JP2002323790A - Toner and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner with which stable developing performance can be obtained from the beginning of use while the toner is left irrelevantly to environment for a cartridge which can be loaded with a large amount of toner. SOLUTION: A plurality of toner storage spaces 16 are formed and connected through openings to allow the toner to move, each toner storage space has at lest one agitating member 20, and the toner is moved by the agitating member or a carrying member from one storage part to another storage part and supplied to a development part holding a toner carrier 18 to perform development. The charged toner contains at least binding resin and a coloring agent and satisfies 0.2<=(Ct/(X×Dt)<=0.8 (1), where X (cm<3> ) is the total capacity X>=2500 of the toner storage p arts, Ct (g) is the stored tone mass, and Dt (g/cm<3> ) is the tap density of the toner, and is characterized by that the jetting index of Carr of the toner is >=80.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner and a process cartridge used in an image forming method such as an electrophotographic method, an electrostatic printing method, and a toner jet method, and more particularly, to developing an electrostatic image. For developing electrostatic charge, and a process cartridge using the toner.

[0002]

2. Description of the Related Art Conventionally, in an electrophotographic image forming apparatus using an electrophotographic image forming process, an electrophotographic photosensitive drum and a process means acting on the electrophotographic photosensitive drum are integrally formed into a cartridge, and the cartridge is formed as a cartridge. Of the image forming apparatus is adopted. By making the cartridge into a cartridge, the user can load the cartridge into the main body of the apparatus, thereby replenishing toner and replacing parts such as an image carrier that has reached the end of its life. Widely used in photographic image forming apparatuses.

[0003] Here, the conventional cartridge is one in which a charger, a developing device, a cleaning unit, and a photosensitive drum are integrated into a single structure, and can be attached to and detached from the image forming apparatus main body. Further, at least the developing means and the electrophotographic photosensitive member are integrally formed into a cartridge so as to be detachable from the image forming apparatus main body.

In such a process cartridge, a toner carrier and a toner are provided as developing means.

With the speeding up of laser beam printers,
Because of the demand for high-speed process cartridges and high durability, it is necessary to increase the amount of toner filled in one process cartridge and increase the capacity of the toner container. However, an increase in the toner filling amount causes a problem that the rise of toner charge is delayed in the conventional container configuration. The toner in the toner container is frictionally charged by coming into contact with the toner carrier and has a predetermined charge amount.However, when the toner filling amount is large, the chance of contact with the toner carrier is reduced. It takes a long time for all the toners inside to reach the predetermined charge amount.

In order to prevent such a phenomenon, there has been proposed a method of controlling the toner circulation between the vicinity of the developing section and the toner container.

One of the methods is to use a toner container having a plurality of toner storage spaces in a toner container and using a single stirring means in each storage space portion. Since the charge gradually rises in the portion, it is shown that the configuration is excellent, but the following problems may occur.

That is, since a plurality of storage spaces are provided in the toner container, when the fluidity of the toner is poor, or when the toner does not move smoothly between the toner storage spaces, a shortage of toner occurs in the developing unit. When the image is whitened, or when the stirring by the stirring member in the toner container is not performed appropriately and the charging is not performed uniformly, an image defect may occur. Further, since the toner has a large capacity, the toner having poor fluidity tends to be packed, and when stored in such a state in a high-temperature and high-humidity state, the toner is easily affected by the environment such as blocking in a cartridge. Also, since it is conveyed at a stretch onto the developing sleeve,
There was a problem that a negative ghost easily occurred.

There are many methods for evaluating the fluidity of a toner as one of the characteristics of the powder, and the fluidity of each toner can be evaluated by any method suitable for the toner. It is true that there is a danger that it may be applied. Therefore, we measured some phenomena and characteristics related to liquidity,
Carr as an index that can comprehensively evaluate the fluidity of powder
There are (Car) fluidity index and jetness index.

The fluidity index literally serves as a measure of the difficulty of powder flowing out due to gravity, and the jetness index is a measure of the likelihood of a flushing phenomenon. Flushing means that the fluidity, which has been reduced in a stationary state, becomes a liquid like state when it starts vibrating and flowing.

This means that the higher the jettability index value, the higher the flowability and jettability of the toner powder.

As a patent defining these values, Japanese Patent Publication No. 59-21549 discloses a toner having a Carr fluidity index of 30 or more. If the fluidity index is high, the toner becomes smoother. However, for a toner applied to a large-capacity cartridge, the fluidity index of 30 or more in a wide range is insufficient for agitating the toner and supplying it to the developing sleeve. Can be In addition, if attention is paid only to the fluidity, there are toners having high fluidity that are difficult to be loosened when packed. That is, when a large amount of toner is filled, the toner compacted at the bottom of the cartridge is hardly agitated by the agitating member due to the weight of the toner, and is difficult to be transported to the toner carrier. There is a problem that it becomes.

Also, Japanese Patent No. 2943035 discloses that
The toner has a jetting index of 50 to 80. However, also in this case, this value is low for use in a large-capacity cartridge, and even when applied to a cartridge capable of filling a large amount of toner in this range, the toner is hardly agitated as described above, and Since supply to the developing sleeve is also difficult, image white spots and the like and deterioration in developability are observed.

Further, in order to change the fluidity of the toner, the physical properties of the resin are changed in JP-A-7-281478, the fluidity is changed by wax in JP-A-2000-284522, and JP-A-06-230604 is disclosed. In the gazette, an attempt is made to change the fluidity index of the magnetic material to change the fluidity of the toner. However, when the physical properties of various raw materials of the toner are changed in order to obtain the desired fluidity index of the toner, the desired good developing performance may not be obtained.

Japanese Patent Application Laid-Open No. 7-160044 discloses a method in which the fluidity index is 40 or more, and the fluidity index is changed depending on the type of external additives and external addition conditions. However, what is described here is mainly only the amount of the external additive and the external processing time, and does not have a sufficient jetting property even if the fluidity is high, so that it is applied to a large-capacity cartridge. Have poor powder properties.

[0016]

SUMMARY OF THE INVENTION The present invention is to solve the above problems. That is, an object of the present invention is to provide a toner and a process cartridge that can obtain a stable developing property from the initial stage of use until the toner runs out, regardless of the environment, in a cartridge that can be filled with a large amount of toner.

Another object of the present invention is to provide a toner and a process cartridge which can store a large amount of toner and which is excellent in long-term preservability in which the toner is not deteriorated by the weight of the toner in a high-temperature and high-humidity environment.

[0018]

SUMMARY OF THE INVENTION The present invention has a plurality of toner storage spaces, each of which is connected via an opening, is capable of moving toner, and has at least one toner storage space therein. A toner used in an image forming method that has one stirring member, moves toner from a storage unit to another storage unit by a stirring member or a conveyance member, and supplies and develops the toner to a developing unit that holds a toner carrier. The toner to be filled includes at least a binder resin and a colorant, satisfies the following expression, and has a Carr jetting index of 80 or more.

0.2 ≦ (Ct / (X × Dt)) ≦ 0.8 (X (cm ³ ): total capacity of toner storage section X ≧ 250)
0, Ct (g): mass of toner contained, Dt (g / c)
m ³ ): Tap density of toner]

According to the present invention, in a process cartridge comprising at least a developing means and a photoreceptor, the developing means has a plurality of toner storage spaces, and each toner storage space is connected via an opening so that toner can be moved. And has at least one stirring member in each toner storage space, and moves the toner from the storage unit to another storage unit by the stirring member or the transport member, and transfers the toner to the developing unit that holds the toner carrier. A developing means for supplying and developing, wherein the toner to be filled contains at least a binder resin and a colorant, satisfies the above expression, and has a Carr jetting index of greater than 80; The process cartridge.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The process cartridge used in the present invention has a toner accommodating space of 2500 cm ³ or more, and the filling rate of the toner satisfies the formula: 0.2 ≦ (Ct / (X × Dt)) ≦ 0.8 (X (cm ³ ): total capacity of toner storage unit, Ct)
(G): mass of stored toner, Dt (g / cm ³ ): tap density of toner] The toner is filled with a toner having a Carr jetting index greater than 80, and the image is formed from the start of use until the toner is used up. For the purpose of preventing white spots and poor development, stable images can be obtained even after long-term storage in a high-temperature and high-humidity environment.

The toner container and the toner which provide such an effect have the following configurations.

First, the toner container has a plurality of toner storage spaces. This makes it possible to speed up the charging rise of the toner near the developing unit. Each toner storage space is connected through an opening, and is arranged so that the toner can be moved. At this time, the capacity of the toner storage unit is 2500 cm ³ or more, and the filling rate of the toner satisfies the expression.

0.2 ≦ (Ct / (X × Dt)) ≦ 0.8 [X (cm ³ ): total capacity of toner storage unit, Ct
(G): mass of stored toner, Dt (g / cm ³ ): tap density of toner)

More preferably, 0.3 ≦ (Ct / (X × D
t)) ≦ 0.7, more preferably 0.4 ≦ (Ct / (X
× Dt)) It is preferable that the toner is filled in the range of ≦ 0.7 in terms of stable toner supply.

