carrier adhesion. However, it has been found that a magnetic carrier that can stably obtain high-quality images even after long-term use can be obtained.
That is, the present invention comprises a resin-filled magnetic core particle having a porous magnetic core and a filling resin existing in the pores of the porous magnetic core, and a resin existing on the surface of the resin-filled magnetic core particle. A magnetic carrier having a coating layer,
In the pore size distribution of the porous magnetic core,
The peak pore diameter that maximizes the differential pore volume in the range of 0.1 μm or more and 3.0 μm or less is 0.40 μm or more and 1.00 μm or less.
The pore volume, which is the integral value of the differential pore volume in the range of 0.1 μm or more and 3.0 μm or less, is 58 mm ³ / g or more and 100 mm ³ / g or less.
The magnetic carrier is located in a region R1 and a region R2 defined as follows.
The mass-based proportions of the composition derived from the resin component were defined as JR1 and JR2, respectively, and the mass-based proportions of the composition derived from the porous magnetic core were defined as FR1 and FR2, respectively.
Further, when JR1 / FR1 is MR1 and JR2 / FR2 is MR2, the MR1 and the MR2 are
0.20 ≤ MR2 / MR1 ≤ 0.90
It is a magnetic carrier characterized by satisfying the above relationship.
(Region R1 is a cross-sectional image of the magnetic carrier, in which a line segment having the maximum length of the resin-filled magnetic core particles is drawn, and two lines are parallel to the line segment and 2.5 μm apart from the line segment. Let the straight lines be straight lines A and B
A straight line that passes through the intersection of the line segment and the contour line of the resin-filled magnetic core particles and is orthogonal to the line segment is defined as a straight line C.
When a straight line D parallel to the straight line C and 5.0 μm away from the straight line C toward the center of the magnetic carrier is defined as a straight line D.
It is a region surrounded by the contour line of the resin-filled magnetic core particles and the straight lines A, B and D, and in contact with the straight line C.
The region R2 is a region surrounded by the straight lines A, B, and D and a straight line E parallel to the straight line D and 5.0 μm away from the straight line D toward the center of the magnetic carrier. )
Further, the present invention is a two-component developer containing a toner containing a binder resin, a colorant and a mold release agent, and a magnetic carrier.
The magnetic carrier is a two-component developer that is the magnetic carrier.
Further, the present invention relates to a charging step of charging an electrostatic latent image carrier.
An electrostatic latent image forming step of forming an electrostatic latent image on the surface of the electrostatic latent image carrier,
A developing step of developing the electrostatic latent image with a two-component developer to form a toner image.
An image forming method comprising a transfer step of transferring the toner image to a transfer material with or without an intermediate transfer body, and a fixing step of fixing the transferred toner image to the transfer material.
This is an image forming method in which the two-component developer is the above-mentioned two-component developer.
Further, the present invention relates to a charging step of charging an electrostatic latent image carrier.
An electrostatic latent image forming step of forming an electrostatic latent image on the surface of the electrostatic latent image carrier,
A developing process in which the electrostatic latent image is developed using a two-component developer in a developing device to form a toner image.
It has a transfer step of transferring the toner image to the transfer material with or without an intermediate transfer body, and a fixing step of fixing the transferred toner image to the transfer material.
An image forming method in which a replenishing developer is replenished to the developing device according to a decrease in the toner concentration of the two-component developing agent in the developing device.
The replenishing developer contains a magnetic carrier and a toner containing a binder resin, a colorant and a mold release agent.
The replenishing developer contains 2 parts by mass or more and 50 parts by mass or less of the toner with respect to 1 part by mass of the magnetic carrier.
The magnetic carrier is an image forming method that is the magnetic carrier.
Further, the present invention is a replenishing developer for use in the above image forming method.

By using the magnetic carrier of the present invention, fog of the image and density unevenness in the image plane are suppressed, and a stable and high-quality image can be obtained even after long-term use.

Explanatory drawing of regions R1 and R2 relating to the magnetic carrier of this invention Schematic diagram of the image forming apparatus used in the present invention Schematic diagram of the image forming apparatus used in the present invention Schematic diagram of the method for defining the coating resin content in the GPC molecular weight distribution curve Schematic diagram of the method for defining the coating resin content in the GPC molecular weight distribution curve Schematic diagram of the device for measuring the specific resistance of the magnetic carrier used in the present invention. Schematic diagram of the measuring device for the current value of the magnetic carrier used in the present invention.

In the present invention, the description of "○○ or more and XX or less" and "○○ to XX" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.
The magnetic carrier of the present invention exists on the surface of resin-filled magnetic core particles having a porous magnetic core and a filling resin existing in the pores of the porous magnetic core, and the resin-filled magnetic core particles. A magnetic carrier having a resin coating layer,
In the pore size distribution of the porous magnetic core,
The peak pore diameter that maximizes the differential pore volume in the range of 0.1 μm or more and 3.0 μm or less is 0.40 μm or more and 1.00 μm or less.
The pore volume, which is the integral value of the differential pore volume in the range of 0.1 μm or more and 3.0 μm or less, is 58 mm ³ / g or more and 100 mm ³ / g or less.
The magnetic carrier is located in a region R1 and a region R2 defined as follows.
The mass-based proportions of the composition derived from the resin component were defined as JR1 and JR2, respectively, and the mass-based proportions of the composition derived from the porous magnetic core were defined as FR1 and FR2, respectively.
Furthermore, when JR1 / FR1 is MR1 and JR2 / FR2 is MR2, MR1 and MR2 are
0.20 ≤ MR2 / MR1 ≤ 0.90
It is characterized by satisfying the relationship of.

Here, the definition of the region R1 will be described with reference to FIG. In the cross-sectional image of the magnetic carrier, two straight lines parallel to the line segment having the maximum length of the resin-filled magnetic core particles and 2.5 μm apart from the line segment are designated as A and B. A straight line C that passes through the intersection of the line segment and the contour line of the resin-filled magnetic core particles, is parallel to the straight line C, and is 5.0 μm from the straight line C toward the center of the magnetic carrier. Assume a distant straight line D.
The region surrounded by the contour lines of the resin-filled magnetic core particles between the straight lines A and B and the straight lines A, B, and D and in contact with the straight line C is defined as R1.
Further, the region R2 is a region surrounded by straight lines A, B, and D, and a straight line E that is parallel to the straight line D and is 5.0 μm away from the straight line D toward the center of the magnetic carrier.

That is, in the present invention, the filling resin abundance ratio (MR1) with respect to the abundance ratio of the component derived from the magnetic core particles in the outermost layer portion of the magnetic carrier is set to the filling resin abundance ratio (MR1) with respect to the abundance ratio of the component derived from the magnetic core particles inside the magnetic carrier. It is characterized in that it is slightly larger than MR2).
Normally, when the coating resin is coated on the resin-filled magnetic core particles having irregularities, the film thickness of the coating resin becomes uneven slightly following the irregularities of the core material. As a result, micro-unevenness is formed in the chargeability of the surface of one carrier particle, and as a result, the charge distribution of the toner becomes slightly broad.
When the charge amount distribution of the toner becomes broad, so-called "fog" occurs in which the toner that is not sufficiently charged is transferred to the non-image portion in a high temperature and high humidity environment. In a normal temperature and low humidity environment, excessively charged toner is present, so that the amount of toner loaded on the image portion varies, and density unevenness occurs on the image surface.

As a result of diligent studies for the purpose of improving "fog" and "in-plane concentration unevenness" in long-term use, the present inventors have obtained a pore size distribution of 0.1 μm or more and 3.0 μm for the porous magnetic core. The peak pore diameter that maximizes the differential pore volume in the following range is 0.40 μm or more and 1.00 μm or less.
Regarding the pore size distribution of the porous magnetic core, the pore volume, which is the integral value of the differential pore volume in the range of 0.1 μm or more and 3.0 μm or less, is 58 mm ³ / g or more and 100 mm ³ / g or less.
In the regions R1 and R2 defined as follows, the magnetic carrier is a resin in which the mass-based ratio of the composition derived from the resin component is JR1 and JR2, and the mass-based ratio of the composition derived from the magnetic core is FR1 and FR2. Ratio of composition derived from components to composition derived from magnetic core When JR1 / FR1 is MR1 and JR2 / FR2 is MR2, MR1 and MR2 are
0.20 ≤ MR2 / MR1 ≤ 0.90
We found that it was important to satisfy the relationship.
Satisfying these indicates that a certain amount of filling resin is present on the surface layer of the magnetic carrier. Therefore, it is considered that the coating resin could be prevented from flowing into the inside from the surface layer of the magnetic core particles when the coating resin was coated, so that the resin could be uniformly coated on the uneven core material without uneven film thickness. ..

It is preferable that 0.23 ≦ MR2 / MR1 ≦ 0.86 from the viewpoint of extending the life and improving “fog” and “in-plane density unevenness”.
If MR2 / MR1 is less than 0.20, the coating layer may be locally thickened during resin coating. Therefore, there is a place on the surface of the magnetic carrier where charge relaxation property cannot be locally obtained, and "in-plane concentration unevenness" is likely to occur. When MR2 / MR1 is larger than 0.90, the coating layer is locally thinned at the time of resin coating. Therefore, there is a place on the surface of the magnetic carrier where the charge mitigation property is locally increased, and "fog" is likely to occur.
MR2 / MR1 can be controlled by the amount and viscosity of the filling resin.

The present invention is a magnetic carrier having resin-filled magnetic core particles containing a filling resin in the pores of the porous magnetic core and a resin coating layer existing on the surface of the resin-filled magnetic core particles. As a result, the charge relaxation property of the magnetic carrier can be controlled, and not only the life of the developer is extended, but also the density stability and the color tone stability of the image are enhanced.
It is preferable to use a curable resin composition for filling the filling resin. As the resin composition before curing, a resin composition having high impregnation property is preferable. By using a resin composition having a high impregnation property, the capillary phenomenon works more effectively, which is preferable in adjusting MR2 / MR1 to the above range. As an index of impregnation property, the kinematic viscosity of the resin composition itself can be mentioned. Preferably the kinematic viscosity is comparatively small resin composition, for example, preferably a 0.5 mm ² / s or more 200.0mm ² / s to be less that MR2 / MR1 in order to adjust the above range.

It is important that the porous magnetic core used in the present invention has a peak pore diameter in the range of 0.1 μm or more and 3.0 μm or less in the pore diameter distribution of 0.40 μm or more and 1.00 μm or less.
If it is less than 0.40 μm, the filling resin does not sufficiently enter the pores of the porous magnetic core, so that the coating layer may be locally thickened during resin coating. Therefore, there is a place on the surface of the magnetic carrier where charge relaxation property cannot be locally obtained, and "in-plane concentration unevenness" is likely to occur.
On the other hand, if it exceeds 1.00 μm, the filling resin excessively enters the pores of the porous magnetic core, and a portion where the coating layer becomes locally thin occurs when the resin is coated. Therefore, there is a place on the surface of the magnetic carrier where the charge relaxation is locally large, and "fog" is likely to occur.
The peak pore diameter is preferably 0.45 μm or more and 0.95 μm or less. The peak pore diameter can be controlled by the particle size of the calcined ferrite finely pulverized product, the firing temperature of the porous magnetic core, and the firing time.

Similarly, it is important that the pore volume, which is the integral value of the differential pore volume in the range of 0.1 μm or more and 3.0 μm or less in the pore diameter distribution, is 58 mm ³ / g or more and 100 mm ^{3 / g or less.} be. When the pore volume is ^{less than 58 mm 3} / g, the filling resin does not sufficiently enter the pores of the porous magnetic core, so that the coating layer becomes too thick at the time of resin coating. Therefore, there is a place on the surface of the magnetic carrier where charge relaxation property cannot be locally obtained, and "in-plane concentration unevenness" is likely to occur.
On the other hand, ^{if it exceeds 100 mm 3} / g, the filling resin will enter too much into the pores of the porous magnetic core, and the coating layer will be locally thinned at the time of resin coating. Therefore, there is a place on the surface of the magnetic carrier where the charge relaxation is locally large, and "fog" is likely to occur. In addition, carrier adhesion is likely to occur due to scattering of magnetic carriers.
The pore volume is more preferably 60 mm ³ / g or more and 95 mm ³ / g or less. The pore volume can be controlled by the particle size of the calcined ferrite finely pulverized product, the firing temperature of the porous magnetic core, and the firing time.