The toner to be filled in the process cartridge contains at least a binder resin and a colorant. The toner used in the present invention has a Carr jetting index of greater than 80. Preferably, the fluidity index of the toner is greater than 60.

The fluidity index and jetness index described in this specification were measured by the following methods.

Using a powder tester P-100 (manufactured by Hosokawa Micron Corporation), parameters such as angle of repose, collapse angle, difference angle, degree of compression, degree of cohesion, degree of spatula and degree of dispersion are measured. The values obtained for each are applied to the Carr's liquidity index table and jettable index table, converted into respective indexes of 25 or less, and the sum of the indexes obtained from each parameter is used as the liquidity index and jettable index. Calculated. The measurement method of each parameter is shown below.

Angle of repose 150 g of the toner is deposited on a circular table having a diameter of 8 cm through a mesh having an opening of 710 μm.
At this time, the toner is accumulated to such an extent that the toner overflows from the end of the table. At this time, the angle formed between the ridge line of the toner deposited on the table and the circular table surface was measured with a laser beam to obtain the angle of repose.

Compressibility The degree of compression can be determined from the loosely filled bulk density (loose apparent specific gravity A) and the tapping bulk density (solid apparent specific gravity P).

Compressibility (%) = 100 (PA) / P ○ Loose apparent specific gravity measuring method Diameter 5 cm, height 5.2 c
m, gently pour 150 g of toner into a cup having a capacity of 100 cc. When the toner is filled into the measuring cup at the peak, the surface of the toner is wiped, and the apparent specific gravity of the looseness is calculated from the amount of toner filled in the cup. ○ Hardened apparent specific gravity measurement method Add the attached cap to the measuring cup used at the loose apparent specific gravity. Fill the cup with toner and tap the cup 180 times. When the tapping is completed, remove the cap and wipe off excess toner piled up in the cup. The apparent apparent specific gravity is calculated from the amount of toner filled in the cup. Both apparent specific gravity values are inserted into the expression of the degree of compression to determine the degree of compression.

The spatula angle is set such that the bottom of the bat having a size of 10 cm × 15 cm is in contact with the spatula having a size of 3 cm × 8 cm. The toner is deposited on the spatula. At this time, the toner is deposited so as to rise on the spatula. Thereafter, only the bat is gently lowered, and the inclination angle of the side surface of the toner remaining on the spatula is measured by a laser beam. Then, after applying a shock once with a shocker attached to the spatula, the spatula angle is measured again. The average of the measured value and the measured value before giving an impact was calculated as a spatula angle.

Cohesion degree On the vibrating table, the openings 250 μm, 150 μm,
Set sieves in order of 75 μm. 1m vibration amplitude
m, the vibration time is 20 seconds, and 5 g of the toner is gently placed and vibrated. After stopping the vibration, the mass remaining on each sieve is measured. [(Amount of toner remaining on upper sieve) ÷ 5 (g)] × 100 a ((amount of toner remaining on middle sieve) ÷ 5 (g)] × 100 × 0.6 b ((lower sieve) Calculated as (amount of toner remaining on sieve) ÷ 5 (g)] × 100 × 0.2... Ca + b + c = aggregation degree (%).

The value obtained from the parameter is represented by Carr
Table of Fluidity Index and Spouting Index of Chemicals (Chemical E
ngineering. Jan. 18.1965) to convert to an index of 25 or less, and sum of those values ++
+ = Carr's fluidity index.

Collapse Angle After the angle of repose is measured, a shock is applied to the bat on which the circular table for measurement is placed with a shocker three times. Thereafter, the angle of the toner remaining on the table is measured using a laser beam, and the angle is determined as the collapse angle.

Difference Angle The difference between the angle of repose and the angle of collapse is the difference angle.

Dispersion: Ten grams of toner is dropped from a height of about 60 cm onto a watch glass having a diameter of 10 cm. Then, the toner remaining on the watch glass is measured, and the degree of dispersion is determined by the following equation. Dispersion (%) = [10− (toner remaining on plate)] ×
10

The sum of the index that can be converted from the value of and the index corresponding to the fluidity index value obtained above can be obtained as the jetness index from the above-mentioned Carr table.

When this measurement is performed, a toner having a good jetting property such that the jetting property index shows a value larger than 80 is a case where a large-capacity cartridge is filled at a somewhat high filling rate. Also, since the fluidity of the toner is easily returned by the agitating member in the cartridge during the agitation, the toner is easily conveyed from each toner storage portion in the cartridge toward the developing sleeve. For this reason, an excessive force is applied to a part of the stirring member, so that toner adhesion and image whiteout do not occur, the toner can be stably stirred from the initial use of the cartridge until the toner runs out, and good developing performance can be obtained. Can be given.

When a large amount of toner is filled, the toner tends to be more densely packed due to its weight. But,
By combining with this toner having a high jetting property, the toner is hardly aggregated even when stored in a high-temperature and high-humidity environment, and a good image can be obtained even when an image is output with a printer thereafter.

At this time, if the fluidity index is greater than 60, the supply of the toner amount is constant even in long-term durability in a high-temperature and high-humidity environment, so that the image density does not decrease and stable image characteristics can be obtained. Is more preferable.

When the jettability index is 80 or less, high fluidity can be obtained, but once it is clogged, it is difficult to flow even when a force is applied. When the toner is transported by the stirring member, the toner is not easily transported.As a result, the toner is hardly transported to the sleeve, the toner is charged unevenly on the sleeve, and the toner is also charged. The image becomes non-uniform and the image becomes uneven.

When the jettability index is 80 or less and the fluidity is 60 or less, the toners tend to aggregate and hardly flow, and it is difficult for the toner to be transported from the toner storage section in the cartridge to the adjacent storage section. Therefore, the toner is not conveyed, causing image white spots or the like, or an appropriate amount of toner does not exist on the sleeve, and the amount of toner on the sleeve is reduced, resulting in sleeve ghosting,
Further, problems such as deterioration of fog due to excessive rise in toner tribo arise.

In order to achieve the jetting index and the fluidity index of the toner of the present invention, not only the particle diameter of the toner and the amount of the external additive are changed, but also the shape of the stirring blade used at the time of external addition, One guideline is to change the specific surface area ratio between the toner before external addition and the toner after external addition to a certain value or more by changing the stirring state by changing the filling amount into the mixing device and the stirring mode. Becomes At this time, the ratio of the BET specific surface area is
It is preferably about 1.6 to 2.4. If the ratio of BET after external addition / BET before external addition is within this range, the added external additive is in a state where the external additive is uniformly loosened without agglomeration on the surface of the toner, and some external additive is added. Some external additive particles adhere to the toner surface with an appropriate adhesive force, and some external additive particles have a strong adhesive force, and some exist in a free state. By mixing various states of the external additive that are embedded in the toner by the impact force, the desired jetting property of the toner can be obtained. At this time, by changing various conditions of the external addition process of the toner,
The ratio of each existing state of the external additive changes, the powder characteristics of the toner change, and the jetting index can be changed.

At this time, if the ratio of the BET before and after the external addition is preferably in the range of 1.7 to 2.3, more preferably in the range of 1.8 to 2.2, the state of the external additive on the toner surface can be further improved. Is appropriate, and the jettability index of the toner can show a value larger than 80.

As a method of measuring BET, nitrogen gas was adsorbed on the sample surface using a specific surface area measuring device Gemini 2375 (Shimadzu Corporation) in accordance with the BET method.
The specific surface area was calculated using the multipoint method.

Examples of the apparatus for external treatment include Henschel mixer (manufactured by Mitsui Mining); super mixer (manufactured by Kawata); ribocorn (manufactured by Okawara Seisakusho); Nauta mixer, turbulizer, cyclomix (Hosokawa micron). Spiral Pin Mixer (manufactured by Taiheiyo Kiko Co., Ltd.); Ledige Mixer (manufactured by Matsubo).

In order to achieve the above-mentioned externally added state using these devices, the above-described Henschel mixer will be described as an example.
The toner is filled at an apparent volume filling rate of ３０30%, and the stirring blade at the time of processing includes a blade shape for convection of powder deposited at the bottom of the container over the entire container, It is preferable to use a combination of blade shapes that can be subjected to mechanical treatment while pushing back the powder that has risen to the shearing force to the lower part of the container. Under the above conditions, since the dust concentration in the container is not too high, it is possible to have a void necessary for the external addition treatment. For this reason, the high agitation force and the agitation force are given to the toner by the agitation blade, so that the external additive in various states can be present on the toner surface, and the toner having the desired high jetting property can be obtained. Can be. Also,
As the stirring mode used at this time, in order to mix the external additive adhesion state in various states, the number of rotations of the stirring blade is changed in several steps in the processing time, or after the processing is performed once, It is preferable to select a stirring form in which a force is applied at an accelerated rate by repeating the processing several times.

Further, the process cartridge of the present invention
The configuration is as follows.

A toner container frame having an opening for storing toner, a toner seal for sealing the opening of the toner container frame, and a developing frame supporting the toner carrier and being joined to the toner container frame. A toner seal automatic winding device provided with a toner seal winding shaft for opening the toner seal in the process cartridge having the toner cartridge.

When the amount of toner charged becomes large, the mass of the cartridge itself becomes heavy. Therefore, in a printer which is basically maintained by a user, the difficulty of handling due to the weight easily causes a problem.

In particular, after opening the cartridge, the user must pull out the toner seal for sealing the opening of the toner container frame, and set it in the printer. Therefore, in the present invention, in which the toner seal is automatically wound when the cartridge is set in the printer main body, the cartridge has high usability without requiring the user to pull the toner seal even when the mass of the toner cartridge is large. . However, when the toner is automatically opened, in order to obtain a good image from the first sheet, it is necessary to immediately supply the toner to the toner carrier regardless of the ratio of the charged toner. In the present invention, if the toner has a jetting property within the range specified in the present invention, the toner fluidity can be restored with a small force even after packing, so that the toner seal can be broken with a slight load, and the automatic opening is performed. Becomes possible. Further, since the jetting property is high, the toner is supplied to the toner carrier immediately after the seal is opened, so that a good image can be obtained from the first printout sheet. If the jetting property of the toner is out of the specified range, the weight of the toner is applied to the seal when the toner seal is drawn, and the seal entrainment portion causes
Since the seal entrains the toner, it is more intense to pull the seal incompletely. In addition, when an excessive force is applied, the seal is broken from the middle, so that the function of automatic opening cannot be performed, and the opening becomes insufficient.
Further, the supply to the toner carrier becomes insufficient, and image density unevenness due to toner supply unevenness occurs.

In the process cartridge, the free length of the toner regulating elastic blade member set in contact with the toner carrier is 7.0 to 10.0 mm, and
The length (nip end) of the elastic blade at the free end side from the nip portion is 0.5 to 2.5 mm, and the contact pressure of the elastic blade in contact with the toner carrier is 0.10 linear pressure. ０．４0.40N is preferred. More preferably, the free length of the toner regulating elastic blade member is 7.5 to 7.5.
9.5 mm, and the length (nip end) of the elastic blade at the free end side from the nip portion is 1.0 to 2.
0 mm, and the contact pressure of the elastic blade in contact with the toner carrier is 0.20 to 0.30 N in linear pressure.

The large-capacity toner cartridge in which the toner is stored is applied to a machine that prints at a higher speed as the structure of the machine body. For this reason, when printing is performed at a high speed, if the rise of the toner charge on the developing sleeve that rotates at a high speed is not fast, problems such as ghost and poor development may occur. Therefore, it is necessary to determine the setting of the elastic blade in order to accelerate the rise of the toner charge on the sleeve. Therefore, by setting the free length, the free end length, and the contact pressure of the blade member in the above range, the blade member can be applied to a process cartridge capable of filling a large amount of toner satisfying the above expression. Good developability without image unevenness or ghost can be exhibited from the beginning.

Further, in the process cartridge, when the developing means is formed by using a toner having a jettability index larger than 80, and preferably a flowability index larger than 60, the ease of movement of the toner, Because of the ease of movement, it is easy to enter between the elastic blade and the sleeve, and it is possible to maintain an appropriate spike height on the sleeve because it is supplied stably. Then, since the toner is uniformly rubbed between the sleeve and the blade due to the high fluidity, the rise of the charging becomes faster. Also, the toner enters between the blade and the sleeve, so that a high load is applied to the blade.However, when the toner having a low jetting property is filled, the load becomes too high, and the blade is worn at the nip width, resulting in abrasion of the blade. In addition, the charge of the toner becomes non-uniform, and a phenomenon called “sand background” in which many white dots are observed particularly in an image at the start of printing such as halftone occurs frequently. (See Fig. 9)

Further, in a process cartridge provided with a cleaning means for removing toner on the surface of the photoreceptor, the cleaning means is a rubber elastic blade,
Further, it is preferable that a setting angle of the blade with respect to a tangent to the surface of the photoreceptor be set in a range of 10 to 30 °, and a tip thickness of the rubber blade be 0.5 to 2.5 mm.

As described above, a process cartridge containing a large amount of toner is mainly applied to a high-speed machine capable of printing out a large amount in a short time. In such a high-speed machine, since the photosensitive drum and the developing sleeve also rotate at a high speed, the temperature inside the cartridge or inside the machine tends to increase. Therefore, a considerable load and temperature are applied to the cleaning blade that comes into contact with the photosensitive drum and scrapes off the transfer residual toner on the surface.

Therefore, in the cartridge described in this document which can store a large amount of toner, the setting angle of the blade with respect to the tangent to the surface of the photoreceptor is set in the range of 10 to 30 °, and the tip thickness of the rubber blade is 0.5 to 30. 2.5mm
Then, even if it is in contact with the photosensitive drum rotating at high speed,
The load received can be reduced. As a result, much of the transfer residual toner can be collected, so that good developing properties can be obtained without turning over the blade or causing cleaning failure even during long-term durability.

In the structure of the process cartridge, when the process cartridge is formed by using a toner having a jettability index larger than 80, and preferably a flowability index larger than 60, the ease of movement of the toner is improved. Because of the good mobility, the toner is easily diffused when collected on the photoconductor drum, and the friction coefficient of the blade is constant at all parts, enabling stable contact with the photoconductor drum Becomes However, when the toner does not satisfy the jetting property, the toner hardly diffuses when collected by the cleaning blade, and the toner is unevenly present between the blade and the photosensitive drum. As a result, the friction coefficient difference between the blade where the toner is present and the blade where the toner is not present increases, and the blade is turned up from the part of the blade having the large friction coefficient, which may cause image defects.

In the present invention, the set angle of the blade with respect to the tangent to the surface of the photoreceptor is preferably set in the range of 15 to 21 °, and the tip thickness of the rubber blade is set to 1.
Preferably, it is in the range of 2 to 1.8 mm. When this range is satisfied, a stable image can be obtained even in a high-temperature and high-humidity environment without poor cleaning or blade turnover even in long-term durability.

The resin composition according to the present invention has a glass transition temperature (Tg) of from 45 to 80 from the viewpoint of storage stability.
° C, preferably 50 to 70 ° C. If Tg is lower than 45 ° C, it causes deterioration of the toner in a high-temperature atmosphere and offset during fixing. When Tg exceeds 80 ° C.,
The fixability tends to decrease.

As a method for measuring the glass transition temperature of the resin of the present invention, a differential thermal analysis measuring device (DSC measuring device),
DSC-7 (manufactured by PerkinElmer), EXSTAR
It can be measured under the following conditions using 6000, SSC / 5200 (manufactured by Seiko Instruments Inc.), DSC2920MDSC (manufactured by TA Instruments Inc.), or the like.

<Method of Measuring Glass Transition Temperature of Resin> Sample: 0.5 to 2 mg, preferably 1 mg Temperature curve: Heating I (20 ° C. to 180 ° C., heating rate 10 ° C./min) Cooling I (180 ° C. 10 ° C, temperature drop rate 10 ° C / min) Temperature rise II (10 ° C to 180 ° C, temperature rise rate 10 ° C / min) Measurement method: A sample is placed in an aluminum pan, and an empty aluminum pan is used as a reference. The intersection of the line at the midpoint of the base line before and after the endothermic peak appeared and the differential heat curve was defined as the glass transition point Tg.

The binder resin component used in the present invention has a molecular weight of Mn measured by GPC of a THF-soluble component.
(Number average molecular weight) 3000 to 20000, and Mw
(Weight average molecular weight) is preferably in the range of 50,000 to 500,000.

These binder resin components may be mixed and dispersed in advance with a wax component when producing a magnetic toner. In particular, a method in which the wax component and the high molecular weight polymer are preliminarily dissolved in a solvent during the production of the binder, and then mixed with the low molecular weight polymer solution is preferable. By mixing the wax component and the high molecular weight component in advance, the phase separation in the micro region is reduced, the high molecular weight component is not re-aggregated, and a good dispersion state with the low molecular weight component can be obtained.

In the present invention, the toner or the binder resin
The molecular weight distribution by GPC using THF (tetrahydrofuran) as a solvent is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and the column at this temperature was treated with THF as a solvent.
At a flow rate of 1 ml / min.
Measure by injecting 0 μl. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. The standard polystyrene samples for preparing the calibration curve, for example, Tosoh Corporation, or used as molecular weight of Showa Denko KK is about 10 ² to 10 ^7, it is appropriate to use at least about 10 standard polystyrene samples . An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, Shodex GPC KF-801, 802, 80 manufactured by Showa Denko KK
3,804,805,806,807,800P or TSKgelG1000H (H
_{XL), G2000H (H XL)} , G3000H (H XL),
_{G4000H (H XL), G5000H (} H XL), G60
00H (H _XL ), G7000H (H _XL ), TSKgua
rdcolumn can be mentioned.

A sample is prepared as follows.