The content of the filling resin of the magnetic carrier is preferably 2.0 parts by mass or more and 7.0 parts by mass or less, and 2.5 parts by mass or more and 6.5 parts by mass or less with respect to 100 parts by mass of the porous magnetic core. More preferably. When it is 2.0 parts by mass or more, the coating layer is less likely to be locally thinned during resin coating, and "fog" can be suppressed. On the other hand, when it is 7.0 parts by mass or less, the coating layer is unlikely to be locally thickened at the time of resin coating, and "in-plane concentration unevenness" can be suppressed.

The content of the coating resin forming the resin coating layer is preferably 1.0 part by mass or more and 3.0 parts by mass or less, and 1.2 parts by mass or more and 2. It is more preferably 8 parts by mass or less. When it is 1.0 part by mass or more, the coating layer is less likely to be locally thinned at the time of resin coating, and "fog" can be suppressed. On the other hand, when it is 3.0 parts by mass or less, the coating layer is unlikely to be locally thickened at the time of resin coating, and "in-plane concentration unevenness" can be suppressed.

The current value of the magnetic carrier when 500 V is applied is preferably 10.0 μA or more and 50.0 μA or less, and more preferably 12.0 μA or more and 48.0 μA or less. When it is 10.0 μA or more, it is easy to suppress “in-plane density unevenness”, and when it is 50.0 μA or less, it is easy to suppress “fog”. The current value when 500 V is applied can be controlled by the magnetization of the porous magnetic core and the content of the filling resin and the coating resin.
The specific resistance value of the magnetic carrier at an electric field strength of 2000 V / cm is preferably 1.0 × 10 ⁶ Ω · cm or more and 1.0 × 10 ⁹ Ω · cm or less, preferably 2.0 × 10 ⁶ Ω · cm or more. more preferably not more than 9.0 × 10 ⁸ Ω · cm. When it is 1.0 × 10 ⁶ Ω · cm or more, “fog” is easily suppressed, and when it is 1.0 × 10 ⁹ Ω · cm or less, “in-plane density unevenness” is easily suppressed. The resistivity value can be controlled by the magnetization of the porous magnetic core and the content of the filling resin or the coating resin.

Next, the method for manufacturing the magnetic carrier of the present invention will be described.
(Manufacturing method of porous magnetic core)
The porous magnetic core can be manufactured by the following steps.
As the material of the porous magnetic core, magnetite or ferrite is preferable. Further, it is more preferable that the material of the porous magnetic core is ferrite because the porous structure of the porous magnetic core can be controlled and the resistance can be adjusted.
Ferrite is a sintered body represented by the following general formula.
(M1 ₂ O) _x (M2O) _y (Fe ₂ O ₃ ) _Z
(In the formula, M1 is a monovalent metal and M2 is a divalent metal. When x + y + z = 1.0, x and y are 0 ≦ (x, y) ≦ 0.8, respectively, and z is 0.2 <z <1.0.)

In the formula, as M1 and M2, it is preferable to use one or more kinds of metal atoms selected from the group consisting of Li, Fe, Mn, Mg, Sr, Cu, Zn and Ca.
In the magnetic carrier, it is required to make the uneven state of the surface of the porous magnetic core suitable in order to maintain an appropriate amount of magnetization and to make the pore diameter within a desired range. Further, it is also required that the rate of the ferrite formation reaction can be easily controlled and the specific resistance and magnetic force of the porous magnetic core can be preferably controlled. From the above viewpoint, Mn-based ferrite, Mn-Mg-based ferrite, Mn-Mg-Sr-based ferrite, and Li-Mn-based ferrite containing an Mn element are more preferable.
An example of the manufacturing process when ferrite is used as the porous magnetic core will be described below.

・ Process 1 (weighing / mixing process):
The ferrite raw material is weighed and mixed. Examples of the ferrite raw material include the following. Metal particles such as Li, Fe, Mn, Mg, Sr, Cu, Zn, Ca, and oxides, hydroxides, carbonates, oxalates and the like thereof.
Examples of the mixing device include the following. When a hydroxide or a carbonate is used as the raw material species to be blended, the pore volume tends to be larger than when the oxide is used. Ball mill, planetary mill, geot mill, vibration mill. A ball mill is particularly preferable from the viewpoint of mixing. Specifically, weighed ferrite raw materials and balls are placed in a ball mill, and preferably pulverized and mixed for 0.1 hours or more and 20.0 hours or less.

-Step 2 (temporary firing step):
The pulverized and mixed ferrite raw material is pelletized using a pressure molding machine or the like, and then calcined. As described above, since the calcination step is important for obtaining the magnetic carrier of the present invention, it is important to carry out under the above-mentioned conditions. For example, calcination is carried out for 2.5 hours or more and 5.0 hours or less in a firing temperature range of 1050 ° C. or higher and 1100 ° C. or lower to convert the raw material into ferrite. At this time, the charging amount is appropriately adjusted so that the ferrite formation reaction proceeds sufficiently. Further, it is preferable to adjust the atmosphere, especially by lowering the oxygen concentration such as in a nitrogen atmosphere, because the ferrite formation reaction is more likely to proceed. For firing, for example, the following furnace is used. Examples include a burner type firing furnace, a rotary type firing furnace, and an electric furnace.

-Step 3 (crushing step):
The calcined ferrite produced in step 2 is crushed with a crusher. The crusher is not particularly limited as long as a desired particle size can be obtained. However, the calcined product produced by the above method has a higher hardness than the conventional calcined product because it is a calcined product in which a ferriticization reaction is partially advanced. Therefore, in order to obtain a desired particle size, it is preferable to increase the pulverization strength. It is preferable to increase the pulverization strength, make the particle size of the finely pulverized product of calcined ferrite finer, and control the particle size distribution.
In addition, controlling the particle size and particle size distribution of the finely pulverized product correlates with the average pore size of the porous magnetic core, the pore volume, and the degree of unevenness on the surface of the magnetic carrier, and the resin abundance rate of the magnetic carrier. It also leads to control of.

In order to control the particle size distribution of the finely pulverized product of calcined ferrite, for example, it is preferable to control the material and operation time of the balls and beads used in the ball mill and the bead mill. Specifically, in order to reduce the particle size of the calcined ferrite, a ball having a heavy specific gravity may be used or the crushing time may be lengthened. The material of the balls and beads is not particularly limited as long as a desired particle size and distribution can be obtained. For example, the following can be mentioned.
Glass such as soda glass (specific gravity 2.5 g / cm ³ ), sodaless glass (specific gravity 2.6 g / cm ³ ), high specific gravity glass (specific gravity 2.7 g / cm ³ ), and quartz (specific gravity 2.2 g / cm). ³ ), Titania (specific gravity 3.9 g / cm ³ ), silicon nitride (specific gravity 3.2 g / cm ³ ), alumina (specific gravity 3.6 g / cm ³ ), zirconia (specific gravity 6.0 g / cm ³ ), steel (specific gravity 6.0 g / cm 3) Specific gravity 7.9 g / cm ³ ), stainless steel (specific gravity 8.0 g / cm ³ ).
Of these, alumina, zirconia, and stainless steel are preferable because they have excellent wear resistance. The particle size of the balls and beads is not particularly limited as long as the desired particle size and distribution can be obtained. For example, as the ball, a ball having a diameter of 4 mm or more and 60 mm or less is preferably used. Further, as the beads, beads having a diameter of 0.03 mm or more and 5 mm or less are preferably used. Further, in the ball mill and the bead mill, the wet type has higher crushing efficiency than the dry type because the crushed product does not fly up in the mill. Therefore, the wet type is more preferable than the dry type.
It is more preferable that the calcined product having high hardness is first roughly pulverized by a dry method and then finely pulverized by a wet method to adjust the particle size.

・ Process 4 (granulation process):
For example, a dispersant, water, a binder, and, if necessary, a pore adjusting agent are added to the finely pulverized product of the calcined ferrite. Examples of the pore adjusting agent include a foaming agent and resin fine particles. As the binder, for example, polyvinyl alcohol is used. When pulverized in a wet manner in step 3, it is preferable to add a binder and a pore adjusting agent if necessary in consideration of the water contained in the ferrite slurry.
The obtained ferrite slurry is dried and granulated using a spray dryer, preferably in a warm atmosphere having a temperature of 100 ° C. or higher and 200 ° C. or lower. The spray dryer is not particularly limited as long as a desired particle size can be obtained. For example, a spray dryer can be used.
Next, the granulated product is burned off with a dispersant and a binder at a temperature of preferably 600 ° C. or higher and 800 ° C. or lower. In particular, setting the combustion removal temperature to 700 ° C. or higher is preferable because it is easy to adjust the pore diameter of the porous magnetic core to a specific range.

-Step 5 (main firing step):
Then, in an electric furnace in which the oxygen concentration can be controlled, firing is performed in an atmosphere in which the oxygen concentration is controlled, preferably at a temperature of 1000 ° C. or higher and 1300 ° C. or lower for 1 hour or more and 24 hours or less. By controlling the temperature, the pore volume can be controlled. For example, by increasing the temperature, the pore volume becomes smaller. Incidentally, the pore volume of the porous magnetic core is preferably 58.0 mm ³ / g or more 100.0 mm ³ / g or less.
In the tentative firing step, although the ferriticization reaction has progressed sufficiently, just in case, the time for raising and lowering the temperature passing through the temperature range of 700 ° C. to 1100 ° C., which is the temperature range in which the ferriticization reaction proceeds, is shortened. It is preferable to control so that the ferrite formation reaction does not proceed.
On the other hand, the holding time of the top temperature is preferably 3.0 hours or more and 5.0 hours or less. At that time, a rotary electric furnace, a batch electric furnace, a continuous electric furnace, etc. are used, and the atmosphere at the time of firing is also charged with an inert gas such as nitrogen or a reducing gas such as hydrogen or carbon monoxide to oxygenate. The concentration may be controlled. Further, in the case of a rotary electric furnace, firing may be performed many times by changing the atmosphere and firing temperature.

・ Process 6 (sorting process):
After crushing the calcined particles, low magnetic force products are separated by magnetic beneficiation, if necessary. Coarse particles and fine particles may be removed by wind classification or sieving with a sieve.
・ Surface treatment process:
If necessary, the surface can be heated at a low temperature to apply an oxide film treatment, and the resistance can be adjusted. For the oxide film treatment, a general rotary electric furnace, a batch electric furnace, or the like can be used, and heat treatment can be performed at, for example, 300 ° C. or higher and 700 ° C. or lower.

The volume distribution reference 50% particle size (D50) of the porous magnetic core obtained as described above is preferably 28.0 μm or more and 78.0 μm or less. By doing so, the particle size of the final magnetic carrier is likely to be 30.0 μm or more and 80.0 μm or less, which is a preferable particle size. As a result, the triboelectric charging property to the toner can be improved, the image quality of the halftone portion can be satisfied, fog can be suppressed, and carrier adhesion can be prevented.
In the specific resistance measuring method described later, the porous magnetic core has a developability when the specific resistance at an electric field strength of 300 V / cm is 1.0 × 10 ⁶ Ω · cm or more and 1.0 × 10 ⁹ Ω · cm or less. It is preferable because it can be made high.

(Manufacturing method of resin-filled magnetic core particles)
A preferred method for filling the pores of the porous magnetic core with the filling resin is a method of adding the filling resin to the pores of the porous magnetic core. The filling resin is preferably a thermosetting resin that does not elute even if a solvent is used when coating the coating resin. More preferably, it is a silicone resin that can be filled without diluting with a solvent. As a result, there is no shrinkage of the resin component during solvent removal, and MR2 / MR1 can be easily adjusted to a desired range.
As the silicone resin, a silicone oligomer such as a methyl silicone oligomer or a methylphenyl silicone oligomer, a methyl silicone resin, or the like can be used.
Examples of the method of filling the pores of the porous magnetic core with resin include a method of impregnating the resin solution with the porous magnetic core by a dipping method, a spray method, a brush coating method, and a coating method such as a fluidized bed.

A method in which the filled resin composition containing the filled resin at normal pressure is filled in the pores of the porous magnetic core and cured by heating is preferable. Since the filled resin is impregnated inside the pores due to the capillary phenomenon, the resin with higher impregnation property is impregnated with the resin inside the porous magnetic core. In order to adjust MR2 / MR1, for example, in the dipping method, MR2 / MR1 can be increased by using a resin having a high impregnation property.