After the sample was put in THF and left for several hours,
Shake well and mix well with THF (until the sample is no longer united) and let sit for at least 12 hours. At this time, THF
The time for which the sample is left inside is set to 24 hours or more. Thereafter, the sample processing filter (pore size 0.
45 to 0.5 μm, for example, Mysholidisk H-25
-5, manufactured by Tosoh Corporation, and manufactured by Exiclodisc 25CR Germanic Science Japan) can be used as a GPC measurement sample. The sample concentration is
The resin component is adjusted to be 0.5 to 5 mg / ml.

The kind of the binder resin in the present invention is as follows.
Styrene resin, styrene copolymer resin, polyester resin, polyol resin, polyvinyl chloride resin, phenol resin, natural modified phenol resin, natural resin modified maleic resin, acrylic resin, methacryl resin, polyvinyl acetate, silicone resin, polyurethane Resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, cumarone indene resins, and petroleum resins.

As comonomers for the styrene monomer of the styrene copolymer, styrene derivatives such as vinyltoluene, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-acrylic acid Acrylates such as ethylhexyl and phenyl acrylate; methacrylates such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate and octyl methacrylate; maleic acid; butyl maleate, methyl maleate and dimethyl maleate Dicarboxylic acid esters having a double bond such as: acrylamide, acrylonitrile, methacrylonitrile, butadiene; vinyl chloride; vinyl esters such as vinyl acetate and vinyl benzoate; ethylene and propylene Emissions, such as ethylene-based olefin butylene; vinyl methyl ketone, such as vinyl vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl propionate ether. These vinyl monomers are used alone or in combination of two or more.

The binder resin used in the present invention is 1 to 100 m
It preferably has an acid value in the range of gKOH / g. Particularly preferred is a resin having an acid value of 1 to 70 mgKOH / g.

Examples of the monomer for adjusting the acid value of the binder resin include acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, cinnamic acid, vinyl acetic acid, isocrotonic acid, angelic acid and the like. α-
Alternatively, β-alkyl derivatives, fumaric acid, maleic acid, citraconic acid, alkenyl succinic acid, itaconic acid, mesaconic acid, dimethyl maleic acid, unsaturated dicarboxylic acids such as dimethyl fumaric acid and monoester derivatives or anhydrides thereof, and the like. Such a monomer can be used alone or as a mixture and copolymerized with another monomer to produce a desired polymer. Among them, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid for controlling the acid value.

More specifically, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate,
Monoesters of α, β-unsaturated dicarboxylic acids such as monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate, etc .; monobutyl n-butenylsuccinate, monomethyl n-octenylsuccinate, Monoesters of alkenyldicarboxylic acids such as monoethyl n-butenylmalonate, monomethyl n-dodecenylglutarate, monobutyl n-butenyladipate, and the like are included.

The carboxyl group-containing monomer as described above may be added in an amount of 0.1 to 20 parts by mass, preferably 0.2 to 15 parts by mass, based on 100 parts by mass of all the monomers constituting the binder resin.

The polymerization method that can be used in the present invention as a method for synthesizing the binder resin of the present invention includes a solution polymerization method, an emulsion polymerization method and a suspension polymerization method.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, the reaction heat can be easily adjusted, and the phase in which the polymerization is performed (oil phase composed of a polymer and a monomer)
And the aqueous phase are separate, so that the termination reaction rate is low, resulting in a high polymerization rate and a high degree of polymerization. Further, due to the relatively simple polymerization process and the fact that the polymerization product is fine particles, in the production of toner,
There is an advantage as a method for producing a binder resin for a toner because it is easy to mix with a colorant, a charge control agent and other additives.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to remove the polymer. To avoid this inconvenience, suspension polymerization is advantageous.

In the suspension polymerization, 100 parts by mass or less of the monomer (preferably 1 part by mass) is added to 100 parts by mass of the aqueous solvent.
(0 to 90 parts by mass). Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, and calcium phosphate, and are generally used in an amount of 0.05 to 1 part by mass based on 100 parts by mass of the aqueous solvent. The polymerization temperature is suitably from 50 to 95 ° C., but is appropriately selected depending on the initiator used and the intended polymer.

The binder resin used in the present invention is preferably formed by using a polyfunctional polymerization initiator alone or in combination with a monofunctional polymerization initiator as exemplified below.

Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-
3,3,5-trimethylcyclohexane, 1,3-bis- (t-butylperoxyisopropyl) benzene,
2,5-dimethyl-2,5- (t-butylperoxy)
Hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2 -Di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate , Di-t-butylperoxytrimethyladipate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-t-
Polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule such as butylperoxyoctane and various polymer oxides,
And a functional group having a polymerization initiating function such as a peroxide group in one molecule such as diallyl peroxydicarbonate, t-butyl peroxymaleic acid, t-butyl peroxyallyl carbonate and t-butyl peroxyisopropyl fumarate And a polyfunctional polymerization initiator having both a polymerizable unsaturated group.

Of these, more preferred are 1,
1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxy Azelate and 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, and t-butylperoxyallyl carbonate.

These polyfunctional polymerization initiators are preferably used in combination with a monofunctional polymerization initiator in order to satisfy various performances required as a binder for a toner. In particular, it is preferable to use the polyfunctional polymerization initiator together with a polymerization initiator having a half life of 10 hours lower than the decomposition temperature for obtaining a half life of 10 hours.

Specifically, benzoyl peroxide,
1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (t
-Butylperoxy) valerate, dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, di-t
Organic peroxides such as -butyl peroxide; and azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene.

These monofunctional polymerization initiators may be added to the monomer at the same time as the polyfunctional polymerization initiator. However, in order to maintain the efficiency of the polyfunctional polymerization initiator properly, It is preferable to add it after the half-life indicated by the polyfunctional polymerization initiator in the process.

These initiators are preferably used in an amount of 0.05 to 2 parts by mass based on 100 parts by mass of the monomer from the viewpoint of efficiency.

It is also preferable that the binder resin is crosslinked with a crosslinking monomer.

As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used.
Specific examples include aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by an alkyl chain (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4 -Butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6
Hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylate compounds linked by an alkyl chain containing an ether bond (for example, diethylene glycol diacrylate, triethylene glycol) Diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate); Diacrylate compounds linked by a chain containing, for example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propanediacryle DOO, polyoxyethylene (4) -
2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; further, polyester-type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)) ). As the multifunctional crosslinking agent, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds are replaced with methacrylate. And triallyl cyanurate and triallyl trimellitate.

These cross-linking agents can be used in combination with other monomer components 10
It is preferable to use 0.00001 to 1 part by mass, preferably 0.001 to 0.05 part by mass with respect to 0 parts by mass.

Among these crosslinkable monomers, those which are preferably used from the viewpoints of toner fixability and anti-offset property include aromatic divinyl compounds (particularly, divinylbenzene), which are linked by a chain containing an aromatic group and an ether bond. Diacrylate compounds.

As other synthesis methods, a bulk polymerization method and a solution polymerization method can be used. However, in the bulk polymerization method, a polymer having a low molecular weight can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control. In that regard, the solution polymerization method utilizes a difference in radical chain transfer depending on the solvent,
Further, it is preferable to adjust the amount of the initiator and the reaction temperature because a polymer having a desired molecular weight can be easily obtained under mild conditions. In particular, in terms of minimizing the amount of initiator used and minimizing the effects of residual initiator,
A solution polymerization method under a pressurized condition is also preferable.

The composition of the polyester resin used in the present invention is as follows.

Examples of the dihydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol and 1,5-pentanediol. , 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
Hexanediol, hydrogenated bisphenol A, and bisphenol represented by formula (E) and derivatives thereof;

[0094]

Embedded image (Wherein R is an ethylene or propylene group, x,
y is an integer of 0 or more, and the average value of x + y is 0 to 10. )

Diols represented by the formula (F):

[0096]

Embedded image

As the divalent acid component, for example, phthalic acid,
Benzenedicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides and lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides and lower alkyl esters; n- Alkenyl succinic acids or alkyl succinic acids such as dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides and lower alkyl esters thereof; fumaric acid, maleic acid, citraconic acid, unsaturated dicarboxylic acids such as itaconic acid or anhydrides, lower acids And dicarboxylic acids such as alkyl esters; and derivatives thereof.

It is preferable to use a trivalent or higher valent alcohol component and a trivalent or higher valent acid component which function as a crosslinking component.

The trihydric or higher polyhydric alcohol component includes
For example, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol,
1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,
3,5-trihydroxybenzene and the like.

The polyvalent carboxylic acid component having three or more valences in the present invention includes, for example, trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid,
2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,2
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-
Octanetetracarboxylic acid, empol trimer acid, and anhydrides and lower alkyl esters thereof;

[0101]

Embedded image (Wherein X is an alkylene group or alkenylene group having 5 to 30 carbon atoms having at least one side chain having 3 or more carbon atoms), such as tetracarboxylic acids, and anhydrides and lower alkyl esters thereof. And polyvalent carboxylic acids and derivatives thereof.

The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol%.
%, 60 to 40 mol% as an acid component, preferably 5%
It is preferably from 5 to 45 mol%. The content of the trivalent or higher polyvalent component is preferably 5 to 60 mol% of all components.