Further, as described above, the resin composition before curing is preferably one having high impregnation property.
After the filled resin composition is filled, it is heated by various methods as needed, and the filled resin composition is brought into close contact with the porous magnetic core. The heating method may be either an external heating method or an internal heating method, for example, a fixed or fluid electric furnace, a rotary electric furnace, a burner furnace, or baking by microwaves.
The amount of the filling resin is preferably 2.0 parts by mass or more and 7.0 parts by mass with respect to the porous magnetic core from the viewpoint of improving the coating property of the coating resin composition and retaining the charge.

Further, it is preferable that the filled resin composition contains a silane coupling agent. The silane coupling agent has good compatibility with the filling resin, and the wettability and adhesion between the porous magnetic core and the filling resin are further enhanced. Therefore, the filling resin is filled from the pores inside the porous magnetic core. As a result, the surface of the resin-filled magnetic core particles has an uneven shape due to pores, which is preferable from the viewpoint of surface tension of the coating resin composition as described above.
For example, the filled resin composition preferably contains a silicone oligomer and a silane coupling agent. Further, it is preferable to contain a solvent such as methyl silicone resin and toluene, and a silane coupling agent. The filling resin is preferably a thermosetting product of these filling resin compositions.

The silane coupling agent used is not particularly limited, but an aminosilane coupling agent is preferable because the presence of the functional group improves the affinity with the coating resin composition.
The reason why the aminosilane coupling agent further enhances the wettability and adhesion between the porous magnetic core and the filling resin and improves the affinity with the coating resin composition is considered as follows.
The aminosilane coupling agent has a portion that reacts with an inorganic substance and a portion that reacts with an organic substance, and it is generally considered that a functional group in which an alkoxy group has an inorganic substance and an amino group reacts with the organic substance. Therefore, the alkoxy group of the aminosilane coupling agent reacts with the portion of the porous magnetic core to improve wettability and adhesion, and the functional group having an amino group is oriented toward the packed resin side, whereby the coating resin composition. I think that it will also increase the affinity with.
The amount of the silane coupling agent to be added is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the filling resin. More preferably, it is 5.0 parts by mass or more and 10.0 parts by mass or less. The above range is preferable from the viewpoint of improving the wettability and adhesion between the porous magnetic core and the filling resin.

(Manufacturing method of magnetic carrier)
The method of coating the surface of the resin-filled magnetic core particles with the resin coating layer is not particularly limited. Examples thereof include a method of treating the surface of the resin-filled magnetic core particles by a coating method such as a dipping method, a spray method, a brush coating method, a dry method, and a fluidized bed using the coating resin composition.
As the coating resin forming the resin coating layer, a vinyl-based resin which is a copolymer of a vinyl-based monomer having a cyclic hydrocarbon group in the molecular structure and another vinyl-based monomer is preferable. More preferred are a (meth) acrylic acid ester having an alicyclic hydrocarbon group and a copolymer of a monomer containing a macromonomer (hereinafter referred to as a coating resin A). The coating resin A includes a (meth) acrylic acid ester having an alicyclic hydrocarbon group, other (meth) acrylic monomers other than the (meth) acrylic acid ester having an alicyclic hydrocarbon group, and a (meth) acrylic monomer. More preferably, it is a copolymer of macromonomers.
The coating resin A smoothes the coating film surface of the resin layer coated on the surface of the ferrite core material. As a result, it has a function of suppressing adhesion of toner-derived components to magnetic carriers and suppressing deterioration of chargeability. It has the function of suppressing the adhesion of toner-derived components to the magnetic carrier and suppressing the decrease in chargeability. In addition, the macromonomer improves the adhesion to the resin-filled magnetic core particles and improves the image density stability. Further, in the present invention, the charge leakage of the thin coat portion can be reduced in a high humidity environment for a long period of time, and the concentration and fine line reproducibility after being left to stand are stable.

Examples of the (meth) acrylic acid ester (monomer) having an alicyclic hydrocarbon group include cyclobutyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cycloheptyl acrylate, dicyclopentenyl acrylate, and dicyclopentenyl acrylate. Cyclopentanyl, cyclobutyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, cycloheptyl methacrylate, dicyclopentenyl methacrylate, dicyclopentanyl methacrylate and the like can be mentioned. These may be used by selecting one kind or two or more kinds.
The amount of the (meth) acrylic acid ester monomer having an alicyclic hydrocarbon group used is preferably 34.0% by mass or more and 95.0% by mass or less based on all the monomers of the coating resin A, and more. It is preferably 40.0% by mass or more and 90.0% by mass or less.

The macromonomer is not particularly limited, but is selected from the group consisting of methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, styrene, acrylonitrile and methacrylonitrile. It is preferably a polymer of at least one monomer to be used.
The amount of the macromonomer used is preferably 10% by mass or more and 50% by mass or less, and more preferably 15% by mass or more and 40% by mass or less, based on all the monomers of the coating resin A.
The weight average molecular weight Mw of the macromonomer is preferably 2000 or more and 10000 or less, and more preferably 2500 or more and 8000 or less.

The weight average molecular weight (Mw) of the coating resin A is preferably 20,000 or more and 120,000 or less, and more preferably 30,000 or more and 100,000 or less, from the viewpoint of coating stability.

Further, examples of other (meth) acrylic monomers other than the (meth) acrylic acid ester having an alicyclic hydrocarbon group include the following.
For example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate (n-butyl, sec-butyl, iso-butyl or tert-butyl; the same applies hereinafter), butyl methacrylate, 2-butyl acrylate. Ethylhexyl, 2-ethylhexyl methacrylate, acrylate or methacrylic acid and the like.

A case where two or more kinds of resin compositions are used for the resin coating layer will be described.
In the present invention, it is more preferable to use the coating resin A in a blended manner with a resin having a specific acid value (hereinafter referred to as the coating resin B), as compared with using the coating resin A alone. The resin B is preferably a polymer of a monomer containing at least the other (meth) acrylic monomer.
As a result, the reduction of the charge leakage portion and the improvement of the coating film strength of the resin coating layer can be achieved at the same time, a stable image can be output for a longer period of time, and the stability after being left to stand is also improved.
When the coating resin A and the coating resin B are used for the resin coating layer, the mass ratio (A: B) thereof is preferably 9: 1 to 1: 9.
The oxidation of the resin coating layer is preferably 0.1 mgKOH / g or more and 30.0 mgKOH / g or less.

The acid value of the coating resin A is preferably 0.0 mgKOH / g or more and 3.0 mgKOH / g or less, and more preferably 0.0 mgKOH / g or more and 2.5 mgKOH / g or less.
The acid value of the coating resin B is preferably 3.5 mgKOH / g or more and 50.0 mgKOH / g or less, and more preferably 4.0 mgKOH / g or more and 50.0 mgKOH / g or less.
The weight average molecular weight (Mw) of the coating resin B is preferably 30,000 or more and 120,000 or less, and more preferably 40,000 or more and 100,000 or less, from the viewpoint of coating stability.

Further, the coating resin composition may contain particles having conductivity or particles or materials having charge controllability. Examples of the conductive particles include carbon black, magnetite, graphite, zinc oxide, and tin oxide.

The amount of the conductive particles added is preferably 0.1 part by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the coating resin in order to adjust the resistance of the magnetic carrier.
Particles having charge controllability include organic metal complex particles, organic metal salt particles, chelate compound particles, monoazo metal complex particles, acetylacetone metal complex particles, hydroxycarboxylic acid metal complex particles, and polycarboxylic acid metal. Complex particles, polyol metal complex particles, polymethylmethacrylate resin particles, polystyrene resin particles, melamine resin particles, phenol resin particles, nylon resin particles, silica particles, titanium oxide particles, alumina particles, etc. Can be mentioned. The amount of particles having charge controllability is preferably 0.5 parts by mass or more and 50.0 parts by mass or less with respect to 100 parts by mass of the coating resin in order to adjust the triboelectric charge amount.

Next, the composition of the preferable toner will be described in detail below.
The toner preferably contains a binder resin, a colorant and a mold release agent. Examples of the binder resin include vinyl resin, polyester resin, epoxy resin and the like. Among them, vinyl resin and polyester resin are more preferable in terms of chargeability and fixability. Polyester resin is particularly preferable.
Monopolymers or copolymers of vinyl-based monomers, polyesters, polyurethanes, epoxy resins, polyvinyl butyral, rosin, modified rosins, terpene resins, phenol resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, etc. If necessary, it can be mixed with the above-mentioned binder resin and used.
When two or more kinds of resins are mixed and used as a binder resin, it is preferable to mix those having different molecular weights in an appropriate ratio as a more preferable form.

The glass transition temperature of the binder resin is preferably 45 ° C. or higher and 80 ° C. or lower, and more preferably 55 ° C. or higher and 70 ° C. or lower. The number average molecular weight (Mn) is preferably 2,500 or more and 50,000 or less, and the weight average molecular weight (Mw) is preferably 10,000 or more and 1,000,000 or less.
As the binder resin, the polyester resin shown below is also preferable.
Based on all the monomer units constituting the polyester resin, it is preferable that 45 mol% or more and 55 mol% or less is an alcohol component, and 45 mol% or more and 55 mol% or less is an acid component.

The acid value of the polyester resin is preferably 90 mgKOH / g or less, more preferably 50 mgKOH / g or less, and the OH value is preferably 50 mgKOH / g or less, more preferably 30 mgKOH / g or less. This is because as the number of terminal groups of the molecular chain increases, the charging characteristics of the toner become more environmentally dependent.

The glass transition temperature of the polyester resin is preferably 50 ° C. or higher and 75 ° C. or lower, and more preferably 55 ° C. or higher and 65 ° C. or lower. The number average molecular weight (Mn) is preferably 1,500 or more and 50,000 or less, and more preferably 2,000 or more and 20,000 or less. The weight average molecular weight (Mw) is preferably 6,000 or more and 100,000 or less, and more preferably 10,000 or more and 90,000 or less.

The following crystalline polyester resin may be added to the toner for the purpose of promoting the plastic effect of the toner and improving the low temperature fixability.
Examples of the crystalline polyester include a polycondensate of a monomer composition containing an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms as main components.

The aliphatic diol having 2 or more and 22 or less carbon atoms (more preferably 6 or more and 12 or less carbon atoms) is not particularly limited, but is preferably a chain-like (more preferably linear) aliphatic diol. Among these, linear aliphatics such as ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,6-hexanediol, α, ω-diol are preferably exemplified.
Of the alcohol components, preferably 50% by mass or more, more preferably 70% by mass or more, is an alcohol selected from an aliphatic diol having 2 or more and 22 or less carbon atoms.

Polyhydric alcohol monomers other than aliphatic diols can also be used. Examples of the dihydric alcohol monomer among the polyhydric alcohol monomers include aromatic alcohols such as polyoxyethylene bisphenol A and polyoxypropylene bisphenol A; 1,4-cyclohexanedimethanol and the like.
As the trihydric or higher polyhydric alcohol monomer, aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1, , 2,5-Pentantriol, glycerin, 2-methylpropantriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, aliphatic alcohols such as trimethylrolpropane and the like.
Further, monovalent alcohol may be used to the extent that the characteristics of the crystalline polyester are not impaired.

On the other hand, the aliphatic dicarboxylic acid having 2 or more and 22 or less carbon atoms (more preferably 6 or more and 12 or less carbon atoms) is not particularly limited, but is a chain (more preferably linear) aliphatic dicarboxylic acid. Is preferable. Hydrolyzed amounts of these acid anhydrides or lower alkyl esters are also included.
Of the carboxylic acid components, preferably 50% by mass or more, more preferably 70% by mass or more is a carboxylic acid selected from aliphatic dicarboxylic acids having 2 or more and 22 or less carbon atoms.

A polyvalent carboxylic acid other than the above-mentioned aliphatic dicarboxylic acid having 2 or more and 22 or less carbon atoms can also be used. Among other polyvalent carboxylic acid monomers, the divalent carboxylic acid includes aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids of n-dodecylsuccinic acid and n-dodecenylsuccinic acid; cyclohexanedicarboxylic acids. Examples thereof include alicyclic carboxylic acids such as acids, and these acid anhydrides or lower alkyl esters are also included.
Examples of the trivalent or higher polyvalent carboxylic acid include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromerit. Aromatic carboxylic acids such as acids, 1,2,4-butanetricarboxylic acids, 1,2,5-hexanetricarboxylic acids, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, and other aliphatic carboxylic acids. Examples include acids, and derivatives such as these acid anhydrides or lower alkyl esters are also included.
Further, it may contain a monovalent carboxylic acid to the extent that the characteristics of the crystalline polyester are not impaired.

The crystalline polyester can be produced according to a conventional polyester synthesis method. For example, the above-mentioned carboxylic acid monomer and alcohol monomer are subjected to an esterification reaction or a transesterification reaction, and then polycondensation reaction is carried out under reduced pressure or by introducing nitrogen gas according to a conventional method to obtain desired crystalline properties. Polyester can be obtained.
The amount of the crystalline polyester used is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, still more preferably, with respect to 100 parts by mass of the binder resin. Is 3 parts by mass or more and 15 parts by mass or less.

When the toner is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite, and ferrite, and iron oxides containing other metal oxides; metals such as Fe, Co, and Ni. Alternatively, alloys of these metals with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V, and Examples thereof include a mixture thereof.

Specifically, as the magnetic material, iron tetraoxide (Fe ₃ O ₄ ) and iron sesquioxide (γ-Fe ₂ O ₃₎
), Zinc iron oxide (ZnFe ₂ O ₄ ), Ithrium iron oxide (Y ₃ Fe ₅ O ₁₂ ), Cadmium iron oxide (CdFe ₂ O ₄ ), Gadrinium iron oxide (Gd ₃ Fe ₅ O ₁₂ ), Copper iron oxide (Gd 3 Fe 5 O 12) CuFe ₂
O ₄ ), lead _{iron oxide (PbFe 12} O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), neodymite iron oxide (NdFe ₂ O ₃ ), barium iron oxide (BaFe ₁₂ O ₁₉ ), magnesium iron oxide (MgFe ₂₎ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), iron lantern oxide (LaFeO ₃ ), iron powder (O 4)
Fe), cobalt powder (Co), nickel powder (Ni) and the like.
These magnetic materials can be used as a colorant. The content of the magnetic material is preferably 20 to 150 parts by mass, more preferably 50 to 130 parts by mass, and further preferably 60 to 120 parts by mass with respect to 100 parts by mass of the binder resin.

Examples of the non-magnetic colorant include the following.
Examples of the black colorant include those adjusted to black using carbon black; a yellow colorant, a magenta colorant, and a cyan colorant.
Examples of the coloring pigment for magenta toner include the following. Examples thereof include condensed azo compounds, diketopyrrolopyrrole compounds, anthracinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds.
Specifically, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221 238, 254, 269; C.I. I. Pigment Violet 19, C.I. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35 can be mentioned.

The colorant may be a pigment alone, but it is preferable to use a dye and a pigment in combination to improve the sharpness of the colorant from the viewpoint of the image quality of a full-color image.
Examples of the magenta toner dye include the following. C. I Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disperse Thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.
Examples of the coloring pigment for cyan toner include the following. C. I. Pigment Blue 1, 2, 3, 7, 15: 2, 15: 3, 15: 4, 16, 17, 60, 62, 66; C.I. I. Bat Blue 6, C.I. I. Acid blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalocyanine methyls are substituted in the phthalocyanine skeleton.

Examples of the yellow coloring pigment include the following. Condensed azo compound, isoindolinone compound, anthraquinone compound, azo metal compound, methine compound, allylamide compound. Specifically, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 155, 168, 174, 180, 181; 185, 191; C.I. I. Bat Yellow 1, 3, 20 can be mentioned.
In addition, C.I. I. Direct green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6 and Solvent Yellow 162 can also be used.
The amount of the colorant used is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably, with respect to 100 parts by mass of the binder resin. Is 3 parts by mass or more and 15 parts by mass or less.

Further, in the above toner, it is preferable to use a binder resin mixed with a colorant in advance and made into a masterbatch. Then, by melt-kneading the colorant masterbatch and other raw materials (binding resin, wax, etc.), the colorant can be satisfactorily dispersed in the toner.

A charge control agent can be used as needed to further stabilize the chargeability of the toner. The charge control agent is preferably used in an amount of 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the binder resin. When it is 0.5 parts by mass or more, sufficient charging characteristics can be easily obtained. On the other hand, when it is 10 parts by mass or less, the compatibility with other materials is unlikely to decrease, and overcharging under low humidity is unlikely to occur.
Examples of the charge control agent include the following.
For example, an organometallic complex or a chelate compound is effective as a load electrical control agent for controlling the toner to load electrical. Examples thereof include monoazo metal complexes, aromatic hydroxycarboxylic acid metal complexes, and aromatic dicarboxylic acid-based metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids, metal salts thereof, anhydrides thereof, esters thereof, and phenol derivatives such as bisphenol.

Examples of the positive charge control agent for controlling the toner to positive charge include modified products of niglosin and fatty acid metal salts, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate and the like. Triphenylmethane dyes and rake pigments thereof (as rake agents, phosphotungstate acid, phosphomolybdic acid, phosphotungenentic acid) Molybdenum acid, tannic acid, lauric acid, galvanic acid, ferricyanic acid, ferrocyanic compounds, etc.), as metal salts of higher fatty acids, diorganosin oxide such as dibutyltin oxide, dioctylstinoxide, dicyclohexylstinoxide, dibutyltinborate, dioctyl Examples thereof include diorgano sulpates such as sulphonate and dicyclohexyl sulphate.

The toner preferably contains a release agent. If necessary, one kind or two or more kinds of mold release agents may be used. Examples of the release agent include the following.
Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax can be preferably used. In addition, oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof; waxes containing fatty acid esters such as carnauba wax, sazole wax, and montanic acid ester wax as main components; and Examples thereof include those obtained by deoxidizing a part or all of fatty acid esters such as deoxidized carnauba wax.

The amount of the release agent is preferably 0.1 part by mass or more and 20 parts by mass or less, and more preferably 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the binder resin.
Further, the melting point defined by the maximum endothermic peak temperature at the time of temperature rise measured by the differential scanning calorimeter (DSC) of the release agent is preferably 65 ° C. or higher and 130 ° C. or lower. More preferably, it is 80 ° C. or higher and 125 ° C. or lower. When the temperature is 65 ° C. or higher, the viscosity of the toner is unlikely to decrease, and the adhesion of the toner to the photoconductor can be suppressed. When the temperature is 130 ° C. or lower, the low temperature fixability becomes good.

As the toner, a fine powder whose fluidity can be increased as compared with that before and after the addition by externally adding to the toner particles may be used as a fluidity improver (external additive). For example, fluororesin powder such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as wet manufacturing silica and dry manufacturing silica, fine powder titanium oxide, fine powder alumina and the like as a silane coupling agent. , Titanium coupling agent, silicone oil, surface treatment and hydrophobization treatment, and treatment so that the degree of hydrophobicity measured by the methanol titration test shows a value in the range of 30 to 80 is particularly preferable. ..
The fluidity improver is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the toner particles.

The magnetic carrier according to the present invention is preferably used as a two-component developer containing a toner and a magnetic carrier. At that time, when the toner concentration in the developer is preferably 2% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 13% by mass or less, good results are usually obtained. If it is 2% by mass or more, the image density is unlikely to decrease, and if it is 15% by mass or less, fog and in-flight scattering can be suppressed.

The two-component developer containing the magnetic carrier of the present invention has a charging step of charging an electrostatic latent image carrier, an electrostatic latent image forming step of forming an electrostatic latent image on the surface of the electrostatic latent image carrier, and the like. A development step of developing an electrostatic latent image with a two-component developer to form a toner image, a transfer step of transferring the toner image to a transfer material with or without an intermediate transfer body, and transfer. It can be used in an image forming method having a fixing step of fixing the toner image to the transfer material.
Further, in the image forming method, the developer has a two-component developer, and the replenishing developer is replenished to the developer in accordance with the reduction in the toner concentration of the two-component developer in the developer. It may have such a configuration. The magnetic carrier of the present invention can be used as a replenishing developer for use in such an image forming method. The image forming method may have a configuration in which excess magnetic carriers in the developing device are discharged from the developing device as needed.

Further, the replenishing developer for replenishing the developer in response to a decrease in the toner concentration of the two-component developer in the developing device contains 2 parts by mass or more and 50 parts by mass or less of toner with respect to 1 part by mass of the magnetic carrier. It is preferable to do so.
Next, an image forming apparatus including a developing apparatus using a magnetic carrier, a two-component developer, and a supplementary developer will be described by way of example, but the present invention is not limited thereto.

<Image formation method>
In FIG. 2, the electrostatic latent image carrier 1 rotates in the direction of the arrow in the figure. The electrostatic latent image carrier 1 is charged by a charger 2 which is a charging means, and the surface of the charged electrostatic latent image carrier 1 is exposed by an exposure device 3 which is an electrostatic latent image forming means. Form an image. The developer 4 has a developing container 5 for accommodating a two-component developer, the developer carrier 6 is arranged in a rotatable state, and a magnetic field is generated inside the developer carrier 6 to generate a magnet. 7 is included. At least one of the magnets 7 is installed so as to face the latent image carrier.
The two-component developer is held on the developer carrier 6 by the magnetic field of the magnet 7, and the amount of the two-component developer is regulated by the regulating member 8 so that the developing unit faces the electrostatic latent image carrier 1. Be transported. In the developing unit, a magnetic brush is formed by the magnetic field generated by the magnet 7. After that, the electrostatic latent image is visualized as a toner image by applying a development bias formed by superimposing an alternating electric field on the DC electric field. The toner image formed on the electrostatic latent image carrier 1 is electrostatically transferred to the recording medium 12 by the transfer charger 11.
Here, as shown in FIG. 3, the electrostatic latent image carrier 1 may be temporarily transferred to the intermediate transfer body 9, and then electrostatically transferred to the transfer material (recording medium) 12. After that, the recording medium 12 is conveyed to the fixing device 13, where the toner is fixed on the recording medium 12 by heating and pressurizing. After that, the recording medium 12 is discharged to the outside of the device as an output image. After the transfer step, the toner remaining on the electrostatic latent image carrier 1 is removed by the cleaner 15. After that, the electrostatic latent image carrier 1 cleaned by the cleaner 15 is electrically initialized by light irradiation from the pre-exposure 16, and the image forming operation is repeated.

FIG. 3 shows an example of a schematic diagram in which the image forming method of the present invention is applied to a full-color image forming apparatus.
The arrows indicating the arrangement and rotation direction of the image forming units such as K, Y, C, and M in the drawing are not limited thereto. By the way, K means black, Y means yellow, C means cyan, and M means magenta. In FIG. 3, the electrostatic latent image carriers 1K, 1Y, 1C, and 1M rotate in the direction of arrows in the figure. Each electrostatic latent image carrier is charged by a charger 2K, 2Y, 2C, 2M which is a charging means, and on the surface of each charged electrostatic latent image carrier, an exposure device 3K which is an electrostatic latent image forming means, It is exposed by 3Y, 3C, and 3M to form an electrostatic latent image. After that, the electrostatic latent image can be used as a toner image by the two-component developer supported on the developer carriers 6K, 6Y, 6C, and 6M provided in the developing units 4K, 4Y, 4C, and 4M, which are the developing means. It is visualized.
Further, it is transferred to the intermediate transfer body 9 by the intermediate transfer chargers 10K, 10Y, 10C, and 10M which are transfer means. Further, it is transferred to the recording medium 12 by the transfer charger 11 which is a transfer means, and the recording medium 12 is fixed by heating pressure by the fixing device 13 which is a fixing means and is output as an image. Then, the intermediate transfer body cleaner 14, which is a cleaning member of the intermediate transfer body 9, collects the transfer residual toner and the like.
Specifically, as a developing method, it is preferable to apply an AC voltage to the developer carrier to form an alternating electric field in the developing region and perform development in a state where the magnetic brush is in contact with the photoconductor. .. The distance (distance between SD) between the developer carrier (development sleeve) 6 and the photosensitive drum is 100 μm or more and 1000 μm or less, which is good for preventing carrier adhesion and improving dot reproducibility. When it is 100 μm or more, the supply of the developer becomes sufficient and the image density becomes appropriate. When it is 1000 μm or less, the magnetic field lines from the magnetic pole S1 are hard to spread, the density of the magnetic brush becomes appropriate, and the dot reproducibility becomes good. In addition, the force for restraining the magnetic coat carrier becomes appropriate, and carrier adhesion can be suppressed.