The polyester resin can also be obtained by generally known condensation polymerization.

The following are examples of the wax used in the present invention. For example, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax Or a block copolymer thereof; a plant wax such as candelilla wax, carnauba wax, wood wax, jojoba wax; an animal wax such as beeswax, lanolin, and whale wax; a mineral wax such as ozokerite, ceresin, petrolactam; Waxes; waxes mainly containing aliphatic esters such as montanic acid ester wax and caster wax; and those obtained by partially or entirely deoxidizing aliphatic esters such as deoxidized carnauba wax. . Further, saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a longer-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and barinaric acid; stearyl alcohol Saturated alcohols such as eicosyl alcohol, behenyl alcohol, kaunavir alcohol, seryl alcohol, melisyl alcohol, or alkyl alcohols having a longer chain alkyl group; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid amide;
Aliphatic amides such as lauric amide; saturated aliphatic bisamides such as methylenebisstearic acid amide, ethylenebiscapramide, ethylenebislauric amide, hexamethylenebisstearic acid amide; ethylenebisoleic amide, hexamethylenebisolein Acid amide, N, N′-dioleyladipamide, N, N
Unsaturated fatty acid amides such as N'-dioleyl sebacamide; m-xylene bisstearic acid amide;
Aromatic bisamides such as N'-distearyl isophthalic acid amide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metallic soaps); aliphatic hydrocarbons Wax grafted with a vinyl monomer such as styrene or acrylic acid on wax; partially esterified product of fatty acid such as behenic acid monoglyceride and polyhydric alcohol; having hydroxyl group obtained by hydrogenating vegetable oil or fat Methyl ester compounds are mentioned.

These waxes may be obtained by sharpening the molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a liquid crystal deposition method, or a low molecular weight solid fatty acid. Also, those from which low-molecular-weight solid alcohols, low-molecular-weight solid compounds, and other impurities have been removed are preferably used.

As the colorant that can be used in the toner, any suitable pigment or dye can be used. For example, pigments include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara, phthalocyanine blue, indanthrene blue and the like. These are used in an amount sufficient to maintain the optical density of the fixed image. It is preferable to use 0.1 to 20 parts by mass, preferably 1 to 10 parts by mass of the pigment based on 100 parts by mass of the resin. A dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes, and 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass of the dye is preferably used for 100 parts by mass of the resin. .

As the coloring agent of the present invention, magnetic iron oxide may be used. In that case, it can be used as a magnetic toner. As the magnetic iron oxide, iron oxide such as magnetite, maghemite and ferrite is used. Those containing a non-ferrous element on the surface or inside of the iron oxide are preferred.

When the present invention is applied as a magnetic toner, the magnetic iron oxide used therein preferably contains 0.05 to 10% by mass of a different element based on the iron element.
Particularly preferably, the content is 0.1 to 5% by mass.

[0109] These magnetic iron oxides are
It is preferably contained in an amount of 20 to 200 parts by mass with respect to 0 parts by mass. More preferably, the content is preferably 50 to 120 parts by mass.

The different element is preferably an element selected from magnesium, aluminum, silicon, phosphorus and sulfur. Also, lithium, beryllium, boron, germanium, titanium, zirconium,
Tin, lead, zinc, calcium, barium, scandium,
Vanadium, chromium, manganese, cobalt, copper, nickel, gallium, cadmium, indium, silver element, palladium, gold, mercury, platinum, tungsten, molybdenum,
Niobium, osmium, strontium, yttrium,
Metals such as technetium are exemplified.

These magnetic iron oxides have a number average particle size of 0.1.
Preferably from 0.5 to 1.0 μm, more preferably from 0.1 to 0.5 μm
m is preferred. Magnetic iron oxide has a BET specific surface area of 2
の も の 40 m ² / g (more preferably 4 to ²⁰ m ² / g) are preferably used. There is no particular limitation on the shape,
Any shape is used. As the magnetic characteristics, the saturation magnetization is 10 to 200 Am under a magnetic field of 795.8 kA / m.
² / kg (more preferably, 70-100 Am ² / k
g), the residual magnetization is 1 to 100 Am ² / kg (more preferably, ^{2 to 20} Am ² / kg), and the coercive force is 1 to 30 kA.
/ M (more preferably, 2 to 15 kA / m) is preferably used.

The magnetic toner used in the present invention has a density of 1.3 to 2.2 g / cm.
It is desirable to be ³ . Furthermore, 1.5 to 2.0 g /
It is preferably in the range of cm ³ . The mass (density) of the magnetic toner is correlated with the effects of magnetic force, electrostatic force, and gravity acting on the magnetic toner particles. When the density of the magnetic toner is within this range, the action of the magnetic iron oxide is appropriate, so the charging is performed. And the magnetic force are well-balanced, and excellent developing power can be exhibited.

The density of the magnetic toner is 1.3 g / cm.
If it is less than ^3, the effect of the magnetic iron oxide on the magnetic toner is weak, and the magnetic force will be low. For this reason, the electrostatic force for flying to the photosensitive drum at the time of development prevails, resulting in excessive development, which leads to fog and an increase in consumption. On the other hand, when the density of the magnetic toner is more than 2.2 g / cm ³ , the action of the magnetic iron oxide on the magnetic toner becomes strong and the magnetic force exceeds the electrostatic force, and the strong magnetic force action becomes large and the specific gravity becomes heavy. Therefore, it is difficult to fly from the sleeve at the time of development, resulting in a state of insufficient development, which leads to low image density and image deterioration.

The density of the magnetic toner can be measured by any of several methods. In the present application, when measuring the magnetic toner, a gas replacement method using helium is employed as an accurate and simple method.

The measurement was performed using an accupic 1330 (manufactured by Shimadzu Corporation). The measuring method was a stainless steel inner diameter of 18.5 mm, a length of about 39.5 cm, and a capacity of 6.7.
4 g of the measurement sample is placed in a 32 cm ³ cell. Next, the volume of the magnetic toner in the sample cell is measured by a change in the pressure of helium, and the density of the magnetic toner is determined from the determined volume and the weight of the sample.

In some cases, the magnetic iron oxide used in the magnetic toner of the present invention may be treated with a silane coupling agent, a titanium coupling agent, titanate, aminosilane or the like.

The toner of the present invention preferably contains a charge control agent.

The following compounds can be used to control the toner to be negatively charged.

Organic metal complexes and chelate compounds are effective, and examples thereof include monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and metal complexes of aromatic dicarboxylic acids. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives of bisphenol.

Among them, an azo metal complex represented by the following formula (I) is preferable.

[0121]

Embedded image [Wherein, M represents a coordination center metal, and Sc, Ti, V, C
r, Co, Ni, Mn or Fe. Ar is an aryl group, is an aryl group such as a phenyl group and a naphthyl group, and may have a substituent. In this case, the substituent includes a nitro group, a halogen group, a carboxyl group,
Anilide group and alkyl group having 1 to 18 carbon atoms, 1 carbon atom
There are ~ 18 alkoxy groups. X, X ', Y and Y' are -O-, -CO-, -NH-, -NR- (R is
To 4 alkyl groups). C ⁺ represents a counter ion, and represents hydrogen, sodium, potassium, ammonium, aliphatic ammonium or a mixed ion thereof. ]

In particular, the central metal is preferably Fe or Cr, the substituent is preferably a halogen, an alkyl group or an anilide group, and the counter ion is preferably hydrogen, alkali metal, ammonium or aliphatic ammonium. A mixture of complex salts having different counter ions is also preferably used.

The following compounds control the toner to be positively charged.

Nigrosine modified with nigrosine and fatty acid metal salts; tributylbenzylammonium-1-
Quaternary ammonium salts such as hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts, which are analogs thereof, and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (As the lake-forming agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; dibutyltin oxide, dioctyltin Diorganotin oxides such as oxide and dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate and dicyclohexyltin borate; guanidine compounds; imidazole Compounds, and the like. These can be used alone or in combination of two or more.
Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used. The following formula (II)

[0125]

Embedded image Wherein R ₁ represents H or CH ₃ , and R ₂ and R ₃ represent a substituted or unsubstituted alkyl group (preferably, C ₁ -C ₄ ); A copolymer with a polymerizable monomer such as styrene, acrylate or methacrylate described above can be used as a positive charge control agent. In this case, the homopolymer and the copolymer have a function as a charge control agent and a function as (all or part of) a binder resin.

As a method for incorporating the charge control agent into the toner, there are a method of adding the charge control agent inside the toner particles and a method of externally adding the charge control agent. The use amount of these charge control agents is determined by the type of the binder resin, the presence or absence of other additives, the toner manufacturing method including the dispersion method, and is not limited to a specific one. Preferably, it is used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the binder resin.

In order to obtain a toner having powder characteristics larger than the jettability index of 80, which is the object of the present invention, it is necessary to devise various external addition methods as described above. For example, this can be achieved by changing the configuration of the stirring blades of the external addition processing device used at the time of external addition, the filling ratio of the toner into the mixing device, and the stirring mode by changing the stirring mode.