The voltage (Vpp) between the peaks of the alternating electric field is preferably 300 V or more and 3000 V or less, and more preferably 500 V or more and 1800 V or less. The frequency is preferably 500 Hz or more and 10000 Hz or less, more preferably 1000 Hz or more and 7000 Hz or less, and each of them can be appropriately selected and used depending on the process. In this case, examples of the AC bias waveform for forming the alternating electric field include a triangular wave, a square wave, a sine wave, and a waveform in which the duty ratio is changed.
In order to cope with the change in the formation rate of the toner image, it is preferable to apply a development bias voltage (intermittent alternating superimposed voltage) having a discontinuous AC bias voltage to the developer carrier for development. When the applied voltage is 300 V or more, a sufficient image density can be easily obtained, and the fog toner in the non-image portion can be recovered satisfactorily. Further, when the voltage is 3000 V or less, the latent image is less likely to be disturbed via the magnetic brush, and the image quality is less likely to deteriorate.

By using a two-component developer having a well-charged toner, the fog removal voltage (Vback) can be lowered and the primary charge of the photoconductor can be lowered, so that the life of the photoconductor can be extended. can. The Vback is preferably 200 V or less, more preferably 150 V or less, although it depends on the developing system. As the contrast potential, 100 V or more and 400 V or less are preferably used so as to obtain a sufficient image density.
Further, although it is related to the process speed, the configuration of the electrostatic latent image-bearing photoconductor is usually the same as that of the photoconductor used in the image forming apparatus. For example, a photoconductor having a structure in which a conductive layer, an undercoat layer, a charge generation layer, a charge transport layer, and a charge injection layer, if necessary, are sequentially provided on a conductive substrate such as aluminum or SUS can be mentioned.
The conductive layer, the undercoat layer, the charge generation layer, and the charge transport layer may be those usually used for a photoconductor. As the outermost surface layer of the photoconductor, for example, a charge injection layer or a protective layer may be used.

<Measurement of resistivity of magnetic carrier, porous magnetic core, magnetic core>
The specific resistances of the magnetic carrier and the porous magnetic core are measured using the measuring device outlined in FIG. The magnetic carrier measures the specific resistance at an electric field strength of 2000 (V / cm), and the porous magnetic core measures the specific resistance at an electric field strength of 300 (V / cm).
The resistance measurement cell A is a cylindrical container (made of PTFE resin) 17 with a hole having a cross-sectional area of 2.4 cm ² , a lower electrode (made of stainless steel) 18, a support pedestal (made of PTFE resin) 19, and an upper electrode (made of stainless steel). It is composed of 20. A cylindrical container 17 is placed on the support pedestal 19, the sample (magnetic carrier or porous magnetic core) 21 is filled to a thickness of about 1 mm, and the upper electrode 20 is placed on the filled sample 21 to obtain the thickness of the sample. To measure. As shown in FIG. 6 (a), the gap when there is no sample is d1, and as shown in FIG. 6 (b), the gap d2 when the sample is filled so as to have a thickness of about 1 mm. The thickness d of is calculated by the following formula.
d = d2-d1 (mm)
At this time, the mass of the sample is appropriately changed so that the thickness d of the sample is 0.95 mm or more and 1.04 mm or less.
The resistivity of the sample can be determined by applying a DC voltage between the electrodes and measuring the current flowing at that time. An electrometer 22 (Kesley 6517A, manufactured by Kessley) and a processing computer 23 for control are used for the measurement.
A control system and control software (LabVEIW National Instruments Co., Ltd.) manufactured by National Instruments Co., Ltd. are used as a processing computer for control.
As the measurement conditions, the measured value d is input so that the contact area between the sample and the electrode S = 2.4 cm ² and the thickness of the sample is 0.95 mm or more and 1.04 mm or less. Further, the load of the upper electrode is 270 g, and the maximum applied voltage is 1000 V.
Specific resistance (Ω ・ cm) =
(Applied voltage (V) / measured current (A)) x S (cm ² ) / d (cm)
Electric field strength (V / cm) = applied voltage (V) / d (cm)
For the specific resistance at the electric field strength of the magnetic carrier and the porous magnetic core, the specific resistance at the electric field strength on the graph is read from the graph.

<Measurement method of volume average particle size (D50) of magnetic carrier and porous magnetic core>
The particle size distribution is measured by a laser diffraction / scattering type particle size distribution measuring device "Microtrack MT3300EX" (manufactured by Nikkiso Co., Ltd.).
The volume average particle diameter (D50) of the magnetic carrier and the porous magnetic core is measured by attaching a sample feeder "One-shot dry type sample conditioner Turbotrac" (manufactured by Nikki So Co., Ltd.) for dry measurement. As the supply condition of Turbotrac, a dust collector is used as a vacuum source, the air volume is about 33 L / sec, and the pressure is about 17 kPa. Control is done automatically on the software. For the particle size, the 50% particle size (D50), which is the cumulative value of the volume average, is determined. Control and analysis are performed using the attached software (version 10.3.3-202D). The measurement conditions are as follows.
SetZero time: 10 seconds Measurement time: 10 seconds Number of measurements: 1 time Particle refractive index: 1.81%
Particle shape: Non-spherical measurement upper limit: 1408 μm
Lower limit of measurement: 0.243 μm
Measurement environment: 23 ° C, 50% RH

<Measurement of magnetization amount>
The amount of magnetization is measured by the following procedure using a vibration magnetic field type magnetic characteristic automatic recording device BHV-30 manufactured by Riken Denshi Co., Ltd.
The sample is packed sufficiently densely in a cylindrical plastic container, while an external magnetic field of 79.6 (kA / m) (1000 oersted) is created, and the magnetization moment of the sample filled in the container is measured in this state. .. Further, the actual mass of the sample filled in the container is measured to determine the magnetization strength (Am ² / kg) of the sample.

<Measurement of pore diameter and pore volume of porous magnetic core>
The pore size distribution of the porous magnetic core is measured by the mercury intrusion method.
The measurement principle is as follows.
In this measurement, the pressure applied to mercury is changed, and the amount of mercury that has penetrated into the pores at that time is measured. The conditions under which mercury can penetrate into the pores can be expressed as PD = -4σcosθ from the balance of forces, where θ and σ are the pressure P, the pore diameter D, the contact angle of mercury, and the surface tension, respectively. If the contact angle and surface tension are constants, the pressure P and the pore diameter D through which mercury can penetrate at that time are inversely proportional. Therefore, the horizontal axis P of the PV curve, which can be measured by changing the pressure at the pressure P and the infiltrated liquid amount V at that time, is directly replaced with the pore diameter from this equation, and the pore distribution is obtained. There is.
As a measuring device, Autopore IV9520 manufactured by Shimadzu Corporation is used, and measurement is performed under the following conditions and procedures.
Measurement conditions Measurement environment 20 ° C
Measurement cell Sample volume 5 cm ³ , press-fit volume 1.1 cm ³ , application Powder measurement range 2.0 psia (13.8 kPa) or more, 59989.6 psia (413.7 kPa) or less Measurement step 80 steps
(When the pore diameter is taken logarithmically, the steps are carved so that they are evenly spaced.)
Press-fit parameter Exhaust pressure 50 μmHg
Exhaust time 5.0min
Mercury injection pressure 2.0 psia (13.8 kPa)
Equilibrium time 5 secs
High pressure parameter Equilibrium time 5 secs
Mercury parameter forward contact angle 130.0 degrees
Backward contact angle 130.0 degrees
Surface tension 485.0 mN / m (485.0 days / cm)
Mercury density 13.535g / mL
Measurement procedure (1) Weigh about 1.0 g of the porous magnetic core and put it in the sample cell.
Enter the weighing value.
(2) Measure the range of 2.0 psia (13.8 kPa) or more and 45.8 psia (315.6 kPa) or less in the low pressure part.
(3) Measure the range of 45.9 psia (316.3 kPa) or more and 59989.6 psia (413.6 kPa) or less in the high pressure part.
(4) The pore size distribution is calculated from the mercury injection pressure and the mercury injection amount.
(2), (3) and (4) are automatically performed by the software attached to the device.
From the pore diameter distribution measured as described above, the peak pore diameter that maximizes the differential pore volume in the pore diameter range of 0.1 μm or more and 3.0 μm or less is read.
Further, the pore volume obtained by integrating the differential pore volume in the pore diameter range of 0.1 μm or more and 3.0 μm or less is calculated using the attached software and used as the pore volume.

<Measurement method of acid value>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. That is, the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids and the like contained in 1 g of a sample is called an acid value.
In the present invention, the acid value is measured according to JIS K 0070-1992. Specifically, the measurement is performed according to the following procedure.
(1) Preparation of Reagents 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water is added to make 100 mL to obtain a phenolphthalein solution.
Dissolve 7 g of special grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. As for the factor of the potassium hydroxide solution, 25 mL of 0.1 mol / L hydrochloric acid was placed in a triangular flask, several drops of the phenolphthaline solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization was performed. Obtained from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, those prepared according to JIS K 8001-1998 are used.
(2) Operation (A) Main test 2.0 g of the sample is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene / ethanol (2: 1) is added, and the mixture is dissolved over 5 hours. Then, a few drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.
(B) Blank test Titration is performed in the same manner as described above except that no sample is added (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) Calculation of acid value Substitute the obtained result into the following formula to calculate the acid value.
AV = [(BA) x f x 5.61] / S
Here, AV: acid value (mgKOH / g), A: addition amount of potassium hydroxide solution in blank test (mL), B: addition amount of potassium hydroxide solution in this test (mL), f: potassium hydroxide Solution factor, S: sample (g).

<Separation of resin coating layer from magnetic carrier and separation of coating resins A and B in resin coating layer>
As a method of separating the resin coating layer from the magnetic carrier, there is a method of taking the magnetic carrier in a cup and eluting the coating resin with toluene.
After the eluted resin is dried, it is dissolved in tetrahydrofuran (THF) and sorted using the following apparatus.
[Device configuration]
LC-908 (manufactured by Nippon Analytical Industry Co., Ltd.)
JRS-86 (the company; repeat injector)
JAR-2 (the company; autosampler)
FC-201 (Gilson; Hula Cushion Collector)
[Column structure]
JAIGEL-1H-5H (20φ x 600mm: preparative column) (manufactured by Nippon Analytical Industry Co., Ltd.)
[Measurement condition]
Temperature: 40 ° C
Solvent: THF
Flow rate: 5 ml / min.
Detector: RI
Based on the molecular weight distribution of the coating resin, the elution time at which the peak molecular weight (Mp) of the coating resin A and the coating resin B is reached is measured in advance using the resin composition specified by the following method, and each resin is before and after that. Separate the ingredients. After that, the solvent is removed and dried to obtain a coating resin A and a coating resin B.
The atomic group can be specified from the absorption wave number using a Fourier transform infrared spectroscopic analyzer (Spectrum One: manufactured by PerkinElmer), and the resin configurations of the coating resin A and the coating resin B can be specified.

<Measurement of weight average molecular weight (Mw), peak molecular weight (Mp), and content ratio of coating resin A, coating resin B, and coating resin in the resin coating layer>
The weight average molecular weight (Mw) and peak molecular weight (Mp) of the coating resin A, the coating resin B, and the coating resin are measured by gel permeation chromatography (GPC) according to the following procedure.
First, the measurement sample is prepared as follows.
The sample (coating resin separated from the magnetic carrier, coating resin A and coating resin B separated by a preparative device) and tetrahydrofuran (THF) were mixed at a concentration of 5 mg / ml, and the mixture was mixed at a concentration of 5 mg / ml for 24 hours at room temperature. The sample was dissolved in THF by allowing it to stand. Then, a sample that has passed through a sample processing filter (Maishori Disc H-25-2, manufactured by Tosoh Corporation) is used as a GPC sample.
Next, using a GPC measuring device (HLC-8120GPC manufactured by Tosoh Corporation), measurement is performed under the following measurement conditions according to the operation manual of the device.
(Measurement condition)
Equipment: High-speed GPC "HLC8120 GPC" (manufactured by Tosoh Corporation)
Column: 7 series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: THF
Flow velocity: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the weight average molecular weight (Mw) and peak molecular weight (Mp) of the sample, the calibration curve is a standard polystyrene resin (TSK standard polystyrene F-850, F-450, F-288, F-128, manufactured by Tosoh Corporation). Molecular weight calibration curve created by F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500) To use.
The content ratio is determined by the peak area ratio of the molecular weight distribution measurement. As shown in FIG. 4, in the case where the region 1 and the region 2 are completely separated, the resin content ratio is obtained from the area ratio of each region. When the regions overlap as shown in FIG. 5, the GPC molecular weight distribution curve is divided by a line perpendicular to the horizontal axis from the polarization point, and the content ratio is calculated from the area ratio of the regions 1 and 2 shown in FIG. Ask for.

<Separation of porous magnetic core from magnetic carrier>
For example, in the case of a magnetic carrier filled and coated with a thermoplastic resin, the porous magnetic core can be separated from the magnetic carrier by the following method, and the peak pore diameter and the like can be measured.
A Put about 5 g of magnetic carrier in a 100 ml beaker.
B Put about 50 ml of toluene in a beaker and shake with an ultrasonic shaker for 5 minutes.
C After the shaking is completed, the sample in the beaker is allowed to stand for several minutes, and the sample in the beaker is stirred 20 times by tracing the bottom of the beaker, and then only the toluene solution in which the coating resin and the filling resin are dissolved is flowed as a waste liquid.
While holding the sample in the D beaker from the outside with a neodymium magnet, put about 50 ml of toluene into the beaker again, and repeat the above operations B and C 10 times.
E The solvent is changed to chloroform, and the above operations B and C are further performed once.
The F beaker is put into a vacuum dryer to dry and remove the solvent (a vacuum dryer with a solvent trap is used, the temperature is 50 ° C., the degree of vacuum is −0.093 Mpa or less, and the drying time is 12 hours).
G Remove the beaker from the vacuum dryer and leave it for about 20 minutes to cool.

<Measurement of current value>
Weigh 800 g of the magnetic carrier and expose it to an environment with a temperature of 20 to 26 ° C. and a humidity of 50 to 60% RH for 15 minutes or more. After that, the current value is measured at an applied voltage of 500 V using a current value measuring device in which the magnet roller and the Al element tube shown in FIG. 7 are used as electrodes and the distance between them is 4.5 mm.

<Measurement of MR1 and MR2 of magnetic carrier cross section>
1. Cross-section cutting A focused ion beam processing observation device (FIB) and FB-2100 (manufactured by Hitachi High-Technologies Corporation) are used for cross-section processing of the magnetic carrier. A sample is prepared by applying a carbon paste on a sample table (metal mesh) for FIB, fixing a small amount of magnetic carriers on the sample table (metal mesh) so that each particle exists independently, and depositing platinum as a conductive film. The sample is set in the FIB apparatus, rough-processed (beam current 39 nA) using an acceleration voltage of 40 kV and a Ga ion source, and then finish-processed (beam current 7 nA), and the carrier cross section of the sample is carved out.
The magnetic carrier cross section selected as the measurement sample is a magnetic carrier having D50 × 0.9 ≦ H ≦ D50 × 1.1, where H is the length of the line segment that is the maximum length of the carrier particle cross section. As a target, 100 cross-section samples within this range are prepared.
2. Analysis of components derived from the porous magnetic core of the magnetic carrier and resin components Using a scanning electron microscope (manufactured by Hitachi, Ltd., S4700), the elements of the magnetic components and resin components of the magnetic carrier cross-sectional sample can be scanned. The analysis is performed using the elemental analysis means (energy dispersive X-ray analyzer EDAX) attached to the electron microscope.
The observation magnification is set to 10000 times or more, and the region composed of only the magnetic component is observed at an acceleration voltage of 20 kV and an intake time of 100 sec to identify an element in the component derived from the porous magnetic core. Similarly, the elements in the resin component are also specified.
The component derived from the porous magnetic core is the element specified above, but it is difficult to specify the content ratio of oxygen because it is contained in both the component derived from the porous magnetic core and the resin component. Therefore, it is excluded from the components derived from the porous magnetic core. That is, the component derived from the porous magnetic core in the present invention is a metal element in ferrite constituting the porous magnetic core.
The resin component is an element specified above, but oxygen is contained in both the magnetic component and the resin component, and it is difficult to specify the content ratio, so it is excluded from the resin component. Further, since hydrogen cannot be specified by the energy dispersive X-ray analyzer used in the present invention, hydrogen is also excluded from the resin component. That is, in the present invention, when an acrylic resin composed of carbon, hydrogen, and oxygen is used, the element that becomes the resin component is only carbon. In the case of silicone resin, carbon and silicon are used.
3. Measurement of metal component abundance and resin abundance in the cross section Using a scanning electron microscope, observe the magnetic carrier cross section at a magnification of 2000 times.
In the obtained cross-sectional image, two straight lines parallel to the line segment having the maximum length of the resin-filled magnetic core particles and separated from the line segment by 2.5 μm are designated as A and B. A straight line C passing through the intersection of the line segment and the contour line of the resin-filled magnetic core particles, parallel to the straight line C, and 5 from the straight line C toward the center of the magnetic carrier. Assume a straight line D at a distance of 0.0 μm.
The region surrounded by the contour lines of the resin-filled magnetic core particles between the straight lines A and B and the straight lines A, B, and D and in contact with the straight line C is defined as R1.
By dividing the region in this way, it is possible to measure under conditions in which the influence of the coating resin component is suppressed as much as possible.
Further, a region surrounded by the straight lines A, B, and D and a straight line E parallel to the straight line D and 5.0 μm away from the straight line D toward the center of the magnetic carrier is defined as R2.
The mass ratio (mass%) of the elements is measured with respect to the regions R1 and R2 using an elemental analysis means at an acceleration voltage of 20 kV and an uptake time of 100 sec.
For example, in the case of a magnetic carrier in which the component of the magnetic core particles is Mn-Mg-Sr-based ferrite, the silicone resin is filled, and the acrylic resin is coated, the elements of the metal component are iron, manganese, magnesium, and strontium. , The elements of the resin component are carbon and silicon. At this time, the total mass ratio of the elements of carbon and silicon (mass%) in the R1 region is JR1, and the total mass ratio of the elements of iron, manganese, magnesium, and strontium (mass%) is FR1. Become. Further, the total mass ratio of the elements of carbon and silicon (mass%) in the R2 region is JR2, and the total mass ratio of the elements of iron, manganese, magnesium, and strontium (mass%) is FR2.
MR2 / MR1 of one magnetic carrier particle is calculated from the above values, and the arithmetic mean value of 80 particles obtained by cutting 10 points above and below in the cross-sectional measurement of 100 particles is defined as MR2 / MR1 of the magnetic carrier cross section.

<Measuring method of weight average particle size (D4) and number average particle size (D1)>
The weight average particle size (D4) and the number average particle size (D1) of the toner are the precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, Beckman Coulter 3) by the pore electric resistance method equipped with an aperture tube of 100 μm. Coulter Coulter) and the attached dedicated software "Beckman Coulter Particle 3 Version 3.51" (Beckman Coulter Co., Ltd.) for setting measurement conditions and analyzing measurement data were used. The measurement was performed with 25,000 effective measurement channels, and the measurement data was analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.
Before measuring and analyzing, the dedicated software was set as follows.
In the dedicated software "Change standard measurement method (SOM) screen", set the total count number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). The value obtained using (manufactured by) is set. By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flush of the aperture tube after measurement.
On the "pulse to particle size conversion setting screen" of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Approximately 200 ml of the electrolytic aqueous solution is placed in a 250 ml round bottom beaker made of glass dedicated to Multisizer 3 and set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "flash of the aperture tube" function of the dedicated software.
(2) Put about 30 ml of the electrolytic aqueous solution in a 100 ml flat bottom beaker made of glass. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted 3 times by mass with ion-exchanged water, and about 0.3 ml is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and are placed in the water tank of the ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W. Add a certain amount of ion-exchanged water. About 2 ml of the contaminanton N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, the toner is about 10 m.
g is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the electrolytic aqueous solution of (5) in which toner is dispersed is dropped onto the round bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to about 5%. .. Then, the measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) and the number average particle size (D1) are calculated. When the graph / volume% is set in the dedicated software, the "average diameter" of the analysis / volume statistical value (arithmetic mean) screen is the weight average particle size (D4), and the graph / number% is set in the dedicated software. The "average diameter" on the analysis / number statistical value (arithmetic mean) screen is the number average particle size (D1).

<Calculation method of fine powder amount>
The amount of fine powder (number%) based on the number of pieces in the toner is calculated as follows.
For example, the number% of particles of 4.0 μm or less in the toner is set to graph / number% with (1) dedicated software after the measurement of Multisizer 3 is performed, and the chart of the measurement result is displayed as number%. do. (2) Check "<" in the particle size setting part on the format / particle size / particle size statistics screen, and enter "4" in the particle size input section below it. Then, (3) the numerical value of the “<4 μm” display unit when the analysis / number statistical value (arithmetic mean) screen is displayed is the percentage of the number of particles of 4.0 μm or less in the toner.

<Calculation method of coarse powder amount>
The volume-based crude powder amount (volume%) in the toner is calculated as follows.
For example, the volume% of particles of 10.0 μm or more in the toner is the above-mentioned Multisizer.
After performing the measurement of 3, (1) set the graph / volume% with the dedicated software and display the chart of the measurement result in volume%. (2) Check ">" in the particle size setting part on the format / particle size / particle size statistics screen, and enter "10" in the particle size input section below it. Then, (3) the numerical value of the "> 10 μm" display unit when the analysis / volume statistical value (arithmetic mean) screen is displayed is the volume% of the particles of 10.0 μm or more in the toner.

<Measurement of the amount of resin filled in the magnetic carrier>
For example, when the coating resin is not dissolved in toluene and a thermoplastic resin is used as the filling resin, the amount of the filling resin can be measured from the magnetic carrier by the following method.
A Weigh about 5 g of the sample to be measured and grind it sufficiently with a mortar.
B A 100 ml beaker is precisely weighed (measured value 1), then the entire amount of the sample mashed in a mortar is put in, and the total mass of the sample and the beaker is precisely weighed (measured value 2).
Put about 50 ml of C toluene in a beaker and shake with an ultrasonic shaker for 5 minutes.
D After shaking, let stand for several minutes, stir the sample in the beaker with a neodymium magnet 20 times by tracing the bottom of the beaker, and then flow only the toluene solution in which the filling resin is dissolved as a waste liquid.
While holding the sample in the E beaker from the outside with a neodymium magnet, about 50 ml of toluene is put into the beaker again, and the above operations B and C are repeated 10 times.
The F solvent is changed to chloroform, and the above operations B and C are further performed once.
The G beaker is put into a vacuum dryer to dry and remove the solvent (a vacuum dryer with a solvent trap is used, the temperature is 50 ° C., the degree of vacuum is −0.093 Mpa or less, and the drying time is 12 hours).
The beaker is taken out from the H vacuum dryer, left to cool for about 20 minutes, and then the mass is precisely weighed (measured value 3).
I From the measured values obtained as described above, the filling amount (mass%) is calculated according to the following formula.
Filled resin amount = (initial sample weight-sample weight after melting of filled resin) / sample weight x 100
In the above formula, the sample weight is calculated by calculating (measured value 2-measured value 1), and the sample weight after dissolving the filling resin is calculated by calculating (measured value 3-measured value 1).

<Measurement of the amount of coating resin on the magnetic carrier>
For example, when the filling resin is not dissolved in toluene and a thermoplastic resin is used as the coating resin, the amount of the coating resin can be measured from the magnetic carrier by the following method.
A A 100 ml beaker is precisely weighed (measured value 1), then about 5 g of the sample to be measured is put in, and the total mass of the sample and the beaker is precisely weighed (measured value 2).
B Put about 50 ml of toluene in a beaker and shake with an ultrasonic shaker for 5 minutes.
C After shaking, let stand for several minutes, stir the sample in the beaker with a neodymium magnet 20 times by tracing the bottom of the beaker, and then flow only the toluene solution in which the coating resin is dissolved as a waste liquid.
While holding the sample in the D beaker from the outside with a neodymium magnet, put about 50 ml of toluene into the beaker again, and repeat the above operations B and C 10 times.
E The solvent is changed to chloroform, and the above operations B and C are further performed once.
The F beaker is put into a vacuum dryer to dry and remove the solvent (a vacuum dryer with a solvent trap is used, the temperature is 50 ° C., the degree of vacuum is −0.093 Mpa or less, and the drying time is 12 hours).
G Take out the beaker from the vacuum dryer, leave it for about 20 minutes to cool, and then weigh the mass (measured value 3).
H From the measured values obtained as described above, the amount of coating resin (mass%) is calculated according to the following formula.
Amount of coating resin = (Initial sample mass-Sample mass after dissolution of coating resin) / Sample mass x 100
In the above formula, the sample mass is calculated by calculating (measured value 2-measured value 1), and the sample mass after dissolving the coating resin is calculated by calculating (measured value 3-measured value 1).