An external additive is added to the toner according to the present invention. Preferred materials for the external additive include inorganic fine particles such as silica, titania, alumina and zirconia, and metal oxides. For example, dry silica is preferably used. This silica utilizes a thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this manufacturing process, it is possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with the silicon halide. They are also included. The average particle size of the inorganic fine powder is preferably in the range of 0.001 to 2 μm, particularly preferably 0.002 to 0.2 μm.
It is preferable to use an inorganic fine powder in the range of μm.

Further, inorganic fine powders such as silica, titania, alumina and zirconia, and fine powders obtained by subjecting a metal oxide to a hydrophobic treatment are more preferable. It is particularly preferable that the treated inorganic fine powder is obtained by treating the inorganic fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

The method for imparting hydrophobicity is provided by chemically treating an organic silicon compound or the like which reacts or physically adsorbs fine powder. As a preferred method, an inorganic fine powder produced by the vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethtridimethylchlorosilane,
α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, and Si located at the terminal unit and one each for Si And a dimethylpolysiloxane having a hydroxyl group bonded thereto. Further, a silicone oil such as dimethyl silicone oil may be used. These are used alone or as a mixture of two or more.

Good results are obtained when the specific surface area by nitrogen adsorption measured by the BET method is 30 m ² / g or more, preferably 50 m ² / g or more. 0.01 to 8 parts by mass, preferably 0.1 to 4 parts by mass of inorganic fine powder with respect to 100 parts by mass of toner
It is good to use parts by mass.

The method for producing the toner of the present invention includes the following.
After sufficiently mixing the above-mentioned toner constituent materials with a ball mill or other mixer, the mixture is well kneaded using a heat kneader such as a hot roll kneader or an extruder, and after cooling and solidifying, is mechanically pulverized to obtain a pulverized powder. A method of obtaining a toner by classification is preferable. Another method is a polymerization method in which a predetermined material is mixed with a monomer to constitute a binder resin to form an emulsified suspension and then polymerized to obtain a toner. In the microcapsule toner, a method in which a predetermined material is contained in a core material or a shell material, or both of them; a method in which a constituent material is dispersed in a binder resin solution and then spray-dried to obtain a toner. Further, if necessary, desired additives and toner particles can be sufficiently mixed by a mixer using the above-mentioned various methods to produce the toner of the present invention.

For example, as a mixer, Henschel mixer (manufactured by Mitsui Mining); super mixer (manufactured by Kawata); ribocorn (manufactured by Okawara Seisakusho); Nauta mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron); Spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); Ledige mixer (manufactured by Matsubo), and kneading machines include KRC kneader (manufactured by Kurimoto Iron Works); bus co-kneader (manufactured by Buss); TEM Mold extruder (manufactured by Toshiba Machine Co.); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three-roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); Decks (manufactured by Mitsui Mining Co., Ltd.); MS-type pressurized kneader, Nidder Ruder (manufactured by Moriyama Seisakusho); And a pulverizer such as a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); an IDS-type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic) and a cross jet mill (Kurimoto Tekko) Ullmax (Nisso Engineering); SK Jet
O-Mill (manufactured by Seishin Enterprise); Kryptron (manufactured by Kawasaki Heavy Industries); Turbo Mill (manufactured by Turbo Kogyo). Classifiers include Crasheal, Micron Classifier, and Spedd Classifier (Seishin Company). Turbo Classifier, Super Rotor (manufactured by Nisshin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron); Elbow Jet (manufactured by Nippon Steel Mining), Dispersion Separator (New Japan) YM Micro Cut (manufactured by Yasukawa Shoji Co., Ltd.). Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resonace Seeb, Gyro Shifter (Tokuju) Kakushosha); Vibrasoni (Manufactured by Dalton Co., Ltd.) click system; Soni clean (Sintokogio Co., Ltd.); (manufactured by Turbo Kogyo Co., Ltd.) turbo screener; (manufactured by Makino Mfg. Co., Ltd.) micro-shifter; circular vibration sieve, and the like.

[0137]

Examples of the present invention will be described below. Note that the present invention is not limited to the range shown in the following examples.

Examples and comparative examples were carried out using the following process cartridges.

FIG. 1 is a sectional view of a process cartridge used in the embodiment. 11 is a photosensitive drum, 18
Is a developing sleeve, 14 is a cleaning blade, and 12 is a charging member.

The developing means comprises a toner, a developing container, a developing sleeve 18 and an elastic blade (doctor blade or D blade) 19. The developing sleeve 18 is formed by coating an aluminum core with a phenol resin in which carbon graphite is dispersed. By providing a magnet (not shown) in the developing sleeve, the magnetic toner containing magnetite is attracted onto the developing sleeve 18, and the developing sleeve 1 is
8 is uniformly coated with toner.

On the other hand, the toner container 16 has a circular bottom of three bumps below, and three stirring members 20a, 2a
0b and 20c. Each stirring member forms a toner stirring area by the partition members 37-1 and 37-2. The width of the opening formed between the partition member 37 and the toner container was 15 mm.

Each of the stirring members has a structure in which a sheet material is provided on a stirring shaft. In this embodiment, 20 a is a PPS (polyphenylene sulfide) sheet having a thickness of 50 μm (Young's modulus: 3 GPa), and a rotation radius of 20 mm is used. .167
Rotate at a speed of s- ¹ . 20b and 20c have a thickness of 1
A PPS sheet having a thickness of 00 μm (Young's modulus: 3 GPa) is employed, and rotates at a speed of 0.0333 s ⁻¹ with a rotation radius of 30 mm. The amount of PPS sheet entering the container is 3m.
m.

Further, the following examples and comparative examples were examined using the toner before addition obtained by the following toner prescription and manufacturing method.

—Toner Material Composition— 100 parts by weight of binder resin 95 parts by weight of magnetic iron oxide 4 parts by weight of polypropylene wax 2 parts by weight of charge control agent The binder resin is a styrene-acrylic resin [glass transition by DSC measurement] Temperature Tg is 58 ° C, acid value is 23.0mgK
OH / g, Mn (number average molecular weight) 700 by GPC
0, Mw (weight average molecular weight) 400,000, monomer ratio: styrene 72.5 parts, n-butyl acrylate 20
Part, mono-n-butylmalate 7 parts, divinylbenzene 0.5 part]; the above magnetic iron oxide (average particle size: 0.20 μm
m, BET specific surface area: 8.0 m ² / g, coercive force: 3.7
kA / m, saturation magnetization: 82.3 Am ² / kg, residual magnetization: 4.0 Am ² / kg); the above polypropylene wax (melting point: 143 ° C, penetration at 25 ° C: 0.5 m)
m); As the charge control agent, an iron complex of an azo compound having a t-butyl group as a substituent is used.

The materials used in Example 1 were also used in the following Examples and Comparative Examples.

The above compound was melt-kneaded with a biaxial extruder heated to 130 ° C., and the cooled kneaded product was roughly pulverized with a hammer mill. The pulverization was performed by mechanical pulverization using a turbo mill (manufactured by Turbo Kogyo KK). The ultrafine powder and coarse powder were strictly classified and removed from the obtained finely pulverized material by a multi-segmentation classifier using a Coanda effect (an elbow jet classifier manufactured by Nittetsu Mining Co., Ltd.) to obtain a classified powder. BET of classified powder is 1.1
0 m ² / g, the weight average diameter of the obtained classified product is 6.8 μm
Met.

(Preparation of Toner 1) Classified powder 100 parts by mass Hydrophobic silica 1.2 parts by mass The hydrophobic silica was hydrophobized with dimethyl silicone oil and hexamethyldisilazane.
² / g, hydrophobic silica with methanol wettability of 68%. In the following examples and comparative examples, hydrophobic silica refers to this material.

The above materials were mixed with a Henschel mixer FM10
At C / l (manufactured by Mitsui Mining Co., Ltd.), the toner is filled so that the apparent volume filling ratio of the toner is 12%, and the stirring blades are selected from Y1 (FIG. 4) and S0 (FIG. 5) and rotated. Number 5
1 minute at 3.33 s ^-1 and then ¹ at 66.67 s ^-1
After that, the toner 1 was obtained.

The ratio of the specific surface area (BET) between the obtained toner 1 and the toner before external addition was 2.1, the jettability index measured by the method described in the specification was 90, and the fluidity index was 70. Was. These parameters, the angle of repose, is 26.7 °
(Index 24), spatula angle 53.0 ° (index 16),
Compressibility 25.0% (index 15), Cohesion 3.2% index (15), collapse angle 11.7 ° (index 24), difference angle 15.
The degree was 0 ° (index 15) and the degree of dispersion was 60% (index 25). Table 1 shows the toner external addition conditions and the toner powder characteristic measurement results.
Shown in

(Preparation of Toner 2) Using the same external additives and amounts as in toner 1, using a Henschel mixer FM10C / l
The stirring blades Y1 and S0 are selected and filled so that the apparent volume filling ratio of the toner becomes 12%, and the number of rotations is 41.67 s ^-1.
, And then processed at 53.33 s ^-1 for 2 minutes to obtain Toner 2.