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following formulations, parts are mass-based unless otherwise noted.

<Production example of porous magnetic core 1>
Process 1 (Weighing / mixing process)
Fe ₂ O ₃ 68.3% by mass
MnCO ₃ 28.5% by mass
Mg (OH) ₂ 2.0% by mass
SrCO ₃ 1.2% by mass
The above ferrite raw materials were weighed, 20 parts of water was added to 80 parts of the ferrite raw material, and then wet mixing was performed with a ball mill for 3 hours using zirconia having a diameter (φ) of 10 mm to prepare a slurry. The solid content concentration of the slurry was 80% by mass.
Step 2 (temporary firing step)
After drying the mixed slurry with a spray dryer (manufactured by Ohkawara Kakohki Co., Ltd.), it is calcined in a batch electric furnace under a nitrogen atmosphere (oxygen concentration 1.0% by volume) at a temperature of 1050 ° C. for 3.0 hours. Ferrite was prepared.
Process 3 (crushing process)
After crushing the calcined ferrite to about 0.5 mm with a crusher, water was added to prepare a slurry. The solid content concentration of the slurry was 70% by mass. A slurry was obtained by pulverizing with a wet ball mill using 1/8 inch stainless beads for 3 hours. Further, this slurry was pulverized for 4 hours with a wet bead mill using zirconia having a diameter of 1 mm to obtain a calcined ferrite slurry having a volume-based 50% particle size (D50) of 1.3 μm.
Process 4 (granulation process)
To 100 parts of the calcined ferrite slurry, 1.0 part of ammonium polycarboxylic acid as a dispersant and 1.5 parts of polyvinyl alcohol as a binder were added, and then granulated into spherical particles by a spray dryer (manufactured by Ohkawara Kakohki Co., Ltd.). , Dried. After adjusting the particle size of the obtained granulated product, it was heated at 700 ° C. for 2 hours using a rotary electric furnace to remove organic substances such as a dispersant and a binder.
Step 5 (firing step)
In a nitrogen atmosphere (oxygen concentration 1.0% by volume), the time from room temperature to the firing temperature (1100 ° C.) was set to 2 hours, and the temperature was maintained at 1100 ° C. for 4 hours for firing. Then, the temperature was lowered to 60 ° C. over 8 hours, returned to the atmosphere from the nitrogen atmosphere, and taken out at a temperature of 40 ° C. or lower.
Process 6 (sorting process)
After crushing the agglomerated particles, the coarse particles are removed by sieving with a sieve having a mesh size of 150 μm, the fine particles are removed by wind power classification, and the low magnetic force is removed by magnetic beneficiation to remove the porous magnetic core 1. Got The obtained porous magnetic core 1 was porous and had pores. Table 1 shows the manufacturing conditions and physical property values of each step of the obtained porous magnetic core 1.

<Production Examples of Porous Magnetic Cores 2 to 14 and Magnetic Core 1>
The firing temperature and time were changed so that the physical property values of the porous magnetic core became the values shown in Table 1, and the porous magnetic cores 2 to 14 were prepared. Further, the magnetic core 1 was manufactured by adjusting the firing temperature in step 5. Table 1 shows the physical property values of the obtained porous magnetic cores 2 to 14 and the magnetic core 1.

<Manufacturing of filled resins 1 to 3>
Table 2 shows that methylsilicone oligomer (KR-400: manufactured by Shinetsu Silicone Co., Ltd.) was used as a resin component and γ-aminopropyltriethoxysilane (KBM-903: manufactured by Shinetsu Silicone Co., Ltd.) was used as an additive. Filling resin 1 was obtained by mixing at the described ratio.
Further, the filling resin 2 was obtained in the same manner as the filling resin 1 except that a methylphenyl silicone oligomer (KR-401: manufactured by Shinetsu Silicone Co., Ltd.) was used as the resin component.
Further, a filling resin 3 was obtained in the same manner as the filling resin 1 except that a methyl silicone resin (KR-251: manufactured by Shin-Etsu Silicone Co., Ltd.) was used as a resin component and toluene was used as a solvent component.

<Manufacturing of coating resins A-1 to A-3>
The raw materials shown in Table 3 (109.0 parts in total) were added to a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen suction tube and a ground-glass stirrer, and further 100.0 parts of toluene and 100 parts of methyl ethyl ketone were added. 0.0 part and 2.4 parts of azobisisovaleronitrile were added and kept at 80 ° C. for 10 hours under a nitrogen stream to obtain a coating resin A-1 solution (solid content 35% by mass).
Further, using the raw materials shown in Table 3, coating resins A-2 to A-3 were obtained in the same manner. The physical characteristics are shown in Table 3.

<Manufacturing of coating resins B-1 to B-7>
The raw materials shown in Table 4 (101.6 parts in total) were added to a four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen suction tube and a ground-glass stirrer, and further 50.0 parts of toluene and 100 parts of methyl ethyl ketone were added. 0.0 part and 2.4 parts of azobisisovaleronitrile were added and kept at 80 ° C. for 10 hours under a nitrogen stream to obtain a coating resin B-1 solution (solid content 40% by mass).
Further, using the raw materials shown in Table 4, coating resins B-2 to B-7 were obtained in the same manner. The physical characteristics are shown in Table 4.

<Manufacturing example of magnetic carrier 1>
Process 1 (filling process)
100 parts of the porous magnetic core 1 is placed in a stirring container of a mixing stirrer (Dalton's universal stirrer NDMV type), the temperature is maintained at 60 ° C., and the filling resin 1 shown in Table 2 is 5 at normal pressure. Partially dropped.
After completion of the dropping, stirring was continued while adjusting the time, the temperature was raised to 70 ° C., and the particles of each porous magnetic core were filled with the resin composition.
The resin-filled magnetic core particles obtained after cooling are transferred to a mixer (drum mixer UD-AT type manufactured by Sugiyama Heavy Industries, Ltd.) having spiral blades in a rotatable mixing container, and placed at 2 ° C./ The temperature was raised to the curing temperature shown in Table 5 with stirring at a heating rate of 1 minute. Then, heating and stirring were continued at 140 ° C. for 50 minutes.
After that, the particles were cooled to room temperature, the ferrite particles filled with the resin and cured were taken out, and the non-magnetic material was removed using a magnetic dressing machine. Further, the coarse particles were removed by a vibrating sieve to obtain a resin-filled magnetic core particle 1 filled with a resin.
Step 2 (resin coating step)
-Resin-filled magnetic core particles 1 100 parts-Resin A-1 1 part-Resin B-1 1 part For 100 parts of resin-filled magnetic core particles, the above coating resins (A-1 and B-1 (A-1 and B-1) The formulation is shown in Tables 3 and 4)) was diluted with toluene so that the resin component was 5%, and a sufficiently stirred resin solution was prepared. After that, the resin-filled magnetic core particles 1 were placed in a planetary motion type mixer (Nautamixer VN type manufactured by Hosokawa Micron Co., Ltd.) maintained at a temperature of 60 ° C., and the above resin solution was charged. As a method of charging, 1/2 amount of the resin solution was charged, and the solvent was removed and the coating operation was performed for 30 minutes. Next, a further 1/2 amount of the resin solution was added, and the solvent was removed and the coating operation was performed for 40 minutes.
After that, the magnetic carrier coated with the coating resin composition is transferred to a mixer having spiral blades (drum mixer UD-AT type manufactured by Sugiyama Heavy Industries, Ltd.) in a rotatable mixing container, and the mixing container is rotated 10 times per minute. The mixture was heat-treated in a nitrogen atmosphere at a temperature of 120 ° C. for 2 hours with stirring. The obtained magnetic carrier was separated into low magnetic force products by magnetic beneficiation, passed through a sieve having an opening of 150 μm, and then classified by a wind power classifier to obtain a magnetic carrier 1. Table 6 shows each physical property value.

<Manufacturing example of magnetic carriers 2 to 22>
Magnetic carriers 2 to 22 were obtained in the same manner as in Magnetic Carrier Production Example 1 except that the type of material, the amount added, and the production conditions were changed as shown in Table 5. Table 6 shows each physical property value.

<Manufacturing example of magnetic carrier 23>
A magnetic carrier 23 was obtained in the same manner as in Production Example 1 of the magnetic carrier except that step 1 was not performed and the type of material, the amount added, and the production conditions were changed as shown in Table 5. Table 6 shows each physical property value.

[Toner manufacturing example]
100 parts of binder resin (Tg: 57 ° C., acid value: 12 mgKOH / g, hydroxyl value: 15 mgKOH / g) polyester (dihydric alcohol component: polyoxypropylene (2.2) -2,2-bis (4-) Hydroxyphenyl) Propane 0.20 mol Polyvalent carboxylic acid component: Terephthalic acid 0.17 mol Anhydrous trimellitic acid 0.01 mol))
・ C. I. Pigment Blue 15: 3 5.5 parts, 3,5-di-t-aluminum salicylate compound 0.2 parts, normal paraffin wax (melting point: 90 ° C) 6 parts Henschel mixer (FM- After mixing well in 75J type, manufactured by Mitsui Mine Co., Ltd., feed amount of 10 kg / hr with a twin-screw kneader (trade name: PCM-30 type, manufactured by Ikekai Steel Co., Ltd.) set at a temperature of 130 ° C. (The temperature of the kneaded product at the time of discharge was 150 ° C.). The obtained kneaded product was cooled, coarsely crushed with a hammer mill, and then finely pulverized with a mechanical crusher (trade name: T-250, manufactured by Turbo Industries, Ltd.) at a feed amount of 15 kg / hr. Then, particles having a weight average particle size of 5.5 μm, containing 55.6% by volume of particles having a particle size of 4.0 μm or less and 0.8% by volume of particles having a particle size of 10.0 μm or more were obtained. ..
The obtained particles were classified by a rotary classifier (trade name: TTSP100, manufactured by Hosokawa Micron Co., Ltd.) to cut fine powder and coarse powder. Cyan has a weight average particle size of 6.0 μm, an abundance rate of particles having a particle size of 4.0 μm or less is 27.8% by volume, and an abundance rate of particles having a particle size of 10.0 μm or more is 2.2% by volume. Toner particles 1 were obtained.
Furthermore, the following materials were put into a Henshell mixer (trade name: FM-75 type, manufactured by Nippon Coke Industries Co., Ltd.), the peripheral speed of the rotary blade was set to 35.0 (m / sec), and the mixture was mixed in a mixing time of 3 minutes. By doing so, an external additive was adhered to the surface of the cyan toner particles 1 to obtain cyan toner 1. -Cyantoner particles 1: 100 parts-Silica particles: 3.5 parts (Silica particles prepared by the fumed method are surface-treated with 1.5% by mass of hexamethyldisilazane and then adjusted to a desired particle size distribution by classification. )
-Titanium oxide particles: 0.5 part (Anatase-type crystalline metatitanium acid surface-treated with an octylsilane compound)
-Strontium titanate particles: 0.5 part (surface treated with octylsilane compound)
Using the above magnetic carriers 1 to 25 and toner 1, each material is shaken with a shaker (YS-8D type: manufactured by Yayoi Co., Ltd.) so that the toner concentration becomes 8%, and two components are used. 300 g of the system developer was prepared. The amplitude condition of the shaker was 200 rpm for 2 minutes.
On the other hand, 90 parts of toner 1 was added to 10 parts of the magnetic carriers 1 to 23, and the mixture was mixed with a V-type mixer for 5 minutes in an environment of normal temperature and humidity of 23 ° C./50% RH to obtain a replenishing developer. .. Table 7 shows the details of the two-component developer, and Table 8 shows the details of the replenishing developer.