The specific surface area (BET) ratio between the obtained toner 2 and the toner before external addition was 2.0, the jettability index measured by the method described in the specification was 86, and the fluidity index was 66. Was. The angle of repose, which is these parameters, is 31.0 °
(Index 22), spatula angle 60.0 ° (index 15),
Compressibility 25.0% (index 15), Cohesion 3.7% index (15), collapse angle 19.0 ° (index 24), difference angle 12.
The degree of dispersion was 0 ° (index 12) and the degree of dispersion was 55.0% (index 25). Table 1 shows the toner external addition conditions and the measurement results of the powder characteristics of the toner.

(Preparation of Toner 3) Classified powder 100 parts by mass Hydrophobic silica 1.0 part by mass Henschel mixer FM10C / l using the above materials
, The stirring blades Y1 and S0 are selected, the toner is filled so that the apparent volume filling ratio becomes 10%, and the rotation speed is set to 50.0.
After stopping for 2 minutes at ^{0 s −1} , the operation is stopped once, and then the number of revolutions is 66.
The mixture was stirred at 67 s ^-1 for 1 minute to obtain toner 3. The ratio of the specific surface area (BET) between the obtained toner 3 and the toner before external addition was 1.9, the jettability index measured by the method described in the specification was 83.0, and the fluidity index was 64.5. there were. The angle of repose, these parameters, is 35.0 ° (index 20),
Spatula angle 62.0 ° (index 12), compressibility 25.0
% (Index 15), cohesion 6.2% index (14.5), collapse angle 24.0 ° (index 21), difference angle 11.0 ° (index 1)
2), the degree of dispersion was 51.0% (index 25). Table 1 shows the toner external addition conditions and the measurement results of the powder characteristics of the toner.

(Preparation of Toner 4) Classified powder 100 parts by mass Hydrophobic silica 0.9 parts by mass Stirring blade Z0 with Henschel mixer FM10C / l.
(FIG. 6) and A0 (FIG. 7) are selected, and the toner is filled so that the apparent volume filling ratio of the toner becomes 9%.
Processing was performed at s ⁻¹ for 5 minutes to obtain toner 4.

The specific surface area (BET) ratio between the obtained toner 4 and the toner before external addition was 1.4, the jettability index measured by the method described in the specification was 73.5, and the fluidity index was 59. .5
Met. The angle of repose, which is these parameters, is 36.
0 ° (index 19.5), spatula angle 56.8 ° (index 16), compressibility 27.0% (index 12), cohesion 11.
0% index (12), collapse angle 26.0 ° (index 19.
5), difference angle 10.0 ° (index 10), degree of dispersion 35.0%
(Index 20). Table 1 shows the toner external addition conditions and the measurement results of the powder characteristics of the toner.

<Example 1> In Example 1, toner 1 was used. The free length of the doctor blade (D blade) is 8.5
mm, nip end is 1.5mm, contact pressure 0.23N,
The setting angle of the cleaning blade (C blade) is 2
At 0 ° and a tip thickness of 1.4 mm, the evaluation was performed by changing the settings of the cartridge as follows.

FIG. 1 is a main cross-sectional view of a process cartridge according to the present invention, FIG. 2 is a main cross-sectional view of an image forming apparatus according to the present invention, and FIG. 3 shows a mechanism of an automatic opening device for the process cartridge.

In FIG. 3, when the process cartridge is mounted on the main body of the image forming apparatus, the opening detecting section 3 in the main body of the apparatus is formed.
5. The attachment detection unit 36 and the detection unit 22 are connected to the contact portions 34b and 34.
c, 34a and 34c. Before the toner seal member 21 is wound, the unsealing detection conductive portion 22a and the mounting detection portion 22b are in a conductive state. This is detected by the opening detection unit 35 and the device detection unit 36 of the image forming apparatus main body. Then, the motor 26 provided as a drive source provided in the image forming apparatus starts driving in the direction of arrow A, winds up the toner seal 21 in the direction of arrow B, and automatically winds up the toner seal. (A) The capacity of the toner container was set to 3200 cm ^3, and the toner 1 was filled so that Ct / (X × Dt) indicating the filling rate of the toner was 0.7, and the evaluation was performed. (Ct192
5g, and ^{Dt0.86g / cm 3) (b)} 2800cm 3 the capacity of the toner storage unit, filled with toner 1 to Ct indicating the filling of the toner / (X × Dt) is 0.6, the evaluation went. (Ct1445
g, and ^{Dt0.86g / cm 3) (c)} 2600cm capacity of the toner storage unit ^3, filled with toner 1 as Ct indicating the filling of the toner / (X × Dt) of 0.6, evaluation Was done. (Ct112
0 g, Dt 0.86 g / cm ³ )

Table 2 shows a table of combinations of cartridge setting conditions and toners.

Next, the prepared magnetic toner and process cartridge were evaluated by the following five methods.

(Image Output Test) A process cartridge was filled with the above magnetic toner, and a laser beam printer LBP950 made by Canon (32 sheets / min. In A4 horizontal feed) was modified so that the process cartridge could be mounted. I did image drawing. The process speed at this time was 144.5 mm / sec.

At this time, when the process cartridge is loaded in the main body, the toner seal is automatically wound up without any problem in any of (a), (b) and (c), and the printout is good from the first printout. Image was obtained.

The obtained images were evaluated for the following items.

Image Density Under the above-mentioned setting conditions, under a low-temperature and low-humidity environment (15.0 ° C., relative humidity 10%) and under a high-temperature and high-humidity environment (32.5 ° C., relative humidity 80
%), An image output test (image forming test) was performed.
20,000 sheets were printed out on ordinary plain paper for copying machines (75 m ² / g). At the start of printing, the image density of the first sheet and the image density after 20,000 sheets of durability were measured.

The durability under a high-temperature and high-humidity environment was evaluated by using a cartridge filled with toner left at room temperature of 50 ° C. and a relative humidity of 0% for 3 days. The image density was measured using a Macbeth reflection densitometer (manufactured by Macbeth).

Fogging 20,000 sheets were printed out on ordinary plain paper for copying machines (75 g / m ² ) under low temperature and low humidity (temperature: 15 ° C., humidity: 10% RH), and the fog at the start and end was evaluated. Was. Fog was calculated from a comparison between the whiteness of the transfer paper measured by a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness on transfer after printing solid white. The larger the value, the worse the fog.

Negative ghost Printed out on a plain paper for copying machines (75 g / m ² ) under low temperature and low humidity (15 ° C., 10% humidity), 20,000 sheets were printed, and the negative ghost was evaluated every 5,000 sheets. To evaluate the image related to the ghost, a solid black band was output for one rotation of the sleeve, and then a halftone image was output. FIG. 8 shows a schematic view of the pattern. The evaluation was performed by using a Macbeth densitometer at a place where a black image was formed on the second round of the sleeve (black print area) and a place where the black image was not formed (non-image area). The difference between the measured reflection densities was calculated as follows. Negative ghost is a ghost phenomenon in which the density of the image that appears in the second round of the sleeve is generally lower than that of the non-image part in the first round, and the shape of the pattern that appears in the first round appears as it is. The evaluation was performed based on the difference in reflection density using the difference in density.

Reflection density difference = reflection density (location where no image is formed) −reflection density (location where an image is formed)

Table 3 shows the average value. The smaller the difference between the reflection densities, the better the level and the better the ghost does not occur. The ghost was evaluated in five stages of ５, △, △, △ ×, and ×. (Reflection density difference): 0.00 to 0.02 △: 0.02 to 0.04: 0.04 to 0.06 ×: 0.06 to 0.08 ×: 0.08 to

Evaluation of Sandy Ground When a halftone image is output in a low-temperature and low-humidity environment, countless white dots (sandy grounds) may appear and image defects may occur. For this reason, the evaluation of the present invention was made at the time of printing start and at the 50th, 100th, 200th, and 50th sheets.
When the halftone was printed out on the 0th sheet, it was evaluated whether or not sand was present (see FIG. 9).

[0170] The evaluation was made by setting a circle where sand was seen only at the start of printing, a triangle where sand was seen up to the 100th sheet, and a x where sand was seen even on the 500th sheet.

Image white spots In a high-temperature, high-humidity environment, if a solid black image is output during the endurance, if the toner transportability is poor, the toner may not be developed and the image may become white. for that reason,
As evaluation of the present invention, 5000 from the start of printing
A solid black image was printed out for each sheet up to a total durability of 20,000 sheets, and evaluation was made as to whether or not the image was blank.

Blade turning In a high-temperature, high-humidity environment, ordinary paper for copying machines (75 g
/ M ² ), and the blade turn-up from the start of printing (at the start of the machine) to the end of printing was evaluated.

The above six items were evaluated.

Evaluation was made on a, b, and c in which the capacity and the filling rate of the toner storage section were changed. As a result, the developability was excellent in both a low-temperature, low-humidity environment and a high-temperature, high-humidity environment. , B2.0% and c1.9%. Further, phenomena such as sleeve ghost, white stripes, white spots on the image, and turning over of the blade were not observed.

Table 3 shows the evaluation results.

<Example 2> In Example 2, toner 2 was used. The capacity of the toner container is 3000 cm ³ , and Ct / (X × Dt) indicating the toner filling rate is 0.6 (Ct1475).
g, Dt 0.84 g / cm ³ ), when the setting angle of the C blade was 20 ° and the tip thickness was 1.4 mm, the evaluation was performed by changing the setting of the cartridge as follows. (A) Evaluation was performed using a blade with a D blade having a free length of 7.5 mm, a nip end of 1.2 mm, and a contact pressure of 0.20 N. Excellent developability was obtained in both a low-temperature, low-humidity environment and a high-temperature, high-humidity environment. The fog was as good as 2.7%. Also, sleeve ghosts, white streaks, image voids,
No phenomenon such as turning over of the blade was observed. (B) Evaluation was performed using a blade with the free length of the D blade set to 9.0 mm, the nip end set to 2.0 mm, and the contact pressure set to 0.27 N. The fog was as good as 1.2%. Also, sleeve ghosts, white streaks, image voids,
No phenomenon such as turning over of the blade was observed.

At this time, when the process cartridge is loaded in the main assembly, the toner seal is automatically wound up without any problem in any of (a) and (b), and a good image is obtained from the first printout. Was done.

<Embodiment 3> In Embodiment 3, toner 3 is used. The capacity of the toner container is 3000 cm ³ , and Ct / (X × Dt) indicating the toner filling rate is 0.6 (Ct1475).
g, Dt 0.84 g / cm ³ ), the free length of the D blade is 8.5 mm, the nip end is 1.5 mm, and the contact pressure is 0.2.
The evaluation was performed by changing the setting of the cartridge as follows using a blade set to 3N. (A) The setting angle of the C blade is 24 ° and the tip thickness is 1.8 m
When the evaluation was performed at the time of m, the developability was excellent in both the low-temperature and low-humidity environment and the high-temperature and high-humidity environment, and the fog was as good as 2.3%. Further, phenomena such as sleeve ghost, white stripes, white spots on the image, and turning over of the blade were not observed. (B) The setting angle of the C blade is 20 ° and the tip thickness is 1.2 m
When the evaluation was carried out at m, evaluation was excellent in both a low-temperature and low-humidity environment and a high-temperature and high-humidity environment, and the fog was as good as 1.8%. Further, phenomena such as sleeve ghost, white stripes, white spots on the image, and turning over of the blade were not observed.

At this time, when the process cartridge is loaded into the main unit, the toner seal is automatically wound up without any problem in any of (a) and (b), and a good image is obtained from the first printout. Was done.

<Comparative Example 1> In Comparative Example 1, toner 4 was used. The cartridge has a toner seal automatic winding device as in the embodiment, and is set in the printer machine main body as shown in FIG. When the cartridge is loaded inside the main body, the seal is automatically wound by the winding member provided at the end of the cartridge shown in FIGS. The capacity of the toner container is 3000 cm ³ ,
The toner is charged such that Ct / (X × Dt) indicating the toner filling rate becomes 0.6 (Ct 1440 g, Dt 0.8
0 g / cm ³ ), the free length of the D blade is 8.5 mm, the nip end is 1.5 mm, the contact pressure is 0.23 N, the set angle of the C blade is 20 °, and the tip thickness is 1.4 mm. went.

At the time of automatic opening, unevenness occurred in the toner supply state, and unevenness in density occurred.

In a low-temperature and low-humidity environment, although the image density did not decrease, fading was observed at the edges.

The level of fog was as poor as 5.2%, and the level of negative ghost was also poor. In addition, many sand areas were also noticeable in the 500th halftone image. Although the image density itself did not decrease in a high-temperature and high-humidity environment, it was found that the density was uneven and thin, and white spots occurred when the print density exceeded 15,000 sheets. The evaluation was terminated because turning over occurred.

[0184]

[Table 1]

[0185]

[Table 2]

[0186]

[Table 3]

[0187]

According to the present invention, when a toner having a jetting index according to the present invention is used and applied to a large-capacity cartridge capable of storing a large amount of toner, the charge rises rapidly in a low-temperature and low-humidity environment, and fog / negative ghost is reduced. Does not occur. Also,
It is less affected by the environment, exhibits good developability until the toner is exhausted even after storage at high temperatures, and does not cause image white spots or blade turning.

[Brief description of the drawings]

FIG. 1 is a sectional view of a process cartridge used in the present invention.

FIG. 2 is a sectional view of an image forming apparatus used in the present invention.

FIG. 3 is a diagram of an automatic opening device mechanism used in the present invention.

FIG. 4 is a schematic view of a stirring blade Y1 used in the present invention.

FIG. 5 is a schematic view of a stirring blade S0 used in the present invention.

FIG. 6 is a schematic view of a stirring blade Z0 used in the present invention.

FIG. 7 is a schematic view of a stirring blade A0 used in the present invention.

FIG. 8 is a diagram of negative ghost evaluation.

FIG. 9 is a diagram of sandy land evaluation.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Discharge roller 2 ... Discharge part 3 ... Registration roller 4 ... Fixing device 5 ... Transfer roller 6 ... Sheet cassette 7 ... Conveyance roller 8 ... Exposure device 11 .. Photosensitive drum 12 charging member 13 cleaning frame 14 cleaning blade 15 process cartridge 16 toner container 17 developing container frame 18 developing sleeve (Toner carrier) 19 doctor blade (development blade) 20a / 20b / 20c stirring member 21 toner seal member 22 detector 23 winding member a gear Part c: claw part 24: second coupling gear 25: main body second coupling 26: main body motor 29: vibrating gear 27, 28 Reference Signs List 30 idler gear 31 opening 32 stirring gear 33 idler gear 34 sheet metal part 35 body opening detector 36 body mounting detector 37-1 / 37- 2 ··· Partition member

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 21/10 G03G 15/08 507L 21/00 318 (72) Inventor Tsutomu Konuma 3-chome Shimomaruko, Ota-ku, Tokyo No. 30-2 Canon Inc. (72) Inventor Hirohide Tanikawa 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term (reference) 2H005 DA05 EA07 EA10 2H077 AA02 AA06 AB03 AB12 AB18 AC03 AD06 AD13 AD17 AD23 AE03 AE04 EA14 GA02 2H134 GA01 GB02 HD01 KD05 KF03 KH04 KH15

Claims (7)

[Claims] A plurality of toner storage spaces, each toner storage space being connected via an opening, capable of moving toner, and having at least one stirring member in each toner storage space; In the toner used in the image forming method in which the toner is moved from the storage unit to another storage unit by the stirring member or the transport member, and the toner is supplied to the developing unit that holds the toner carrier and developed, the toner to be filled is at least A toner comprising a binder resin and a colorant, satisfying the following expression, and having a Carr jetting index of 80 or more. 0.2 ≦ (Ct / (X × Dt)) ≦ 0.8 [X (cm ³ ): total capacity X of toner storage section X ≧ 250
0, Ct (g): mass of toner contained, Dt (g / c)
m ³ ): Tap density of toner] 2. The toner according to claim 1, wherein the fluidity index of Carr is a value greater than 60. 3. A process cartridge comprising at least a developing means and a photosensitive member, wherein the developing means has a plurality of toner storage spaces, each toner storage space is connected via an opening, and the toner can be moved. ,
A developing unit that has at least one stirring member in each toner storage space, moves toner from the storage unit to another storage unit by the stirring member or the transport member, and supplies and develops the toner to the developing unit that holds the toner carrier. A process cartridge, wherein the toner to be filled contains at least a binder resin and a colorant, satisfies the following expression, and the toner has a Carr jetting index of greater than 80. 0.2 ≦ (Ct / (X × Dt)) ≦ 0.8 [X (cm ³ ): total capacity X of toner storage section X ≧ 250
0, Ct (g): mass of toner contained, Dt (g / c)
m ³ ): Tap density of toner] 4. A toner container frame that contains toner and has an opening, a toner seal that seals the opening of the toner container frame, and a developing frame that supports the toner carrier and is joined to the toner container frame. The process cartridge according to claim 3, further comprising: a toner seal automatic winding device having a toner seal winding shaft for opening the toner seal. 5. A free length of the toner regulating elastic blade member set in contact with the toner carrier is 7.0 to 10.0 m.
m, and the length (nip end) of the elastic blade on the free end side from the nip portion is 0.5 to 2.5 mm, and the contact pressure of the elastic blade in contact with the toner carrier is linear. The process cartridge according to claim 3, wherein the pressure is 0.10 to 0.40 N. 6. A cleaning device for removing toner on the surface of the photoconductor, wherein the cleaning device is a rubber elastic blade, and a setting angle of the blade with respect to a tangent to the surface of the photoconductor is set in a range of 10 ° to 30 °. And the tip thickness of the rubber blade is 0.5 to 2.5 mm
The process cartridge according to any one of claims 3 to 5, wherein 7. The process cartridge according to claim 3, wherein a toner having a Carr fluidity index greater than 60 is used.