<Examples 1 to 18 and Comparative Examples 1 to 5>
The following evaluations were carried out using this two-component developer and a supplementary developer.
As an image forming apparatus, a Canon color copier imagePRESS C850 modified machine was used.
A two-component developer was put into each color developer, a replenishing developer container containing each color replenishing developer was set, an image was formed, and various evaluations were performed before and after the durability test.
As a durability test, a chart of FFH output with an image ratio of 1% was used in a printing environment with a temperature of 23 ° C. and a humidity of 5 RH% (hereinafter, “N / L”). Further, under a printing environment of a temperature of 30 ° C. and a humidity of 80 RH% (hereinafter, “H / H”), a chart of FFH output having an image ratio of 1% was used. FFH is a value obtained by displaying 256 gradations in hexadecimal, 00h is the first gradation of 256 gradations (white background portion), and FFH is the 256th gradation of 256 gradations (solid portion). ..
The number of image outputs was 20,000 in each environment.
(conditions)
Paper: Laser beam printer paper CS-814 (81.4 g / m ² ) (Canon Marketing Japan Inc.)
Image formation speed: A4 size, full color, modified to output at 90 (sheets / min).
Development conditions: The development contrast can be adjusted by any value, and it has been modified so that the automatic correction by the main unit does not work. The voltage (Vpp) between the peaks of the alternating electric field was modified so that the frequency could be changed from 0.7 kV to 1.8 kV in 0.1 kV increments at a frequency of 2.0 kHz. Each color was modified so that the image could be output in a single color.
Each evaluation item is shown below.

(1) Evaluation of in-plane density unevenness An FFH image (toner loading amount on paper: 0.35 mg / cm ² ) with a size of 200 mm x 280 mm is output on A4 size paper (CS-814) under an N / L environment. Then, the obtained images were divided into 140 images every 20 mm × 20 mm, and the density at the center of each image was measured with an X-Rite color reflection densitometer (Color reflection density meter X-Rite 404A). Among the obtained image densities, the maximum one was Dmax and the minimum one was Dmin, and the difference Dmax-Dmin was calculated to evaluate the in-plane density unevenness according to the following criteria. Further, after performing the durability test under the above-mentioned conditions in the N / L environment, the in-plane density unevenness was evaluated in the same manner as before the durability test.
<Evaluation criteria>
A: 0.00≤Dmax-Dmin≤0.02
B: 0.02 <Dmax-Dmin ≤ 0.05
C: 0.05 <Dmax-Dmin ≤ 0.08
D: 0.08 <Dmax-Dmin≤0.10
E: 0.10 <Dmax-Dmin ≦ 0.13
F: 0.13 <Dmax-Dmin ≦ 0.15
G: 0.15 <Dmax-Dmin ≦ 0.18
H: 0.18 <Dmax-Dmin ≦ 0.20
I: 0.20 <Dmax-Dmin ≦ 0.25
J: 0.25 <Dmax-Dmin

(2) Evaluation of carrier adhesion An FFh image was output in an N / L environment, and a transparent adhesive tape was adhered and sampled on an electrostatic latent image carrier before the power was turned off during image output and cleaning was performed. .. Then, the number of magnetic carrier particles adhering to the electrostatic latent image carrier in 30 mm × 30 mm was counted and evaluated according to the following criteria. Further, after performing the durability test under the above-mentioned conditions in the N / L environment, the carrier adhesion was evaluated in the same manner as before the durability test.
<Evaluation criteria>
A: 2 or less B: 3 or more and 4 or less C: 5 or more and 6 or less D: 7 or more and 8 or less E: 9 or more

(3) Evaluation of Fog A solid image (solid white image) having an image ratio of 100% and 00h was printed on A3 size paper (CS-814) under an H / H environment, and the judgment was made according to the following criteria. The 6-point average reflectance Dr (%) of non-printed paper and the 6-point average reflectance Ds (%) of printed paper are converted into a reflector meter ("REFLECTOMETER MODEL TC-6DS" manufactured by Tokyo Denshoku Co., Ltd. " ), And the fog rate (%) was determined. Further, after performing the durability test under the above-mentioned conditions in the H / H environment, the fog rate was calculated under the same development conditions as before the durability test.
Fog rate (%) = Dr (%) -Ds (%)
<Evaluation criteria>
A: Fog rate is less than 0.2% B: Fog rate is 0.2% or more and less than 0.4% C: Fog rate is 0.4% or more and less than 0.6% D: Fog rate is 0.6 % Or more and less than 0.8% E: Fog rate is 0.8% or more and less than 1.0% F: Fog rate is 1.0% or more and less than 1.2% G: Fog rate is 1.2% or more , Less than 1.4% H: Fog rate is 1.4% or more, less than 1.6% I: Fog rate is 1.6% or more, less than 2.0% J: Fog rate is 2.0% or more

(4) Comprehensive judgment The evaluation ranks in the above evaluation items (1) to (3) were quantified, and the total value was judged according to the following criteria.
Regarding the evaluation items (1) and (3), A = 20, B = 18, C = 16, D = 14, E = 12, F = 10, G = 8, H = 6, I = 4, J = 2 and the evaluation item (2) was A = 10, B = 8, C = 6, D = 4, and E = 2.
A: 95 or more and 100 or less B: 85 or more and less than 95 C: 75 or more and less than 85 D: 50 or more and less than 75 E: less than 50 The results are shown in Table 9.

1, 1K, 1Y, 1C, 1M: Electrostatic latent image carrier, 2, 2K, 2Y, 2C, 2M: Charger, 3, 3K, 3Y, 3C, 3M: Exposed device, 4, 4K, 4Y, 4C 4, 4M: developer, 5: developing container, 6, 6K, 6Y, 6C, 6M: developer carrier, 7: magnet, 8: regulatory member, 9: intermediate transfer body, 10K, 10Y, 10C, 10M: intermediate Transfer Charger, 11: Transfer Charger, 12: Transfer Material (Recording Medium), 13: Fixer, 14: Intermediate Transfer Cleaner, 15, 15K, 15Y, 15C, 15M: Cleaner, 16: Pre-Exposure, 17: Cylindrical container, 18: lower electrode, 19: support pedestal, 20: upper electrode, 21: magnetic carrier or porous magnetic core, 22: electrometer, 23: processing computer, d1: gap in the absence of sample, d2: Gap when filling the sample

Claims (12)

Resin-filled magnetic core particles having a porous magnetic core and a filling resin existing in the pores of the porous magnetic core, and
A resin coating layer existing on the surface of the resin-filled magnetic core particles,
It is a magnetic carrier with
In the pore size distribution of the porous magnetic core,
The peak pore diameter that maximizes the differential pore volume in the range of 0.1 μm or more and 3.0 μm or less is 0.40 μm or more and 1.00 μm or less.
The pore volume, which is the integral value of the differential pore volume in the range of 0.1 μm or more and 3.0 μm or less, is 58 mm ³ / g or more and 100 mm ³ / g or less.
Magnetic carrier relates abundance ratio of elements is determined by a defined elemental analysis definitive in region R1 and region R2 are as follows:
The mass-based proportions of the composition derived from the resin component were defined as JR1 and JR2, respectively, and the mass-based proportions of the composition derived from the porous magnetic core were defined as FR1 and FR2, respectively.
Furthermore, when JR1 / FR1 is MR1 and JR2 / FR2 is MR2,
The MR1 and the MR2
0.20 ≤ MR2 / MR1 ≤ 0.90
A magnetic carrier characterized by satisfying the relationship of.
(Region R1 is a cross-sectional image of the magnetic carrier, in which a line segment having the maximum length of the resin-filled magnetic core particles is drawn, and two lines are parallel to the line segment and 2.5 μm apart from the line segment. Let the straight lines be straight lines A and B
A straight line that passes through the intersection of the line segment and the contour line of the resin-filled magnetic core particles and is orthogonal to the line segment is defined as a straight line C.
When a straight line D parallel to the straight line C and 5.0 μm away from the straight line C toward the center of the magnetic carrier is defined as a straight line D.
It is a region surrounded by the contour line of the resin-filled magnetic core particles and the straight lines A, B and D, and in contact with the straight line C.
The region R2 is a region surrounded by the straight lines A, B, and D and a straight line E parallel to the straight line D and 5.0 μm away from the straight line D toward the center of the magnetic carrier. )

The magnetic carrier according to claim 1, wherein the content of the filling resin is 2.0 parts by mass or more and 7.0 parts by mass or less with respect to 100 parts by mass of the porous magnetic core. The first or second claim, wherein the content of the coating resin forming the resin coating layer is 1.0 part by mass or more and 3.0 part by mass or less with respect to 100 parts by mass of the resin-filled magnetic core particles. Magnetic carrier. The magnetic carrier according to any one of claims 1 to 3, wherein the current value of the magnetic carrier when 500 V is applied is 10.0 μA or more and 50.0 μA or less. The resin coating layer comprises a (meth) acrylic acid ester having at least an alicyclic hydrocarbon group, and other (meth) acrylic monomers other than the (meth) acrylic acid ester having an alicyclic hydrocarbon group. And a copolymer of macromonomers,
The macromonomer is a weight of at least one monomer selected from methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, styrene, acrylonitrile, and methacrylonitrile. The magnetic carrier according to any one of claims 1 to 4, which is a coalescence. The resin coating layer is
i) A copolymer of a (meth) acrylic acid ester having an alicyclic hydrocarbon group and a monomer containing a macromonomer, which has an acid value of 0.0 mgKOH / g or more and 3.0 mgKO.
Coating resin A of H / g or less and
ii) A polymer of other (meth) acrylic monomers other than the (meth) acrylic acid ester having the alicyclic hydrocarbon group, which has an acid value of 3.5 mgKOH / g or more and 50.0 mgKOH / g. The magnetic carrier according to any one of claims 1 to 4, which contains the following coating resin B. The magnetism according to any one of claims 1 to 6, wherein the specific resistance of the magnetic carrier at an electric field strength of 2000 V / cm is 1.0 × 10 ⁶ Ω · cm or more and 1.0 × 10 ^{9 Ω · cm or less.} Career. The magnetic carrier according to any one of claims 1 to 7, wherein the filling resin is a silicone resin. A two-component developer containing a toner containing a binder resin, a colorant and a mold release agent, and a magnetic carrier.
A two-component developer in which the magnetic carrier is the magnetic carrier according to any one of claims 1 to 8. Charging process for charging the electrostatic latent image carrier,
An electrostatic latent image forming step of forming an electrostatic latent image on the surface of the electrostatic latent image carrier,
A developing step of developing the electrostatic latent image with a two-component developer to form a toner image.
An image forming method comprising a transfer step of transferring the toner image to a transfer material with or without an intermediate transfer body, and a fixing step of fixing the transferred toner image to the transfer material.
The image forming method in which the two-component developer is the two-component developer according to claim 9. Charging process for charging the electro-latent image carrier,
An electrostatic latent image forming step of forming an electrostatic latent image on the surface of the electrostatic latent image carrier,
A developing process in which the electrostatic latent image is developed using a two-component developer in a developing device to form a toner image.
It has a transfer step of transferring the toner image to the transfer material with or without an intermediate transfer body, and a fixing step of fixing the transferred toner image to the transfer material.
An image forming method in which a replenishing developer is replenished to the developing device according to a decrease in the toner concentration of the two-component developing agent in the developing device.
The replenishing developer contains a magnetic carrier and a toner containing a binder resin, a colorant and a mold release agent.
The replenishing developer contains 2 parts by mass or more and 50 parts by mass or less of the toner with respect to 1 part by mass of the magnetic carrier.
The image forming method, wherein the magnetic carrier is the magnetic carrier according to any one of claims 1 to 8. Charging process for charging the electrostatic latent image carrier,
Electrostatic latent image forming step of forming an electrostatic latent image on the surface of an electrostatic latent image carrier,
A developing process in which the electrostatic latent image is developed using a two-component developer in a developing device to form a toner image.
It has a transfer step of transferring the toner image to the transfer material with or without an intermediate transfer body, and a fixing step of fixing the transferred toner image to the transfer material.
A replenishing developer for use in an image forming method in which a replenishing developer is replenished to the developing device in response to a decrease in the toner concentration of the two-component developing agent in the developing device.
The replenishing developer contains a magnetic carrier and a toner containing a binder resin, a colorant and a release agent.
The replenishing developer contains 2 parts by mass or more and 50 parts by mass or less of the toner with respect to 1 part by mass of the magnetic carrier.
The magnetic carrier is a replenishing developer which is the magnetic carrier according to any one of claims 1 to 8.

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